厚膜熱電材料應用於平面微型發電元件之研製
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2012
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全球石油蘊藏量日漸枯竭及溫室氣體的排放造成全球暖化，世界各國對再生或新興能源的研究日益重視。熱電材料具有可將熱能與電能相互轉換產生發電或致冷功能的特性，熱電微發電元件具有體積小、無汙染、高壽命且容易與IC元件整合等優點，故熱電發電技術早已在國外各領域應用。由於精密網印技術可在一次印刷過程中完成功能性厚膜結構製作，故有利於實現產品之快速、大量生產。因此本研究將利用精密網印技術取代傳統熱電能源產生器的製造技術，嘗試使用SU-8負型光阻作為有機黏著劑，並添加Eeonomer R300F導電高分子粉末，以進行特性改良，製作出符合綠色能源之平面厚膜微型熱電發電元件。
研究結果顯示，本研究成功調配出含導電高分子Eeonomer R300F之SU-8負光阻有機黏著劑，並混合p型Sb2Te3與n型Bi2Te熱電粉末，製作成可用於印刷之SU-8版熱電漿料。另外，本研究並將乙基纖維素(Ethyl-cellulose)、a-松油醇(Alpha-terpineol)和Sb2Te3與Bi2Te熱電粉末進行混合，進行乙基纖維素(Ethyl-cellulose, EC)版印刷用熱電漿料之製作，針對兩種不同之有機黏著劑，在不同熱處理溫度與時間的條件下進行探討。
SU-8版熱電材料，在熱處理條件290 oC與12小時的情況下，得到Sb2Te3和Bi2Te3的席貝克值分別為24.99 uV/K、-54.52 uV/K，導電率則是27.47 S/m、16.72 S/m。當熱處理溫度提高到500 oC時，熱電材料的席貝克值變化為42.25 uV/K、-21.45 uV/K，導電率則提高到60.98 S/m、32.05 S/m。乙基纖維素版熱電材料，在熱處理溫度500 oC、熱處理時間2小時的情況下，可得到Sb2Te3和Bi2Te3之席貝克值與導電率分別為106.86 uV/K、-79.17 uV/K，和82.64 x10^2 S/m、84.75 x10^2 S/m。
本研究接著以網版印刷技術，配合先前的漿料調配比例與熱處理參數，進行熱電微型平面發電元件之印製。銀膠電極線寬設計為500 um，印刷厚度約為41.74 um，熱電結構之線寬設計為250~1000 um，印刷SU-8版之p型與n型熱電結構厚度，分別為28.07 um和45.65 um，乙基纖維素版p型與n型熱電結構印刷厚度則分別為37.54 um和26.01 um。
研究結果顯示，本研究中最佳電壓輸出特性之設計，是在線寬500 um、熱電接腳長度10 mm和30對熱電偶的條件下。在溫度差40 K的時候，可得到290 oC、12小時熱退火之SU-8版熱電元件，輸出電壓為26.3 mV，退火條件500 oC、12小時之SU-8版熱電元件，則可得到60.4 mV的輸出電壓，乙基纖維素版熱電元件，在500 oC、2小時熱退火參數時，有196.6 mV的電壓輸出。配合多層堆疊製程，完成500 oC、12小時熱退火條件，SU-8版3D多層微平面熱電能源產生器，並量測其輸出特性。量測結果顯示3層堆疊之熱電模組，可以較單一元件有約2.6倍的電壓輸出和5.8倍的功率輸出，40 K溫差條件下，可得到156.7 mV和88.635 uW的輸出特性。
In view of the oil reserves are depleting, and greenhouse gas emissions blamed for global warming, the world is increasing emphasis on renewable energy research. Thermoelectric materials have the characteristics of heat, and electrical conversion that can use for the power generation or cooling. The thermoelectric micro power generation component has a small, non-polluting, high life, and easy integration with IC components. The thermoelectric power generation technology has been application of various fields in foreign countries. Because of screen-printing has ability in once printing process to product the functional thick-film, so that is beneficial to achieve rapid product, and mass production. Therefore, this study will use of precision screen printing technology to replace traditional fabrication of thermoelectric devices. Trying to use the SU-8 negative photoresist as an organic adhesive, and add conductive polymer Eeonomer R300F in organic adhesive to improve the conductivity. Producing a thick-film planar thermoelectric power generator that to meet green energy requirement. The study results show that organic adhesive of SU-8 photoresist mixing Eeonomer R300F has been successfully developed, and add Sb2Te3 p-type or n-type Bi2Te3 thermoelectric powder, made into a printable thermoelectric inks. In addition, mix Ethyl-cellulose, Alpha-terpineol, and Sb2Te3 or Bi2Te3 to making Ethyl-cellulose, EC version thermoelectric ink. In different annealing conditions, explore two different types of organic adhesives. The SU-8 version thermoelectric materials in the annealing conditions of 290 oC, and 12 hours, Seebeck coefficient of Sb2Te3 and Bi2Te3 are 24.99 uV/K, and -54.52 uV/K, conductivity are 27.47 S/m, and 16.72 S/m. When the annealing temperature rise to 500 oC, Seebeck coefficient changed to 42.25 uV/K, and -21.45 uV/K, conductivity increased to 60.98 S/m, and 32.05 S/m. EC version thermoelectric materials, in the annealing conditions of 500 oC, and 2 hours, Seebeck coefficient, and conductivity of Sb2Te3, and Bi2Te3 were 106.86 uV/K, -79.17 uV/K; 82.64 x10^2 S/m, and 84.75 x10^2 S/m. Then we use screen printing technology, with the proportion of thermoelectric ink, and annealing parameters, to printing the planar thermoelectric generator. The linewidth of silver electrode is 500 um, and thickness is 41.74 um. The linewidth of thermoelectric structure is designed for 250~1000 um, thickness of SU-8 version p-type, and n-type thermoelectric structures are 28.07 um, and 45.65 um, respectively. The thickness of EC version p-type, and n-type thermoelectric structures are 37.54 um, and 26.01 um, respectively. The results show the design of 500 um in linewidth, 10 mm in length, and 30 pairs in thermocouples have maximum output voltage. When a temperature difference of 40 K, the SU-8 version thermoelectric device with 290 oC, and 12 hr annealing has 26.3 mV output voltages, annealing conditions of 500 oC, and 12 hr can get output voltage of 60.4 mV. The EC version thermoelectric devices with 500 oC, and 2 hr annealing can get 196.6 mV output voltages. Then we use multi-layer stacking process, to complete the SU-8 version 3D multi-layer planar thermoelectric generator, and measure its output characteristics. The measurement results show that thermoelectric modules of 3-layers stacked, about 2.6 times of voltage output, and 5.8 times of power output compared with single. When a temperature difference of 40 K, the thermoelectric module has 156.7 mV output voltage, and 88.635 uW output power can be obtained.
In view of the oil reserves are depleting, and greenhouse gas emissions blamed for global warming, the world is increasing emphasis on renewable energy research. Thermoelectric materials have the characteristics of heat, and electrical conversion that can use for the power generation or cooling. The thermoelectric micro power generation component has a small, non-polluting, high life, and easy integration with IC components. The thermoelectric power generation technology has been application of various fields in foreign countries. Because of screen-printing has ability in once printing process to product the functional thick-film, so that is beneficial to achieve rapid product, and mass production. Therefore, this study will use of precision screen printing technology to replace traditional fabrication of thermoelectric devices. Trying to use the SU-8 negative photoresist as an organic adhesive, and add conductive polymer Eeonomer R300F in organic adhesive to improve the conductivity. Producing a thick-film planar thermoelectric power generator that to meet green energy requirement. The study results show that organic adhesive of SU-8 photoresist mixing Eeonomer R300F has been successfully developed, and add Sb2Te3 p-type or n-type Bi2Te3 thermoelectric powder, made into a printable thermoelectric inks. In addition, mix Ethyl-cellulose, Alpha-terpineol, and Sb2Te3 or Bi2Te3 to making Ethyl-cellulose, EC version thermoelectric ink. In different annealing conditions, explore two different types of organic adhesives. The SU-8 version thermoelectric materials in the annealing conditions of 290 oC, and 12 hours, Seebeck coefficient of Sb2Te3 and Bi2Te3 are 24.99 uV/K, and -54.52 uV/K, conductivity are 27.47 S/m, and 16.72 S/m. When the annealing temperature rise to 500 oC, Seebeck coefficient changed to 42.25 uV/K, and -21.45 uV/K, conductivity increased to 60.98 S/m, and 32.05 S/m. EC version thermoelectric materials, in the annealing conditions of 500 oC, and 2 hours, Seebeck coefficient, and conductivity of Sb2Te3, and Bi2Te3 were 106.86 uV/K, -79.17 uV/K; 82.64 x10^2 S/m, and 84.75 x10^2 S/m. Then we use screen printing technology, with the proportion of thermoelectric ink, and annealing parameters, to printing the planar thermoelectric generator. The linewidth of silver electrode is 500 um, and thickness is 41.74 um. The linewidth of thermoelectric structure is designed for 250~1000 um, thickness of SU-8 version p-type, and n-type thermoelectric structures are 28.07 um, and 45.65 um, respectively. The thickness of EC version p-type, and n-type thermoelectric structures are 37.54 um, and 26.01 um, respectively. The results show the design of 500 um in linewidth, 10 mm in length, and 30 pairs in thermocouples have maximum output voltage. When a temperature difference of 40 K, the SU-8 version thermoelectric device with 290 oC, and 12 hr annealing has 26.3 mV output voltages, annealing conditions of 500 oC, and 12 hr can get output voltage of 60.4 mV. The EC version thermoelectric devices with 500 oC, and 2 hr annealing can get 196.6 mV output voltages. Then we use multi-layer stacking process, to complete the SU-8 version 3D multi-layer planar thermoelectric generator, and measure its output characteristics. The measurement results show that thermoelectric modules of 3-layers stacked, about 2.6 times of voltage output, and 5.8 times of power output compared with single. When a temperature difference of 40 K, the thermoelectric module has 156.7 mV output voltage, and 88.635 uW output power can be obtained.
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Keywords
網版印刷, 熱電材料, 導電高分子, 平面微型發電元件, screen-printing, thermoelectric material, conductive polymer, planar micro generator