第二章 文獻回顧與理論探討
2.7 微加工技術
2.7.3 電化學沉積法
電化學沉積是利用化學能與電能間相互轉換的機制，將陰陽極放置在含 有電解質的電鍍液中，經由陽極產生氧化反應放出電子，讓電子透過電解質 的離子移動到陰極上，使陰極因得到電子產生還原反應，藉此沉積所需要的 金屬離子。2002 年，Leimkühler 等人以 ITO 玻璃作為基板，在溫度接近 100
℃的HCl 系統鍍液中進行電化學沉積 Sb2Te3之研究。圖32為鍍層底部與頂 部的SEM 形貌圖，圖33為鍍層的XRD 晶格分析結果【46】。2008 年，Glatz 等人利用電化學沉積方式製備Cu/Ni 及 Bi2Te3等熱電材料，製作出熱電能源
產生器，並分析不同熱電接腳長度所產生之效率及輸出功率差異。圖 34 是
熱電元件運作形態示意圖，圖35為電化學沉積之熱電接腳SEM 圖【47】。
Figure 24 Schematic diagram of thermoelectric generator devices【41】.
(a) (b)
Figure 25 (a) Power per couple vs. the segment length for different hot junction temperatures. (b) Net thermal voltage and maximum power output as
a function of temperature applied for seven couples【41】.
Figure 26 SEM top view (left) and cross-sectional (right) images of Bi2Te3 (top) Sb2Te3 (bottom) thin-films【42】.
(a) (b)
(a)
(b)
(c)
Figure 28 (a) Seebeck coefficients and (b) resistivity of Bi-Te films as a function of the deposition temperatures. (c) Te contents as a
function of RF power of Te target【44】.
(a) (b)
(c) (d)
(e) (f)
Figure 29 FESEM images of Bi-Te thin films deposited at (a) 100 °C, (b) 165 °C, (c) 225 °C, (d) 260 °C, (e) 290 °C, and (f) 320 °C【44】.
Figure 30 Thin film thermoelectric generator devices【45】.
Figure 31 The generated output voltage of Bi-Te alloy thin film TEG
Figure 32 SEM images of (left) antimony telluride and (right) antimony【46】.
(a) (b)
Figure 33 XRD pattern of an electrodeposited (a) Sb layer and (b) Sb2Te3【46】.
Figure 34 Working principle of a μTEG connected to a heat source and sink【47】.
2.8 印刷技術應用於熱電元件的製作
複的製程步驟，為了能夠提高微型熱電發電元件的生產效率與產品競爭力，
2008 年，Wüsten 與 Karin 的研究中，先將聚氯乙烯(polyvinylchloride, 鋁和低溫共燒陶瓷(Low-temperature co-fired ceramics, LTCC)基板上，藉此製 作如圖40所示的2D 共平面式微型熱電偶結構，並設計 700、500、300 m 三種不同線寬的結構，在溫度差約 100K 時可量測到每對熱電偶有 5-8 W 輸出功率。接著在LTCC 基板製作如圖41所示的3D 結構微型熱電產生器，
圖42為輸出功率量測結果，Piotr 的研究團隊指出在溫度差大於 60 K 時，每 一對熱電偶可產生1 W 功率【51】。
2010 年，Navone 等人使用機械合金化(Mechanical alloying)將 Bi、Te、
Se 和 Sb 粉末製作成 p 和 n 型的熱電粉末，在使用網版印刷技術將熱電元件
0.06 mW/K2-cm【52】。 末和縮水甘油醚雙酚F 型樹脂(Diglycidyl ether of bisphenol f epoxy resin)材料 結合，使用點膠機(Dispenser printer)將漿料印刷在玻璃基板上，針對不同的
Table 3 Comparison of patterning techniques【48】.
Patterning techniques Dots per inch (m) Ink-jet printing >30 0.1~10 0.001~0.04 >50 Screen printing >70 1~15 0.5~50 >100
Planography >20 0.5~2.5 0.05~0.5 >50K Photogravure printing >30 0.5~8 0.05~0.2 >100K
Flexography >30 0.6~9 0.05~0.5 >20K Hot extension india <5 <1.0 - <10
Photolithography >4 <20 - >10
Micro-indentation <0.1 thin - -
Laser Etching >4 <1.0 - -
Figure 36 Schematic diagrams of the coiled-up TE power generator【49】.
(a) (b)
Figure 38 (a) Schematic diagrams of the experimental setup. (b) Photograph of the screen printed graphite/PVC-(TTF-TCNQ)/PVC-graphite
/PVC junction【50】.
Table 4 Thermoelectric properties of some p-type organic materials【50】.
Pellet PVC layer a
a CT salt to PVC ratio 3：1, PVC solved in tetrahydrofurane (THF), if no value for or ρs is given the sheet resistivity was too high to perform reliable measurements. b Impossible to press as pellet. c Impossible to screen print.
Figure 39 Seebeck voltage and current of graphite (20μm) sheets with different active material to binder (PVC) weight ratios (a) 6 ：1, S = 45.4 μVK-1, (b) 4：1, S = 45.4 μVK-1, (c) 3：1, S =
43.6 μVK-1, (d) 2：1, S = 44.6 μVK-1, (e) 1.67：1, S = 46.1 μVK-1; two measurements per material combination【50】.
Table 5 Thermoelectric properties of some n-type organic materials【50】.
Pellet PVC layer a
Material
(cm) s (cm-1) (VK-1) (2,5-DM-DCNQI)2Cu 9 830 103 14 (2,5-DM-DCNQI)2Li 117 37 106 13 (BEDT-TTF)7/5CuBr2 630 190 106
TTF-TCNQ 32 11 103 48
Figure 40 One of (a) investigated thermopile and (b) thermopile arrangement on heater and radiator【51】.
Figure 41 3-D thick-film thermoelectric micro-generators【51】.
Figure 43 Thermoelectric devices on (a) alumina, and (b) PEN substrates【52】.
Figure 44 Power factor as a function of 473 mJ/cm2 laser pulses【52】.
Figure 45 TE properties of screen-printed ZnSb film after annealing at various temperatures by (a) RTP and (b) furnace【53】.
Figure 46 Photographs of fabricated thermoelectric module【54】.
Figure 48 Measured properties of printed composite films as a function of curing temperature including the power factor【55】.
Figure 49 Measured properties of printed composite films as a function of annealing time including the power factor【55】.
Figure 50 Images of (a) printed 50-couple planar TE device on a flexible polyimide substrate and (b) coiled prototype【56】.
第三章 實驗設計與規劃
microscopy, SEM)及能量分散式光譜分析儀(Energy dispersive spectrometer, EDS)對其觀察、分析以得知表面形貌與成份。針對不同實驗參數變化後的23 m 的鋼絲網進行網版製作，用以印製 325 網目熱電材料粉末所調配之熱
Figure 52 Screen-printed pattern for thermoelectric film.
(a) Screen-printed pattern for n-type Bi2Te3 material.
(b) Screen-printed pattern for p-type Sb Te material.
(c) Screen-printed pattern for electrode pad of Ag paste.
(a) Schematic diagram of the planar thermoelectric micro generator.
Al2O3
ceramic Bi2Te3 Sb2Te3
Ag electrode
Copper rod (b) Schematic diagram of the stacked 3D thermoelectric micro generator.
Figure 55 The thermoelectric micro generator designed in this study.
3.2 實驗規劃 和 0~10 wt.導電高分子 Eeonomer R300F，以 Eeonomer R300F 提高 SU-8 黏著劑的導電性，再添加 15~35 wt.的 SU-8 2000 光阻稀釋劑，用以調整
3.2.2 微熱電能源產生器之實驗規劃 分子 Eeonomer R300F，兩者以 11 wt.與 0~10 wt.的比例進行調配，
然後添加 15~35 wt.的 SU-8 2000 光阻稀釋劑，藉此調整 SU-8 黏著劑
除漿料中光阻本身之有機溶劑和稀釋劑，並固化成型。
Table 6 Composition of the thermoelectric ink.
SU-8 2100 SU-8 2000 Thinner
Eeonomer R300F
Bi2Te3 or Sb2Te3 powder Thermoelectric
ink 11 wt.% 15~35 wt.% 010 wt.% 44 wt.%
Figure 56 Flow chart of thermoelectric device.
(a) Ceramic substrates (d) Screen-printed Ag electrode
(b) Screen-printed n-type Bi2Te3 (e) Cutting off and drilling
(c) Screen-printed p-type Sb2Te3 (f) Devices stacked Al2O3
ceramic Bi2Te3 Sb2Te3
Ag electrode
Copper rod Figure 57 Fabricate process of the planar thermoelectric micro generator.
3.3 實驗設備
Table 7 Experimental facilities used in this study.
曝光機 HB-2510313 Kyowariken 鑫拓實業股份有限公司
精密天平 AR313 OHAUS 尚偉股份有限公司 四點探針 Source Meter 2400 Keithley
多功能電源電錶
Table 8 Experimental chemical reagent used in this study.
(99.999 ) ADV-Engineering 三碲化二銻 Powders Sb2Te3
p-type (99.999 ) Admat Midas Inc.
昇美達國際開發 有限公司
導電高分子 Eeonomer R300F Eeonyx Corpration
柏連企業股份
(a)
Figure 59 UV mask aligner.
Figure 60 Precise balance.
Figure 61 Hot plate.
3.4 結構分析與量測設備
Figure 63 SEM and EDS system.
Figure 65 Automatic houillon viscometers.
3.5 熱電特性量測
W 40 時，就必須乘上一數值為 4.53 的修正因子(Geometric correction factor) C，
此時片電阻可寫成(10)式【57】。
在量測開路電壓的情況下，將 I 視為接近 0，可改寫成(13)式和(14)式。
Figure 66 Measurement equipment of Seebeck coefficient (ITRI).
Figure 67 Schematic diagram of electrical conductivity equipment【57】.
Figure 69 Schematic of thermoelectric characteristics measurement equipment.
第四章 實驗結果與討論
(Ethyl-cellulose)和-松油醇(Alpha-terpineol)，以 0.8 wt.和 19.2 wt.的比例 混合，形成有機黏著劑後，加入 80 wt.的熱電粉末，作為比較用之乙基纖4.1.2 熱電膜與熱電結構之印製
(a) Bi2Te3
Table 9 Printing condition of thermoelectric film and structure.
Figure 71 Conductivity of thermoelectric structures with Eeonomer R 300F added under different ratios.
Thermoelectric film Printing ink Off-contact
(mm)
Squeegee force (kgw)
Printing speed (mm/s) Thermoelectric
ink 0.3 1.75 65
Thermoelectric structure Thermoelectric
ink 0.5 1.75 80
4.2 熱電材料之特性量測
勢。由實驗結果顯示，乙基纖維素版在使用 570 C 進行熱處理製程後之表
差異，是因為在高溫環境中乙基纖維素版的有機黏著劑已經大量移除，讓熱
測是因為 SU-8 光阻受到氣氛控制的保護，使光阻材料在突破 380 C 極限溫
黏著劑的熱傳較差，且具有耐高溫特性故不易去除，因此在 SU-8 版熱電材 料中，熱量的傳遞無法如同乙基纖維素版熱電材料一樣容易，讓晶粒的成長 與接觸受到影響，因此導致席貝克值較乙基纖維素版低，席貝克值變化趨勢 也因此受到影響。
綜合電性與席貝克係數的比較下，本研究最後將選用 SU-8 版 N2氣氛下 290 C、12 小時，H2 7 %—Ar 93 %氣氛下 500 C、12 小時，和乙基纖維素 版 H2 7 %—Ar 93 %氣氛下 500 C、2 小時的製程條件，作為後續熱電發電 元件製作之熱處理溫度。SU-8 版熱電漿料參數為：SU-8 2100 負光阻 11 wt.、導電高分子 Eeonomer R300F 10 wt.、SU-8 2000 稀釋劑 35 wt.及熱 電粉末 44 wt.。SU-8 版 Sb2Te3和 Bi2Te3的漿料黏度分別為 3678 cps 和 8163 cps。乙基纖維素版熱電漿料參數為：乙基纖維素 0.8 wt.，混合-松油醇 19.2 wt.的有機黏著劑，再加上熱電粉末 80 wt.，乙基纖維素版 Sb2Te3和 Bi2Te3的漿料黏度分別為 20133 cps 和 41423 cps。
Table 10 Annealing process of different temperatures.
(a) SU-8 version Sb2Te3 (b) SU-8 version Bi2Te3
(c) EC version Sb2Te3 (d) EC version Bi2Te3 Figure 72 SEM images of thermoelectric film without annealing.
(a) 250 C (b) 270 C
(c) 290 C (d) 430 C
(e) 500 C (f) 570 C
Figure 73 SEM images of SU-8 version Sb2Te3 film with different annealing temperatures.
(a) 250 C (b) 270 C
(c) 290 C (d) 430 C
(a) 430 C (b) 430 C
(c) 500 C (d) 500 C
(d) 570 C (e) 570 C
Figure 75 SEM images of EC version Sb2Te3(left), and Bi2Te3(right) film with different annealing temperatures.
(a) SU-8 version
(a) 250 C (b) 270 C
(c) 290 C (d) 430 C
(d) 500 C (e) 570 C
Figure 77 SEM images of SU-8 version Sb2Te3 film with different annealing temperatures.
(a) 250 C (b) 270 C
(c) 290 C (d) 430 C
(a) 430 C (b) 430 C
(c) 500 C (d) 500 C
(d) 570 C (e) 570 C
Figure 79 SEM images of EC version Sb2Te3(left), and Bi2Te3(right) film with different annealing temperatures.
(a) SU-8 version
(a) Sb-Te
(b) Bi-Te
Figure 81 EDS measurement of SU-8 version thermoelectric films with different annealing temperatures.
(a) Sb-Te
(a) SU-8 version
(b) EC version
Figure 83 Seebeck coefficient of thermoelectricmaterials with different annealing temperatures.
Table 11 Thermoelectric properties with different annealing parameters.
4.3 熱電微型發電元件之製作與特性量測
4.3.2 熱電微型發電元件之發電特性量測
出電壓分別為 28.6 mV 和 19.6 mV，可看出隨著線寬和接腳長度的不同，一
開始就有相應的差異產生。當對偶數和接腳長度產生變化後，500 m-5
mm-30、500 m-10 mm-30 和 1000 m-10 mm-15，可以在 40 K 溫差的情況 下得到約兩倍的 22.3 mV、60.4 mV 和 39.6 mV 輸出電壓。電壓輸出斜率則 是從 0.309 mV/K、0.704 mV/K 和 0.494 mV/K，變化為 0.546 mV/K、1.53 mV/K 和 1.028 mV/K。500 m-5 mm 在 15 對和 30 對的情況下，功率因子分別為 mm-15、500 m-10 mm-15 和 1000 m-5 mm-15，分別得到 48.2 mV、102.4 mV 和 68.6 mV 的輸出電壓。500 m-5 mm-30、500 m-10 mm-30 和 1000 m-10 mm-15，可以分別得到 40 K 輸出電壓為 96.4 mV、196.6 mV 和 114.8 mV。
電壓斜率的部分，從 1.224 mV/K、2.613 mV/K 和 1.707 mV/K，提高至為 2.458 mV/K、2.844 mV/K 和 5.004 mV/K。乙基纖維素板熱電元件在 500 m-5 mm 的 15 對和 30 對情況下，功率因子分別為 0.141 10-3 W/m-K2和 0.129 10-3
測可能是因為乙基纖維素在高溫熱退火時，有機物質被完全移除，使材料產
Table 12 Printing conditions of thermoelectric micro generator.
Thermoelectric structure Printing ink Viscosity
(cps)
Silver paste ~50000
0.5 1.75
35
5X
5X
10X
Figure 85 OM images of SU-8 version Bi2Te3 structures.
5X
5X
10X
Figure 87 OM images of EC version Bi2Te3 structures.
SU-8 version Sb2Te3 structures SU-8 version Bi2Te3 structures
EC version Sb2Te3 structures EC version Bi2Te3 structures
5X
10X Figure 89 OM images of silver electrodes.
Figure 90 Thickness of silver electrodes on ceramic substrate.
Table 13 Geometric conditions of planar thermoelectric micro generator.
*Reference【55】
(a) SU-8 version, 290 C annealing Thermoelectric pairs
Linewidths (m)-lengths (mm)-pairs
500-05-30 500-10-15 500-10-30 1000-05-15 1000-10-15 500-05-15
400-05-50*
(b) SU-8 version, 500 C annealing
Table 14 Thermoelectric properties of SU-8 version 2D-TEG with 290 C annealing.
Table 15 Thermoelectric properties of SU-8 version 2D-TEG with 500 C annealing.
Table 16 Thermoelectric properties of EC version 2D-TEG with 500 C annealing.
Parameters
Figure 93 Overview of stacked planar thermoelectric micro generator module.
(b) Output power
Figure 94 Output characteristics measurement of single-layer, and stacked thermoelectric micro generator module.
Table 17 Thermoelectric properties of single-layer, and stacked 2D-TEG.
Parameters
Seebeck coefficient
(V/K)
Electrical conductivity
(105 S/m)
Power factor (10-3 W/m-K2) Single-layer 2D-TEG 52.83 2.85 0.795 Three-layers 2D-TEG 44.18 7.43 1.449
第五章 結論與未來展望
導電率分別為 42.25 V/K、-21.45 V/K 與 60.98 S/m、32.05 S/m。乙基 纖維素版熱電材料在 500 C、2 小時熱處理下，得到 Sb2Te3和 Bi2Te3之 席貝克值分別為 106.86 V/K、-79.17 V/K，導電率則為 82.64 102 S/m、84.75 102 S/m。45.65 m，乙基纖維素版 p 型與 n 型熱電結構厚度則分別為 37.54 m 和
5.2 未來展望
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