Supplementary Material Multiple silicon nanowire complementary tunnel transistors for ultralow-power flexible logic applications M. Lee,1 Y. Jeon,1 J.-C. Jung,2 S.-M. Koo,2,a) and S. Kim1,b) 1 Department of Electrical Engineering, Korea University, Anam-dong, Seongbuk-gu, Seoul 136-713, Korea 2 Department of Electronic Materials Engineering, Kwangwoon University, Wolgye-dong, Nowon-gu, Seoul 139-701, Korea Electronic mail: a) smkoo@kw.ac.kr, b) sangsig@korea.ac.kr 1 1. Transfer printing and device fabrication The fabrication of the flexible silicon nanowire (SiNW) tunnel field-effect transistor (TFET) on a plastic substrate begins with the transfer of the as-fabricated p+-i-n+ SiNWs from a donor Si chip to a receiver plastic substrate (see Figs. S1 and S2). A 50-nm-thick ultraviolet (UV)-curable resin (Q-sys, NIR Q1) with a low viscosity of 6.5 cps at 25˚C, which is a liquid photopolymer that cures when exposed to UV light, was laminated on the plastic by a spincoating process (Fig. S1(a)). Then, the receiver plastic coated with the UV-curable resin was brought into conformal contact with a donor Si chip containing the SiNWs under controlled temperature and contact pressure (Fig S1(b)). Since the viscosity of the resin used for the transfer of the SiNWs is low, the SiNWs are anchored on the surface of the plastic, not on the surface of the resin. Subsequently, after the resin layer was cured by exposing it to UV light (Fig. S1(b)), the receiver plastic was peeled off from the donor Si chip, bringing the SiNWs with the plastic, as the crystalline connections to the supporting post at the ends of the SiNWs was broken (Figs. S1(c) and S2(b)). Finally, the resin layer was completely removed by oxygen plasma etching and/or ethanol solution, leaving the SiNWs on the plastic in organized arrays by the van der Waals interactions with the surface of the plastic (Figs. S1(d) and S2(c)). To make the representative p+-i-n+ SiNW on the plastic into contact with the metal source and drain electrodes, the patterned source and drain regions of the p+-i-n+ SiNW were deposited by thermal evaporation using aluminum (Al)/gold (Au) (80/20 nm) metals after buffered hydrogen fluoride (BHF) treatment and subsequent rinsing in deionized (DI) water in order to remove native oxides and promote the formation of ohmic contacts. After the liftoff process, a 10-nm-thick Al2O3 gate dielectric layer was deposited by an atomic layer deposition (ALD) technique using trimethylaluminium (TMA) and H2O at 150˚C. In the final step, the top-gate electrode (Al: 150 nm) was formed by photolithography, thermal 2 evaporation and lift-off processes, to complete the fabrication of the p+-i-n+ SiNW TFET on the plastic substrate. Figure S1. Method of transferring as-fabricated SiNWs from donor Si chip to plastic substrates. (a) Laminating an UV-curable resin on the plastic by a spin-coating process. (b) Contacting the receiver plastic coated with the resin with the donor Si chip containing the SiNWs under controlled temperature and contact pressure, and solidifying the resin layer by UV light exposure. (c) Peeling the receiver plastic from the donor Si chip, bringing SiNWs with the plastic, as the crystalline connections to the supporting post at the ends of the SiNWs was broken. (d) Removing the resin layer by oxygen plasma etching and/or ethanol solution, leaving the SiNWs on the plastic in organized arrays by the van der Waals interactions with the surface of the plastic. 3 Figure S2. (a) Photographs illustrating direct transfer method. Entire array of the SiNWs is successfully transferred from a donor Si chip to a plastic substrate, with a few broken SiNWs arising from mechanical forces during the transfer process. (b-c) Optical images illustrating as-transferred SiNWs on the plastic substrate. The comparision between the images taken (b) before and (c) after the removal of the resin shows that the SiNWs are efficiently transferred onto the plastic and anchored on it by surface adhesion. 2. Device simulation The simulation was performed for a two-dimensional (2-D) device structure, which had been cut horizontally along the channel transport direction of the SiNW TFETs, using Silvaco Atlas, version 5.14.0.R, which uses a non-local Hurkx band-to-band tunneling (BTBT) model.S1 The non-local BTBT model has a more physical basis compared with local BTBT model and does not depend on the electrical field local to each mesh point and calculates tunneling-induced generation-recombination rate more accurately, taking into account the spatial variation of the energy bands.S2 Fermi-Dirac statistics were assumed and Shockley-Read-Hall (SRH) recombination and drift-diffusion models were used to model carrier transport. Bandgap narrowing was applied, while gate leakage was ignored. Only the n-type devices were studied: therefore, we refer to the p+-doped region as the source and the 4 n- and/or n+-doped region as the drain. Three different device structures were considered. The first (Reference Device) uses a symmetric source-drain doping: 1×1020 cm-3 p-type for the source, and the same but n-type for the drain. The second (Device A) employs an asymmetric source-drain doping: 1×1020 cm-3 p-type for the source, and 1×1017 ~ 1×1020 cm-3 n-type for the drain. The third (Device B) incorporates a gate-to-drain underlap: gate underlap length from 0 to 2 μm. In all simulations, the channel (2 μm in length) was p-type doped with a uniform doping concentration of 1×1015 cm-3 and a graded junction profiles were used for the source and drain, where the doping concentration is reduced from the source and drain regions to the channel region by 2 nm/dec. A high-κ gate dielectric Al2O3 (10 nm in thickness) with dielectric constant of 8.4 and Al metal gate with a work function of 4.28 eV were used. To better understand the effect of the drain doping concentration (from 1×1017 to 1×1020 cm-3 for Device A) and gate underlap length (from 0 to 2 µm for Device B) on the ambipolar conduction, we have performed further experimental characterization and numerical simulations. In addition, in order to study the mechanical properties of the devices, we have also performed systematic tests by bending the flexible plastic substrate mechanically along the channel transport direction to achieve convex (or tensile) and concave (or compressive) surface strain values of 0.67%. The applied strain value was estimated by using the radius of bending curvature and the thickness of the plastic substrate. Fig. S3(a) shows the normalized drain current (log(Ids/Vgs2)) as a function of the inverse gate voltage (Vgs-1) obtained from the experimental data for the different devices in the flat and strained states. In this figure, regions I and II are the regimes where the experimental results follow Kane’s model with ambipolar- and on-state BTBT behavior, respectively,S3 whereas region III represents offstate leakage of the devices. In region II, the slopes of the dotted lines for the devices in the flat and strained states are almost identical, indicating that there is no significant change in the on-state BTBT generation rate after the application of surface strains (up to 0.67%) on the 5 plastic substrate. Note that the slope of the straight line is related to the tunneling reduced effective mass and the bandgap of the material, such that an increase in the slope implies a decrease in the BTBT generation rate. In region III, it can also be seen that the off-state leakage of the devices is not significantly affected by applied strains of up to 0.67% as well. In region I, the Reference device clearly follows Kane’s model with ambipolar BTBT behavior. The slope of the dotted line decreases with increasing drain voltage because it moves the turn-on point of the ambipolar tunneling current toward a more positive value in gate voltage, due to the influence of the drain potential on the ambipolar tunnel junction. In contrast, both Device A and B show the clear suppression of ambipolar conduction, independent of the applied drain voltage. The numerical simulation results are shown in Fig. S3(b) for the corresponding structures of the Reference device, Device A, and Device B. It shows qualitatively the same tendency as the experimental data, but it allows to examine the effect of drain doping concentration and gate underlap dimension on the ambipolar I-V characteristics in further detail. For Device A, the ambipolar conduction can be suppressed for drain doping concentration of less than 1×1018 cm-3. In the case of Device B, a rather small gate underlap of ~20 nm results in the complete suppression of ambipolar conduction which, in turn, requires the sacrifice of the off-state leakage. Fig. S4 shows the 2-D electron current density distribution profiles across the channel in the ambipolar state (Vgs=-3 V and Vds=1 V) for Device A with various drain doping concentrations from 1×1017 to 1×1020 cm-3, and for Device B with various gate underlap lengths from 0 to 2 µm, respectively. In the case of Device A, as the drain doping concentration decreases from 1×1020 to 1×1017 cm-3, the electron current density in the n+ drain of the channel surface gradually decreases from ~0.1 A/cm2 down to ~0.03 A/cm2, as shown in Fig. S4(a). For drain doping levels below 1×1018 cm-3, the BTBT electrons from the channel to the drain region are effectively blocked and, consequently, the ambipolar 6 conduction is completely turned off at a drain doping level of 1×1017 cm-3. On the other hand, as clearly shown in Fig. S4(b), Device B also exhibits a drastic decrease in the electron current density from ~0.1 A/cm2 down to ~0.01 A/cm2 as the gate underlap length increases from 0 to 2 µm, which implies that the ambipolar tunneling can be effectively controlled by making a slight change in the gate underlap dimension. Note that as long as a small gate underlap length of ~20 nm is present, hardly the electrons tunnel from the channel to the drain region, thereby suppressing the ambipolar conduction of the device. Figure S3. Experimental measurement and simulation results for different SiNW TFETs in flat and strained states. a) Normalized drain current (log(Ids/Vgs2)) as a function of the inverse gate voltage (Vgs-1) obtained from the experimental data for the different devices in the flat and strained states. Regions I and II are the regimes where the experimental results follow Kane’s model with ambipolar- and on-state BTBT behavior, respectively, whereas region III represents off-state leakage of the devices. b) Corresponding simulation results showing the effect of the drain doping concentrations and gate underlap dimensions on the ambipolar conduction. 7 Figure S4. 2-D electron current density JTUN distribution profiles across the channel (Vgs=-3 V and Vds=1 V). (a) Device A with various drain doping concentrations from 1×1017 to 1×1020 cm-3. (b) Device B with various gate underlap lengths from 0 to 2 µm. 3. Multiple SiNW fabrication Fig. S5 schematically summarizes the key process steps to generate the multiple SiNWs (p+-n0-n--n+ SiNWs for n-TFET and n+-p0-p--p+ SiNWs for p-TFET) from bulk Si wafers by using a fully CMOS-compatible top-down route. Note that the crystalline connections to the supporting posts at the end of the SiNWs are not shown to provide clarity. With an oxide/nitride stack defining the 400-nm-wide active Si lines (Fig. S5(a)), the Si substrate was etched anisotropically until the desired trench depth was reached (Fig. S5(b)). Subsequently, the wafer was dipped in tetramethylammonium hydroxide (TMAH, (CH3)4NOH; 25% diluted in water) solution to generate the triangular Si wires (Fig. S5(c)). Thermal oxidation of the Si wires was subsequently carried out in a wet ambient to reduce the size of the SiNWs down to sub-100 nm (Fig. S5(d)). After the nitride film was completely stripped in hot phosphoric acid, n- and p-wells on the SiNWs (for n- and p-TFET, respectively) were separately formed by a conventional twin-well process, where masked P+ and B+ ion implantations were performed with a dose of 1×1012 cm-2 at ion energies of 40 and 15 keV, respectively (Fig. S5(e)), and then Si wafer was annealed at 1100˚C for 90 min in a nitrogen ambient. In order to form the lightly doped drain (LDD) extension regions (n- drain for n-TFET and p- drain for p-TFET), each of the n- and p- drain extension regions was formed separately by masked ion implantations (As+ 1×1013 cm-2 at 80 keV and BF2+ 1×1013 cm-2 at 50 keV, respectively), in 8 an attempt to suppress the ambipolar conduction (Fig. S5(f)). Additionally, in order to make source tunnel junction and drain contact regions of the SiNWs doped heavily (p+ source/n+ drain for n-TFET and n+ source/p+ drain for p-TFET), As+ and BF2+ ions with a dose of 5×1015 cm-2 were implanted as n- and p-type dopants at ion energies of 80 and 50 keV, respectively, after the source and drain contact regions in the SiNWs were defined in turn with separate photomasks (Fig. S5(g)). Next, the wafer was firstly annealed at 900˚C for 60 min in nitrogen ambient, followed by rapid thermal annealing (RTA) at 1000˚C for 10 s in order to activate the implanted dopants with uniform diffusion and eliminate defects. By removing the surrounding oxide using buffered oxide etchant (BOE) solution, the SiNWs were released from the Si substrate and, thus, the freestanding multiple p+-n0-n--n+ SiNWs and n+-p0-p--p+ SiNWs for n- and p-TFET were formed (Fig. S5(h)). Shown in Fig. S6 is the SEM image of the multiple SiNWs taken after size reduction oxidation of the Si wires and the subsequent nitride strip. Note that, in order to distinguish the clear SiNWs from the surrounding oxide layer, chemical staining in BOE solution was performed after deposition of 150-nm-thick polycrystalline silicon. Clearly, the multiple SiNWs have dimensions of approximately 100 nm and are completely surrounded by the oxide layer. Notably, the multiple SiNWs are electrically isolated from the Si substrate and can be easily transferred onto flexible plastic substrates. Fig. S7 shows the secondary ion mas spectroscopy (SIMS) analysis for the arsenic and boron profiles in SiNWs after the thermal steps. It is confirmed that the boron and arsenic concentrations in the p+ source, n- drain extension and n+ drain contact regions of the SiNW n-TFET are approximately at the 1020~1021, 1017~1018 and 1020~1021 cm-3 levels, respectively (Fig. S7(a)). In the case of the SiNW p-TFET, the arsenic and boron concentrations in the n+ source, p- drain extension and p+ drain contact regions are also approximately at the 1020~1021, 1017~1018 and 1020~1021 cm3 levels, respectively (Fig. S7(b)). 9 Figure S5. Key process steps to generate the multiple SiNWs from bulk p-type (100) Si wafers. (a) Definition of 400-nm-wide Si active lines on a oxide/nitride stack (10/150 nm). (b) Si trench etching using the nitride film as a hard mask. (c) Crystallographic wet-chemical etching in 25 wt.% TMAH solution to generate the triangular Si wires. (d) Thermal oxidation of the Si wires to reduce the dimension of the SiNWs down to sub-100 nm. (e) Masked n- and p-well implantation doping in the SiNWs (P+ 1×1012 cm-2 at 40 keV and B+ 1×1012 cm-2 at 15 keV, respectively), followed by annealing at 1100˚C for 90 min in a nitrogen ambient. (f) Masked n- and pimplantation doping of the SiNWs (As+ 1×1013 cm-2 at 80 keV and BF2+ 1×1013 cm-2 at 50 keV, respectively) to form the LDD regions in the SiNWs, in an attempt to suppress the ambipolar conduction in TFETs. (g) Masked n+ and p+ implantation doping of the SiNWs (As+ 5×1015 cm-2 at 80 keV and BF2+ 5×1015 cm-2 at 50 keV, respectively) to form the heavily doped source and drain contact regions in the SiNWs, followed by annealing at 900˚C for 60 min and RTA 1000˚C for 10 s in a nitrogen ambient to activate the implanted dopants with uniform diffusion and eliminate defects. (h) Release of the SiNWs via wet-chemical etching in BOE solution to form the freestanding multiple p+-n0-n--n+ SiNWs and n+-p0-p--p+ SiNWs for n- and p-TFET, respectively. 10 Figure S6. SEM images of the multiple SiNWs taken after size reduction oxidation of the Si wires and the subsequent nitride strip. Note that, in order to distinguish the clear SiNWs from the surrounding oxide layer, chemical staining in BOE solution was performed after polysilicon deposition. Figure S7. SIMS analysis. (a) Boron (BF2+ 5×1015 cm-2 at 50 keV) and arsenic (As+ 1×1013/5×1015 cm-2 at 80 keV) profiles for p+ source and n-/n+ drain extension/contact regions in the SiNW n-TFET, respectively. (b) Arsenic (As+ 5×1015 cm-2 at 80 keV) and boron (BF2+ 1×1013/5×1015 cm-2 at 50 keV) profiles for n+ source and p-/p+ drain extension/contact regions in the SiNW p-TFET, respectively. The profiles were analyzed after activation annealing at 900˚C for 60 min and RTA at 1000˚C for 10 s. The analysis was performed with a double-focusing magnetic sector mass spectrometer (CAMECA IMS-7f) using a 10 kV Cs+ primary beam for arsenic and a 10 kV O2+ primary beam for boron. 11 References S1 G. A. M. Hurkx, D. B. M. Klaassen, and M. P. G. Knuvers, IEEE Trans. Electron Devices 39, 331 (1992). S2 Atlas User’s Manual, Silvaco Int., Santa Clara, CA, May 26, (2006). S3 The BTBT generation rate GBTBT, known as Kane’s model, is given as: Gbtbt Akane E 2 1 / 2 g Bkane E g3 / 2 exp (S1a) q 2 m01/ 2 m01/ 2 Akane , Bkane 18 2 2q (S1b) where m0 is the tunneling reduced effective mass, Eg is the bandgap of the material, and the constant q and ħ are the electron charge and the reduced Planck’s constant, respectively. Rewriting equation (S1) in terms of Vgs, for Ids ∞ Gbtbt, we get B E 3/ 2 I ds Akane D 2 E g1/ 2Vgs2 exp kane g DV gs (S2) where the constant D obviously parameterizes the influence of the gate capacitance and other effects relating to the gate control of the maximum electric field across the tunneling junction, yielding ξ=DVgs. Taking the natural log of the normalized drain current (Ids /Vgs2), we get I B' ' log ds2 log( A' ' ) V Vgs gs A' ' B E Akane D 2 , B' ' kane g 1/ 2 D Eg (S3a) 3/ 2 (S3b) Thus, plotting log(Ids /Vgs2) as a function of Vgs-1, one would expect a straight line with a slope determined by the value of B”, while the intercept giving A” value. 12