報告學生：陳天文
授課老師：吳坤憲
半導體感測元件 報告
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Ⅴ.
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 化學感測器通常指的是一種體積小、靈敏度高且
對環境(空氣及水)中 特種化合物 有相當 高選擇性
之感測器。
例如: 葡萄糖生化感測器專門為偵測血液中葡
萄糖而設計。
 化學感測器不僅用在學術研究 ， 且可用在生化樣
品偵測以做醫學診斷 ； 及環境污染現場分析 。
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І.

(1)
(2)
(3)
(4)
化學感測器依感應元件之種類及目的不同一般分
為四大類 :
壓電晶體 化學感測器(piezoelectric sensors)
電化學 感測器(electrochemical sensors)
光學 感測器(optical sensors)
生化 感測器(biological sensors)
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І.
臨床及生醫 藥物測試，醫療儀器之診斷與治療用
研究
工業 藥廠品管，發酵製程，廢水廢棄物監測
農業 成熟度、儲藏、農藥與運輸過程之檢測
安全防衛 毒性物質檢測
環保
機器人
空氣、水質污染
自動化檢測應用
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І.
半導體製程 薄膜製程 厚膜印刷製程
相對成本 高 中
可微小化程度 次微米-奈米 次微米-微米
特殊製程之彈性 低 高
元件單價 不一定
再現性與穩定性 最高
低
高
低
微米
中
最低
中
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І.
 一般說來，要構成化學感測器（sensor）必須要有兩個
基本部分：一是 分子辨識單元 （molecular recognition unit）、二是 信號轉換單元 （signal transduction unit）。
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І.
 如何得知待測物(分析物)? 就要靠 「 分子辨識 」， 而推動
分子辨識的主要動力是「分子間的作用」 ；愈多受質
(substrate)與受體(receptor)分子間的作用存在，則愈
可有效的分子辨識。
 用來與待測受質（即分析物）交互作用（interaction）
的部分。也就是類似一個 「陷阱」 ，可以 吸引受質並「捕
獲」住 ；再接著引起後續的信號傳遞（signal transduction）。設計分子辨識單元有兩項指標： 愈高的
選擇性（selectivity）及愈強的親和力（affinity）愈
好。
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І.


因我們無法直接看到 受質 是否被分子辨識單元「 辨識 」，因此
感測器中需要有告知我們的讀出單元（readout unit），即將
分子的辨識行為直接（direct） 轉換為可被讀出的訊號 。常用
的轉換信號方式有兩種：可轉換成 電化學訊號
（electrochemical signal）或 光學信號 （optical signal）。
分子辨識與信號傳遞兩單元的整合 是相當重要的，它直接反應
到微觀（microscopic）的分子行為是否能有效的被直接巨觀
（macroscopic）讀出。有極佳的分子辨識單元但無法輕易被
觀察，算是設計不良的感測器；有極靈敏的信號傳遞單元但無
法辨識特定受質，也是無用。
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Ⅱ .
Potentiometric
– Ion Selective Electrode
– Redox Electrode
– Field Effect Transistor, FET
– Gas-sensing electrodes
Amperometric
– Oxygen electrode
– Glucose electrode
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Interfacial Phenomenon of Electrochemical System electrode
-
-
-
-
ne -
O x
R ed double layer
C d
+
+
+
+
+
O x solution
R ed
R
Ω
R ct
Z w
Z f
R
Ω is solution resistance
C dl is capacitance of electro-double layer
Z f is faradaic impedance
R ct is charge transfer resistance
Z w is warburg impedance
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Ⅱ
• 常用的非金屬薄膜包括有 SiO
2
、 Si
3
N
4
、 olysilicon 、 silicon oxynitride 、 SiC 、 SiB 、等，而影響薄膜的
重要參數包括有鍍膜的溫度、薄膜的內部應力與形
變、被覆的邊緣、對蝕刻液的抵抗、及針孔的生
成。特別是薄膜的應力與製程有十分的關係，需
特別注意。
• 有機分子薄膜 可用以 改善表面的機械特性 (friction)
或 形成疏水區域 (hydrophobic region) ，通常可以
用 PECVD 生成 .
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Ⅱ .
1. 雙電極式 2. 三電極式
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Ⅱ .
General circuitry for measurement of potential at non-ISE(Ion Selective Electrode) type indicating electrode
1. Indicating electrode.
2. Biological material on indicating electrode.
3. Reference electrode.
4. Electrolyte containing material to be measured.
5. High impedance potentiometer.
6. Display unit.
7. Operational amplifier current follower.
8. Comparator circuit.
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Ion Selective Electrode & Redox Electrode
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Ⅱ .
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Ⅱ .
Ion-sensitive field effect transistor
(ISFET) :
1970 first reported by Bergveld
1974 first pH ISFET with Si
3
N by Matsuo and Wise
1980 first enzyme sensor by
Caras and Janata
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(penicillin) diversified microsensor development for multianalytes measurement in clinical applications
(Glucose, Urea, Blood Gas..)
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Ⅱ .
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Ⅱ
Field Effect Transistor :
V
G
: applied voltage to gate
V
D
: applied voltage to drain
Source and Substrate tied to Ground.
The source and drain allow the conductivity of the inversion layer at the surface of the p-type substrate to be measured. The current that flows from the drain to the source, I as a function of V
G and V
D
D
.
, is measured
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Ⅱ .
(CHEMFET)
Unsaturated region :
V
D
< V
G
-V
T
(V
Dsat
)
I
D
= μ n
WC
0x
(V
G
-V
T
-E ref
- ?
sol-mem
V
D
/2)/L
I
Satuurated region :
V
D
> V
G
-V
T
(V
Dsat
)
D
= μ n
WC
0x
(V
G
- V
T
-E ref
- ?
sol-mem
)²/2L
1. Silicon substrate 2. insulator
3. Chemically sensitive membrane
4. Source
6. Insulating encapsulant
5. drain
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Ⅱ .
• Solid-state membranes : mostly for pH sensing
Si
ZrO
2
Al
2
3
N
O
4
3
SiO
Ta
2
O
2
5 hydration in aquesous solutions good pH sensitivity (52-58 mV/pH), fast response
(sec) neglible drift, little hysteresis
• Polymer membranes :multiple casting for "pin-hole" free membrane
PVC + ionophore for specific ions valinomycin K + tHODPP C a 2
+
• Heterogeneous membranes : compatable with semi-conductor processes, using finly divided powder of inorganic salt, immobilized in a polymer matrix.
PNF + silver chloride Cl-
PNF + silver iodide + silver sulphide I , CN -
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Ⅱ . Enzyme-based FET (ENFET)
Applying a thin layer of gel which contains the enzyme over the ion-selective membrane which typically is pH-sensitive
ISFET.
Penicillinase
Penicillin --------> Penicilloate + H+
GOD
Glucose + O2 ---->Gluconate+H + +H
2
O
2
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Ⅱ . Immunochemical FET (IMFET)
The solution-membrane interface acts as a perfect capacitor. Then the
HEMFET can measure the adsorption of charged species at the interface.
Since antibodies, antigens, and proteins are generally electrically charged molecules, so the polarized
CHEMFET could be used to monitor their non-specific adsorption at the solution-membrane interface.
Ab + Ag <----> AbAg
K = [AbAg]/[Ab][Ag]
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Ⅱ .
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Ⅱ
By applying a potential between a reference and indicating electrode can give rise to a current which may be related to the concentration of an electroactive analyte in solution. The rate of the heterogeneous electron transfer process can be controlled by variation of the applied potential. The reaction current is diffusion limited and can be controlled by electrode surface area, temperature, stirring speed,..etc.
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Ⅱ
Cycle Voltametric and Electron Transfer :
In aqueous solution, one can apply potential "window" from about +1.0 to -0.6
V vs. reference electrode to monitor electroactive analytes. By scanning the
"window" potential with different rate, or different waveform, one can determine the adsorption substance and concentration from the recording CV.
However, the major problems are electrode fouling by proteins and filming of the electrode by the product or products of the electron transfer reaction.
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Ⅱ .
• 研發方向:
– 最小侵入式
– 微電流式化學感測
– MEMS 及CMOS製程
– 可攜式儀表系統
– 酵素固定化
• 利用聯電UMC 0.5uM DPDM 標準 CMOS製程
(die size: 1.0 mm x 1.0 mm , electrode size: 600 u x 800 u)
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Ⅱ .
Microsensor for Glucose Measurement :
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Ⅱ
2
2
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Signal display
Ⅲ
.
Design Principle of Biosensor
Bio-affinity l signa
Transducers
Electrochemical
Optical
Thermal
Mass-sensitive analyte analyte bio-element reaction product
Bio-catalysis interferent bio-element
Recognition layer
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Ⅲ .
Immobilization Methods
Adsorption
Biological binding
Immobilization of
Bio-elements
Covalent binding
Cross-linking Entrapment 31

Ⅲ
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Cross-sectional schematic of the subsurface, embedded MEMS integrated technology.
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Carbon Nanotubes
• diameters to ca. 1 nm
• mechanically robust
• chemical stability
• metals & semiconductors w/o control
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Current Nanosensor Devices - Porous Silicon
Properties
• Porosity
• Nanocrystallinity
• Photoluminescence
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Current Nanosensor Devices - Porous Silicon
Applications
• Capacitive humidity sensors - metal coated (macro)
• Ion-sensitive Field Effect Transistor (future)
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• Binding of chemical or biological species to the surface of a nanowire will result in depletion or accumulation of carriers.
• The change in carrier concentration due to binding can be directly monitored by measuring the nanowire conductance.
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• A solid state FET, whose conductance is modulated by an applied gate, is transformed into a nanosensor by modifying the silicon oxide surface.
• The conductance of modified SiNWs increases stepwise with discrete changes in pH from 2 to 9. Hence, changes in the surface
38 charge can chemically-gate the SiNW .

 化學感測器為一新興發展的新科技，目前世界
各國無不積極投入研究 。
 結合化學、醫工及半導體技術之智慧型、積體化、
多機能化、微小生物感測器，是相當令人感興趣
的挑戰。
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





電化學分析方法與感測器 講義 :台灣大學醫工所 林啟萬
晶片載具與製程 講義 :台灣大學醫工所 林啟萬
分子辨識與感測器 網頁 : 台大化學系四年級 王宗興
Development of Biosensor and Biosensing Technology
Presented by: 成功大學 Hsien-Chang Chang (張憲彰)
Nanostructured Materials, Nanodevices and Nanosystems used as Nanosensors
Presented by: Laura Bukkosy Smith
化學感測器整合計畫研究規劃與成果報導
師範大學化學研究所 施正雄
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Current Nanosensor Devices - Nanoprobes
Nanosensors - Nanoparticles/Nanoprobes
Optical biochemical sensors for near field optics
Single molecule localization
Intracellular applications - pH, Ca, Na, K, Cl, O, Mg glucose, glutamate
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Enabling Nanotechnology for Sensor Systems
• Cantilevers as resonant/oscillating sensors
• Biomolecular Motors for a new class of sensors
• Self-assembling nanostructures/new nanomaterials for multi-analyte sensors
• Redox-switchable nanoelectronic devices
• Nanowires for efficient diodes, lasers, parallel sensors, optical interconnects
• Technologies to integrate nanodevices at the nano and macro sensing levels
• Nanoscale power sources
46

Enabling Nanotechnology for Sensor Systems
Nanodevices - Cantilevers as Sensors
• AFM sensor tips
• Probes for Specific
DNA Sequences
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Definition of Nanosensors
Three categories of nanosensors:
Nanostructured materials - e.g. porous silicon:
Micro - (features < 2nm)
Meso - (features 2nm - 100nm)
Macro - (features > 100nm)
Nanoparticles/Nanoprobes
Spherical nanosize material
Nanodevices/Nanosystems
Cantilevers, NEMS, mostly theoretical
48

Applications for Nanosensors
Biomedical
In vivo - within the body, intracellular
In vitro - exterior to the body, test tube
Disease detection, cellular repair, drug delivery
Measurement of pH, calcium, sodium, potassium, chloride, oxygen, glucose, glutamate, magnesium
Environmental- methanol, ethanol, 2-propanol, acetone, toluene, airborne chemical/biological agents
Smart Materials
Communications 49

Current Nanosensor Devices - Porous Silicon
Description: Porous silicon is identical to the silicon used in many technological applications today, but its surface contains tiny pores ranging from < 2nm to microns, that can absorb and emit light.
History:
• Material first reported in 1956 by Uhlir as an effect from electrochemical polishing studies using a low current density.
• Chemical etching with HF/HNO3 also produced porous silicon.
• Crystalline etch channels found in early 1970’s by Theunissen.
• Pickering et. al. first noted photoluminescence at room temperature.
• Canham observed room temperature fluorescence in 1990 and suggested Quantum Confinement as origin of fluorescence.
50

Current Nanosensor Devices - Porous Silicon
Manufacturing Methods
• Electrochemical Etching
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Current Nanosensor Devices - Porous Silicon
Manufacturing Methods
• Chemical Etching
• Spark Erosion
• Chemical Vapor Deposition
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Current Nanosensor Devices - Porous Silicon
Properties
• Porosity
• Nanocrystallinity
• Photoluminescence
53

Current Nanosensor Devices - Porous Silicon
Properties
• Electroluminescence
• Reflectivity
• Conduction
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Current Nanosensor Devices - Porous Silicon
Applications
• Reversible Microcavity Chemical Sensor
• Methanol
• Ethanol
• 2-Propanol
• Acetone
• Toluene
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Current Nanosensor Devices - Porous Silicon
Applications
• DNA Microcavity Biosensor
• DNA / c-DNA binding
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Current Nanosensor Devices - Porous Silicon
Applications
• Hot wire anemomemeter to measure fluid flow
• Thin film bolometers for IR radiation detection
• Photodetectors
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Current Nanosensor Devices - Porous Silicon
Applications
• Capacitive humidity sensors - metal coated (macro)
• Ion-sensitive Field Effect Transistor (future)
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Current Nanosensor Devices - Other
Nanostructured Materials
Micro Pen Lithography (MPL) and Ink Jet Printing (IJP) of surfactant-templated mesophase silica - by evaporation
• pH sensor arrays (fluorescence)
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Current Nanosensor Devices - Nanoparticles
Nanosensors - Nanoparticles/Nanoprobes
North Western University - Mirkin Group
• New Nanostructured Materials and Nanosensors
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Current Nanosensor Devices - Nanoparticles
Nanosensors - Nanoparticles/Nanoprobes
CdSe Nanocrystals as biological sensors/labels
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Current Nanosensor Devices - Nanoprobes
Nanosensors - Nanoparticles/Nanoprobes
Optical biochemical sensors for near field optics
Single molecule localization
Intracellular applications - pH, Ca, Na, K, Cl, O, Mg glucose, glutamate
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Future Nanosensors
Nanodevices - Nano Electro Mechanical Systems (NEMS)
• NEMS oscillators (resonant sensors) used to detect
• Magnetic forces of a single spin
• Biomechanical forces
• Adsorbed mass
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Future Nanosensors - Nanoparticles
Nanosensors - Nanoparticles/Nanoprobes
• Magnetite - dextran nanoparticles for MRI diagnosis of liver, lymph node, vascular diseases
• Iodinated nanoparticles-indirect computed tomography lymphography detection of cancerous lymph nodes
• Magnetically responsive spheres to eliminate target cells such as erthrocytes, neuroblastoma cells, Burkitt lymphoma cells
• Improving activity of neuropeptides
• Gene therapy
• Oral vaccinations
64

Conclusions
• Existing nanosensors have realistic applications
• Current envisioned nanosensors are still based on macrosensing techniques that are enhanced or miniaturized
• Future nanosensors will create paradigm shifts
• Enabling nanotechnology and future nanosensors - in vivo nanorobots, sensory and repair systems - will be possible with the development of nanoelectronics, and integratable nanodevices
• Fine line between what is science fiction and science fact
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