摘要
本篇嘗試利用不同的製程方式增強熱電元件的熱電轉換效率。首先研究奈米靜電紡絲作為基板後，於絲膜表面成長銀奈米顆粒的熱電元件。另外我們也嘗試以奈米孔洞材料(陽極氧化鋁)作為模板，於基板上製作出具有奈米結構之熱電元件。推測熱電元件的表面粗糙度為影響熱電轉換效率的主要因素之一，因此我們也特別使用AFM來量測其表面粗糙度性質。
由表面成長銀顆粒之靜電紡絲熱電元件的初步研究成果分為3項，以金屬平板製作之奈米紡絲熱電元件的熱電壓值最高。若銀顆粒在靜電紡絲表面的覆蓋程度越好，會增加元件的導電率，進而使得熱電壓值越高。但導電率過高的熱電元件，卻會增加元件的熱傳導性進而降低熱電元件的效能；以金屬滾筒製作之靜電紡絲熱電元件其銀顆粒成長具有垂直紡絲方向之特性，量測不同紡絲方向熱電壓差大，隨銀顆粒成長時間增加，使銀顆粒成長方向消失，熱電壓差減少；以鼠輪狀滾筒製作之奈米紡絲熱電元件，可製作出具有排列方向之紡絲，量測時其銀顆粒在紡絲上沿順絲方向成長，使垂直紡絲方向量測之熱電壓較高，但若量測含有竿子形成之紡絲，會因竿子形成之紡絲含有較多之銀顆粒，使量測之熱電壓下降。
在以奈米孔洞製作熱電元件的研究方面，我們使用兩種不同材料製備元件，由於不同材料對於奈米孔洞附著的特性不同，使得熱電元件的表面粗糙度隨著不同的孔徑大小、材料而有所不同，進而影響元件的熱電壓值。


關鍵字: 熱電效應、電紡絲、奈米孔洞

Abstract
In this thesis, we try to use different ways to enhance the thermoelectric conversion efficient of the thermoelectric devices. Firstly, we use the electrospinning of nanofibers as a substrate, and growth the silver particles in the nanofiber membrane. In addition, we also try to use nano-hole materials (anodic aluminum oxide) as a template, and use this substrate to fabricate the nanostructure thermoelectric devices. we speculated that the surface roughness is one of the main factors for thermoelectric conversion efficiency of the thermoelectric devices, so we use AFM to measure the properties of surface roughness.
The silver particles grown on the surface of the electrostatic spinning into three thermoelectric elements is divided into three devices. When we use metallic plate to fabricate the nanofiber thermoelectric devices, its thermal voltage are up to maximum. If the degree of coverage of the silver particles in the electrostatic spinning surface as good as possible, it will increase the conductivity of the devices and make the higher the thermal voltage. However, Too higher conductivity of the thermoelectric devices will increase the thermal conductivity of the devices and thus reduce the effectiveness of the thermoelectric element; When we use metallic cylinder to fabricate the nanofiber thermoelectric devices, the growth of its silver particles have a perpendicular direction of the spinning direction. It has a larger difference in thermal voltage in different directions of measurement, as the increasing of the time of the silver particles growth, it will make this direction of the silver particles growth disappear. And then the thermal voltage reduce; When we use metallic wheel to fabricate the nanofiber thermoelectric devices, it can fabricate the aligned fibers. The growth of its silver particles has a parallel direction of the spinning direction. When we measure the perpendicular direction of spinning direction of the devices, it has the higher thermal voltage than parallel direction. But if we measure the devices which include the fibers formed in the pole, this part of fibers will grow more silver particles. And then the thermal voltage decrease.
In the research of the thermoelectric devices of nano-holes, we use two kind of material to prepare devices. Due to the different materials adhesion characteristics in the nano holes, the surface roughness of the thermoelectric devices is varied by the different hole size and materials.













Key words: Thermoelectric effect, electrospinning, nano-hole

目錄
摘要 i
Abstract ii
目錄 iv
圖目錄 vii
表目錄 xi
第一章 簡介 1
1. 1研究目的 1
1. 2研究動機 1
第二章 原理與文獻回顧 3
2. 1熱電效應 3
2.1.1 Seebeck效應 3
2.1.2 Peltier效應 5
2.1.3 Thomson效應 6
2.1.4熱電材料之熱電優質 7
2-2 電紡絲原理簡介 9
2-1-1電紡絲材料在能源材料上的應用 15
2-2-2 PVA性質 18
2-2-3 PVA電紡絲參數 20
2-2-4PVA反應機制與銀顆粒的成長 24
2.3 文獻回顧 26
2.3.1 塊材與奈米尺度之熱電材料 26
2.3.2 奈米結構熱電元件 27
第三章 製程與量測 32
3.1 樣品製程與化學藥品 32
3.1.1 奈米紡絲熱電元件製程 32
3.1.2 奈米孔洞薄膜熱電元件製程 34
3.2 樣品熱電壓量測 35
3.2.1 奈米紡絲熱電元件之熱電壓量測 35
3.2.2 奈米孔洞薄膜熱電元件之熱電壓量測 37
3.3 樣品粗糙度量測 38
第四章 結果與討論 40
4.1 奈米紡絲熱電元件量測 40
4.1.1 以金屬平板製作奈米紡絲熱電元件之量測 40
4.1.2 以金屬滾筒製作奈米紡絲熱電元件之量測 43
4.1.3 以鼠輪狀收集器製作奈米紡絲熱電元件之量測 45
4.2 奈米孔洞薄膜熱電元件量測 49
第五章 結論以及未來工作 53
5.1 奈米紡絲熱電元件 53
5.2 奈米孔洞薄膜熱電元件 53
參考文獻.……………………………………………………………….55

 
圖目錄
第二章
圖2- 1 Seebeck效應示圖。…………………………………………….4
圖2- 2溫差導致載子擴散之示意圖。………………………………....4
圖2- 3 Peltier效應示圖。…………...………………………………….6
圖2- 4熱電效應之應用。…………...………………………………….6
圖2- 5載子濃度與自由電子移動以及晶格震動對熱傳導貢獻。……9
圖2- 6材料Bi2Te3之各種熱電性質之相互關係。…………..………....9
圖2-7泰勒錐形成在針尖端位置。……………………………….......10
圖2-8射流產生彎曲甩動現象。……………………….......................12
圖2-9三種不同類型的不穩定使黏彈性射流分裂…….......................12
圖2-10電紡絲黏彈性高分子溶液過程。….........................................13
圖2-11 PVP與NiO 電紡絲SEM圖。….............................................15
圖2-12 NiO與NiO-SWCNTs纖維放電能力比較。…...........................16
圖2-13 PVP/TiO2電紡絲之SEM圖。…...............................................16
圖2-14在AM1.5照度下的染料敏化電池電流密度與電壓圖。...........17
圖2-15 PVA 分子式。….........................................................................18
圖2-16 以金屬滾筒製作TiO2電紡絲奈米纖維。……………………..19
圖2-17 水解PVAc成PVA反應式。......................................................19 
圖2-18 PVA分子中產生氫鍵鍵結。.....................................................19
圖2-19 溫度對不同水解度PVA之溶解度關係圖。..............................20
圖2-20 不同分子量相同濃度下造成絲形貌改變。.............................21
圖2-21固定分子量濃度提升造成絲形貌改變。..................................21
圖2-22 [η]C值皆為7.5情況下電紡絲之結構形貌相似。................22
圖2-23添加不同酒精濃度對於絲形貌跟線徑影響。……………........23
圖2-24 改變紡絲時之流速對於絲形貌之影響。.................................23
圖2-25 戊二醛化學分子式。..................................................................26
圖2-26 PVA反應反應與銀顆粒成長反應式。.....................................26
圖2-27目前最新熱電材料之熱電優質分布圖。.................................27
圖2-28鍍有Bi0.4Te3Sb1.6薄膜的陽極氧化鋁孔洞。...........................29
圖2-29 PVA與Bi-Ba-Co氧化物的奈米纖維陶瓷材料SEM圖。.........29
圖2-30橫向成長矽奈米線陣列熱電元件。..........................................29
圖2-31 PVA與Bi-Ba-Co氧化物的奈米纖維陶瓷材料SEM圖。……..30
圖2-32具有規律孔洞的矽薄膜之SEM圖與其熱傳導係數量測圖...30
圖2-33 PVA與Bi-Ba-Co氧化物的奈米纖維陶瓷材料熱電量測。…...31

第三章
圖3- 1以金屬平板為收集器之靜電紡絲機台示意圖。........................33圖3-2 以金屬滾筒為收集器之靜電紡絲機台示意圖。......................34
圖3-3鼠輪狀收集器之靜電紡絲機台示意圖。.....................................34
圖3-4靜電紡絲於表面成長銀顆粒後之樣品。....................................34
圖3-5奈米孔洞陣列熱電元件完成圖。..................................................39
圖3-6奈米紡絲熱電元件實驗架設。...................................................40
圖3-7以金屬滾筒製作出之導電奈米紡絲量測示意圖。.....................40
圖3-8 以鼠輪狀收集器製作出之導電奈米紡絲量測示意圖。………37
圖3- 9奈米孔洞薄膜熱電元件實驗架設。…………………………….38
圖3-10 平均粗糙度與方均根粗糙度。……………………………….39
圖3-11 AFM掃描試片示意圖。………………..…………………...39


第四章
圖4-1以金屬平板製作奈米紡絲熱電元件之熱電與粗糙度量測圖。41
圖4-2 以金屬平板製作奈米紡絲熱電元件之SEM圖。…………….42
圖4- 3以金屬平板製作奈米紡絲熱電元件之AFM圖。……………..42
圖4-4以金屬滾筒製作之奈米紡絲之SEM圖。……………………….43
圖4-5以金屬滾筒製作之奈米紡絲熱電元件之熱電壓量測圖。……45
圖4-6以金屬滾筒製作之奈米紡絲熱電元件之SEM圖。…………..45
圖4-7 以鼠輪狀收集器製作奈米紡絲之SEM圖。…………………..46
圖4-8 以鼠輪狀收集器製作之奈米紡絲熱電元件，取竿子與竿子部分之熱電壓量測圖。……………………………………………………46
圖4-9 以鼠輪狀收集器製作奈米紡絲，取竿子與竿子部分成長銀顆粒後之SEM圖。……………………………………….…………………47
圖4-10以鼠輪狀收集器製作之奈米紡絲熱電元件，保留有位在一根竿子上形成的紡絲部分之熱電量測圖。………………………………48
圖4-11 以鼠輪狀收集器製作之奈米紡絲，保留有位在一根竿子上形成的紡絲部分，成長銀顆粒後之SEM圖。………………………….48
圖4- 12 奈米孔洞鍍金薄膜100 nm之熱電與粗糙度量測圖。…….50
圖4- 13奈米孔洞鍍金薄膜100 nm之SEM圖。………………………50
圖4- 14奈米孔洞鍍金薄膜100 nm之AFM圖。……………………51
圖4- 15 奈米孔洞鍍銀薄膜100 nm之熱電與粗糙度量測圖。……51
圖4- 16奈米孔洞鍍銀薄膜100 nm之SEM圖。………………………52
圖4- 17奈米孔洞鍍銀薄膜100 nm之AFM圖。…………………………52























表目錄
表2-1參數影響絲形貌...........................................................................14
 

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