LC) i 0 Electronic Systems for Interfacing with New Materials and Devices <0 00 by Sungjae Ha B.Eng., Pohang University of Science and Technology (2009) S.M., Massachusetts Institute of Technology (2011) Submitted to the Department of Electrical Engineering and Computer Science in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY at the MASSACHUSETTS INSTITUTE OF TECHNOLOGY June 2015 @ Massachusetts Institute of Technology 2015. All rights reserved. Sig nature redacted Author .. Department of Electrical Engineering and Computer Science May 20, 2015 Certified by. Signature redacted Anantha P. Chandrakasan Joseph F. and Nancy P. Keithley Professor Thesis Supervisor Signature redacted AD9 Accepted by . C /\ . ..................... Tomis Palacios Associate Professor Thesis Supervisor / Certified by. ....... Signature redacted ............ lalie A. Kolodziejski Chair, Departmental Committee on Graduate Theses " 5: C Cl) UJ 2 Electronic Systems for Interfacing with New Materials and Devices by Sungjae Ha Submitted to the Department of Electrical Engineering and Computer Science on May 20th, 2015, in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Abstract The focus of this thesis is to explore and demonstrate electronics systems utilizing new materials and devices beyond the traditional ones solely based on Si CMOS technology. The first part of this thesis is to explore the combination of Bio-MEMS devices with traditional electronics as an effective diagnostic tool. In the case study of malaria, we report a microfluidic device as part of a continuous-flow cellular impedance spectroscopy system and a new data analysis method to differentiate Plasmodium falciparum-infected human erythrocytes including the early ring stage. The next parts of this thesis focus on two-dimensional (2D) materials which are believed to be a tool set for future electronics. In particular, graphene is explored as a new infrared sensitive material that can be used for sensors in mid- and long-wavelength infrared spectrum (A = 2- 15pm) imaging systems. We demonstrate a Si CMOS-based readout IC and monolithic integration of an array of > 4000 electronically tunable graphene thermocouples. The prototype system shows that use of 2D material as add-on parts of the conventional technology can lead to development of new types of electronic applications. In addition to combinational uses with Si CMOS technology, 2D materials and their heterostructures have the potential to be used as stand-alone electronic systems. In the latter part of the thesis, we present a computer-aided design (CAD) flow for large-scale MoS 2 electronics. Combined with the state-of-the-art fabrication technology and the physics-based device model for MoS 2 FETs, a switched capacitor DC-DC converter, a half-wave rectifier, and a voltage doubler are implemented, and good agreement between simulation and measurement is observed. The presented CAD flow enables large-scale integrated circuit design on MoS 2 technology and paves the way for ubiquitous, flexible and possibly transparent electronics, such as printed RFID tags and transparent display drivers. Utilizing these design concepts, we push the capability of current electronics beyond its traditional boundaries. 3 Thesis Supervisor: Anantha P. Chandrakasan Title: Joseph F. and Nancy P. Keithley Professor Thesis Supervisor: Toma's Palacios Title: Associate Professor 4 Acknowledgments First and foremost I would like to thank my advisors, Professor Anantha Chandrakasan and Professor Tomas Palacios, for their unceasing care, inspiration, and guidance over the years. I appreciate the priviledge to work with Anantha and Toma's; I cannot imagine my journey to Ph.D. without their mentorship. I would also like to thank my thesis committee, Ming Dao, not only for his time and dedication to this thesis but also for his caring and cheerful comments throughout the years. It had been a great pleasure to collaborate with Ming during my Master's and Doctorate study. To Sarah E Du and Monica Diez-Silva, I am very thankful to have worked with them in such interesting interdisciplinary topic. I also want to show my deep appreciation to Allen L. Hsu, Charles Mackin, Cosmi Yuxuan Lin, and Marek Hempel, for they have spent days and nights in the fab with me and without me. I appreciate Yi Song, Wenjing Fang, and Xu Zhang for FIB and Raman spectroscopy assists; I must have bothered them so much. To Lili Yu, nothing would have been possible without her dedication and great fab works. I thank Amir, Daniel, Min, Ahmad, and everyone else in Palacios group. To Arun Paidimarri and Philip Nadeau, I would like to express special thanks for being with me for past years with the wonderful friendship. To Frank Yaul, it has been such a pleasure to have such a wonderful cube-mate with full of academic curiosity, and I also thank Dina El-Damak for great collaboration. I thank Hyung-Min, Dongsuk, Nachiket, Mehul, Georgios, Avishek, Chuhong, Preet, Chiraag, Bonnie, Sirma, Michael, Gilad, Priyanka, Nathan, Saurav, Marcus, Masood, Margaret, Andreina, and all other ananthagroup members. Pursuing Ph.D. is at times a solitary one, but I am honored to have worked with many brilliant people. To my dear friends, I especially thank Yongjoo Kim, Jeongwon Lee, and Changmin Lee for going through my most difficult moments together. I also thank Chung Jong 5 Yu, Hyangsoo Jeong, Jouha Min, Jeremy Lee, David T. Kim, Hyun Ho Boo, Sung Sik Woo, Donghun Kim, Grace Han, Hokyung Choi and Bon Jun Koo for their great friendship. I also want to express my warm thanks to KGSA, KGSA-EECS, POSTECH alumni, and UNITAS for sharing and supporting my life at MIT. I acknowledge Fulbright Science and Technology Award for financial support. Prof. Sung Jae Kim, Prof. Jongyoon Han, Prof. YongKeun Park and Prof. Subra Suresh helped in the initial system development and discussion in background experimental work. I also acknowledge MIT Center for Integrated Circuits and Systems and Institute for Soldier Nanotechnology for their fundings. The readout IC fabrication was supported by Taiwan Semiconductor Manufacturing Company Limited's University Shuttle program. Other fabrications were carried out at MIT Microsystems Technology Laboratories and US Army Research Laboratory. I would like to thank Prof. Jae-Yoon Sim, Prof. Byungsub Kim, and Taeyoung Chung for fruitful discussions. Internship at Samsung Advanced Institute of Technology and Maxim Integrated has taught me in-field design experience; I enjoyed practicing and excerising circuit design for commercial ICs. In addition, Rev. Dominic Jung, Haepyoung Chung, and Sangbeom Kim were my dearest mentors during my life in Boston. In addition, I want to thank Dr. Austin Patrick Egan at MIT Medical. Moreover, my forever appreiciation goes to my family. My wife, an exceptional violinist, Dr. Yura Hyun, thank you for always standing by my side during this lone journey to dissertation. Since I am yours and you are mine, our cozy little world has become twice as nice. I appreciate my lovely daughter, Irene, for she has taught me what a daily progress meant and how much my father had loved me. My mother, Myungja Kim, who has raised me to be a sincere person, always gives me warm comfort, and my sister, Salim, also has been a big support. In addition to them, I give thanks to all my family members who have sent endless love, care, and prayers from Korea, Saudi Arabia, and Boston. 6 Cleanse me with hyssop, that I may be pure; wash me, and I will be whiter than snow. You will let me hear gladness and joy; the bones you have crushed will rejoice. Psalm 51:9-10 Sungjae Ha Cambridge, MA MAY 20th 2015 7 S Contents 23 1 Introduction 2 1.1 Materials and Devices for Next-Generation Electronics . . . . . . . . 23 1.2 Challenges in System Design with Emerging Technologies . . . . . . . 26 1.3 Thesis Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 Cellular Electric Impedance Spectroscopy for Characterization of 29 Malaria States 2.1 2.2 2.3 2.4 3 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29 2.1.1 Cellular Electric Impedance Spectroscopy . . . . . . . . . . . . 29 2.1.2 Disease States of Malaria and Detection Target for Early Diagnosis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 Materials and Methods . . . . . . . . . . . . . . . . . . . . . . . . . . 32 2.2.1 Microfluidic Probe Device Fabrication . . . . . . . . . . . . . . 32 2.2.2 Malaria-Infected Human Erythrocyte Sample Preparation . . 32 2.2.3 Measurement Setup . . . . . . . . . . . . . . . . . . . . . . . . 34 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . 35 2.3.1 Data Acquisition and Preprocessing . . . . . . . . . . . . . . . 35 2.3.2 Analysis with a Dimensionless Parameter 6 . . . . . . . . . . . 39 2.3.3 Effect of BSA Concentration in Buffer Solution . . . . . . . . 42 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . 44 Graphene-Silicon Hybrid IC for Thermal Imaging 3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 47 47 48 3.1.2 Photovoltaic and Photoconductive Detectors . . . . . . . 3.1.3 Thermal Detectors . . . 52 . . . . 50 53 . . . . . . . . . . . . 54 3.3.1 Readout IC Architecture . . . . . . . . . . . . . . . . . . 54 3.3.2 Sub-Block Designs . . . . . . . . . . . . . . . . . . . . . 56 3.3.3 Considerations for Back-End Graphene Sensor Integration 66 . Mechanically Suspended Graphene Thermocouples 50 Graphene-CMOS Hybrid Infrared Imager . . . . . . . . . . . . . 68 3.4.1 . 3.4 . . . . . . . . . . . . . . . . . . . . . Graphene for Photosensing . . . . . . . . . . . . . . . . . . . . . 3.2.1 68 . Readout IC for Graphene IR Sensor Array . 3.3 . History of Electronics for Infrared Sensing . . . . . . . . . 3.2 3.1.1 Graphene Thermocouple Device for On-Chip Integration an 3.7 73 3.5.1 ADC Characterization . . . . . . . . . . . . . . . . . . . . . 73 3.5.2 Pseudo Photoresponse Measurement . . . . . . . . . . . . . 77 3.5.3 Off-Chip Graphene Thermocouple Measurement . . . . . . . 77 3.5.4 Integrated Graphene Sensor Array Measurement . . . . . . . 81 D iscussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87 3.6.1 Graphene Models for Pixel Readout . . . . . . . . . . . . . . 87 3.6.2 Power Line Shorting Issues . . . . . . . . . . . . . . . . . . . 91 3.6.3 Revised Metalization . . . . . . . . . . . . . . . . . . . . . . 94 Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . 98 . . . . . . . . . . . . . . 3.6 M easurements . . . . . . . . . . . . . . . . . . . . . . . . 3.5 4 MoS 2-Based Next Generation Electronics . . . . . . . . . . . . . 99 4.1.1 Demands for MoS 2-Based Electronics . . . . . . . . . . . . . 100 4.1.2 Material Growth . . . . . . . . . . . . . . . . . . . . . . . 100 4.1.3 Device Fabrication . . . . . . . . . . . . . . . . . . . . . . 101 4.1.4 Design Flow . . . . . . . . . . . . . . . . . . . . . . . . . . 102 Computer-Aided Design Flow . . . . . . . . . . . . . . . . . . . . 104 . . . . 4.2 Introduction . . . . . . . . . . . . . . . . . . 4.1 99 10 4.3 4.4 5 4.2.1 Modeling of MoS 2 -Based Devices . . . . . . . . . . . . . . . . 105 4.2.2 Technology Library and Parameterized Cell for MoS 2 Layout 110 Circuit Design Demonstration . . . . . . . . . . . . . . . . . . . . . .111 . . . . . . . . . . . . .111 4.3.1 Switched Capacitor DC-DC Converter 4.3.2 Half-Wave Rectifier . . . . . . . . . . . . . . . . . . . . . . . . 115 4.3.3 Voltage Doubler . . . . . . . . . . . . . . . . . . . . . . . . . . 117 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . 118 Outlook and Future Work 5.1 5.2 121 Thesis Contributions . . . . . . . . . . . . . . . . . . . . . . . . . . . 121 5.1.1 Cellular Electric Impedance Spectroscopy . . . . . . . . . . . . 121 5.1.2 Graphene-Silicon Hybrid Infrared Imager . . . . . . . . . . . . 122 5.1.3 MoS 2 -Based Electronics . . . . . . . . . . . . . . . . . . . . . 124 Future Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125 5.2.1 2D Scan Imaging with Graphene Thermocouple Array . . . . 125 5.2.2 MoS 2 RFID Tags . . . . . . . . . . . . . . . . . . . . . . . . . 126 5.2.3 MoS 2 Display Driver . . . . . . . . . . . . . . . . . . . . . . . 129 Appendices 130 A Process Flow 131 A.1 EIS Probe Device Fabrication . . . . . . . . . . . . . . . . . . . . . . 131 A.2 Graphene IR Imager Integration . . . . . . . . . . . . . . . . . . . . . 134 A.3 MoS 2 Device Fabrication . . . . . . . . . . . . . . . . . . . . . . . . . 143 B Test Setup and PCB Design B.1 PCB Designs 145 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C CAD Environment 145 153 C.1 Model Implementations for MoS 2 Devices . . . . . . . . . . . . . . . . 153 C.2 Technology Library for MoS 2 Device Layout . . . . . . . . . . . . . . 160 162 Bibliography 11 12 List of Figures 1-1 Illustration of a Bio-MEMS device for electric impedance spectroscopy of red blood cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-2 Illustration of monolayer graphene (top) and molybdenum disulfide (bottom ). 2-1 24 . .. ... .. .. . . . . . .. . . . . . .. . . .. . .. .. . 25 Asexual intraerythrocytic phase of the life cycle of Plasmodium f alciparum m alaria parasite [1] . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31 2-2 Fabrication of microfluidic probe chip [2] . . . . . . . . . . . . . . . . 33 2-3 Measurement setup of microfluidic EIS of malaria infected human blood sam ple . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 2-4 Dynamic impedance transitions at cell passage over probe electrodes . 35 2-5 Overlaid transient El results of uninfected RBCs and Pf-iRBCs crossing over the electrodes with the measurement conditions: 2MHz 1Vpp and 0.2% (w/v) BSA-PBS. . . . . . . . . . . . . . . . . . . . . . . . . 2-6 Scatter plot of 113 El data (Ap, AM) consisting of 78 uninfected RBCs, 12 ring stage iRBCs, and trophozoite stage iRBCs. 2-7 37 . . . . . . 38 Block diagram of cellular impedance measurement setup and simplified cellular circuit model. A simplified cellular impedance model is shown in the inset. The extraction of model parameters requires an excitation source with variable frequency. . . . . . . . . . . . . . . . . . . . . . . 2-8 38 Scatter plot of normalized EI transitions of uninfected RBCs in three different BSA-PBS concentrations . . . . . . . . . . . . . . . . . . . . 13 40 2-9 Scatter plot of normalized El transitions for 0.2% BSA-PBS condition and definition of an offset parameter 6 . . . . . . . . . . . . . . . . . 40 2-10 Statistical box chart of two-sample t-test for 6's collected from the Pf-iRBC sample in 0.2% BSA-PBS concentration . . . . . . . . . . . 41 2-11 Statistical box chart of two-sample t-test for 6's collected from the Pf-iRBC sample in 0.5% BSA-PBS concentration . . . . . . . . . . . 42 2-12 Statistical box chart of two-sample t-test for 6's collected from the Pf-iRBC sample in 1.0% BSA-PBS concentration . . . . . . . . . . . 3-1 (a) Illustration of the MEMS-enhanced graphene thermopile. 43 Small holes in the center of the infrared absorber are meant to facilitate suspension of the thermal isolation stack, while the large openings along the periphery help define the thermal isolation legs. (b) The measured signal shown as a function of actuator position. The thermal image was formed by placing a laser cut stainless steel aperture in front of the blackbody source (T = 472 K, fmod = 173 Hz) and scanned in position using a series of motorized X-Y translation stages. The step size was 0.5 mm and the integration time was 3 s per pixel [3,4]. . . . 3-2 Conceptual floorplan for integrated graphene IR imager. 54 An array of 80 by 60 graphene thermocouple pixels is fabricated on top of the Si-CMOS readout IC. . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-3 55 Schematic of an imager block consisting of 8-column by 60-row pixel amplifiers, a 8-to-1 MUX, a variable gain amplifier, and an ADC. The prototype chip consists of 10 of this imager block that complete a 80 x 60 pixels image sensor. . . . . . . . . . . . . . . . . . . . . . . . . . 3-4 55 Circuit model of a graphene photodetector and a transimpedance amplifier. The transimpedance amplifier converts the input current (In) 3-5 into the output voltage (V) by a conversion gain. . . . . . . . . . . . 56 Illustration of photo-signal modulation and extraction scheme. ..... 57 14 3-6 (a) Schematic of the proposed pixel transimpedance amplifier. The bias tail current is set to satisfy the current deviation less than 1% of the bias current. The matching of g, thus minimizing Zi, has fine-tune control by the VB node. (b) Simulated input impedance adjustment of the PTIA with VB range from 1.1V to 1.8V across the process corners. 58 3-7 Schematic of Successive Approximation Register ADC. 61 3-8 Simulated DNL and INL of the capacitive DAC across 8 bit digital . . . . . . . . codes. IDNLIMAX < 0.04 and IINLMAx < 0.07 are achieved. .... 3-9 Timing diagram of the implemented successive approximation logic 62 . 63 3-10 Schematic of a testbench for imager block readout simulation. 8 graphene pixels with unique (R-PD = 'ph values (0 - 12 nA) and low output impedance 150 Q) were assumed. . . . . . . . . . . . . . . . . . . . . 3-11 Simulated Photoresponse Readout of Multiple Pixels . . . . . . . . . 64 65 3-12 Die photo of the readout IC for graphene-CMOS hybrid IR imager. The chip shown is before the integration of graphene thermocouples. . 67 3-13 Diagram of a graphene thermocouple fabricated on top of the CMOS substrate. Two gate metal lines are embedded in Si0 2 passivation layer for electrostatical doping of MLG, and the ohmic contact and plug ensure electrical connection to the pixel amplifier. . . . . . . . . 69 3-14 Fabrication processes for integrated graphene IR imager chip (1)-(4) . 70 3-15 Fabrication processes for integrated graphene IR imager chip (5)-(8) . 71 3-16 Die photos of the fabricated graphene IR imager prototype chip (left) along with the original die for comparison (right) . . . . . . . . . . . 72 3-17 Close-up micrographs of the pixel area shows the fabricated structures, including monolayer graphene, ohmic contacts, and back gates for graphene thermocouple array. . . . . . . . . . . . . . . . . . . . . 72 3-18 Measured linearity of ADC at the sampling rate of 800 kSPS. |DNL| < 0.3 LSB and JINLI < 0.4 LSB across all 8 bit digital codes are achieved. 73 3-19 Measured linearity of ADC at the sampling rate of 800 kSPS. IDNLI < 1 LSB and IINLI < 1 LSB across all 8 bit digital codes are achieved. . 15 74 3-20 FFT plot of ADC output code at 240 kSPS where input tone is at 1.952 kH z . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74 3-21 Measured ENOB of ADC . . . . . . . . . . . . . . . . . . . . . . . . . 75 3-22 Power consumption of ADC . . . . . . . . . . . . . . . . . . . . . . . 76 3-23 (a) Schematic diagram of pseudo photoresponse measurement shows test setup, and (b) sub-nA resolution is measured with linear input current range of 160 nA. . . . . . . . . . . . . . . . . . . . . . . . . . 77 3-24 Schematic diagram (top) and photograph (bottom) of discrete graphene thermocouple measurement setup . . . . . . . . . . . . . . . . . . . . 3-25 FFT plot of the photoresponse measured at Pi, = 157 puW and 78 = fmod 250 Hz input. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79 3-26 Estimated photoresponse amplitudes at various Pj,'s by integrating power spectral density of the signal peak at fmod= 2 5 0 Hz . . . . . . . 80 3-27 Average output code measured at various Pi's. The signal nature that only non-negative response is generated allows the photoresponse estimation by simple averaging. . . . . . . . . . . . . . . . . . . . . . 81 3-28 Micrograph of delaminated graphene layers in thermocouple array . 82 3-29 Raman spectroscopy of graphene layers of on-chip thermocouples. . 83 3-30 Raman spectroscopy of graphene layers of on-chip thermocouples shows electrostatical doping of graphene. . . . . . . . . . . . . . . . . . . . . 84 3-31 Measurement setup for graphene-integrated sensor chip. The sensor chip is sealed with a vacuum cap for stable performance. The beam shares the same path described in Figure 3-24. . . . . . . . . . . . . . 85 3-32 IR beam spot size at the focal plane was measured by burn marks of thermal paper and found to be ~30 pm in diameter, which allows in-pixel local heating for thermoelectric effect. . . . . . . . . . . . . . 85 3-33 Graphical user interface for IR detection experiment showing output FFT plot centered at the light modulation frequency (center) and 2-D colored map for array readout. . . . . . . . . . . . . . . . . . . . . . . 16 86 3-34 Signal peak values extracted from FFT of the photoresponse measured by an graphene-integrated readout IC show a linear relationship to . laser excitation duty cycle. . . . . . . . . . . . . . . . . . . . . . . . 86 3-35 Readout architecture with pixel transimpedance amplifier and Norton equivalent circuit model of the graphene photodetector. Contact resis. tance is neglected .. . . . . . . . . . . . . . . . . . . . . . . . . . . . 87 3-36 Readout architecture with pixel transimpedance amplifier and Thevenin . equivalent circuit model of graphene photodetector. . . . . . . . . . 88 3-37 Readout architectures with pixel transimpedance amplifier including . . . . . . . contact resistance from ohmic metal-graphene junctions. 88 3-38 Illustration of a single-junction model (left) and a parallel multi-junction . m odel (right) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89 3-39 Schematic circuit of a series multi-junction model (left) and its illus. tration (right) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90 3-40 Scratches occurred during graphene integration process; Narrow spac. ing in top metal layout should be avoided. . . . . . . . . . . . . . . 92 3-41 Scratches and excessive metal residue at pad region cause electrical short 93 94 3-43 SEM image of a FIB cut near pad region . . . . . . . . . . . . . . . 94 3-44 SEM image of disconnected metal routing at dummy gap region . . 95 3-45 SEM image of metal-filled gap in the dummy metal region 96 . . . 3-42 Excessive graphene residue at pad region cause electrical short. . . . . . . . . . be either of 300 or 60 .. . . . . . . . . . . . . . . . . . . . . . . . . . . 97 3-47 SEM image showing sidewall coverage from tilted metal deposition. . 3-46 Aluminum wedge piece for tilted metal deposition. The tilt angle can 97 17 4-1 (a) A schematic illustration of the MoS 2 growth by CVD. (b) The temperature profile for the growth process. [5] (c) Optical micrographs and thickness profile (inset) of monolayer MoS 2 . (d) High resolution TEM image and the corresponding selected area electron diffraction (SAED) pattern (inset) show the hexagonal crystal nature and the 101 4-2 Gate-first fabrication process for MoS 2 FET . . . . . . . . . . . . . 102 4-3 Performance comparison of gate-last and gate-first processes: (a) I-V . . high quality lattice structure [6]. . . . . . . . . . . . . . . . . . . . . characteristics in linear (right y-axis) and log scale (left y-axis) and (b) Gate-first devices have average VT of 0.54V with standard deviation of 0.12V while those from gate-last process have average VT of -4.20V and standard deviation of 175V [6]. .. ............ ... . . 103 4-4 Proposed design flow for large-scale MoS 2 integrated circuit development103 4-5 Gate-Drain connected MoS 2 FET was used as MoS 2 diode. . . . . . . 105 4-6 Fitted diode equation shows a good agreement with the measurement. 106 4-7 High order polynomial equation cannot model the reverse bias diode current due to its non-monotonicity and large error. . . . . . . . . . . 107 4-8 Comparison plot of MoS 2 FET models . . . . . . . . . . . . . . . . . 4-9 Layout of MoS 2 thin-film transistors (W/L = 40[m/ 4pm and 20pim/2pm) 109 using P-cells in Cadence software. The layer definition is given in the legend........ .................................... 111 4-10 Schematic diagram of the switched capacitor converter and micrograph of the fabricated converter . . . . . . . . . . . . . . . . . . . . . . . . 112 4-11 Optical Micrograph of the fabricated test chip using CVD-grown monolayer MoS 2 , showing arrays of FETs, diodes and switched capacitor DC-DC converters . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113 4-12 Photos of the probe station setup showing (a) an optical microscope and probe tips (a), and closed up view of ground plate and held chip (b ,c) . . . . . . . . . . . . . . .. .. 18 . . . . . . . . . . . . . . . . . . . 113 4-13 Simulation (dotted) and measurements (solid) of the output voltage . versus the load current of MoS 2 SC DC-DC converter . . . . . . . . 114 4-14 Schematic diagram of testbench for diode rectifier (left) and micro. . . . . . . . . . . . . . . . . graph of fabricated MoS 2 diode (right) 115 4-15 Transient waveforms of 1 MHz 8 V,, sinusoidal input and measured output voltage of the diode rectifier circuit along with the simulated . . . . . . . . . . . . . . . . . . . . . . . . . . . output (dashed line) 116 4-16 Rectifier output at various frequencies at 10 pA load current where 116 4-17 Schematic diagram of voltage doubler circuit . . . . . . . . . . . . . 117 . 7 VP.. and Ct . = 10 nF . . . . . . . . . . . . . . . . . . . . . Vin= 4-18 Voltage doubler outputs at 6 V,_, sinusoidal input and IL = 0.1, 1, 10 118 .................................. 3-Phase Development Plan for MoS 2 RFID Tags . . . . . . . . . . . 126 5-2 Illustration of Wireless Power Link Operation with On-Chip Inductor 127 5-3 Simulated transferred power at various coupling coefficient (k) . . . 128 5-4 Full-wave rectifier with cross-coupled FETs and two diodes . . . . . 128 5-5 Testbench of MoS 2 LED driver array . . . . . . . . . . . . . . . . . 129 B-1 PCB for ADC characterization . . . . . . . . . . . . . . . . . . . . . 146 B-2 Wirebonding Diagram for ADC characterization . . . . . . . . . . . 147 B-3 PCB for Graphene Sensor Array Test . . . . . . . . . . . . . . . . . 148 . . . . . . 5-1 . [A.............. B-4 Wirebonding Diagram for Graphene Sensor Array Test . . . . . . . . 149 . . . . . . . . 150 . . . . . . . . . . . . . . . 151 B-6 Wirebonding diagram for unified testing 19 . . B-5 PCB for Unified Testing . . . . . . . . . . . . . . . . 20 List of Tables . . . . . . . . . . . 26 [7] 49 1.1 Research highlights on 2D-material-based devices 3.1 Comparison table of D* for various infrared detection technologies 3.2 Summary of ADC performance 4.1 Qualitative comparison table of device models . . . . . . . . . . . . . 109 . . . . . . . . . . . . . . . . . . . . . 21 76 22 Chapter 1 Introduction The silicon semiconductor industry has been advancing and expanding at an exponential rate over the last few decades, making the silicon CMOS technology used everywhere. However, no matter how much traditional silicon technology is improving every year, demands for interfacing materials always exist. Due to the inevitable need for extra materials or devices, silicon-based electronics have utilized other materials not only as sensor interfaces, such as biochemical detectors, piezoelectric films, non-Si solar cells and many, but also in actuator interfaces including MEMS resonators, light emitting diodes (LEDs), and acoustic speakers. 1.1 Materials and Devices for Next-Generation Electronics More recently, a broad range of new materials and devices, including nano-materials, such as quantum dots, carbon nanotube, graphene, hexagonal boron nitride, and transition metal dichalcogenides, have been introduced for a wide range of applications. First, some of the new materials and devices are capable of providing new features to the silicon-based electronics, as in the recent demonstrations of carbon nanotube chemical sensors [8], biological cell interfaces [9-12], DNA-sequencing IC [13] and many more. In other cases, the non-Si emerging materials and devices have been 23 Figure 1-1: Illustration of a Bio-MEMS device for electric impedance spectroscopy of red blood cells adopted for performance improvement of the traditional electronics, as in GaInP/GaInAs/Ge solar cells [14], quantum dot and OLED displays [15,16], MEMS-based RF oscillators [17,18], high speed graphene interconnects [19], and graphene infrared detectors [20]. Furthermore, the increasing interest in foldable and lightweight electronic devices has raised the need for new materials more than ever. Alternative technologies are necessary where applications require the electronic devices to be flexible and/or transparent such as flexible touch screen displays, flexible solar cells, printed RFIDs, film speakers, and flexible lightings [21]. Bio-MEMS Among innovative materials and devices introduced to address new applications, biomedical (or biological) micro-electromechanical systems (Bio-MEMS) are especially interesting in terms of their unique capability to interface with biological targets. The Bio-MEMS devices, PDMS-based microfluidic devices in particular, such as illustrated in Figure 1-1, have gained a great interest for their compatibility to biological targets and effective uses in miniaturized biosensors [12, 22], point-of-care diagnostic chips [23-25], and other electrophoresis and electric impedance spectroscopy applications [26-28]. Moreover, Bio-MEMS devices are not just limited to discrete parts, as on-silicon-CMOS integration of microfluidic devices, also, has been explored [29,30]. 24 *Mo Figure 1-2: Illustration of monolayer graphene (top) and molybdenum disulfide (bottom) Two-Dimensional Materials Two-dimensional (2D) materials offer excellent mechanical flexibility, optical transparency, and favorable transport properties for realizing electronic, sensing, and optical systems on arbitrary surfaces. As recent research efforts toward 2D-materialbased devices have brought improvements in material growth, switching frequency, subthreshold slope, on-off current ratio, and complex circuit design (see Table 1.1), 2D materials are believed to bring dramatic changes in the electronics market with atomically thin, lightweight, bendable, and low-power devices [31]. Among a variety of 2D materials, graphene and MoS 2 , illustrated in Figure 1-2, are exceptionally attractive from a circuit/system designer's standpoint, since they can be grown in large sheets and then be subsequently patterned and etched using standard lithography methods, so results in better control and higher reproducibility and possibly large-scale circuits and system-level demonstrations. First, graphene is a planar sheet composed of carbon atoms, exhibiting high intrinsic mobility [32,33], high current capacity [34-36], tunable optical absorption [37], large mechanical strength [38], and most importantly as discussed later in the thesis, it offers a thermal interface [20,39]. While the majority of graphene research focuses on methods to improve the material quality or finding innovative device architectures, 25 Table 1.1: Research highlights on 2D-material-based devices Material Report [40] Graphene [41] [42] Work Switching device with micromechanical cleavage. 100-GHz electronics based on graphene grown on SiC. Large-area reproducible monolayer growth by CVD. This Large-scale integration with Si CMOS. h-BN [43] [44] CNT-based TFET with SS < 60 mV/dec. Atomically thin insulating layer growth on metal. WS 2 [45] CVD growth of WS 2 on glass substrate. WSe 2 [46] [47] [48] [5] CMOS inverter on WSe 2 flake. Monolayer MoS 2 flake transistor Complex circuits based on MoS 2 flakes. Large-area reproducible monolayer growth by CVD. Computer-aided design of large-scale CVD-grown MoS 2 IC. CNT1 MoS 2 This the research focus must extend to interfacing circuit design and integration with Si CMOS. At the same time, monolayer MoS 2 , consisting of molybdenum atoms sandwiched by two layers of sulfur atoms, exhibits excellent semiconducting characteristics with the bandgap of 1.8 eV, different from graphene (0 eV) and that of its bulk phase (1.3 eV, indirect). While research efforts in material growth and device fabrication extend beyond the scope of this thesis, the outstanding maturity of the technology compared to those of other transition-metal dichalcogenides makes the atomically thin material ready for system level design. 1.2 Challenges in System Design with Emerging Technologies The use of emerging technologies in system level applications can enable gamechanging advantages, such as highly selective sensing of cancer cells, lOx performance enhancement, drastically improved energy efficiency, and so on. However, while new materials and devices provide a great tool set for new designs, it is very important to consider the broad aspects of the interface, which includes that new devices often 1Carbon nanotube is not considered as 2D material. 26 come with highly variable parameters. For example, in the case of a chemical sensor, when the fundamental sensing mechanism or noise characteristic of the device are not fully understood, one may not properly model the device and may end up in a wrong topology for the system. In addition to that, the sensing mechanism can be altered after the design process is finished, as technology evolves. In another common case, if the fabrication technology is immature, the designer may have to deal with the devices with enormous variations. Therefore, the designer is required to have an excellent understanding of both readout circuit design and interfacing material/device design. Trade-offs should be made depending on the degree of uncertainty. For example, if SNR is a concern, further characterization of the device should be conducted, so that a proper signal processing scheme (modulation and filtering) can be used to improve SNR. If the variation between devices is a problem, the readout may be designed to have large dynamic range at cost of sensitivity and power. Furthermore, the topology should be determined based on whether the device can be integrated with the readout electronics or if it is better to have discrete sensor devices. This thesis had to deal with many of the issues described above. 1.3 Thesis Overview The thesis explores three applications of new materials and devices at a system level. Chapter 2 presents an electric impedance spectroscopy system with a microfluidic probe device to interface with human red blood cells, which aims for more accurate malaria diagnosis. Chapter 3 discusses a Si CMOS readout IC and its monolithic integration with a graphene-based thermocouple array to realize a new type of infrared imager. Chapter 4 introduces integrated circuits based on molybdenum disulfide and a computer-aided design flow which makes large-scale design feasible. Utilization of new materials and devices, that can expand the boundary of traditional electronic systems, is studied along three directions: (1) as discrete add-on devices for sensing, (2) as monolithically integrated add-ons, and (3) as stand-alone electronic systems. 27 Finally, chapter 5 briefly discusses future work and opportunities. 28 Chapter 2 Cellular Electric Impedance Spectroscopy for Characterization of Malaria States 2.1 2.1.1 Introduction Cellular Electric Impedance Spectroscopy Cellular electric impedance spectroscopy (EIS) is a technique to measure biochemical changes in live cells and has been widely studied in the development of various biosensors [49]. The first system in the history of microfluidic single-cell analysis system is the Coulter counter introduced in 1956 [50] in which the conductivity of a narrow fluidic channel is monitored to detect the flow of insulating particles or biological cells. While the basic mechanism to monitor the impedance of fluidic channel remained the same from the Coulter counter, cellular impedance analysis systems have introduced new concepts such as high frequency and multi-frequency measurement with microfabricated electrodes [51-54], highly confined flow of cells [55], and digitally coded excitation [56], and thus enabled cell characterization based on cellular electric impedance. As a result of the development of more sensitive analytic systems, it has been suggested that cellular EIS can offer a fast, effective and low-cost 29 technique for detection of intracellular variation in electrical properties of cells which may be induced by malaria infection [57,58]. In this thesis, a microfluidic device [2] is utilized to probe tiny (diameter < 10pm) human red blood cells (RBCs) with an accurate measurement setup, seeking for cellular impedance change induced by malaria infection. 2.1.2 Disease States of Malaria and Detection Target for Early Diagnosis The cause of malaria is Plasmodium parasites. Among four types of Plasmodium parasites which infect human, P. falciparum is the most common, causing more than 90% of the deaths [59]. The parasites undergo three reproduction stages after the invasion: ring, trophozoite and schizont. In most of the real life cases, the parasites are tranferred by infected female mosquitos and introduced into the blood stream. They make their first way to the liver to invade liver cells. Once inside, a single parasite, also called as a sprozoite, multiplies to produce thousands of merozoites. They make liver cell swell and, eventually, burst, so that they flow into the circulation beginning invasion of erythrocytes (RBCs). The asexual intraerythrocytic phase of the life cycle of Plasmodium falciparum malaria parasite is illustrated in Figure 2-1. As the parasite invades a human erythrocyte, it forms a spherical shape by engulfing a portion of erythrocyte cytosol so that in section it appears as a thin ring. The ring stage parasite grows to become a trophozoite. After that, the parasite subdivides into 20 - 30 daughter merozoites at the schizont stage. These merozoites burst the host erythrocyte and flow into the blood stream again to start a new cycle. The overall reproduction cycle takes about 48 hours [1]. While a P. falciparum parasite grows and develops in a host erythrocyte, the infected cell undergoes pathological modifications of its optical, mechanical, magnetic property and also the electrical property classified as impedance [60-63]. Especially, a study on malaria infected human erythrocytes trapped in a microfabricated structure already suggested a potential use of cellular impedance spectroscopy for diagnostic 30 RBC parasite Invasionof malaria parasite released parasites a b e d C ) Ringstage Trophozoite stage SchiZontStag Figure 2-1: Asexual intraerythrocytic phase of the life cycle of Plasmodium falciparum malaria parasite [1] screening [63]. However, an effective malaria diagnostic test requires much higher throughput (>100,000 cells per hour), because the parasitemia of malaria (as the ratio of the number of infected RBCs to the entire RBC population) is very low, often under 0.002%, at the early stage of the disease [64]. Therefore, microfluidic EIS with continuous cell flow is essencial for such applications. In addition and more importantly, the detection of the early (ring) stage infected erythocytes is critical for diagnostic test since the infected population in the blood circulation are dominantly in their early stage. Thus highly demanded was a microfluidic EIS system as a characterization tool for malaria states including the ring stage, which had never been reported yet. 31 2.2 2.2.1 Materials and Methods Microfluidic Probe Device Fabrication Figure 2-2 shows the overall process of microfluidic device fabrication. The fabrication is conducted at Microsystems Technology Laboratories, MIT. While photopatternable silicone (PPS) and an epoxy-based negative photoresist (SU-8) are widely used in microfluidic device fabrication, thanks to convenience of fabrication without silicone etching process. However, the pattern resolutions are limited to 10tm and 6pm, respectively [65]. While planar geometry is determined by the exposure pattern, the fluidic channel height is determined by the depth of the pattern. In case of PPS or SU-8, the film thickness sets the depth, which can be controlled by spinning speed. Once we targeted a channel height of a few times higher of the thickness disk-shaped RBCs to make sure the concentrated cell flow with the consistent orientation of RBCs, the patternable film thickness around 5pm must be achieved. Therefore, in this study, the standard silicon etching techniques are applied, which etch a bare silicon wafer with SF6 plasma. This ensures higher resolution and uniform patterns across the large area wafer and, more importantly, better control of the depth of the mold structure. Details of the fabrication process are provided in Appendix A. 2.2.2 Malaria-Infected Human Erythrocyte Sample Preparation Human blood samples were prepared with the malaria parasites, P. falciparum,by Monica Diez-Silva as described in [28]. The parasites were cultured in leukocyte-free human blood samples (Research Blood Components, Brighton, MA) under an atmosphere of 5% CO 2 balanced with N 2 , at 5% hematocrit in RPMI culture medium 1640 (Gibco Life Technologies) supplemented with 25 mM HEPES (Sigma), 200 mM hypoxanthine (Sigma), 0.20% NaHCO 3 (Sigma) and 0.25% Albumax II (Gibco Life Technologies). The cultured samples contained a mixture of multi-stage infected erythrocytes (iRBCs) and uninfected erythrocytes (uRBCs) at the parasitemia of 5% 32 5 mm H20 (a150 Un (b) Microchannel mask design (a) Electrodes mask design Silicon substrate Glass substrate I I I I Develop - PR Reactive ion etching - Ti-Au PDMS deposition curing I I Hole Lift-off -- PR W M . Alignment & bonding (c) Fabrication process (e) Full view of probe part (d) Electrodes alignment with microchannel Figure 2-2: Fabrication of microfluidic probe chip [2] 33 punching Faraday cage Rsmicroflpidic cha nt- Ilm 2pm$ cell fjlw- Figure 2-3: Measurement setup of microfluidic EIS of malaria infected human blood sample to 8%. To maintain osmotic pressure and prevent RBC adhesion to the microfluidic channel, the working solution for El measurement was phosphate-buffered saline (PBS; 2.67 mmol/1 KCl, 1.47 mmol/1 KH 2 PO 4 , 137.93 mmol/1 NaCl, 8.06 mmol/l Na 2 HPO 4 .7H 2 0) mixed with Bovine Serum Albumin (BSA) (Sigma-Aldrich, St Louis, MO). Three concentrations of BSA-PBS, 0.2%, 0.5%, and 1% weight/volume (w/v) were utilized in the experiments to achieve optimum performance and sensitivity of EI measurement. The cultured P. falciparum samples were cooled down to room temperature after being removed from the incubator, then washed with PBS solution at 2000 rpm for 5 minutes at 21'C and diluted by 200 times in the working solution. 2.2.3 Measurement Setup Figure 2-3 illustrates the measurement setup. The EIS was performed under continuous flow precisely controlled by water column pressure difference, allowing minimum hydrodynamic disturbance during EI measurement. The actual flow rate was around 150 fL/s to capture the optical image of the cell in the flow. This extremely slow flow is only necessary when visual data acquisition is required to provide the relation between EI data and the disease states. In other words, 100x speed can be easily achieved for EIS only system. The probe electrodes were connected to an LCR meter 34 (Agilent Technology, Inc.), and the El data were collected using an interface program (LabVIEW). The excitation source in the LCR meter was set to be 1 Vp.. at 2 MHz while the magnitude and the phase of the channel impedance were measured at the of sampling rate of 50 Hz. While continuously measuring the electrical impedance the channel, each cell passing over the electrodes was visually monitored with a 100 x magnification optical microscope (Olympus IX71) to make sure single-cell analysis and to identify the disease state. To remove electrical signal interference, the device was surrounded by a grounded Faraday cage made of aluminum foil with a hole for the microscope lens. The test samples were also ready in three different BSA concentrations (2%, 5%, and 10% in PBS). In each measurement, the steady flow was acheived by manual control of water column height. Preprocessing of the raw data to extract El transition for each cell is conducted by E Du, and each EI transistion is mapped with its disease states as confirmed by the visual inspection. 2.3 2.3.1 Results and Discussion Data Acquisition and Preprocessing When a cell approaches and crosses the electrodes, the presence of the cell at the measuring zone forms a lossy capacitor, creating a dynamic impedance transition Electric Impedance Spectroscopy on RBCs 0.0 0.02- Uninfected RBC -. 2infected RC -0.06 0 20 40 80 60 100 120 140 Time Figure 2-4: Dynamic impedance transitions at cell passage over probe electrodes 35 AZ as shown in Figure 2-4. The impedance transition from the base impedance is given by Zmedium to Zedium+RBC Z\Z=Zedium+RBC - Zmedium = (M + AM)eOw - Me3n (2.1) (2.2) where the magnitude deviation AM and the phase deviation Ao are taken from the center peaks of each impedance transition. They are complex functions of cell size, composition, dielectric properties of cytoplasm and the cell membrane, and the enclosure of the medium surrounding the cell. The present El measurement was performed under a single frequency of 2 MHz with sampling rate of 50 Hz in order to probe both interfacial and intracellular changes of Pf-iRBCs. selection falls into the f The frequency dispersion regime (within the range of 0.1 - 10 MHz for biological cells) [66] where the large discrepancy in conductivity of cellular membrane and cytoplasm causes a lag in charging response of the intracellular and extracellular substances. Figure 2-5 shows a typical example of the transient EI measured when cells crossing over the electrodes. The magnitude and phase transitions, AM and A O, are shown in two sub-plots, respectively. The insert in the phase sub-plot displays a representative image of each sub-population, from uninfected RBCs to Pf-iRBCs at ring stage, trophozoite stage, and schizont stage, respectively. The working solution was 0.2% w/v BSA-PBS. The ring stage iRBCs only have delicate parasitic cytoplasm with single or double small chromatin dots. In contrast, the trophozoites have denser cytoplasm with yellow pigment and the schizonts have dense dark pigment. The differntiation of the cells are not trivial with the transient plot, but it at least shows that the proposed continuous flow cellular EIS system possesses a cell-counting function. Figure 2-6 shows the initial measurement data of 113 erythrocytes including 78 uRBCs, 12 ring stage iRBCs, and trophozoite stage iRBCs. The El changes (Ao, AM) are only plotted noting that the magnitude of the base channel impedance 36 0.1 0 -0.1 9- Nonmifected Trophozoite Ring Schizont -02 -0-3 600 400 200 -L14 0 -200 0 2 6 4 8 10 12 Time (Sec) Figure 2-5: Overlaid transient El results of uninfected RBCs and Pf-iRBCs crossing over the electrodes with the measurement conditions: 2MHz 1Vp-p and 0.2% (w/v) BSA-PBS. 37 2MHz EIS Results 1000 - 0 - 900 00 - * 800 0 0. 0 700 - 0 600 - 0 a) * Ec as ** 0 - 500 0 400 - ) .) 300 - E - 200 - 0 -0.5 Normal Ring Trophozoite * 0 100 -0.45 -0.4 -0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0 phase shift(deg) Figure 2-6: Scatter plot of 113 El data (Aro, AM) consisting of 78 uninfected RBCs, 12 ring stage iRBCs, and trophozoite stage iRBCs. Simplified Circuit Model membrane (buffer solution E E cytoplasm E 0 0. Rfeedback Excitation Source Eedbc ADC DFT Figure 2-7: Block diagram of cellular impedance measurement setup and simplified cellular circuit model. A simplified cellular impedance model is shown in the inset. The extraction of model parameters requires an excitation source with variable frequency. 38 (OOkQ-1MQ) is much larger than that of transitions. The plot hinted that we might be able to classify the cells just by their data point locations. It is a different approach from traditional cellular EIS systems which often assumed a circuit model for the target cell and tried to extract the circuit parameters, such as Rcytopasm and as in Figure 2-7, to classify the cells by the range of the parameters and also possibly differentiate infected cells from healthy ones [63]. Although the analysis Cmembrane with circuit models, whether simplified or complicated, may provide a good physical interpretation of the cell structure and the pathological modifications, the measurements is subject to extremely large cell-to-cell variation (which can be treated as noise) [63]. Moreover, the model fitting often require a frequency sweep measurement which results in low throughput due to the slow multi-frequency measurement. 2.3.2 Analysis with a Dimensionless Parameter 61 In order to systematically evaluate different experimental conditions, EI transitions (Ap, AM) were normalized by, x = A O/A y = A M/A M (2.3) (2.4) where A~p and AM are the mean values of the phase change and the magnitude change of uninfected erythrocytes for each experimental condition. Figure 2-8 plots the normalized El transitions of uRBCs where the mean values are (1.0, 1.0) for each group, along with their linear fitting lines and the line equations in form of, y = kx + a. (2.5) As Figure 2-8 shows, the normalized El transitions of uRBCs at each BSA concentrations can be well-fitted with the linear curves despite of the cell-to-cell variations. Utilizing these curves as reference lines, we introduced a dimensionless parameter, El offset 6, as the graphical distance from each data point of Pf-iRBC to the reference 'Original data and figures are from [28] 39 2.0 1.5 II X 1.0 - 0.5 X *.2%BSA y=O.3953x+O.60 4 8 0I.5%BSA 7 y=.621x+O.53 9 X 1% BSA y=0.4088x+0.5912 0.0 1.5 1 0.5 0 x=a/ 2.5 2 p Figure 2-8: Scatter plot of normalized EI transitions of uninfected RBCs in three different BSA-PBS concentrations 2.0 1.5 Ii 0AI* -0 c et4 1.0 0.5 * Uninfected e Trophozoite " Ring " Schizont 0.0 0 1 0.5 1.5 Figure 2-9: Scatter plot of normalized El transitions for 0.2% BSA-PBS condition and definition of an offset parameter J 40 p<0.001 1.5 p<0.001 1.0- p<0.00 1 LO a4 -0.5 0.51P<o-00 Uninfected Ring 1 P <.0 1 Trophozoite Schizont Figure 2-10: Statistical box chart of two-sample t-test for 6's collected from the PfiRBC sample in 0.2% BSA-PBS concentration line as depicted in Figure 2-9. In other words, 6 = -(kx, + a - ys)/ /k 2 + a2 (2.6) where k and a are the linear interpolation coefficients of the reference lines as in Eq. 2.5, and x, and y,, are the normalized impedance transitions of individual RBCs. From 6 in Figure 2-9, uRBCs and Pf-iRBCs at various stages indicated a monotonic trend in the relation of 6 and the pathological progress. We also noted that the normalized El transitions varied between the experiments even in the same conditions as we replaced samples and devices in the experimental setup. However, the similar scatter pattern was observed. To collect a vast number of data points, we combined data from each experiment using the commonly aligned reference lines from the scatter plots of EI transitions for Pf-iRBCs. El offsets 6 for various Pf-iRBC stages were systematically compared using statistical box charts for different BSA concentrations. The statistical analysis was carried out using a two-sample t-test. When BSA concentration was 0.2% w/v, all intraerythrocytic stages of Pf-iRBCs showed a statistically significant difference (P<0.001), 41 P< 0.001 p<0-001 1.0 p<0.00 1 - 0.0 p 0.0 2 pz -0.5 .0 5 I Uninfected Ring Trophozoite Schizont Figure 2-11: Statistical box chart of two-sample t-test for 6's collected from the PfiRBC sample in 0.5% BSA-PBS concentration as indicated in Figure 2-10. We found that our new El measurement method can be used to effectively distinguish Pf-iRBCs not only from uRBCs but also between adjacent asexual stages (ring vs. trophozoite, and trophozoite vs. schizont) with high statistical significance. 2.3.3 Effect of BSA Concentration in Buffer Solution While BSA was added to maintain osmotic pressure and prevent RBC adhesion to the microfluidic channel, we studied the effect of BSA concentration in the working solution within a reasonable range of concentrations. The same EIS experiments were performed on Pf-iRBC samples with BSA concentration of 0.5% and 1.0% (w/v), and the results were as shown in Figure 2-11 and 2-12. In the case of 0.5% BSA, all stages of Pf-iRBCs were still statistically distinguished (P<0.001). When BSA concentration was increased further to 1% w/v, the ring stage bears only moderate statistical significance (P = 0.134) despite trophozoite and schizont stages still having high statistical significance (P<0.001). It was clear that the EI offset 6 was less scattered at higher BSA concentrations. In addition, the 42 p< 0.001 1.5 p<0.00 1 - 1.0 p 00. 13 * 0.0 pzQ009 p=O.O 7 -0.5 Uninfected Ring Trophozoite Schizont Figure 2-12: Statistical box chart of two-sample t-test for 6's collected from the PfiRBC sample in 1.0% BSA-PBS concentration overlap between uRBCs and Pf-iRBCs, especially for ring and trophozoite stages, increased with BSA concentration making classification difficult. While deeper investigation in the electro-chemical effect of BSA in the sample solution is still required, it is believed that BSA introduce more mobile ions in the solution which can effectively shield the electric field across the cell, reducing the measurement sensitivity. The sensitivity of the Pf-iRBC detection and the performance of the present cellular EIS system were found to be significantly influenced by BSA concentration and a number of other relevant factors, such as cell concentration, flow rate, and sampling rate. The results indicate that 0.2% w/v BSA in PBS is optimum for the present measurements with sufficient detection sensitivity while minimizing cell adhesion to microfluidic channel. The newly developed analytic method using a composite parameter 6, instead of extracting circuit model parameters or using only one of EI components, is also expected to be more broadly applicable in differentiating other types of diseased cells for disease diagnostics and cell separation. 43 2.4 Concluding Remarks In conclusion, we reported a cellular EIS system for electrical screening test of the malaria parasites in human erythrocytes [28], which achieved a high SNR not just enough to distinguish intracellular electro-chemical changes of tiny live cells but also capable of early stage malaria detection. The fabrication of microfluidic probe device and the proper measurement setup allowed highly sensitive electric impedance measurement of individual erythrocytes. We further developed an dimensionless parameter 6 to quantify the deviation in the magnitude and phase shift of electric impedance of malaria infected cells. With the newly introduced analytical method, the ring stage malaria parasites were confirmed, suggesting a use in early diagnosis with fully electrical tests. Since there had been no available automated, low-cost and miniaturized electrical diagnostic tests for malaria, this opens up a possibility in development of such devices. In this study, the detection of the ring stage P. falciparum iRBCs was achieved along with the use of the very high parasitemia sample and the visual monitoring setup for the cell states verification. However, we can actually leverage the fact that uninfected erythrocytes are the vast majority in the blood stream (>99.8% before immunes show symptoms and >90% even at severe mortality) [64] and get rid of the visual monitoring by defining the reference lines for 6 analysis based on the entire population without the need of selective uRBC data. This allows the measurement setup and analysis to be simplifed by far, and significant differentiation of infected RBCs still be possible for in-field tests. However, given that the specificity of this diagnostic test has not been verified, the test may result in false positives in cases of (1) infection by malaria parasites other than P. falciparum and (2) RBC's cellular modification induced by other diseases. While selective detection is not guaranteed, the cellular EIS can still be used as an effective screening test for the abnormality in RBCs. The present cellular EIS system provides not only a breakthrough in electrical diagnostic tools that directly interface with biological cells but also a fine example 44 of electronics with non-traditional add-on devices (i.e. the microfluidic probe device). By this example, it is clearly shown that new interface materials can bring an additional feature of sensing pathological modification of biological cells. 45 46 Chapter 3 Graphene-Silicon Hybrid IC for Thermal Imaging While in the previous chapter, the thesis has focused on a biomedical sensing application utilizing microfluidic devices to interface biological cells with an impedance analyzer, in the next part of the thesis, we discuss a graphene-silicon hybrid infrared (IR) imager where a graphene-based sensor interfaces IR light with a silicon readout IC. The presented system utilizes an array of graphene thermocouples to detect midand long-wavelength infrared spectrum (A = 8 - 15pm), wavelengths at which the photon energy is lower than the direct bandgap of Si, and a readout IC built in commercially available Si-CMOS technology. This hybrid integrated circuit provides an example of electronic systems closely integrated with emerging 2D materials, in our study, graphene. It also leads silicon based technology to broaden its application's range, thanks to the capability added by the new materials. However, it is important to acknowledge the inherent issues with the new materials, both from their intrinsic properties and due to their early developmental phase. 3.1 Introduction Before discussing the details of the proposed hybrid imaging IC, we first review some background of traditional electronics for photosensing applications. 47 3.1.1 History of Electronics for Infrared Sensing Radiation detectors, as a more general term for photodetector, span far beyond the visible part of the spectra not only in direction of X-rays and gamma (-y) particles (high energy) but also in the other direction of millimeter waves and microwaves (low energy). Interestingly, one of the first photodetectors invented was the thermal radiation receiver which reacted to the temperature change in sensing elements, where the heating by radiation often occurs in the infrared spectrum. This principle is still widely used since Thomas A. Edison used compressed carbon as a temperature sensitive resistor and called it tasimeter [67]. The device was then further improved as S. P. Langley developed the bolometer, an instrument which used a blackened platinum strip for the same purpose [68]. Inherited from them, thermal detectors, including thermopile, microbolometer, and Golay cells, are generally sensitive to all infrared wavelengths and operate at room temperature. Another family of detectors, the photon detectors, were mainly developed during the 20th century. These devices are based on intrinsic and extrinsic transitions of electron induced by photon absorption within the semiconductor grid. Lead sulfide (PbS)-based photon detector was the first practical IR sensing system with sensitivity to infrared wavelengths up to ~ 3pm. While efforts to improve sensitivity and response time had continued, discovery of variable bandgap HgCdTe alloy [69] opened a new area in IR detector technology and has provided an unprecedented degree of freedom in detector design. However, the main drawback is operating temperature, in other words, cryogenic cooling is required to suppress thermally excited electrons. There are a few types of detectors that do not need cooling such as Ge and InGaAsbased ones, but the response spectra is limited in high photon energy regime far from long- and very long-wavelength infrared range (A > 8[tm) [70]. Improvements in uncooled thermal detectors and high performance photon detectors would trigger the adoption of these technologies in applications, such as, IR imaging in medical diagnostics, Fourier transform IR spectroscopy, IR astronomy, assisted car driving, global monitoring of environmental pollution and climate changes, 48 Table 3.1: Comparison table of D* for various infrared detection technologies [7] Response Operating D* Spectra Temperature (cmHz1/2/W) Ge InGaAs 0.8-1.8 0.7-1.7 (K) 300 300 Photovoltaic Ex. InGaAs InAs 1.2-2.55 1-3.1 253 77 Photoconductive InSb HgCdTe PbS PbSe InSb Type Detector (m) 77 77 300 300 213 77 300 300 ined DDetemBolometer by window 300 300 material 1-5.5 2-16 1-3.6 1.5-5.8 2-6 2-16 HgCdTe Thermopile Golay cell PZT, TGS, LiTaO 3 chemical process monitoring, and others. 1, 000 x 108 50, 000 x 108 2, 000 x 108 100 x 108 200 x 108 100 x 108 10 x 101 x 108 20 x 108 200 x 108 6 x 10 8 1 X 108 10 x 108 2 x 108 While the interest has mainly centered on the wavelengths of the two atmospheric windows from 3 - Sjm and 8 - 141Lm, there has been an increasing interest in longer wavelength detection for applications in astronomy. In summary, Table 3.1 shows a variety of infrared detection technologies in terms of wavelength, detectivity, and operating temperature. In comparing the different IR detection technologies, it is convenient to use a figure of merit, which is the detectivity (D*), defined as Rt SAdAf NEP (3.1) -f where Ad is the active area, Af is the bandwidth, NEP is the noise equivalent power, R is responsivity (V/W), and V is the total noise voltage of the detector, respectively. This figure of merit gives a normalized parameter in terms of the area, thus, is useful not only for performance comparison among various sensing technologies, but also for understanding the fundamental limitations of the detectors. It should be also noted that the field of infrared imaging is already a field where 49 silicon technology requires heavy leveraging on other materials in an integrated form, regardless of the maturity, high yield, and low cost of silicon technology. In the following sections, we take a deeper look in the three main phenomena utilized for infrared detection and then graphene-based infrared detectors. 3.1.2 Photovoltaic and Photoconductive Detectors The photovoltaic and photoconductive effects are two main operating mechanisms of optical infrared detectors. Incident photons are converted into excited charged carriers in optical detectors, and either a measurable voltage or a change in conductivity is generated. In order for these to occur, the material's electronic band structure must allow direct transition (or excitation) between the valence band and the conduction band induced by infrared light. Therefore, for LWIR detection, materials with appropriate band gap (0.024-0.3 eV), such as InSB or HgCdTe family, have been traditionally used [71-74]. In addition to the direct bandgap detectors, extrinsic intraband photodetectors and quantum well infrared photodetectors (QWIPs) can be used, where electrons can be excited from mid-bandgap states or from quantum well intersubbands, respectively [75-77]. In the optical infrared detectors, the carriers require excitation by low energy photons, therefore, thermal energy from the ambient environment can also lead to excess carriers. In order to suppress the thermal generation of excess carriers, optical detectors often require cooling to liquid nitrogen temperature (77K). 3.1.3 Thermal Detectors In addition to the photon-based systems, thermal detectors are another important group of infrared detectors. In the thermal infrared detectors, incident infrared photons are absorbed and transformed into a temperature gradient. While thermal detectors benefit from broadband absorbance depending on the choice of the absorption material and the window material, background radiation has to be taken into account. Besides, the response time of thermal detectors are slow in general because 50 the time constant of the device is mainly limited by the thermal time constant rather than the electronic time constant. In short, with properly designed thermal detection system and its isolation, the temperature increment induced by infrared radiation can be translated into electrical signal by a few different thermoelectric transduction mechanisms. Bolometer Bolometers utilize a material that changes electrical conductivity depending on the These type of thermal detectors are commonly adopted in thermal temperature. imaging applications. The output voltage of a bolometer can be expressed as Votal = Ke, where aTCR hiasRo(1 + aTCR)AT AV AT = aTCRIbiasfRO (3.2) (3.3) is the temperature dependent change in resistivity (TCR) of the material. The current state-of-the-art materials, in terms of large TCR, are amorphous silicon with 2.5%/K and vanadium oxide with >4%/K [78]. Since a bolometer uses a passive resistor (Ro) and needs to measure the change in resistance, the detection mechanism requires a bias current to convert the conductance change into voltage signal, and the output voltage can be increased by setting Iias large. Therefore, bolometers can consume more power to achieve higher sensitivity. However, trade-off exists since the larger bias current results in self-heating effect as well as additional shot noise. Thermopile Thermopile's or thermocouples operate on another mechanism to convert temperature gradient to electronic signal. Thermocouples directly generate voltage signal in active manner, as a temperature gradient across the detector induces thermoelectric voltage. The output voltage of a thermocouple is linearly dependent on the temperature gradient, that is, 51 V = SAT (3.4) where S is the Seebeck coefficient (V/K), and Kcom, = AV = S AT (3.5) Although the signal from these devices is limited by the magnitude of the Seebeck coefficient (~ 10-100 pV/K), they have large dynamic range and good linearity. Thus, it is possible to cascade many thermocouples in series in order to increase the signal magnitude. In addition, since they have self-powering nature without the need for an input bias, the noise contributions from shot noise and flicker noise are minimized. Therefore, higher detectivities compared to bolometers are achievable as shown in Table 3.1. A wide variety of materials (metals and semiconductors) are available for thermoelectric detectors, but in order to create a large thermal voltage, two materials of different carrier type (p-type or n-type) are required. 3.2 Graphene for Photosensing While we have discussed the conventional detectors for the infrared regime, we now change the subject to graphene applications for the IR detection. Many experiments have begun to explore graphene's unique optoelectronic properties, attempting to make use of its unusual broadband optical absorption from the far-infrared all the way to the visible regime [39, 79-83]. In the near-infrared (NIR) regime (Eph= 0.8-1.6eV), atomically thin monolayer graphene (MLG) have been adopted for broadband photodetectors and optical modulators, capable of ultra-fast response times (>10 GHz) [84, 85]. However, these demonstrations were limited in high energy spectra where photon energies are much larger than the intrinsic energies of the system, such as the optical phonon energy (Eo, ~ 0.2eV) or the electrostatically controllable Fermi energy of MLG (Ef ~ 0.5eV) [84,86-88]. For detection of lower energy photons with graphene, very recent 52 work has shown active modulation due to Pauli blocking [37,89] as well as interesting plasmonic effects [90-92]. However, more recent experiments in the visible regime have begun to show that not only are optical effects possible within graphene, but thermal effects as well [86-88]. Furthermore, a tunable ambipolar thermocouple operating at LWIR regime has been demonstrated, in which MLG plays a key role in a hybrid ambipolar infrared thermocouple, converting a temperature gradient into a voltage signal at the thermocouple junction [20]. While current technologies for infrared (A = 5 - 15pim) imaging, such as HgCdTe-based photovoltaic detectors, can achieve high performance [7], graphene-based thermocouples have a potential to avoid drawbacks of photon based detectors, for example, low yield, ROIC integration, as well as cooling requirement. 3.2.1 Mechanically Suspended Graphene Thermocouples In very recent work of our team at MIT, led by Allen L. Hsu and Patrick Herring, a graphene-based thermal imaging system has been demonstrated by using graphenebased tunable thermopile that offers high sensitivities at operating temperature of 300K [3,4]. Unlike graphene photovoltaic detectors, where the photovoltaic signal can only be generated by photons absorbed by the graphene layer, the graphene thermal detector benefits from decompling on the materials used for heat absorption and thermoelectric conversion to maximize sensor performance. Therefore, by choosing better infrared absorbing materials and by integrating with silicon MEMS structures as shown in Figure 3-1(a), the graphene-based ambipolar thermopile achieves sensitivities able to detect the emitted radiation from a black body source as shown in Figure 3-1(b). Furthermore, analysis suggests the intrinsic performances to surpass state-ofthe-art thermopile imagers, when ultra-high carrier mobility of graphene is involved. This enables new classes of low cost, environmental-friendly, and high performance thermal imagers when integrated with Si ROIC technologies. 53 H (b) a. Thermal (SiN/SiOA)I 10 15 M0 25 x (mm) Figure 3-1: (a) Illustration of the MEMS-enhanced graphene thermopile. Small holes in the center of the infrared absorber are meant to facilitate suspension of the thermal isolation stack, while the large openings along the periphery help define the thermal isolation legs. (b) The measured signal shown as a function of actuator position. The thermal image was formed by placing a laser cut stainless steel aperture in front of the blackbody source (T = 472 K, fmod = 173 Hz) and scanned in position using a series of motorized X-Y translation stages. The step size was 0.5 mm and the integration time was 3 s per pixel [3,4]. 3.3 Readout IC for Graphene IR Sensor Array In parallel to developing the graphene thermocouple for IR sensing, we have worked on building an integrated imager solution to bring this graphene application to the next level. 3.3.1 Readout IC Architecture The readout IC (ROIC) for 4,800-pixels IR image sensor is proposed as illustrated in Figure 3-2. Each pixel contains a graphene IR sensor fabricated on the top surface and a pixel amplifier built in the Si substrate. The differential output lines of 8x60 pixels are connected to an ADC through a column selection multiplexer (MUX) and a variable gain column amplifier, thus each set completes a fully functional imager block as shown in Figure 3-3. The full chip contains ten of the imager blocks as in column-parallel architecture. The column-parallel architecture allows not only a good-trade-off between frame rate and power consumption, but also proves scalability of the sensor. The prototype chip size including pads is 5mm by 5mm. 54 Pixel Transimpedance Amplifier In 0. , Parallel ADCs lOMOOOOEEODDDDD=D0D Graphene sheet ~30um x 10 um 5mm Figure 3-2: Conceptual floorplan for integrated graphene IR imager. An array of 80 by 60 graphene thermocouple pixels is fabricated on top of the Si-CMOS readout IC. * 0 L 0000 0 0 0 0 0 0 6000 0 8-1 MUX SAR ADC 8 Figure 3-3: Schematic of an imager block consisting of 8-column by 60-row pixel amplifiers, a 8-to-1 MUX, a variable gain amplifier, and an ADC. The prototype chip consists of 10 of this imager block that complete a 80 x 60 pixels image sensor. 55 3.3.2 Sub-Block Designs This section discusses the design of sub-block circuits. The pixel transconductance amplifier is the front-end block directly connected to the graphene thermocouple. To properly design the pixel amplifier, the signal source must be carefully characterized. Unfortunately, at the time of initiating the IC design, the specifications of the sensor device were not fully confirmed, and the graphene-based sensor was assumed to be a photon-based detector, not thermal detectors as we developed later. Photoresponse of the sensor was thought, initially, to be generated at the p-n junction of a graphene sheet or a graphene-metal junction. Interestingly, the graphene junctions in either case can only have low impedance, thus, it cannot collect the charge over time and store in the junction capacitance, unlike Si p-n junction photodiodes do. Therefore, a high speed (large bandwidth) direct conversion of photovoltage or photocurrent signal was required for a pixel amplifier which also needs to meet the area constraint of 10pbm by 3 0 pm. Pixel Transconductance Amplifier 3.2nA 3kg' -V Graphene Photodetector Trans-Z Amplifier Figure 3-4: Circuit model of a graphene photodetector and a transimpedance amplifier. The transimpedance amplifier converts the input current ('in) into the output voltage (V,,) by a conversion gain. The pixel amplifier design required a different photoresponse integration scheme because of the graphene device's nature of low output impedance. While high impedance 56 Signal Amplitude Extraction Modulated IR Photoresponse + Noise '-"ke Square Wave at Modulation Frequency Figure 3-5: Illustration of photo-signal modulation and extraction scheme. sensors, such as Si p-n junction based photodetectors, often use an integration capacitor, either intrinsic or extrinsic, at the front-end to accumulate the signal and cancel out high frequency noise, our device would provide a significant leakage path by its own sensing material. As shown in Figure 3-4, the earlier detector model was assumed to be a -3.2 nA current source with 200 -3, 000 Q output impedance, where the values vary depending on the doping of graphene, the device geometry, the material quality, and the choice of contact metal. Despite that the graphene device was yet assumed to be an active sensor that does not require bias current or static power consumption, a transimpedance amplifier with low input impedance (< 1 kQ) was desired. Although the charge integration scheme often employed in high impedance photovoltaic detectors where longer light exposure (longer charge integration) improves SNR, we used a current amplification scheme with input light modulation. As shown in Figure 3-5, amplitude of a noisy photoresponse can be extracted from the correlation of the detector output signal and a square waveform at the modulation frequency. In this scheme, on-time signal and off-time signal are sampled multiple times. By extracting the signal component at the modulation frequency, the dark current (off-time response) can be effectively canceled out just as the correlated double sampling (CDS) technique does [93-95]. In this scheme, noise reduction is achieved by longer expo57 (a) 1 2 =+ Igbs (b) 1 FF Q1MA pg 0-l1kfl Zin Graphene Photodetector Model MPI MP2 MN1 -cuit) MN2 (Norton circuit) - - - - I 0-6kQ MN4 MN3 - -- - FS TT - adjustment Zin 1~p Figure 3-6: (a) Schematic of the proposed pixel transimpedance amplifier. The bias tail current is set to satisfy the current deviation less than 1% of the bias current. The matching of gm, thus minimizing Zij, has fine-tune control by the VB node. (b) Simulated input impedance adjustment of the PTIA with VB range from 1.1V to 1.8V across the process corners. sure which results in more sampling points and thus improves spectral resolution and SNR. The schematic of the proposed pixel transimpedance amplifier (PTIA) is shown in Figure 3-6(a). The PTIA is implemented with thick oxide I/O transistors for gain and output dynamic range. The PTIA utilizes a cross-coupled pair of NMOS (MN1 and MN2) and diode-connected PMOS (MP1 and MP2), which minimizes the input impedance (Zin) looking from the tails of the NMOS pair when the transconductances of PMOS and NMOS transistors match (gm,p = gm,n). An additional pair of NMOS tail transistors (MN3 and MN4) are added to fine-tune gm,n, thus Zin, with the VB node. This topology allows medium-to-large I-V conversion gain and low input impedance at the same time. A similar topology was also adopted in a highly energyefficient current-mode receiver circuit [96], removing bias current and reducing load 58 impedance at the same time. In this amplifier design, the bias tail current was set to 1pA. Assuming the largest current deviation induced by the graphene photodetector to be less than 1% of the bias current, gm matching can be assured during the photodetector operation. The input impedance of the amplifier (Zi,) can be fine-tuned to near zero by a bias voltage (VB) of the tail NMOS transistors in triode regime as shown in Figure 3-6(b). In the end, however, we need to note that the initial graphene photodetetor is later replaced with an electrostatically tunable ambipolar graphene-based thermocouple as discussed in the previous section. The consequences of the change in the key detection device must be reviewed. Although the graphene thermocouple operates on a different fundamental mechanism, it can still be modeled as a Norton equivalent circuit in terms of signal amplitude as long as it is a single-junction and two-port device. When modeled, the new thermocouple devices would result in typical parameters of 10 kQ resistance and 5 nA photocurrent. They are actually better values for the PTIA scheme compared to those of the graphene photodetector devices. Especially, the increased resistance of the detector device would ease the requirement for the gm matching in PTIA, therefore, the original design could still be applied for the new devices. However, the current amplification scheme with the proposed PTIA is not optimal when we include the effect of the contact resistance between the graphene device and the readout circuit. The contact resistance is serially added to the amplifier's input impedance, thus it can significantly reduce the input current, while the effect is neglected in high-impedance voltage-input amplification. We will discuss on this matter in depth in Section 3.6. Analog-to-Digital Converter Another key block in the readout IC is the ADC where a major portion of power is consumed. In the column-parallel architecture, the requirements of ADC can be relaxed in terms of speed and area. In comparison, single-ADC readout schemes require super-fast data conversion rates to read out N-pixels within a reasonable time 59 frame. On the other hand, in-pixel-ADC schemes suffer from the area constraints related to placing an ADC in each pixel including the routing of the data lines. Traditionally, in a column-parallel architecture, single/dual-slope ADCs have been one of the favorable choices for image sensor readout ICs not only because that type of ADC offers a good trade-off in resolution, speed and power when tightly areaconstrained, but also because it is straightforward to implement with the CDS feature [97-99]. However, in the present prototype IC, a successive approximation register (SAR) ADC was used for ease of design. SAR ADCs, in general, are considered a good choice for medium-to-high-resolution (8-16 b) with moderate sampling rates (< 5 MSPS) [100}. SAR ADCs also provide low power consumption as well as a small form factor, thus becoming our choice in the readout architecture of 8-bit resolution, 1.2-MSPS speed, small area (< 0.05 mm 2) with a moderate power consumption (< 200pW). Given the small number of pixels and the large pixel pitch compared to those of concurrent state-of-the-art focal plane arrays in the visible, our ADC area constraint is not too tight. Furthermore, we get serialized output data in binary code for free. Therefore, SAR ADC was an effective choice to reduce the design complexity. The schematic of the proposed SAR ADC is shown in Figure 3-7. It consists of a binary weighted capacitive DAC, a clocked comparator, and the control logic implementing the successive approximation algorithm. Each data conversion of the ADC takes a sampling phase where the input signal is sampled by the capacitive DAC, and a bit cycling phase where the digital output bits are resolved by the comparator. In each cycle of the bit cycling phase, one most significant bit (MSB) is resolved, and then DAC is reconfigured for the next MSB until it gets to LSB. In the proposed ADC, differential MSB-split capacitive DACs are used for sampling input signal and generate comparator inputs to reduce power consumption of ADC (by 37% compared to the conventional array [101]). In SAR ADCs, the linearity of DAC is critical for integral non-linearity (INL) and differential nonlinearity (DNL) of the system. The DNL in units of LSB (least significant bit) for each code transition is defined as the deviation from the ideal LSB, and the INL for each code is defined as the deviation from the ideal output. In the binary weighted capacitive 60 8bit Differential SAR ADC Main DAC VIN ,I 4 II - Vrefp 4 Vref* SuDA7 8C 4 C2 CP C Co parator SAR I CLK Timing Manager 8 - VCM 00 i Bit Decision Figure 3-7: Schematic of Successive Approximation Register ADC. 61 DNL (in LSB) 0.04 0.02I -0.02 -0.04 I 1 11 161 177 1 11 1 1 1 1 1 1 I INL (in LSB) 0.1 0.05 -0.05 -0.1 1 17 33 49 65 81 97 113 129 145 193 209 225 241 Code Figure 3-8: Simulated DNL and INL of the capacitive DAC across 8 bit digital codes. IDNLIMAx < 0.04 and |INL|MAX < 0.07 are achieved. DAC, skews in the DAC capacitors, especially the skew of the MSB capacitors, have the biggest impact in DNL and possibly in INL. To minimize the skews, good layout of the capacitor array is crucial, and it requires some iterations of tuning and extraction of the layout. Starting from the common centroid layout , iterative fine-tune of the capacitor matching resulted in IDNLIMAX < 0.04 and IINLIMAX < 0.07 in LSBs with C+CC layout extraction as shown in Figure 3-8. While the global clock and the reference voltages are fed off-chip, an internal timing generator controls the cycles for the successive approximation algorithm. Figure 3-9 shows SAR cycles at consecutive data conversions; (1) Once conversion is triggered (TRIG), the internal timing controller asserts a one-clock-period START signal and purge the capacitors. (2) For the following two cycles, the input signal is sampled by the DAC capacitors, and (3) output bits are resolved in the rest cycles. 62 TRIG CLK START a) CYCLE L - SE M~ -o ~ ~ cc~~ E M~o~ Figure 3-9: Timing diagram of the implemented successive approximation logic Full Chip Verification The transient response of the full chip is verified in a testbench simulation. An imager block containing 16 active graphene detectors is assumed in Figure 3-10. Each graphene detector model is assigned with different photocurrent value. The row- column selection logic chooses one pixel connected to ADC at a time. Figure 3- 11 shows the transient response at the column output, which is fed to the ADC input after level shifter circuit, and the ADC output codes. The simulation clearly shows the readout function of the imager block even at very conservative device assumptions, such as very small output impedance and photocurrent of the graphene device (Ro,G-PD = 150 Q, Iph = 0 - 12nA). 63 Pixel Amp Array Row SeIe4f Co.# T Col#1 Column Select Gain ctr Column Amp_ & Level Shifter One ADC reads __3V 1.8V ADC 8x60 pixels as RS and CS select Data Output Valid Code Figure 3-10: Schematic of a testbench for imager block readout simulation. 8 graphene pixels with unique Iph values (0 - 12 nA) and low output impedance (Ro,G-PD = 150 Q) were assumed. 64 1 Col-Row Column Output (p) /__ vae Value Column Output (n) -- 1 00' 700 60C - =: ~ 50'0 040 2C 150 0 125 0 -- ColO0 Row 6 3 nA ColO0 Row 5 2 nA 0ColO0 Row 4 1 nA 3( ColO0 Row 7 4nA Col Row 0 8 nA Coil Row 1 12 nA Col1 Row 2 6 nA 32 64 93 Col1 Row 3 0 nA ADC Output Code 100 .075 0 50 . F-b I I -1 1 - goo 16 8 0 24 0 AJ I -25 I l0 0o l 0 ol col0o RO3IROW41IRow5I RowS 160 180 200 220 col0 Row7 240 time (us) col col RORawl 260 280 col Rw 2 300 colI Row 3 320 Figure 3-11: Simulated Photoresponse Readout of Multiple Pixels 65 3.3.3 Considerations for Back-End Graphene Sensor Integration Additionally, the design of the readout chip had to consider post-fabrication steps for graphene IR detectors in its layout as well as in its schematic design. The layout was required to ease the post-fabrication process, or at least make it possible, including standard electron-beam lithography, metalization, etching, and graphene transfer steps. The readout chip, shown in Figure 3-12, was fabricated in 0.18-pm technology through TSMC's University Shuttle program. First of all, the extended chip size (5mm x 5mm) was intended to ease handling of the chip during the graphene integration process. The active sensor area of the chip, 4mm x 3mm, is filled with the 80 by 60 array of the graphene thermocouple pixels. By locating the regularly patterned pixel array at the center of the chip and other CMOS only components on the sides, it is handy to avoid the issues in lithography involving uneven resist thickness toward the chip edge. The side regions of the chip are used for the row and column selection logic, current sources, column amplifiers, and ADCs. In addition, a discrete imager block is implemented for component characterization and testing off-chip detector readout. The area of each pixel is 50pum x 50pm; a pixel amplifier and signal paths occupy the small portion of each pixel area, leaving over 60% of the area empty and flat. This flat region within the pixel plays a key role when fabricating back gate electrodes for the graphene thermocouple and transferring graphene layer. Each pixel also has two contact metal plugs towards the top surface of the chip for ohmic contact to the graphene thermocouples. Again for the graphene detector, the contact plugs are placed within the flat region but still maximizing the space in between. 66 Figure 3-12: Die photo of the readout IC for graphene-CMOS hybrid IR imager. The chip shown is before the integration of graphene thermocouples. 67 3.4 Graphene-CMOS Hybrid Infrared Imager Integration of Si CMOS and graphene thermocouple array is one of the main challenges to complete the hybrid IR imaging system. Once realized, the integrated system not only provides a new type of IR image sensor but also confirms the feasibility of electronic systems that employ graphene devices in a large scale. In our work, it was indeed a big challenge to develop fabrication processes to integrate >4,000 graphene thermocouples on the CMOS readout chip, and it had been conducted in collaboration with Allen L. Hsu, Charles Mackin, Marek Hempel, Yuxuan Lin, and Young Cheol Shin. 3.4.1 Graphene Thermocouple Device for On-Chip Integration Figure 3-13 shows the integrated graphene thermocouple structure. Although the graphene based thermocouple fabricated on a suspended MEMS structure showed an exceptional IR detection performance thanks to good thermal isolation as described in the previous section, the proposed thermocouple array for the initial integrated solution is not built on such suspended structure. Instead, as shown in Figure 3-13, the thermocouple structure is stacked on top of the CMOS passivation layer, made of Si0 2 , and electrically connected to the readout circuit. The dielectric layer works as IR absorption material and also provides thermal isolation. 68 Ohmic Contact MLG Plug CMOS Substrate Gate Metal Figure 3-13: Diagram of a graphene thermocouple fabricated on top of the CMOS substrate. Two gate metal lines are embedded in SiO 2 passivation layer for electrostatical doping of MLG, and the ohmic contact and plug ensure electrical connection to the pixel amplifier. 3.4.2 Fabrication of On-Chip Graphene Sensor Array The floor plan of the chip is already shown in Figure 3-2. The fabrication processes are initially developed by Allen Hsu [4] and revised as shown in Figures 3-14 and 3-15; (1) Begin with a bare CMOS die received from TSMC. (2) CF4 plasma etch with and without patterned PMMA mask to expose M6 plugs. (3) Sputter of ohmic plug, local gate, and gate routing metal. (4) Dielectric deposition, and (5) Via hole etching follow. (6) Transfer MLG. (7) Sputter ohmic contact metal, and (8) Plasma etch to pattern the graphene layer. After all, the chip is ready for packaging and testing. Further details are provided in Appendix A. Die photo of the fabricated prototype chip is shown in Figure 3-16 (left) along with a original die for comparison (right). A closer look at the pixel area (Figure 3-17) shows MLG, ohmic contacts, and back gate structures fabricated on top of the CMOS substrate. 69 (1) Start from the Bare CMOS IC Die (2) Pattemed I Global CF 4 Etch for Passivation Removal (3) Sputter of Ohmic Plug and Local Gate Metal Layers (4) Si02 Gate Dielectric Deposition Figure 3-14: Fabrication processes for integrated graphene IR imager chip (1)-(4) 70 (5) CF4 Etch to Open Ohmic Contact Via Holes (6) Graphene Transfer (7) Sputter Ohmic Contact Metal Layer (8)02 Etch to Pattem Graphene Figure 3-15: Fabrication processes for integrated graphene IR imager chip (5)-(8) 71 Figure 3-16: Die photos of the fabricated graphene IR imager prototype chip (left) along with the original die for comparison (right) Figure 3-17: Close-up micrographs of the pixel area shows the fabricated structures, including monolayer graphene, ohmic contacts, and back gates for graphene thermocouple array. 72 3.5 3.5.1 Measurements ADC Characterization Characterization of the SAR ADC is conducted using the ADC test block in the off-chip sensor readout compartment shown in Figure 3-12. It is assumed that the ADCs used for readout of the graphene thermocouple array have similar performance to this replica ADC. Figures 3-18 and 3-19 show the linearity of the ADC, measured at the sampling rates of 800-kS/s and 1.2-MS/s, respectively.While we tried to minimize capacitor mismatch through post-layout extraction, IDNLI < 0.3 LSB and JINLI < 0.4 LSB across the full range input were achieved. At higher sampling rate (1.2 MSPS), the linearity is degraded to IDNLI < 1 LSB and IINLI < 1 LSB at the full range input. @ 800-kSPS INL (BEST END-POINT FIT) 1r ........ - -.................-.................- 0 .5 ------- -- - - -0 -1 0 50 150 100 DIGITAL OUTPUT CODE 200 250 200 250 DNL 1 0 ........-..-..-- 0 50 -- --------- -- 150 100 DIGITAL OUTPUT CODE Figure 3-18: Measured linearity of ADC at the sampling rate of 800 kSPS. |DNLI < 0.3 LSB and JINLI < 0.4 LSB across all 8 bit digital codes are achieved. 73 @ 1.2-MSPS INL (BEST END-POINT FIT) 1 0.5 -- --- -~~~ ---------- U, 0 -j zj -0.5 -1 50 150 100 DIGITAL OUTPUT CODE 200 250 200 250 DNL 0.5 ------------- - - - a, 0 -- -0.5 -1 -1 0 50 --- -- - - 0 150 100 DIGITAL OUTPUT CODE Figure 3-19: Measured linearity of ADC at the sampling rate of 800 kSPS. IDNLI < 1 LSB and JINLI < 1 LSB across all 8 bit digital codes are achieved. FFT PLOT 0 - -20 -40 - L0 -60 I-- 11 I1 -80 -100 -120 'L 0 2000 8000 6000 4000 ANALOG INPUT FREQUENCY (Hz) 10000 12000 Figure 3-20: FFT plot of ADC output code at 240 kSPS where input tone is at 1.952 kHz 74 Figure 3-20 shows the FFT of the ADC output at 240-kS/s, with input tone of 1.952kHz. The second harmonic distortion term appears below -70dB thanks to the differential operation. The measured ENOB was above 7.37 at sampling rates up to 1.2-MS/s, as shown in Figure 3-21. The power consumption of the ADC is plotted in Figure 3-22, and the total power consumption at 1.2-MS/s is measured 171 pW. In Table 3.2, the measured ADC characteristics are summarized. ENOB [bits] 9 8 6 - -_ -----___ _ 5 4 3 2 1 -- ~- _ __ _ _ _ _ __ _ 0 100,000 1,000,000 Sampling Rate [samples/s] Figure 3-21: Measured ENOB of ADC 75 _ _ _ ADC+IO Power Consumption + -U--Analog Power Digital Power 1.OOE-03 1.00E-04 E-05 .01.00 10 E06~n 1,000,000 100,000 Sampling Rate [samples/s] Figure 3-22: Power consumption of ADC Table 3.2: Summary of ADC performance Process Resolution Active Area 0.18 pm 8 b 0.0485 mm2 Supply 1.8 V Sampling Rate Power Consumption (including IO Power) 1.2 MS/s Input Range 2.4 Vp-p,diff 171 pW 73 ENOB (fin = 145 kHz) 45.57 dB 62.48 dB 0.861 pJ/conv.step SNDR SFDR FOM 76 Pseudo Photoresponse Measurement 3.5.2 Before applying the readout chip to the graphene sensors, we tested the off-chip sensor readout compartment (shown in Figure 3-12) to verify the readout performance. As shown in Figure 3-23(a), an off-chip current source is connected to one of the four pixel amplifiers that have pad routings for external connection. The current source mimics the graphene IR detectors. The measured response is plotted in Figure 323(b) where the linear response range is from -60nA to 100 nA, which allows enough dynamic range for graphene IR detectors. The resolution in this configuration was 581 pA/code, thus enabling sub-nA photocurrent detection while noise is suppressed. For instance, we expect 9-LSB output from 5 nA input photocurrent. (b) (a) lava DVv -~ r100 -~ 80 . --1 1 y = -5.81E-01x - 60 +99.99 - 40 VB 'avg 17 nA] - 20 ADC Off-Chip Current rOnA DOUT Output Code Source P- Current range: -60nA ~ 100nA -.- -0 -20 +- -40 - -60 Resolution: 581pA/code Figure 3-23: (a) Schematic diagram of pseudo photoresponse measurement shows test setup, and (b) sub-nA resolution is measured with linear input current range of 160 nA. 3.5.3 Off-Chip Graphene Thermocouple Measurement Figure 3-24 shows the laser scanning setup used in the demonstration of off-chip graphene thermocouples. A temperature stabilized 1W CO 2 infrared laser (Access Laser Company) provides infrared radiation at 10.6 /im. The power of laser source 77 A = 10.6pm alvo Mirror PC CO,Laser Z L1 Excitation Source GUI Light Modulation 5V,, I _LU-L ."3 7 L3 ZeSn Window Scryostat Graphene 400mTorr Vacuum Thermocouple Pump] .. ... p Pu.. Readout IC PCB Vacuum Pumping Figure 3-24: Schematic diagram (top) and photograph (bottom) of discrete graphene thermocouple measurement setup is controlled by the duty cycle of 5 V,.. square wave from a function generator (Tektronix). A beam combiner optics (ULO optics) is used to add a collinear laser (A = 632 nm) for alignment. A galvanometer controlled mirror produces angular deflection centered at the focal point of lens 1 (L1 in Figure 3-24). The deflection is then mapped through a relay of confocal optics (L1 and L2) onto the back focal plane of an objective (L3). The IR beam is mechanically chopped by a modulator wheel operating at 78 20Hz to 1kHz. The modulated beam hits the sensor substrate through an objective (L3) and a ZnSe anti-reflection coated window, producing distortion free scanning over a large (> 4 x 4 mm2 ) area. The incident laser power at the sensor surface was pre-calibrated by a reference power meter (Thor labs). The optical cryostat (Janis) allows measurements to be done under vacuum and at low temperatures (77K < T < 300K), but the presented measurements were only conducted at room temperature. To stabilize the device, the cryostat was lightly vacuum pumped to 200-400 mTorr. Two source-drain pads from the graphene thermocouple device and two gate pads are routed out through BNC cables. The source-drain contacts are connected to the pixel amplifier input of the chip, and the gate bias for the device was applied from external sourcemeters (not shown in the figure). The photoresponse was recorded by an FPGA and a PC graphic user interface (GUI). - FFT PLOT 2.5 X: 248.9 Y: 2.514 -- 1.5 - 2 0- 0.5- 0- 0 500 1500 1000 ANALOG INPUT FREQUENCY (Hz) 2000 Figure 3-25: FFT plot of the photoresponse measured at Pi = 157 p-W and fmod = 250 Hz input. 79 Figure 3-25 shows the FFT of the raw ADC output codes measured at the incident laser power (Pi,) of 157 pW and the chopper frequency (fmod) of 250 Hz. A clear signal peak near 250 Hz and the harmonics were observed. Due to the square waveform of the photoresponse, strong 3rd (~750 Hz) and 5th (-1.25 kHz) harmonics were observed, while the 4th (-l kHz) was due to ADC nonlinearity. We also noted that the graphene thermocouples show 1/f noise characteristic at a frequency below -150 Hz. By integrating the power spectrum density over the signal peak, we estimated the signal amplitude as the voltage swing at the ADC input node. Figure 3-26 plots the signal amplitude filtered at the modulation frequency over various incident laser power level, where the power was limited up 400 pW to prevent burning of the device. In addition to frequency selective signal estimation, a simple averaging of the output codes can estimate the photoresponse because of the non-negative photoresponse even when the chopper blocks the beam path. The averaged output codes along with the DC offset is shown in Figure 3-27, noting enhanced (- 10x) output swing due to the mechanically suspended sensor structure. Signal Amplitude at the Chopping Frequency 10 --- - - - I- - --- -- -- _ -- ---- - - 100 -- - 60--- 20-- 50 - - 40 - 100 150 - -_ -_- 80 _ - 120 - -- 140 - ----250 200 Input Power (pW) 300 350 400 Figure 3-26: Estimated photoresponse amplitudes at various Pm's by integrating 250 Hz power spectral density of the signal peak at fmod= These measurements demonstrate the readout ability of the presented readout IC. 80 Mid-IR Photoresponse 120 110- 1000 0 0 0) DC offset 0 (zero input response) 70 ------------------------...............................------- 60 F 100 r 150 F 200 r F 250 300 350 Input Power (pW) Figure 3-27: Average output code measured at various Pm's. The signal nature that only non-negative response is generated allows the photoresponse estimation by simple averaging. Furthermore, the whole data acquisition equipment set, including the lock-in amplifier and the DAQ board (National Instrument), in the previous measurement setup [4] can now be replaced by a compact PCB with the readout IC. 3.5.4 Integrated Graphene Sensor Array Measurement Graphene and Dielectric Quality After integration of the graphene thermocouple array, the quality of the graphene layer and the gate dielectric were inspected. As Figure 3-28 shows, the structural integrity of graphene layers were visually inspected under a microscope. The yield chip. of the thermocouples with clean monolayer was higher than 80% across the Furthermore, the graphene's quality was investigated by Raman spectroscopy on four locations picked across the chip as shown in Figure 3-29. The Raman spectroscopy 81 confirmed the low sample doping, as shown by the 2D-band G-band (WG - 1585cm-1) intensity ratio (I2D /IG (W2D - 2668cm-') to 2), and a low concentration of defects as indicated by the low D-band to G-band intensity (ID/IG = 0.15 0.4) [102, 103]. Row 57 Delaminated Graphene Row 58 Row 59 Col 20 Col 21 Co1 22 l Co1 23 Figure 3-28: Micrograph of delaminated graphene layers in thermocouple array The gate electrodes for the graphene thermocouple are routed to carry two different voltages usually in different polarity. In each pixel, the two gate electrodes (GI and G2) have 700nm lateral spacing from each other and 70nm vertical spacing to the graphene layer and metal contacts. Since the gate bias requires an operation in high voltages ranging from -15 V to +15 V, the quality of gate dielectric layer had to be verified. At VG, = +16V and VG2 = -16V bias condition, the leakage current was less than 1 ptA, confirming that neither short between the gate electrodes nor short through Si CMOS was observed. Once we confirmed the good dielectric quality, testing of electrostatic doping of onchip graphene was conducted. Figure 3-30 shows the Raman shift of on-chip graphene 82 LO 2400 D-peak 220 2D-peak G-peak 2 O01 8001600D - 1 400 a 1200 600- - 1000- 1000 1200 1400 1600 1800 2000 Raman Shift (cm-) 2200 2400 2600 2800 3000 Figure 3-29: Raman spectroscopy of graphene layers of on-chip thermocouples. at various gate bias conditions. While the trend of the Raman shift indicates changes in the carrier concentration, the transition from p-type to n-type was not clearly observed within the (-15 V, +15 V) gate bias range. IR Scanning Setup for Graphene-Integrated Chip For the measurement of the photoresponse by on-chip graphene thermocouples, the measurement setup was modified as shown in Figure 3-31. While the chip had to be placed in the socket of the testing PCB, the testing board was too large to put in the cryostat. Therefore, we replaced the cryostat by an aluminum vacuum cap with the ZnSe anti-reflection coated window, which allows similar measurement condition to that of the discrete detector measurement. The testing circuit board was securely placed on a XYZ stage for IR focusing and spot placement. The size of the IR beam spot at the focal plane was measured by burning a sheet of thermal paper and found to be around 30pm in diameter, which allows in-pixel local heating for thermoelectric effect, as shown in Figure 3-32. 83 On-Chip Graphene Raman Shift with Electrostatic Doping 2675 1600 -+-G-peaks -- D2-peaks 1598 2673 1596 2671 1594 2669 1592 2667 1590 2665 0 1588 2663 2661 4 1586 0 1584 2659 1582 2657 2655 1580 -20 -15 -10 0 -5 5 10 15 20 Gate Voltage [V] Figure 3-30: Raman spectroscopy of graphene layers of on-chip thermocouples shows electrostatical doping of graphene. Preliminary Results In the prototype chip with integrated graphene thermocouples, unfortunately, there was an issue with electrical short of IOVDD power line to IOVSS ground line caused by the graphene integration process. While more details are discussed in the following section, we could eventually salvage the chip and were able to run the measurement with limited row-column selection capability. To make the experiment possible, we scanned the IR beam across a large area with continuous readout from a fixed pixel. While the process of moving the beam spot around by a few micrometers until it gets on the right pixel was extremely time-consuming, we managed to put the beam on the right place. In the meantime, a graphical user interface (GUI) allowed us to efficiently run the experiment. Figure 3-33 shows the GUI which contains a zoomedin FFT plot centered at modulation frequency in the middle and the color-coded plot for multi-pixel readout on the right. While the shown data was taken in multi-pixel scan mode, the overlapped signal peaks in the circle and the fact that all tiles have similar color on the right map 84 Figure 3-31: Measurement setup for graphene-integrated sensor chip. The sensor chip is sealed with a vacuum cap for stable performance. The beam shares the same path described in Figure 3-24. Figure 3-32: IR beam spot size at the focal plane was measured by burn marks of thermal paper and found to be rv30 µm in diameter, which allows in-pixel local heating for thermoelectric effect. first indicate malfunction of row-column selection in this chip. Figure 3-34 plots the extracted signal peak values at various input power in terms of excitation duty cycle, where the chopping frequency was 79Hz and the gate bias was V01 = +16V and V02 = -16V. While a complete 2D scanning readout demonstration must be followed for imaging application, this preliminary result proves the integrability of 2D material-based devices with Si CMOS IC. 85 OWl Tesbench vI.1 204E 4 q484A C w..Uweooe.Ooom..WmxmORLG 4E483 OW row FFFF U sf*. "j en" AOC2 4 Riz PK istsett 46. M I ft 100 f1024 MU 7660 ALMO IOVER I f IMMYJ FL IUS 4A Photorqsponsei (6.16 H I peak t f, F I&I 78 785 79 79-5 80 Figure 3-33: Graphical user interface for IR detection experiment showing output FFT plot centered at the light modulation frequency (center) and 2-D colored map for array readout. Extracted Peak Height 300 Chopping at 79Hz, Gate bias: 16V 250 54 L5U - 200 100 50 0 35% 45% 40% Laser Source Duty Cycle 50% Figure 3-34: Signal peak values extracted from FFT of the photoresponse measured by an graphene-integrated readout IC show a linear relationship to laser excitation duty cycle. 86 3.6 3.6.1 Discussion Graphene Models for Pixel Readout Pixel Amplifier Graphene Photodetector U t Figure 3-35: Readout architecture with pixel transimpedance amplifier and Norton equivalent circuit model of the graphene photodetector. Contact resistance is neglected. Figure 3-35 shows an transimpedance amplifier architecture with a Norton model of graphene photodetector (G-PD as a current source). The input current of the amplifier (Ij,,) is given by a function of the photocurrent Iph, the output impedance of graphene (RG), and the input impedance of the amplifier (RI ), so that IIN = Ro Ro + Ri _Iph(36 Assuming the transimpedance of the amplifier is Gm, the output voltage is given by Vo = GmIin = Gm Ro Ro + R7 p(37 To maximize the output signal amplitude at given Iph and RO, it is desired to maximize Gm and minimize Ri. A similar analysis applies to the architecture with a Thevenin model of graphene photodetector (i.e. G-PD as a voltage source) shown in Figure 3-36. The output voltage is given by Vo = GmIin = Gn- p h(38 RO + Ri 87 Pixel Amplifier Graphene Photodetector amamamama mmmaam 33535 a 'in am mamas mama a~m~a~g a a a a a a a a a U a a aO f :R. a -~ + a a a a a U a a a a a a a amso NNO a a a a a a a a a a a a a a mmmmmammmmmmmmmmmaammmm U Figure 3-36: Readout architecture with pixel transimpedance amplifier and Thevenin equivalent circuit model of graphene photodetector. Pixel Amplifier Graphene Photodetector aO a IN: *p "o a . .. R,4,,I 7 . .. .a. . 1 Figure 3-37: Readout architectures with pixel transimpedance amplifier including contact resistance from ohmic metal-graphene junctions. 88 Contact Resistance Considering the contact resistance (Rc), as shown in Figure 3-37, the output of each architecture is given by, VONorton VO,Thevenin = (39) GmRo Ro + Rc + Ri M RO + Rc + Ri (3.10) Roft+-ft R Therefore, the output reduces by a factor of Vph in both cases. Since we + + Ro + Rc + RI only care about the signal amplitude, not the power, both models are interchangeable. For best performance, Rc << RO+fR is desired, however, this is not trivial to achieve along with on-chip integration. Along with the practical limitation in minimizing contact resistance and the moderate output impedance (-10 k2) of the integrated graphene thermocouples, the readout of the thermoelectric voltage may be optimized with voltage-input amplifiers. Multi-Junction Graphene Photodetectors Multi-junction graphene photodetectors may be used to gain better photocurrent or photovoltage out of the sensor. Figure 3-38 shows a graphene device with parallel multiple junctions is equivalent to a single graphene junction using the same area. Therefore, we only consider a series multi-junction devices as shown in Figure 3-39. Figure 3-38: Illustration of a single-junction model (left) and a parallel multi-junction model (right) 89 N2,RNoRc R, VO + N Vpanf Figure 3-39: Schematic circuit of a series multi-junction model (left) and its illustration (right) The output voltage of N-junction photodetector (or thermocouple) is given by, = Gm N 7 h N2Ro+ N 2 Rc + Ri Gm R N(Ro+Rc) + H where N is a positive integer, and 100% area utilization is assumed. (3.11) (3.12) ( VoMJ The multi- junction device has advantage over a single-junction device when Vouti/V,ingl, > 1, that is, N (Ro + Rc) + - < Ro + Rc + R, N (3.13) (N - 1) (Ro + Rc) < (NN)Ri (3.14) Ro + Rc < HN (3.15) Here RO and Rc highly depend on the material quality and device fabrication. The input impedance of transimpedance amplifiers is small, and the condition given by Eq. 3.15 is hard to meet with N > 1. Thus, we conclude that the single-junction device always outperform the multi-junction device. Furthermore, more degradation is expected when we take the area overhead for fabricating multi-junction pixels into account. 90 3.6.2 Power Line Shorting Issues Electrical short of power routes (VDD's) to ground routes(VSS's) is one of the most severe problems in chip testing since the chip cannot be powered at all once it occurs. As in this work, the additional fabrication process can increase this risk by (1) unintentional scratches, (2) excessive metalization, and (3) excessive graphene residue. Due to this problem, we lost the row-column selection control in our prototype chip and could only demonstrate a single pixel photoresponse to infrared laser input as presented in the previous chapter. Top Metal Power Routes The main issue with the initial graphene-integrated chip was electrical short in its power lines. The chip pads were designed to share a common IOVDD/IOVSS lines running along the chip edges. While the power lines were kept safe during most of the post-fabrication process, a few top metal routings of IOVDD and IOVSS get exposed (or nearly exposed) after the passivation etch process. In addition, the routings of each IO power were placed very close to each other by 1 prm spacing making the chip vulnerable even to mild scratches as shown in Figure 3-40. To reduce the risk of shorting the metal routings during the graphene integration process, the layout of the readout IC should (1) minimize routings in top metal layer and (2) make the line spacing in the top metal extensively wider. 91 Figure 3-40: Scratches occurred during graphene integration process; Narrow spacing in top metal layout should be avoided. Excessive Metal Deposition Excessive metal deposition on undesired locations can occur during the fabrication process. It is often due to overdose of electron beam lithography and over- developement of resists. Pads are one of the locations where excessive metal can short two different power routes. As Figure 3-41 shows, we inspected these types of electrical short a few times during the integration process. To reduce this kind of risk, wider pad spacing should be used. 92 Figure 3-41: Scratches and excessive metal residue at pad region cause electrical short. Excessive Graphene Residue Electrical short by graphene layer is an additional challenge we had during the fabrication. For fabrication of >4,000 graphene devices at once, the graphene layer that we transfer onto the silicon substrate has to be large enough to cover the whole chip. The uncontrollable nature in manual graphene transfer processi, such as sheet's rollup, tear out, and mislocating, often leads to excessive graphene residue on the chip's near-edge area. Although mesa etching of graphene can clean up those regions, the residue may occasionally remain as shown in Figure 3-42. However, fortunately, electrical short due to graphene can be alleviated by relatively easy treatments such as additional mesa etching, local FIB cutting, or flowing excessive current to burn the material. Focused Ion Beam Cuttings Focused ion beam (FIB) cutting tools offer handy post-fabrication fixes. Unlike an electron microscope, FIB is inherently destructive to the specimen since it uses highenergy gallium (Ga) ions to strike the sample. The ion beam sputters atoms from the 'The graphene transfer process consists of CVD growing of monoloayer graphene on a sheet of Cu foil, PMMA spin-coating, Cu etching in acid or base solution, manual fishing of floated graphene by the substrate chip, and solvent cleaning steps. 93 Figure 3-42: Excessive graphene residue at pad region cause electrical short. sample surface, so excessive metal or graphene structures can be removed. However, it should also be noted that re-sputtering of the removed material can leave residues on the sidewalls. A beam current of 0.28 - 0.93 nA, with an approximate dose of 2-5 nC/ptm 2 , was sufficient to cut most metal lines as shown in Figure 3-43, and the continuous SEM option on the FIB of CMSE was used to monitor the etch. Figure 3-43: SEM image of a FIB cut near pad region 3.6.3 Revised Metalization In addition to the original process developed by Allen Hsu, we developed a metalization process that replaces the patterned sputtering step for ohmic plug metalization. The revised process made in-house-only fabrication possbile while better conforming 94 Figure 3-44: SEM image of disconnected metal routing at dummy gap region to the in-house fabrication rules in order to reduce the risk of sample and equipment 2 contamination. The details are provided in Appendix A. Gap Filling Metal The original Si CMOS chips fabricated from the vendor has regularly patterned top metal dummies to meet the metal density requirement. As the received chips were lacked surface planarization, the gaps in between the dummy patterns caused routing disconnections as shown in Figure 3-44. To alleviate the surface roughness, deposition of 400nm-thick Ti/Au stack has been conducted at desired locations as Figure 3-45 depicts. After this, regular routing patterns can be deposited over the dummies. Tilted Ohmic Plug Deposition In the revised process, an electron-beam evaporator (ebeamFP) replaced the sputterer for metal deposition, and it resulted in less sidewall coverage. As the subsequent 3 electrical opens at the amplifier input metal plugs (L2) and in-pixel gate routing (L3) 4 had arose, we switched the order of two deposition steps and had L2 deposition on a tilted (300) wedge (Figure 3-46). As a result of tilted metal deposition, the The process was developed in collaboration with Yuxuan Lin, Marek Hempel, and Charles Mackin. 3 Ohmic Plug mask in the process given in Appendix A 4 Gate electrode mask in the process given in Appendix A 2 95 Figure 3-45: SEM image of metal-filled gap in the dummy metal region sidewall coverage was recovered (Figure 3-47). 96 Figure 3-46: Aluminum wedge piece for tilted metal deposition. The tilt angle can be either of 30' or 600. Figure 3-47: SEM image showing sidewall coverage from tilted metal deposition 97 3.7 Concluding remarks Starting from exploring graphene as a new infrared sensitive material that can be used for sensors in mid- and long-wavelength IR spectrum (A = 2 - 15pm) imaging system, we designed a Si CMOS-based readout IC for graphene thermocouple array. The readout function was demonstrated both using an external current source and a discrete graphene thermocouple device. In the measurement, the presented readout IC replaced the lock-in amplifier and DAQ board combination used in the previous work [4], demonstrating IR sensing system with significantly reduced form factor. Based on the integration process developed previously [4], we fabricated an onchip graphene thermocouple array. The readout IC was used as a substrate for the monolithically integrated array of 4,800 electronically tunable graphene thermocouples. The prototype graphene-Si hybrid IC was presented as a fully-featured sensor system consisting of IR sensors and readout circuitary on a single 5-mmx5-mm die. While the fabrication process was compatible with conventional Si CMOS technology, we noted that the readout architechture and chip layout must be carefully designed to ease the subsequent fabrication process. While further development is in need to realize the 2D scanning imager, the presented column-parallel scheme and single on-chip sensor measurement suggest possible development of new types of graphene-Si hybrid applications. Furthermore, along with the fact that the 2D patterning steps used in this study are applicable to other planar materials, the fabrication and measurement schemes presented here can be widely applied to on-silicon-CMOS-IC integration of other materials or structures. 98 Chapter 4 MoS 2 -Based Next Generation Electronics 4.1 Introduction The recent rediscovery of stable monolayer graphite or graphene has led remarkable interest in the physic and applications of two-dimensional (2D) materials [104-107. Beyond semi-metallic graphene, the rich variety of 2D materials include wide bandgap insulators such as hexagonal boron nitride (h-BN) [108] and semiconductors as observed in transition metal dichalcogenides (TMDs) [109-111]. While either low off-current or saturated on-current is difficult to achieve in devices based on zero-bandgap graphene, the semiconducting TMDs, such as molybdenum disulfide (MoS 2 ), tungsten disulfide (WS 2 ), and tungsten diselenide (WSe 2 ), with bandgaps in the 1 - 2 eV range, can provide excellent on/off current ratio as well as current saturation. The feasibility of 2D material-based stand alone systems has been demonstrated [48,104, 112-115], in addition to heterogeneous combinations with Si. Taking the flexibility and transparency of the carrier transport substrate as unique advantages over other bulk semiconductor substrates, 2D materials also enable a new possible market of flexible, transparent, and ubiquitous electronics. Furthermore, recent theoretical analysis and experiments suggest the device performance can be comparable even to the over-30-year-mature Si CMOS technology that has been a 99 great, and almost the only, main player to provide a variety of ICs in the electronics ranging from high performance computation units to highly energy efficient systems [116, 117]. 4.1.1 Demands for MoS 2 -Based Electronics Among the TMD family, MoS 2 is one of the most promising materials that have already demonstrated higher level circuits and systems, at least with a few transistors, such as [48, 114,118]. While MoS 2 device technology is still in the early development phase, it has the potential to be a key player in realizing the next generation electronics once given: (1) large scale and high quality production of the material, (2) fabrication techniques for performance, stability, and yield, and (3) a computer-aided design flow including good device models to simulate circuit for device performance prediction and computer aided layout for large scale designs. 4.1.2 Material Growth First, production of large-area MoS 2 monolayer is necessary to realize large-scale MoS 2 circuits. While exfoliation of bulk MoS 2 crystal unreliably produces monolayer sheets in limited size, a uniform and highly crystalline MoS 2 monolayer growth is achieved with chemical vapor deposition (CVD) by Xi Ling [5]. Figure 4-1(a) shows the CVD system for material growth, that uses sulfur (S) and molybdenum trioxide (MoO 3 ) as the precursor and perylene-3,4,9,10-tetracarboxylic acid tetrapotassium salt (PTAS) as the seeding promoter to enhance area and uniformity of MoS 2 . The material growth process is conducted at a relatively low temperature (650 0 C), as the furnace temperature profile is shown in Figure 4-1(b). An optical image of the CVD-grown MoS 2 is shown in Figure 4-1(c), demonstrating a good uniformity and a high coverage approaching 100%. The dimensions of monolayer MoS 2 sheets are in order of 30 pm across the sample. The thickness is measured to be 6.9A, a typical monolayer MoS 2 thickness, using atomic force microscopy (Figure 4-1(c), inset). A high resolution TEM as well as the crystal diffraction pattern 100 (a) 65 - - - 5sccm Ar - (b) Gas out-' m in mn Time Figure 4-1: (a) A schematic illustration of the MoS 2 growth by CVD. (b) The temperature profile for the growth process. [5] (c) Optical micrographs and thickness profile (inset) of monolayer MoS 2 . (d) High resolution TEM image and the corresponding selected area electron diffraction (SAED) pattern (inset) show the hexagonal crystal nature and the high quality lattice structure [6]. confirm the high quality of CVD-grown MoS 2 by the highly ordered lattice structure as shown in Figure 4-1(d). 4.1.3 Device Fabrication Secondly, the device fabrication process must be well-established to demonstrate large-scale systems. For conventional MoS 2 FETs, with gate-last processes, dielectric integration is usually conducted at low temperature and/or assisted by seeding layer to protect the atomically thin channel substrate, both resulting in fixed charge and trapped states inside the dielectric or at the interface. This causes extra scattering hence degradation of mobility as well as negative shifts in VT. In this work, in collaboration with Lili Yu, a gate-first process was adopted for the gate metal and dielectric components to be fabricated before the MoS 2 transfer step as illustrated in Figure 4-2.1 By using the gate-first process, high gate dielectric and interface quality is achieved, which also enables potential scaling of the oxide thickness down to a few nanometers. In comparison to the gate-last FETs, the gate1The process details are available in Appendix A. 101 Chnannel source ALD A1203 Dr1ain WALD SIO,/Si Subhst rate --- SiO 2/Si substrate Gate fabrication dielectric layer $FG annealing Via hole etching SD pads deposition MonolayrMoS% MoS 2 transfer Hot KOH MoS 2 rnesa etch SD contacts Passivation Figure 4-2: Gate-first fabrication process for MoS 2 FET first FETs not only show larger VT, 10x larger on-current, 100 x smaller off-current, and steeper subthreshold slope (SS), but also result in far better VT-variation control as shown in Figure 4-3. Among the advantages mentioned, the large VT (thus VT > 0 V) is especially critical for implementation of integrated circuits. Unless enhancement mode operation (normally off) is provided with a positive threshold voltage, one stage of circuit cannot drive the next stage without external level-shifting equipment, which makes the device not attractive for IC. Therefore, the presented gate-first process opens the way to the feasibility of large-scale MoS 2 electronics. 4.1.4 Design Flow Lastly, to realize circuits in larger scale, a complete design flow should be introduced. As shown in Figure 4-4, the proposed design flow consists of two phases: (1) device development phase and (2) circuit design phase. The first phase consists of material growth, device fabrication, and device-level performance characterization. It is followed by the next phase of circuit design that consists of device model implementation, circuit design with simulation, layout generation, fabrication, and system-level measurement. The results in the end of a cycle provides feedback to improve the basic device performance. This feedback loop plays a critical role when the technology is 102 (a 102, 10, .5,(b,.) 30-. . V. I 300 mv/dec 104 10. 20 -- 10-2 V =1.5 V15 115 mv/dec G Gate last Gauss fitting of data 25 2000. - 1 0.5 V 8 010. 10-10 5 -<--, Gate first - -Gate lost -4 -2 0 2 -0 4 0 6 -10 Vgs (V) -8 -6 -4 -2 0 2 V- T(V) Figure 4-3: Performance comparison of gate-last and gate-first processes: (a) I-V characteristics in linear (right y-axis) and log scale (left y-axis) and (b) Gate-first devices have average VT of 0.54V with standard deviation of 0.12V while those from gate-last process have average VT of -4.20V and standard deviation of 1.75V. [6] Device Development rU Caymtit r-dd Circino Comcut Mde Figure 4-4: Proposed design flow for large-scale MOS2 integrated circuit development 103 still in an immature stage, since the performance of devices based on new materials improves as the technology evolves, and the circuit design must adapt as well. As further discussed in the following section, this thesis contribute to the development of the computer-aided design flow for large-scale MoS 2 integrated circuit design. 4.2 Computer-Aided Design Flow Over the last few decades, silicon CMOS industry has leveraged the unified design environment provided by the CAD tools, that support not only circuit simulation but also layout generation and verification process. A CAD flow typically includes physical or empirical models of the active and passive components (i.e. diode, FET, R, L, C), circuit simulators such as SPICE for performance evaluation, parameterized layout cells, as well as verification tools for checking that the layout is compliant with design rules (such as metal spacing) as well as for comparing the layout versus the schematic. Since this CAD flow allows the designer to predict and optimize the performance of the circuits before production of the lithographic masks, significant reduction in the time required for debugging and consequently cost of fabrication of silicon CMOS systems have been achieved. In contrast, circuit design with devices based on new materials has lacked such environment, and the researchers in emerging fields have only been able to take limited advantage of the CAD software. Therefore, implementation of electronics based on new materials has often been conducted by circuit design based on hand calculation and/or intuition and fully manual generation of layout patterns for each lithographic mask. By implementing device models into SPICE or Verilog-A language, the complexity of the designs that can be pursed with such emerging materials can be drastically increased, which enables a new paradigm for its applications. Furthermore, generation of corresponding layout using parameterized cells is another key procedure for time-efficient circuit implementation. In this work, we have developed a CAD flow for MoS 2 -based systems that includes: (1) compact models of MoS 2 devices, (2) schematic design based on circuit simulation, 104 and (3) layout with parameterized cells. In the later part of this chapter, the design of a switched-capacitor (SC) DC-DC converter and a half-wave rectifier is also discussed as examples. 4.2.1 Modeling of MoS 2 -Based Devices For accurate circuit simulations, device models of MoS 2 , either physical or empirical, must be provided in a form compatible with circuit simulator languages, such as SPICE, C, or Verilog-A. To develop the CAD flow for MoS 2 technology, a number of different circuit models were investigated. Analytic Diode Model Since a diode is a two-port device, explicit equations that describe the input-output (VD - ID) relation may be derived. The Shockley ideal diode equation gives the I-V characteristic of an ideal diode as following, ID = Is(eVD/nVT _ 1 (4.1) where Is is the reverse bias saturation current, VT is the thermal voltage (kBT/q), and n is the ideality factor. Compared to the exponential characteristic in ideal diodes, 2111 Figure 4-5: Gate-Drain connected MoS 2 FET was used as MoS 2 diode. our MoS 2 diodes as shown in Figure 4-5, which really are Gate-Drain connected FETs, have less steeper slope increment in the forward bias regime. Therefore, a modified diode equation, instead of Eq. 4.1, is introduced as below, 105 ID = b4 VA + b3 V3 + b2 VD2+ b1VD+ bo ID = ISM (eVD/am - 1) To make it analytic, ID(VD = 0) = 0 and when VD > 0 (4.2a) when VD < 0 (4.2b) dID has to be continuous. Therefore, dVD bo = 0 and b1 = ISM am Figure 4-6 depicts the fitted curve of a MoS 2 diode to the modified diode equation Eq. 4.2. The forward bias current is fitted with a polynomial (Eq. 4.2a) to effectively IL) = IsM (clT/""n - if)- b1~~+ D .2V bV' 1) X104 Forward Bias Region Reverse Bias Region 24 ++ + 45 4 35 3 -2.5 -2 -1' -1 0.5 -05 1 1.5 2 25 3 + 14 35 4 45 i Figure 4-6: Fitted diode equation shows a good agreement with the measurement. model the diode characteristic less steeper than exponential curves. In the demontrated case, it was fitted to a 4th order polynomial, while higher order polynomials resulted in negligible improvement. For the reverse bias current, as shown in Figure 4-7, a polynomial equation cannot provide a saturating current toward negative bias and be monotonic at the same time. Furthermore, it is important to suppress the measurement noise, otherwise, small signal simulation can go chaotic, therefore, the exponential equation (Eq. 4.2b) is applied. With these two explicit equations of VD, 106 and we can also ensure the monotonic I-V characteristic of the modeled diode 2 directly implement the model in Verilog-A code for circuit simulation. ID, Diode Fitting x 10-7 * 4 --- 3 ........ --- Measurement 10th-O rder poly. Exponentia - ------- ------------------- ......... ----- . m t. .. ... H. gh ......... rd................................ p .. 2 F.gu re.4-.: ..... - 44......- -3 ----- 4 4-- .- -- 2--- -1....-. - ---- 0----5 -------------5-1----------------------I-5--------------- -35.. Figure 4-7: High order polynomial equation cannot model the reverse bias diode current due to its non-monotonicity and large error. Empirical FET Model An empirical model of the MoS 2 FET was built using a look-up table derived from the measurement data and implemented with $table.model function in Verilog-A language. The model generates an approximated output current at any input (VGS, VDS) utilizing interpolation and extrapolation of the raw data in the way specified with the 3 optional arguments. The immediate benefit of this behavioral model is that neither prior knowledge on the device physics nor convergence in fitting algorithm is required, since it is based on a look-up table solely derived from data, not from any physical analysis. More importantly, the output current of the model is determined from polynomialfit splines, so it offers the best approximated output values for a given dataset, in terms of the large signal conformity. However, the empirical is subject to capture measurement noises unless preprocessing of data filtered them out. Furthermore, 2 3 The Verilog-A code for the fitted diode model can be found in Appendix C. The Verilog-A code for the empirical model can be found in Appendix C 107 it requires additional modeling for AC characteristics. Therefore, we investigate a physical model which can give comprehensive device description. Drift-Diffusion Compact Model A drift-diffusion compact (DDC) model'is employed to describe the characteristics of the MoS 2 FET. The DDC model is based on the electron transport properties of atomically thin MoS 2 [6,119]. The lateral current in the model (ID) can be simplified as below, ID= where Qj, I2 WF(Vsat) (Qis + Qid) Vsat (4.3) and Qid are the channel charges at source and drain, respectively, and Vsat is the saturation velocity of the carrier. The F(Vsat) is the empirical function for the smooth transition from the linear to saturation regimes, which is given by Qis - Qid F(Vsat) CinviVDSAT = (4.4) 1+ + Qis - Qid (CinviVDSAT) 1 VDSAT = VsatLG (4.5) where Cinvi is the channel-to-gate capacitance at charge inversion, and / is an empirical fitting parameter. The DDC model not only provides a reasonable I-V behavioral description of MoS 2 FET including the subthreshold current but also allows physical understanding of the carrier transport dynamics. Figure 4-8 plots the I-V characteristics of the DDC model and the empirical model along with the measurement, where both of the model provides good agreement to the measurement. In qualitative comparison, shown in Table 4.1, the empirical model has the best agreement to the original data, thus it allows accurate DC analysis. However, for accurate small signal and transient/frequency responses, the DDC model is necessary as the model well-suits for AC simulation thanks to its inherent capacitance parameters. 4 The MoS 2 DDC model is developed by Shaloo Rakheja. 108 3 100 W/L = 40pmi/21 m VGS = OV to 5V (bottom to top) in 1V step 2 40pm/2pm L = ~W Vs=0.9 V r 10-5 0 - -- 0 0 0.5 1 1.5 10. 01 2 -2 0 VDS (V) Measurement -Empirical DDC 4 2 VGS (V) Figure 4-8: Comparison plot of MoS 2 FET models Table 4.1: Qualitative comparison table of device models Large Signal Conformity Small Signal Behavior Channel Length Modulation Sub-Threshold Current AC Characteristics Fair 109 I Poor Fair 6 4.2.2 Technology Library and Parameterized Cell for MoS 2 Layout Custom Technology Library To effectively utilize the Cadence design environment for layout generation, a custom technology library is created. 5 The technology library file defines five main layers: Mesa - to pattern the MoS 2 channel region. Gate - to pattern the gate metal stack of Cr/Au/Pd. Contact - to pattern ohmic contact layer (Au). Pads - to pattern the pad region (Ti/Au). Vial - to define the via holes for creating connection from Gate layer to Pad/Contact layer. Auxi, Aux2 - auxiliary layers for future use. Parameterized FET Layout Cell Based on the layer definitions in the custom technology library, a parameterized cell (P-cell) has been created to allow the automatic generation of the MoS 2 FET layout from the transistor width and length. Figure 4-9 depicts an example layout with Pcells of 40pm/4pm and 20pm/2pm MoS 2 FETs in the Cadence layout environment. The dimensions and relative positions of the corresponding layers, i.e. Mesa, Gate, Contact, Pads, and Vial, are derived from predefined P-cell rules. The user-defined rules also include the range of transistor size, for instance, W = 4 - 200pum and L = 1 - 50pm, according to the fabrication capability. Once P-cells are generated, placement and routing processes are done manually. Then, the full chip layout is exported in gds format for mask production by commercially available vendors. 5The details are provided in Appendix C 110 Figure 4-9: Layout of MoS 2 thin-film transistors (W/ L = 40µm/ 4µm and 20µm/2µm) using P-cells in Cadence software. The layer definition is given in the legend. 4.3 Circuit Design Demonstration The presented design works were conducted in collaboration with Dina El-Damak, while the measurement was conducted with Lili Yu and Dina El-Damak. 4.3.1 Switched Capacitor DC-DC Converter Utilizing the proposed CAD flow, a switched capacitor DC-DC converter was implemented. Figure 4-10 shows the schematic diagram (left) and the micrograph (right). The converter consisted of two MoS 2 switches, a charge transfer capacitor (CJty), and the output capacitor (Gout)· In this implementation, Cfty was 56pF, and the switch size was 40µm/ 2µm. When the switching inputs, <I> 1 and <I> 2 , are applied in 180° out-of-phase, the output voltage of the converter, Vout, is given as a function of DC input voltage (Vin) , load current Uout), switching frequency Usw) and cfly · That is, 111 vi,, vaut Figure 4-10: Schematic diagram of the switched capacitor converter and micrograph of the fabricated converter Vout Vn Cf lyfw Vi - Ref 'out -out (4.6) where Reff is the effective resistance of the switched capacitor. Measurement Setup A prototype MoS 2 IC, fabricated on top of a SiO 2 substrate, containing the converter is shown in Figure 4-11. In addition to the SC DC-DC converters, the chip contains arrays of FETs, diodes and capacitors for basic component re-characterization for model updates and fabrication feedback. The measurement was conducted in a probe station, as shown in Figure 4-12. Tungsten probe tips were used to make electrical contacts to the probing pads of the MoS 2 devices. A function generator (Agilent) is used to drive the switching signals, 4Di and 4D2, at 5V swing, and a sourcemeter (Tektronix) was used to supply Vin and Iut and measure Vut all through BNC cables. Results The measurement results of the output voltage while varying load current and switching frequency along with the simulated output voltage are shown in Figure 4-13. The simulation based on the DDC model of FET allowed a good prediction of the actual circuit performance, proving the effectiveness of the CAD flow. 112 5mm E toE Vi, Figure 4-11: Optical Micrograph of the fabricated test chip using CVD-grown monolayer MoS 2 , showing arrays of FETs, diodes and switched capacitor DC-DC converters Figure 4-12: Photos of the probe station setup showing (a) an optical microscope and probe tips (a), and closed up view of ground plate and held chip (b,c) 113 Measurement (solid) and Simulated (dashed) Output Voltage -f 3 = 10kHz -f = 50kHz -f = 100kHz 2 0 1 0 0 6 2 8 10 Load (pA) Figure 4-13: Simulation (dotted) and measurements (solid) of the output voltage versus the load current of MoS 2 SC DC-DC converter 114 4.3.2 Half-Wave Rectifier Rectifiers are typically used for AC-DC conversion in wireless power transfer and piezoelectric energy harvesting systems. A diode rectifier was implemented in the test chip using a MoS 2 FET with its drain and gate connected and an external ceramic capacitor. Figure 4-14 depicts the test setup where a function generator provide the input sinusoidal signal to the rectifier and the voltage signal across the output off-chip capacitor is probed by an oscilloscope. The size of the output capacitor is selected based on the input signal frequency such that it minimizes the output voltage ripple. Cout Rout -- Figure 4-14: Schematic diagram of test bench for diode rectifier (left) and micrograph of fabricated MoS 2 diode (right) Figure 4-15 shows the measurement result of the half-wave rectifier at 1 MHz 8 V p-p sinusoidal input signal. The output was rectified DC voltage at rv2.6 V with < 150 m V ripple, matching with the simulation. While MoS 2 transistor models worked well as on-off switches in the switched capacitor based circuits, the rectifier demonstration shows that we have good analog simulation capability. Furthermore, the bandwidth of the diode rectifier was measured. As shown in Figure 4-16, a constant rectified output was measured across the frequency range from 100 kHz and up to 20 MHz where the load current is kept at 10 µA. The measurement at higher frequencies were subject to impedance mismatch in the measurement setup, thus suggesting the rectifier bandwidth to be at > 20 MHz. Therefore, this demonstration not only shows the good agreement between simulation and measurement, but also suggests that MoS 2 diode rectifiers are applicable to high frequency applications, particularly 115 for wireless power receivers operating in the 6.78 MHz and 13.6 MHz ISM bands. Half-Wave Rectifier Output (VIN = 8V , fw = 1MHz) 0 -5 -1.5 -2 -0.5 -1 1 0.5 0 1.5 2 Time (ps) Figure 4-15: Transient waveforms of 1 MHz 8 Vp.. sinusoidal input and measured output voltage of the diode rectifier circuit along with the simulated output (dashed line) Half-Wave Rectifier Output , COUT = 10nF) (VIN= 7V 8 - * 7~ ''I' 'i data1 data2 65- - 1 0 105 106 f. [Hz] 107 108 Figure 4-16: Rectifier output at various frequencies at 10 pA load current where Vin= 7 VP-P and C, = 10 nF 116 4.3.3 Voltage Doubler Additionally, a voltage doubler circuit, as shown in Figure 4-17, was implemented. The circuit consists of stacked half-wave rectifiers in seriesand the even order output nodes generate rectified voltages (V2 and V 4 ). In ideal operation, V 2 acts as ground for charge pumping to V4 , thus generating doubled voltage. Measurement results are shown in Figure 4-18. 6 VP.. sinusoidal input was applied for all measurements. The curves of low load current (IL = 0.1 pA) show doubling behavior between V 4 and V 2 at high frequencies. As the input frequency goes low, i.e. slower switching, the reverse bias diode current and capacitor leakage reduce the stored charge in each node significantly, thus, the charge pump efficiency drops. At high load current (IL = 10 pA), the 4th stage charge pump barely delivers the excessive charge over the load consumption, resulting in V 4 ~ V 2 . The negative output voltage in the low frequencies just means that the delivered power through the charge pumps is less than the load power consumption. Cl C V VIN V4 2 C2 C C4 Figure 4-17: Schematic diagram of voltage doubler circuit 117 Voltage Doubler Output 2.5 x - -B- 2 ~ E) >0 1. Il=10pA V4 'L= MA 1 V 2 L= 0pA -. V -- 1.5 V4 - - 1 2 ' L=1pA V 4, 2 V2 1L=0.1p/A .1 A~ ~L l--- 0.5 -0.5 -1 105 107 106 108 f.n [Hz] Figure 4-18: Voltage doubler outputs at 6 Vp.. sinusoidal input and IL = 0.1, 1, 10 pA 4.4 Concluding Remarks In this chapter, a complete CAD flow to realize MoS 2-based large-scale integrated circuits is presented. Device models for MoS 2 diodes and transistors, are developed and implemented in both behavioral and physical forms, which enables circuit simulation for a wide range of digital and analog circuit design. Combined with the state-ofthe-art fabrication technology, we were able to demonstrate a CAD flow, similar to the one of standard silicon IC design flow, and its full procedures by building a SC DC-DC converter, a half-wave rectifier, and a voltage doubler circuits for the first time with MoS 2 devices. In the demonstrated circuits, the simulation has provided good agreement with the measurements. Also, the time-efficient IC fabrication was possible, since the custom technology library and P-cell for MoS 2 have expedited layout process. Meanwhile, the presented CAD flow, including device modeling, circuit simulation and parametric cell-based layout just as in standard Si CMOS technology, is not a unique solution solely for MoS 2 ICs. Rather, it can be applied to other TMDs which share similar mechanical properties, carrier transport mechanism, and device structure (e.g. WSe 2 , WS 2 , and etc.), assuming that large-area material growth and 118 proper circuit models have been achieved. Nevertheless, our CAD flow for MoS 2 technology has verified its use and potential. Therefore, it has paved the way for large-scale MoS 2 electronics as well as applications of other 2D materials, so that the emerging technology of 2D materials and their heterostructures would realize the new family of ubiquitous electronics (e.g. transparent and flexible ICs on arbitrary surfaces) over the edge of the traditional technologies. 119 120 Chapter 5 Outlook and Future Work 5.1 Thesis Contributions In conclusion, I have investigated the utilization of new materials and devices that extend the boundary of traditional electronic systems in three directions: (1) as discrete add-on devices, (2) as monolithically integrated add-ons, and (3) as standalone electronic systems. 5.1.1 Cellular Electric Impedance Spectroscopy Bio-compatible electrical interfaces are the key for low-cost diagnostic tests, health signal monitoring electronics, and fundamental studies in biology and medication. In particular, Bio-MEMS devices in micro-/nano-meter scale provide cellular and molecular interfaces, often in forms of microfluidic devices. In the first part of the thesis, design of a microfluidic device for cellular EIS and electrical malaria diagnostic test was discussed. The fabrication of microfluidic probe device and the proper measurement setup allowed highly sensitive electric impedance measurement of individual erythrocytes. We further developed an analysis method using a dimensionless parameter 6 to quantify the deviation in the magnitude and phase shift of electric impedance of malaria infected cells. In conclusion, the reported cellular EIS system electrically screened human erythrocytes infected by P. falci121 parum malaria parasites, which achieved a high SNR not just enough to distinguish intracellular electro-chemical changes of tiny live cells but also capable of early stage malaria detection, suggesting a use in early diagnosis by fully electrical tests. The presented cellular EIS system provides not only a breakthrough in electrical diagnostic tools that directly interface with biological cells but also a fine example of electronics with non-traditional Bio-MEMS add-on devices. By this example, it was shown that new interface materials and devices could bring an additional feature of sensing pathological modification of biological cells. The following lists contributed publications in this work. " S. Ha, M. Diez-Silva, E. Du, S. J. Kim, J. Han, M. Dao, and A. P. Chandrakasan, "Microfluidic Electric Impedance Spectroscopy for Malaria Diagnosis," 16th Int. Conf. Miniaturized Syst. Chem. Life Sci., pp. 1960-1962, 2012. " E. Du, S. Ha, M. Diez-Silva, M. Dao, S. Suresh, and A. P. Chandrakasan, "Electric impedance microflow cytometry for characterization of cell disease states." Lab on a chip, vol. 13, no. 19, pp. 3903-3909, Oct. 2013. 5.1.2 Graphene-Silicon Hybrid Infrared Imager Graphene has recently gained significant interest for its exceptional electrical, optical, and mechanical properties. Research efforts to improve the graphene technology in terms of bio-chemical functionalization, device performance, and material growth, have enabled numerous graphene-based sensors, high performance RF electronics, and high quality and large area device fabrication. In the 2nd part of the thesis, graphene was investigated for integrated add-on devices for traditional Si technology, focusing on the thermoelectric effect in graphene and its compatibility to Si substrate. In development of the graphene-Si hybrid IR imaging systsem, a readout architecture for graphene IR sensor array was discussed. Light modulation scheme and the front-end transimpedance amplifier were adopted for optimized current readout from the low impedance sensing material. The readout architecture was verified not only 122 with an external current source equipment, but also with a wire-connected discrete graphene thermocouple device. In the prototype chip, >4,000 electronically tunable graphene thermocouples were fabricated using the readout IC as a substrate. The prototype graphene-Si hybrid imager IC consisting of IR sensors and readout circuitary on a single 5-mmx5-mm die was demonstrated. Although the graphene integration process damaged pixelselection function, on-chip photoresponse by single pixel could be measured, suggesting that full 2D scanning imaging is possible in the next batch. To enable the integration of graphene thermocouples, a post-fabrication friendly Si CMOS IC design was also implemented. To ease the graphene integration process, it was desired to have larger chip size, minimized top metal routings, excessive spacing in top metal and pad routings, and most importanly, planarized chip surface. The readout IC design can be further optimized in case of interfacing thermal sensors with moderate output impedance by (1) voltage-input signal amplification to neglect graphene-metal interconnect contact resistance, (2) full pixel area utilization of amplifier design assuming top-side illumination and surface flattening by top metal. While further development is needed to realize the 2D scanning imager, the scalable column-parallel scheme and single on-chip sensor measurement lead to possible development of new categories of graphene-Si hybrid applications. Furthermore, the fabrication and measurement schemes used in this exemplary integrated graphene interface can be widely applied to other 2D materials to provide conventional silicon technology a wide range of integrated add-on devices. The following lists contributed publications in this work. o A. L. Hsu, P. K. Herring, N. M. Gabor, S. Ha, Y. C. Shin, Y. Song, A. P. Chandrakasan, J. Kong, P. Jarillo-Herrero, and T. Palacios, "Graphene-based Thermopile for Thermal Imaging Applications," submitted for publication. o S. Ha, A. L. Hsu, S. Ha, T. Palacios, and A. P. Chandrakasan, "A 0.18um Column Parallel Readout IC for Graphene-based Thermocouple Array," in preparation. 123 5.1.3 MoS 2 -Based Electronics Among 2D materials, which all share atomically thin nature, flexibility, transparency, and large surface-to-volume ratio, Molybdenum disulfide is especially interesting in system designer's perspective. With this one molecular thick planar crystal, re- searchers have not only proven exceptional device performance for flexible/transparent electronics, but also achieved large area material growth and high yield device fabrication. In the last part of the thesis, the focus was to bring the MoS 2 technology to the next level in terms of the scale of integrated circuit. Even though the technology is relatively mature, it is still in a developmental stage, especially when it comes to large scale integrated circuit design. That is, the device performance keeps changing or improving, thus the circuit model and design are required to be continuously updated. To realize large scale ICs in MoS 2 technology, the cycle of design and fabrication has to run quicker, and the gap between design and actual performance should be reduced. In order to do that, a computer-aided . design flow was introduced for MoS 2 First, device models for MoS 2 diodes and transistors, in both behavioral and physical models, were developed and implemented in a circuit simulator language.Also, a custom technology library and P-cell for MoS 2 device layout expedited the chip layout process, so the time-efficient IC fabrication was possible. Within this unified design environment implemented in Cadence software, circuit simulation and layout generation were conducted. Combined with the state-of-the-art fabrication technology, SC DC-DC converter, a half-wave rectifier, and a voltage doubler circuits were demonstrated with MoS 2 devices, and the measurement showed good agreement with the simulation. It should be noted that the presented CAD flow is not a unique solution solely for MoS 2 ICs. Rather, it can be applied to other TMDs and their heterostructures which share similar mechanical properties, carrier transport mechanism, and device structures, assuming that large-area material growth and proper circuit modeling have been achieved. Therefore, the presented CAD flow paves the way for large-scale 124 MoS 2 electronics as well as applications of other 2D materials. The demonstrated MoS 2 technology also suggests that the technology in new materials and devices would realize the new family of stand-alone electronics over the boundary of the traditional electronics. The following lists contributed publications in this work. * L. Yu, S. Ha, D. El-Damak, E. McVay, X. Ling, A. P. Chandrakasan, J. Kong, and T. Palacios, "Two-dimensional materials based transparent flexible electronics," Bull. Am. Phys. Soc., vol. 60, 2015. " L. Yu, D. El-Damak, S. Ha, S. Rakheja, X. Ling, J. Kong, D. Antoniadis, A. P. Chandrakasan, and T. Palacios, "MoS2 FET Fabrication and Modeling for Large-Scale Flexible Electronics," in Symp. VLSI Technology, to be published. 5.2 Future Work While along the thesis, we have investigated the utilization of microfluidic device, graphene thermocouple, and MoS 2 transistor in pursuit of next generation electronics, in the following sections, we examine some future/ongoing work along three different directions: (1) 2D Scan Imaging with Graphene Thermocouple Array, (2) MoS 2 RFID tags, and (3) MoS 2 Display Driver. 5.2.1 2D Scan Imaging with Graphene Thermocouple Array As a follow up of our works discussed in Chapter 3, we are pursuing the demonstration of 2D scan imaging by the on-chip graphene thermocoule array. While most of the issues with the original design and fabrication process are already addressed in Section 3.6, we will add additional pixel structures on the chips of the new batch. This is to have functional verification of integrated graphene thermocouples in the pixel level, while we could not probe on-chip graphene thermocouple devices externally in the previous chips. 125 5.2.2 MoS 2 RFID Tags1 MoS 2 Rectifier Phase #1: Wireless Power Link w/ LED Load - %-- - - - - - - - - - - - - - - - -- ---------------------------------------- - - -- MoSt devices LDO A - Phase #2: Wireless Transmitter 47 IV - Phase #3: REID ----- Ref. Gen. Reu I ---- ---- ------------------- I - Figure 5-1: 3-Phase Development Plan for MoS 2 REID Tags Figure 5-1 shows the 3-phase development plan for MoS 2 RFID tags. In the first phase, we are demonstrating a wireless power link with MoS 2 technology. While active power consumption of target RFID tag is estimated in order of 100 PW, we set the demonstration goal for 1st phase chip to deliever 1 mW. At that level of power consumption, a low current LED can be used as the load component. The key MoS 2 component in the 1st phase chip is the rectifier. Since we have seen in Chapter 4 that the bandwidth of MoS 2 diode goes above 20 MHz, it does make sense to implement an MoS 2 RF rectifier (13.56 MHz) with a corresponding LC tank. Figure 5-2 depicts such system made on a sapphire substrate. The bottom coil is an external RF source, e.g. PCB coil, and power is transferred through the inductive coupling of two adjacent 'This work is in collaboration with Lili Yu and Dina El-Damak. 126 coils. The RF signal is then rectified and stored on a capacitor as well as turning on the LED. Caps Light Emission Sapphire substrate Rectifr Li Figure 5-2: Illustration of Wireless Power Link Operation with On-Chip Inductor The concept design is supported by the simulation. As shown in Figure 5-3, power transfer > 30pW is expected given k = 0.02 and the resonance at 13.56 MHz. In the full-wave rectifier, replacing two diodes with a pair of cross-coupled FETs (Figure 54) allows 50% efficiency improvement over 4-diode rectifier, by reducing the effective threshold voltage of the MoS 2 diodes. In the 2nd phase of project, we will focus on demonstration of impedance modulation telemetry and digital logics. Then, we will go for integrationi of everything on chip to make RFID tag in the 3rd phase. 127 Load Power [mVWJ 700 Of Of M Jl2 06 i , --- 04__.X 6.49 6 4 M k= M -.m-k=0.08 -+-k=0.06 I -U-k=0.04 -@-k=0.02 3 Li L2 2.61 2 1 0.594 0.030 0 92 94 96 98 - a0 0 100 C2 [pF] 102 0-0-. 104 106 108 - LED light emission detectable at >1 pW k > 0.0 is desired Figure 5-3: Simulated transferred power at various coupling coefficient (k) VDD 320/2 VN VP 300/2 Vss Figure 5-4: Full-wave rectifier with cross-coupled FETs and two diodes 128 5.2.3 MoS 2 Display Driver In parallel to the RFID development, we are investigating MoS 2 circuit as heteroplane of organic LED (OLED) displays. 2 While we eventualy aim for a transparent display driver circuit integrated with 1" x1" OLED panel, we were able to test the LEDdriving component by connecting a low current LED as shown in Figure 5-5. for MoS2 -.- Display Driver Figure 5-5: Testbench of MoS 2 LED driver array In the preliminary works, the driver circuit has shown good performance in atmosphere for a limited time. Therefore, as the following steps, we will need to develop a good passivation technique for MoS 2 devices to enable long-term in-air operation as well as the integration process for OLED array. 2 This work is in collaboration with Lili Yu. 129 Appendices 130 Appendix A Process Flow EIS Probe Device Fabrication A.1 The process is adopted from [2]. A.1.1 Probe Electrode Parts 1. Start with 0.500mm-thick 6-inch Pyrex glass wafers (Sensor Prep Service Inc.) 2. TRL Hotplate 2 - Bake at 115'C for 3 minutes to get rid of moisture that degrades the resolution of photoresist (PR). 3. TRL Coater - Spin coat with a negative PR NR71-3000P (Futurrex Inc.) at 3000 rpm for 40 seconds. 4. TRL Hotplate 2 - Prebake at 140*C for 3 minutes. 5. TRL EV-LC Exposure for 10 seconds with 365nm UV. 6. TRL Hotplate 2 - Postbake at 110'C for 3.5 minutes. 7. Develop PR RD6 developer solution for 25 seconds. Check the pattern under microscope. 131 8. Clean with DI water and dry with N 2 gas. 9. Ebeam-FP - Metal Deposition 10 nm Ti - No rotation, Deposition rate = 0.1nm/s 100 nm Au - No rotation, Deposition rate = 0.2nm/s 10. Lift-off Left in RR41 resist remover overnight then use pipette. Sonicate with Acetone/IPA and N 2 dry. Check the pattern under microscope. Use Microstrip to remove PR residues if necessary. 11. Diesaw A.1.2 Silicon Mold Part for Microfluidic Channel 1. Start with 6-inch bare Si wafers 2. TRL Oven - Bake at 95'C for 3 minutes to dehydrate. 3. HMDS run A 0-44. rVDT TRL Coater - QSpin CCoat AZ5214 at 3000 rpm for 40 seconds. 5. TRL Oven - Prebake at 95'C for 3 minutes. 6. TRL EV-LC Exposure for 15 seconds with 365nm UV. 7. TRL Oven - Postbake at 120'C for 3.5 minutes. 8. Develop PR RD6 developer solution for 25 seconds. 132 Check the pattern under microscope. 9. Clean with DI water and dry with N 2 gas. 10. TRL-STS 1 RIE for 5pm Check the depth with AFM 11. TRL-Asher 800W for 30 minutes. A.1.3 PDMS Curing and Bonding Process 1. Start with Si mold wafers. 2. Prepare polydimethylsiloxane (PDMS) base gel and curing agent. 3. PDMS base gel and curing agent in ratio of 10:1. 4. De-gas in a vacuum chamber for 1 hour. 5. While waiting for de-gas, coat Si wafer by trichlorosilane (HSiCl3 ). 6. Pour PDMS mixture on the Si mold and remove air bubbles if any. 7. Bake on hot plate at 95'C for 2 hours, then PDMS is solidified. 8. Peel off PDMS and cut into 1 inch by a half inch cells. 32 microfluidic channel parts per wafer 9. Puncture holes for inlet and outlet of fluid. 10. Oxygen plasma excitation of both the top surface of electrode substrate and the bottom surface of PDMS cell. 11. Align and bond them under microscope. 133 A drop of IPA can ease the alignment process 12. Bake on hot plate at 95'C for 2 hours for stronger covalent bonding between PDMS and glass substrate. 13. Attach copper tape or wires to the electrodes and tubes to the fluidic inlet and the outlet. A.2 Graphene IR Imager Integration This process is initially developed by Allen Hsu [4] and revised by Sungjae Ha. A.2.1 Sample Preparation 1. Solvent Clean Acetone/IPA/N2 with ultrasonics in teflon beakers (PWR = 5-6) A.2.2 Passivation Etching - Patterned 1. TRL Coater - MMA/PMMA Layers MMA 8.5 EL 11.5 (750 rpm for 2s, 4000 rpm for 60s) TRL Hotplate 2 - Bake at 175 'C for 7 minutes/ Cool for 3 minutes PMMA A8 (750 rpm for 2s, 4000 rpm for 60s) TRL Hotplate 2 - Bake at 175 'C for 7 minutes/ Cool for 3 minutes 2. Elionix 125 (Li-ETCH) Beam Current = 30nA Dwell Time = 0.08[ts Dose = 2400 puC/cm 2 3. Develop Bilayer Resist (slight agitation) 134 MIBK:IPA 1:3 for 90s METH:IPA 2:1 for 20s IPA for 60s N 2 and check in microscope 4. Plasmaquest CF4AH.rcp (213 W/ 24 W/ 313 V - chiller at 15 0 C - Substrate at 21 0C) Etch for 2 minutes/ Cool down for 3 minutes Repeat 7x more etching for 2 minutes/ Cool down for 3 minutes Take out and inspect sample for shiny exposed metal A.2.3 Passivation Etching - Global 1. Solvent Clean Acetone/IPA/N2 with ultrasonics in teflon beakers (PWR = 5-6) 2. Asher-TRL 800W for 30 minutes 3. Plasmaquest CF4_AH.rcp (213 W/ 24 W/ 313 V - chiller at 15'C - Substrate at 21'C) Repeat 1-2x etching for 2 minutes/ Cool down for 3 minutes Take out and inspect sample SEM/AFM plug structures to ensure that all of the top passivation has been removed and to measure the step height from the top of the passivation to the area in between metal structures 135 Gap Filling A.2.4 This step is added to make sure continuous gate metal routings across the M6 tile structures. 1. TRL Coater MMA 8.5 EL 11.5 (750 rpm for 2s, 4000 rpm for 60s) TRL Hotplate 2 - Bake at 175'C for 7 minutes / Cool down for 3 minutes / Cool down for 3 minutes PMMA A8 (750 rpm for 2s, 4000 rpm for 60s) TRL Hotplate 2 - Bake at 175'C for 7 minutes 2. Elionix 125 (L2-GapFill) Beam Current = 30nA Dwell Time = 0.08pis Dose = 2400 pC/cm 2 3. Develop Bilayer Resist (slight agitation) MIBK:IPA 1:3 for 90s METH:IPA 2:1 for 20s IPA for 60s N 2 and check in microscope - make sure deep undercuts in the bilayer resist. 4. ebeamFP (may be replaced by Sputterer) Deposit Ti - Thickness 10nm, Rate = 0.1 nm/s, Rotation OFF Deposit Au - Thickness 390nm, Rate = 0.2 nm/s, Rotation OFF 5. Liftoff Left in aceton overnight Place sample in acetone (Teflon beaker) for 2 minutes, ultrasonic PWR 5 136 Place sample in acetone (quartz beaker) for a couple of seconds Place sample in IPA (Teflon beaker) for 2 minutes, ultrasonic PWR 3 N 2 and check with optical microscope the metal structures 6. Asher-TRL 800W for 30 minutes A.2.5 Gate Electrodes 1. TRL Coater PMMA A8 (750 rpm for 2s, 4000 rpm for 60s) TRL Hotplate 2 - Bake at 175'C for 7 minutes 2. Elionix 125 (L3-GATE) Beam Current = 10/30nA (fine/coarse structures) Dwell Time = Depending on dose Dose = 2200-2400 pC/cm 2 3. Develop PMMA MIBK:IPA 1:3 for 90s IPA for 60s N 2 and check in microscope 4. Asher-TRL 800W for 1 minutes 5. ebeamFP Deposit Ti - Thickness 10nm, Rate = 0.1 nm/s, Rotation OFF Deposit Pt - Thickness 20nm, Rate = 0.1 nm/s, Rotation OFF 137 6. Liftoff Acetone/IPA/N2 and check under microscope 7. Asher-TRL 800W for 30 minutes 8. DC Probe Station Test connection of Ti/Pt electrodes A.2.6 Ohmic Plugs 1. TRL Coater MMA 8.5 EL 11.5 (750 rpm for 2s, 4000 rpm for 60s) TRL Hotplate 2 - Bake at 175'C for 7 minutes / Cool down for 3 minutes PMMA A8 (750 rpm for 2s, 4000 rpm for 60s) TRL Hotplate 2 - Bake at 175 C for 7 minutes / Cool down for 3 minutes 2. Elionix 125 (L2-PLUG) Beam Current = 30nA Dwell Time = 0.08ps Dose = 2400 pC/cm 2 3. Develop Bilayer Resist (slight agitation) MIBK:IPA 1:3 for 90s METH:IPA 2:1 for 20s IPA for 60s N 2 and check in microscope - make sure deep undercuts in the bilayer resist. 4. ebeamFP (may be replaced by Sputterer) 138 This step requires a wedge piece to hold tilted sample for side wall coverage. Use the wedge sample holder to put NW corner of the chip 30 degrees up. Deposit Ti - Thickness 5nm, Rate = 0.1 nm/s, Rotation ON Deposit Au - Thickness 45nm, Rate = 0.2 nm/s, Rotation ON Remount the sample putting SE corner of the chip 30 degrees up. Deposit Ti - Thickness 5nm, Rate = 0.1 nm/s, Rotation ON Deposit Au - Thickness 45nm, Rate = 0.2 nm/s, Rotation ON 5. Liftoff Place sample in acetone (Teflon beaker) for 2 minutes, ultrasonic PWR 5 Place sample in acetone (quartz beaker) for a couple of seconds Place sample in IPA (Teflon beaker) for 2 minutes, ultrasonic PWR 3 N 2 and check with optical microscope the metal structures Check the ohmic interconnects in DC probe station on test dummy structures to make sure the ohmic connection is achieved. 6. Asher-TRL 800W for 30 minutes A.2.7 Gate Dielectric 1. TRL STS-CVD HFSiOLT Recipe for 1 minute Target thickness = 75 nm Deposition temperature = 250 C Deposition rate = 73.85 (nm/min) - calibration required. 139 A.2.8 Gate Vias 1. TRL Coater MMA 8.5 EL 11.5 (750 rpm for 2s, 4000 rpm for 60s) TRL Hotplate 2 - Bake at 175 C for 7 minutes / Cool down for 3 minutes / Cool down for 3 minutes PMMA A8 (750 rpm for 2s, 4000 rpm for 60s) TRL Hotplate 2 - Bake at 175'C for 7 minutes 2. Elionix 125 (L2-PLUG) Beam Current = 30nA Dwell Time = 0.08[s Dose = 2400 pC/cm 2 3. Develop Bilayer Resist (slight agitation) MIBK:IPA 1:3 for 90s METH:IPA 2:1 for 20s IPA for 60s N 2 and check in microscope - make sure deep undercuts in the bilayer resist. 4. Asher-TRL 800W for 1 minutes 5. Plasmaquest CF4_AH.rcp (213 W/ 24 W/ 313 V - chiller at 15'C - Substrate at 21 'C) Etch for 2 minutes/ Cool down for 3 minutes 6. Solvent Clean Acetone/IPA/N2 with ultrasonics in teflon beakers (PWR = 5-6) 140 7. Asher-TRL 800W for 60 minutes 8. Metrology Inspect using AFM and SEM that the ohmic vias are exposed. A.2.9 Graphene Transfer 1. Graphene transfer is conducted by Marek Hempel and Yong Cheol Shin. 2. Check graphene quality on copper by SEM before transfer on to the rough substrate. 3. Check with optical microsopy and SEM to ensure continuous graphene. 4. Make sure thermal reflow step is done and no spin drying. 5. If graphene transfer is bad, use NSL plasmatherm (90s of testp3.prc) to remove graphene and clean surface before the retransfer 6. Ensure that the PMMA is thin enough to conform to the entire surface 7. Image in SEM at 2.5 keV for graphene contrast using the in-lens detector. A.2.10 Graphene Ohmic Contacts 1. TRL Coater PMMA A8 (750 rpm for 2s, 4000 rpm for 60s) TRL Hotplate 2 - Bake at 175*C for 7 minutes 2. Elionix 125 (L4-OHMIC) Beam Current = 25nA Dwell Time = 0.08 pus 141 Dose = 2000 pC/cm 2 3. Develop PMMA MIBK:IPA 1:3 for 90s IPA for 60s N 2 and check in microscope 4. ebeamFP Deposit Ti - Thickness 1nm, Rate = 0.1 nm/s, Rotation OFF Deposit Au - Thickness 30nm, Rate = 0.2 nm/s, Rotation OFF 5. Liftoff Left in aceton overnight. Do not let the sample flip over or scratch the surface. Acetone/IPA/N2 and check under microscope. No sonication. A.2.11 Graphene Mesa 1. TRL Coater PMMA A8 (750 rpm for 2s, 4000 rpm for 60s) TRL Hotplate 2 - Bake at 175'C for 7 minutes 2. Elionix 125 (L4-OHMIC) Beam Current = 25nA Dwell Time = 0.08 ps Dose = 2000 pC/cmn 2 3. Develop PMMA MIBK:IPA 1:3 for 90s IPA for 60s 142 N 2 and check in microscope 4. NSL-Plasmatherm testp3.prc for 75 seconds (48 V / 128 W) 5. Asher-TRL 800W for 5 minutes 6. Solvent Clean Acetone/IPA/N 2 and check under microscope. Left in acetone for a couple of hours. 7. Chip Ready for packaging A.2.12 Chip Packaging 1. Chip Package and Socket Selection 88-pin QFN package (Quik-Pak) Compatible open top socket for top-side illumination 2. Wirebonding The work was done by a commercial vendor (VLSIP Technology, Inc.) Wire-bonding map is provided in Appendix B. A.3 MoS 2 Device Fabrication The fabrication process is developed by Lili Yu and conducted in collaboration with Sungjae Ha and Lili Yu. 1. Substrate Cleaning Si0 2 /Si substrate 143 Nanostrip' and HCl 2. Gate Electrode 5nm Cr / 30nm Au / 30nm Pd by photolithography 3. Gate Dielectric 20nm Al 2 03 by atomic layer deposition (ALD) Aneal for 30 minutes at 450 'C 4. Via Hole C1 2 /BC1 3 RIE 5. Source/Drain Electrodes and Pads 5nm Ti / 90nm Au by photolithography 6. MoS 2 Transfer Start with CVD-grown sample Coat with PMMA Soak in KOH at 85 'C Transfer to target substrate 7. Mesa Etch 02 plasma etching 8. Ohmic Contact 90nm Au by photolithography 9. Device Ready Additional passivation step may follow. 1A stabilized mixutre of sulfic acid (H 2 SO 4 ) and hydrogen peroxide (H 2 0 2 ). 144 Appendix B Test Setup and PCB Design The CMOS readout chips were packaged in a 88-pin, 0.5-mm pitch open-top QFN package. The chips were placed into a socket, also open-top, on the test PCBs. B.1 PCB Designs Three PBCs were prepared for ADC and graphene thermocouple readout testing, and the corresponding wirebonding maps are provided below. 145 B.1.1 ADC Test Board and Wirebonding Map A test board is designed for ADC characteriation and off-chip detector readout. Since this board is to measure original chip without the graphene structures, the package top should be sealed to reduce interference. .................................. DDH SMA PWvR CL R S LS 1- FM CA G7 1R-BR[--A V4 C 201 4/2"25 f\L'TJGJAE HA Figure B-1: PCB for ADC characterization 146 67 88 56 \I~ 1C uh UUu//Z/g/- == 7= = -T-%7 III\\ 45 22 44 23N Figure B-2: Wirebonding Diagram for ADC characterization 147 B.1.2 Graphene Sensor Array Test Board and Wirebonding Map A test board is designed for readout of the full grid of graphene array. .......................................................... ...... fALLEN KBU: IR-B U2 2114/12/26 sLJN9JAE HA: u borders for vacuum cap. Figure B-3: PCB for Graphene Sensor Array Test 148 67 88 66 ipfe/}j/fejsf/ 1 ,71 ~ i n \ \M 11111111MiT\ 22\V//7/11101111111 4 23 Fiue W -: iebnin o GaheeSesr iarm 149 rayTs 4 B.1.3 Unified Test Board and Wirebonding Map A test board is designed to characterize ADC and to test graphene array readout from the same chip. However, it cuts the output lines of four readout ADCs due short number of the wirebonding pads. 0 '000000 (+ _I2" -0 and 2.V" diameter borders for vacuum cap. I NI WIWuuIssm -------- Figure B-5: PCB for Unified Testing 150 67 88 ~~~~~~~ L MRERM MEIE~fTFF1KF\6 ~ 1~~ 66 11 ;00 i~ ,2V f 25 f i FiueB6cieodn Y YR1 84 4 iga 151 o nfe etn 152 Appendix C CAD Environment C1 Model Implementations for MoS 2 Devices C.1.1 // Analytic Diode Model Diode lum Model 'include "disciplines .vams" 'include "constants .vams" "DLlum_1.va" 'include module DL1 (vp, vn); inout vp, vn; electrical 11 vp, vn; real vd; analog begin vd = V(vp, vn); if (vd > 0) I(vp, vn) <+ bl*vd + b2*pow(vd,2) pow (vd, 3) + b4*pow(vd,4); 153 + b3* 16 else if (vd < 0) I(vp, vn) <+ ism*(pow(am,vd) -1); else I(vp,vn) <+ 0; end endmodule where the fitting is done in MATLAB as code below 1 %% Retreive Data and PolyFit Id - IdDL4_-1; % Diode Measurement Data DevNun = xm 6 1; = [ - 5: 0.1:0]; xp = [0:0.1:5]; yp = Id (51:101) yp (1) =0; ym = Id (1: 51); 11 yin (51) 0; modelFun = @(b, x) b(2) .* start-m = [2; (exp(x./b(1)) - 1 ); le-8]; modelim = fitnim (xmn,yn, modelFun, startm); 16 =(b, polyFun4 startp = x) b(4) .*x.^4+b(3) .*x.^3 + b(2) .*x.^2+b(1) .*x; [le-9; le-6; le-8; -6e-8]; model-p = fitnlm (xp, yp, polyFun4, start _p) ; 154 Empirical FET Model C.1.2 1 6 // MoS2FET Empirical model 'include disciplines .vams" 'include constants .vams" module MoS2FET-emp (D, S ,G) electrical D, S, G; inout D, S; input G; 11 parameter real W= 60u; parameter real L 2u; analog begin real Vds 16 = V(D, S); real Vgs =V(G, S) ; I(DS) <+ (W/L)/(60u/2u) * $table-model (Vds, MoS2FET60um. d at", "3CC,1EL" ); end endmodule where raw data table is given by the "MoS2FET60um.dat" file. 155 Vgs, C.1.3 Drift-Diffusion Compact FET Model The implementation is done by Shaloo Rakheja. // VerilogA transport model for 2D FETs 'include " constants vams" 'include "disciplines .vams" 5 module DD_2DFETv100(d, g, s); inout d, g, s; electrical d, g, s; electrical di, si; 10 /7 Parameters in the MoS2 model parameter integer type = 1 from [-1 // 1] exclude 0; type of transistor. nFET type=1; pFET type=-1 parameter real W = 40e-6 from (0: inf); 15 // Transistor width [m] parameter real Lgdr 77 2e-6 from (0: inf); The designed gate length [m]. parameter real Cinv = 4e-3 from (0: in f); Gate-to-channel areal capacitance at the virtual source / 77 - F/m^2] 20 parameter real nO /7 - 1.5 from [0: inf); Subthreshold swing factor [unit-less] { typically between 1.0 and 2.0} parameter real RsO = 500e-6 from (0: inf); // Access resistance on s-terminal [Ohms-meter] parameter real RdO = 500e-6 from (0: inf) ; 25 // Access resistance on d-terminal [Ohms-meter] 156 parameter real vsat = 0.2e5 from 77 (0:inf); Saturation velocity [m/s] parameter real mu = 20e-4 from (0: inf) ; 30 // mobility [cm^2/V.s] Low-field parameter real beta = 1.7 from // Saturation factor. Typ. nFET=1.8, pFET=1.6 parameter real Tjun = 298 from 77 (0: inf) ; [173:inf); Junction temperature [K] 35 parameter real VtO = 77 0.486; Strong inversion threshold voltage [V] parameter real alpha = 3.5; 7/ Empirical parameter for threshold voltage shift between strong and weak inversion. 40 'define SMALLVALUE (le-10) 'define LARGE-VALUE (40) real Vds , Vgs, Vgsraw, Vgd, Vgdraw, Vdsi, Vgsi , Vgdi, dir; voltages and direction 45 real Rs, Rd; // resistances real phit , nphit , aphit , eVgO, FF0, etas , etad; // for calculating charges real Qref, Qis, Qid, Vdsat, Fsat, Fvsat, Id; // current analog begin 50 /Voltage definitions 157 charges and Vgsraw = type * ( V(g) - V(si) Vgdraw = type * ( V(g) - V(di) (Vgsraw >= if * ( V(d) - V(s) Vds type Vgs type * ( V(g) - V(s) Vdsi type * ( V(di) - V(si ) 55 begin Vgdraw) Vgsi = dir 1; end b egin Vgs type V(s) - V(d) ); V(g) - V(d) ); V(si ( type * Vds * else * 60 Vgsraw; 65 Vdsi = type Vgsi = Vgdraw; dir = ) - V(di) ); -1; end /Parasitic element definition 70 Rs RsO/W; Rd =Rs; 77 7 s-terminal resistance [ohms] d-terminal resistance [ohms] /For symmetric source and drain Rd 75 phit nphit $vt (Tjun); = 77 Rs. Thermal voltage , kT/q [V] nO * phit; Product of n and phit [used as one variable] / aphit = alpha * phit ; Product of alpha and phit [used as one variable] 80 eVgO = exp(( Vgsi - (VtO-0.5*aphit))/ 158 ( aphit )); // Compute eVg factor from uncorrected intrinsic Vgs = 1.0/ FF0 Qref Cinv * 2.0 * nphit; Vdsat = vsat*Lgdr//mu; Fsat Vdsi/Vdsat /(pow((1+pow(Vds/Vdsat etas (Vgsi-(VtO -0.5*aphit *FFO)) /(2.0* nphit) etad 90 1.0 + eVgO ); if = , beta)) ,I.0/ beta)); (Vgsi -(Vdsat*Fsat+Vt0 -0.5* aphit *FFO)) /(2.0* nphit); <= 'LARGE-VALUE) (etas Qis = Qref * ln( begin 1.0 + exp(etas) ) 85 ( end else begin Qis 95 = Qref * etas; end if (etad <= 'LARGE-VALUE) Qid = Qref /7 * begin ln( 1.0 + exp(etad) ); Compute charge w/ uncorrected intrinsic Vgs for use later on in charge partitioning 100 end else begin Qid = Qref * etad; end 105 Fvsat = (Qis-Qid) /(Cinv*Vdsat) /(pow((1+pow (( Qis-Qid) /(Cinv* Vdsat) ,beta)) ,1/beta)) /Total drain current Id = W*vsat*(Qis+Qid)/2.0*Fvsat; 159 110 //Sub- c i r c u it initialization I(di, si) <+ type I(ddi) <+ ( V(d) - V(di) I(si ,s) <+ ( V(si) - V(s) )/ Rs; * dir * Id )/ Rd; end 115 endmodule C.2 Technology Library for MoS 2 Device Layout ( layerDefinitions ( techLayers ( Abbreviation Layer# ( default 0 default ( Mesa 1 MES ( Gate 2 G ( 3 Cont ( Pads 4 PAD ( Vial 5 VI (AUX1 6 AXI ( ATY9 7 A Y9 Contact ) 5 LayerName 10 ) )I ;techLayers PurposeName ( layout ) Purpose# 1 Abbreviation lyo ; techPurposes 20 ;( LayerName Purpose 160 ) techLayerPurposePriorities( ) ( 15 ) ( techPurposes 25 ) ( default ( Mesa drawing ( Gate drawing ( drawing drawing Contact ( Pads drawing ( Vial drawing (AUXi drawing (AUX2 drawing ; techLayerPurposePriorities 30 ( techDisplays LayerName Vis 35 40 Sel Purpose Con2ChgLy Packet DrgEnbl ( Mesa drawing pinkSlashl t t t t t) ( ( Gate drawing limebackSlash t t t t t) Contact drawing bluebackSlash t t t t t) ( Pads drawing grayDot3 t t t t t) ( ( ( Vial drawing redbackSlash t t t t t) AUX1 drawing brownSlashl t t t t t) AUX2 drawing yellowSlashl t t t t t) ) ; techDisplays ) Valid ) ( ; layerDefinitions 161 162 Bibliography [1] K. 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