結論

本實驗室長久以來都以發展各類的微型感測元件為至上的目標，包 括過去的葡萄糖感測元件、以氧化銥為基礎的二氧化碳感測器、三氧 化鎢與氧化銥二極體之 pH 值感測器….等。在上述的眾多元件中，其 製作過程應用了半導體的製程技術來製造我們的微電極晶片，並利用 剝落製程(lift-off)及 RF 濺鍍系統來濺鍍我們所要的薄膜種類，有了這 些技術當後盾，我們才能夠使元件順利的被製作出來。

我們將三氧化鎢及氧化銥薄膜製成的二極體元件，在沒有外加液態 或固態電解質來提供氫離子注入的條件環境下，元件還是可以順利工 作。而其中氫離子的主要來源是氧化銥薄膜所提供的，原因為濺鍍氧 化銥過程中電漿將水分子打成氫離子而夾層在薄膜內，如此，元件中 就有足夠的氫離子可以與電子進行雙重載入(double injection)的氧化 還原反應機制，也就是說電子與氫離子是一對一形式反應的，而我們 更進一步實驗發現元件產生的電流主要是由氫離子濃度的擴散所主 控。

而本元件除了不需外加液態電解質這項優點外，還可以把它當作溫 度感測器來使用，因其工作的溫度範圍可從-90℃~120℃間，在此範 圍內其工作情況非常的穩定，除此之外，本元件在此溫度範圍內還有 極佳的重複記憶性質。綜合而言，本元件的優點為封裝容易、有較長 的壽命、重複性高、穩定性佳、可微型化….等。而目前我們遭遇到 的難題為顯影時間較難拿捏而造成顯影液把三氧化鎢薄膜蝕刻，造成 薄膜損壞，若能將上述問題改善，則元件的運用性就會較為廣泛。

關於未來展望部分，因為此元件的電流負載量可達到數百μA 等 級，而由於能量守衡的關係，我們研判部分能量會以光的型態釋出，

所以我們可將元件照光譜儀，分析探討其釋放出來的光波長，並觀察 是否會有光電流的產生或能階的躍升，於是我們就可發展出一個光電 元件感測器。

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---圖表---

Figure 3.1 microelectrode array pattern .

Figure 3.2 stainless mask .

4 mm

Pt/Cr flag

Silicon/SiO2

/Si3N4

3 mm

Figure 3.3 The sputtering equipment setup.

Quartz cylinder shield Magnetron Sputter source

In line regulator RotaMeters Glass cylinder

(ψ=21cm)

Substrate Holder

Cooling water in

out Matching

Box RF generator

Vacuum Gauge Mechanical Pump

Ar Gas ring

ThermoCouple Gauge

Heater power Supply

O2

---圖表---

Wire connector Screw

Figure 3.4 The dismountable heater.

Nichrome wire / Ceramic insulation

Silver gasket Thermocouple well

Flange

Glass fiber filling

Teflon adhesive tapes Insulated copper wire

0.6 mm

0.4 mm 0.6 mm

0.4 mm 0.3

mm 0.6 mm 0.4

mm

0.4 mm

0.4 mm

Figure 3.5 白金晶方結構圖

IrO

2

thin film

Figure 3.7 IrO

₂

薄膜結構圖

WO

3

thin film

Figure 3.6 WO

₃

薄膜結構圖

Oxide Pt /Cr

SiO2 Si3N4

N type Silicon

Figure 3.8 Schematic side view of the summarized process flow for the lift-off processes.

Positive Photoresist Coating

Exposure ＆ Development

Remove Photoresist Sputtering

Deposition Oxide

SMU Keithley236

銅片

IrO

₂

WO

₃

Ag epoxy

epoxy

Pt

pt WO

₃

IrO

₂

Ag epoxy

Figure 3.10 元件側視圖 Figure 3.9 元件俯視圖

晶方

液態氮

Device

Keithley SMU236

Thermal meter

PC

Output HI

Output Lo Sense HI Sense Lo

Figure 3.11 低溫系統結構圖

Mechanical pump

Ag epoxy Ag epoxy 銅線基座

Epoxy 晶片

玻璃管 漆包電線

銅線

Figure 3.12 元件封裝圖

Auxiliary electrode (Pt wire)

Voltammetric analyzer BAS CV-50

Buffer solution (pH=2)

Reference electrode(SCE) Working electrode

(WO3-IrO2二極體)

Fig.3.13 The setup for measurement of

Cyclic Voltammogram

-300 -200 -100 0 100 200 300 400 500 -10

-5 0 5 10 15 20

Volt age(V)

Temperature (

⁰

C)

Figure 4.1 電壓與溫度關係圖

-6 -4 -2 0 2 -60

-50 -40 -30 -20 -10 0 10 20 30 40 50

Voltage (V)

Cur rent ( µ A)

27

⁰

C

Figure 4.2 I-V characteristics of a WO

₃

/IrO

₂

device

without Electrolyte.

-25 -20 -15 -10 -5 0 5 -50

-40 -30 -20 -10 0 10 20 30 40

-90⁰C -70⁰C -50⁰C -30⁰C 0⁰C 27⁰C

Current (

µΑ

)

Voltage (V)

Figure 4.3 I-V characteristics of a WO3/IrO2 device

at low temperature

-90 -80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 1.0

1.5 2.0 2.5

S w itc h -on Voltage (V)

Temperature (

⁰

C)

Figure 4.4 The plot of the Voltage vs Temperature at a fixed

current of 10μA under forward bias.

Figure 4.5 The plot of Resistance vs Temperature under forward bias.

-90 -80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 80

100 120 140 160 180 200 220 240 260

R (k Ω )

Temperature (

⁰

C)

-90 -80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 90

120 150 180 210 240 270

R (kΩ)

Temperature (⁰C)

Slope= -3.69 (kΩ / ⁰C)

-90 -80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 -20

-15 -10 -5

" Break-down " Volt age(V)

Temperature (

⁰

C)

Figure 4.6 The plot of the Voltage vs Temperature at a

fixed current of -10μA under reverse bias.

Figure 4.7 The plot of Resistance vs Temperature under reverse bias.

-90 -80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30

400 600 800 1000 1200 1400 1600 1800 2000

R (k Ω )

Temperature (

⁰

C)

-90 -80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 600

800 1000 1200 1400 1600 1800 2000

Slope= -9.98 (kΩ / ⁰C)

R (kΩ)

Temperature (⁰C)

-0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0 -6

-5 -4 -3 -2 -1 0

Current dens it y (m A/ c m

2

)

Potential vs. SCE(V) Scan rate = 10 mv/s

Figure 4.8 Injecting H

⁺

in WO

₃

/IrO

₂

diode device.

-20 -15 -10 -5 0 5 -160

-120 -80 -40 0 40 80 120

C u rrent (

µΑ

)

Voltage (V)

-90⁰C -70⁰C -50⁰C -30⁰C 0⁰C 27⁰C

Figure 4.9 I-V characteristics of a WO

₃

/IrO

₂

device

after injecting H

⁺

.

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 0

20 40 60 80 100 120 140 160 180 200

C u rrent (

µΑ

)

A₁=2.85x10^-4cm² A₂=2.97x10^-4cm² A₃=3.38x10^-4cm² A₄=3.92x10^-4cm²

Voltage(V) V

_onset

Figure 4.10 I-V characteristics of four different overlap

area diodes under forward bias.

3.0x10^-4 3.5x10^-4 4.0x10^-4 30

60 90 120 150 180

Current ( µ A)

Overlap Area (cm

²

) Diode1

Diode2 Diode3 Diode4

Figure 4.11 The plot of the current vs different overlap

area at a fixed voltage of 1.5 V.

在文檔中 無電解質之三氧化鎢與氧化銥二極體元件在低溫環境下之電性研究 (頁 34-59)