臺灣博碩士論文加值系統

本實驗是以熔煉法熔煉並研究銅鋅錫硒Cu2ZnSnSe4晶體在太陽能電池吸收層材料之特性。其製程是利用銅、鋅、錫、硒四種元素分別以貧銅(Cupper poor)、計量比(Stoichiometric)、富銅(Cupper rich)之三種成分(分別為Cu/Zn+Sn原子百分比=0.6、1.0、1.5)裝入石英管後真空封管，再利用高溫爐加熱，以熔煉法製備四元化合物Cu2ZnSnSe4晶體，熔煉最高溫度為950 ℃持溫5分鐘後爐冷，再將石英管破壞，取出完成的Cu2ZnSnSe4晶體並利用SEM、EDS、XRD、ICP-MS分析。
本實驗試片經XRD分析後貧銅(Cupper poor)、計量比(Stoichiometric)、富銅(Cupper rich)之三種成分都產生鋅黃錫礦結構(Kesterite)特徵峰(112)，而三者的差異在於，富銅(Cupper rich)較貧銅(Cupper poor)及計量比(Stoichiometric)多了(220)及(312)特徵峰，對比SEM分析後發現，富銅(Cupper rich)的晶粒較無明顯之成長，推測(220)及(312)特徵峰可能會影響晶粒成長的幅度，而貧銅(Cupper poor)及計量比(Stoichiometric)晶粒大小於本實驗室先前研究之薄膜製成晶粒大小約3微米至5微米有顯著成長至少10倍以上。

The purpose of this experiment is to study and investigate the characteristics of copper, zinc, tin, selenium, Cu2ZnSnSe4 crystals in solar cell absorber layer materials with melting process. The process is to use the four elements, copper, zinc, tin and selenium and three components, copper poor, stoichiometric and copper rich (Cu / Zn + Sn atomic percentage = 0.6, 1.0, 1.5 respectively) install into the quartz tube before vacuum-sealed, then heated it in a high-temperature furnace, afterward, the quaternary compound Cu2ZnSnSe4 crystal was prepared by the melting process. The maximum melting temperature is 950 ℃ and the temperature was maintained for 5 minutes, hereafter, taking out the finished Cu2ZnSnSe4 crystal and analyze it by SEM, EDS, XRD, ICP-MS.
The analysis of the crystal by XRD, it shows that all of three components of copper poor, stoichiometric and copper rich are produced the characteristic peaks of the zinc tin structure (112). The difference between three components is that Cupper rich has more (220) and (312) characteristic peaks than Cupper poor and Stoichiometric, comparing with SEM analysis, it was founded that there is no significant growth of Cupper rich, so that it was speculated that the (220) and (312) characteristic peaks may affect the size of the grain growth, furthermore, the grains size of copper poor and Stoichiometric, which were made with thin films in previously studied by our laboratory, was about 3 nm to 5 nm has a significant growth of at least 10 times.

摘要......i
Abstract......ii
誌謝......iii
目錄......iv
表目錄......vii
圖目錄......viii
第一章 簡介......1
1.1前言......1
1.2研究動機......2
第二章 文獻探討......3
2.1薄膜太陽能電池的種類......3
2.1.1 非晶矽（Amorphous Silicon；a-Si:H）薄膜太陽能電池......4
2.1.2非晶矽（a-Si）/ 微晶矽（μc-Si）堆疊薄膜太陽能電池......4
2.1.3碲化鎘（CdTe）薄膜太陽能電池......4
2.1.5銅銦硒（CISe）薄膜太陽能電池......6
2.1.6銅銦鎵硒（CIGSe）薄膜太陽能電池......6
2.1.7銅鋅錫硫(CZTS) 和銅鋅錫硒(CZTSe)太陽能電池......7
2.2太陽能電池工作原理......8
2.3 Ⅰ-Ⅲ-Ⅵ2與I2-II-IV-VI4薄膜太陽能電池結構......10
2.4銅鋅錫硫(CZTS)吸收層製程技術......14
2.5銅鋅錫硫(CZTS)吸收層之發展......16
第三章 實驗流程......25
3.1 實驗材料......25
3.1.1製備Cu2ZnSnSe4之化合物......25
3.2實驗流程......25
3.2.1石英管前處理......25
3.2.2 Cu2ZnSnSe4結晶製備......25
3.3製程設備......26
3.3.1高溫爐......26
3.4實驗分析設備......26
3.4.1 X光繞射儀（X-Ray Diffraction,XRD）......26
3.4.2 掃瞄式電子顯微鏡（Scanning Electron Microscope,SEM）......27
3.4.3 能量散佈光譜儀（Energy Dispersive Spectrometer,EDS）......28
3.4.5 感應耦合電漿質譜儀（Inductively Coupled Plasma-MassSpectrometer ; ICP-MS）......28
第四章 實驗結果與討論......35
4.1顯微結構分析......35
4.2銅鋅錫硒成分分析......37
4.3結晶特性分析......38
第五章 結論......44
參考文獻......46
Abstract......50

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