臺灣博碩士論文加值系統

本研究利用共蒸鍍法與接續硫化製程製作銅-鋅-錫-硫(Copper-Zinc-Tin-Sulfur, CZTS)薄膜，在共蒸鍍製程上採用銅、硫化鋅與錫三種材料，硫化製程則以硫粉加熱至550 OC的高溫，探討不同硫化時間(0.5 hr, 1 hr,1.5 hr, 2hr)對薄膜特性影響。
研究藉由SEM與EDS分析薄膜形貌與成份比例，發現隨著硫化時間增加，薄膜較緻密；在XRD與Raman spectrum中得知共蒸鍍薄膜經二小時硫化後，可得CZTS的單一化合物晶相，以光致發光(PL)光譜得知，經兩小時硫化後的CZTS其能隙約為1.2 eV，霍爾量測得知薄膜具有p-type 半導體特性。

In this study, the copper-zinc-tin-sulfuride (CZTS) thin-film was synthesized via co-evaporation and sequent sulfuration process. Copper, zinc and tin were used as the source for co-evaporation process. The sulfur powder was used for sulfuration process under high temperature 550 oC. The influence of sulfuration time (0.5 hr, 1 hr, 1.5 hr, 2 hr) on characteristic of CZTS thin-film was discussed.
The morphology and compositional ratio of the as-fabricated CZTS thin-film was investigated used SEM and EDS, respectively. When the sulfuration time increases, the surface of CZTS thin-film is denser. In the XRD and Raman spectra of post-sulfurated sample, the purity CZTS crystalline phase was found. The band gap of the CZTS with sulfuration time 2 hr2 is around 1.2 eV in the photoluminescence spectra and the CZTS thin-film has the p-type semiconductor behavior in the Hall measurement.

誌　　謝 i
中文摘要 ii
Abstract iii
第一章、緒論 1
1.1前言 1
1.2太陽能電池 2
1.3 銅-鋅-錫-硫材料介紹 6
1.4文獻回顧 8
1.5研究目的 12
第二章、理論 14
2.1半導體能隙分類 14
2.2材料吸收 16
2.3光致發光 17
2.4晶相分析 18
2.5結構分析 20
2.6霍爾效應 22
第三章、實驗流程與架構 25
3.1基板選用與清洗 25
3.2熱蒸鍍系統 26
3.3硫化製程 28
3.4材料特性分析用儀器 30
3.4.1掃描式電子顯微鏡 31
3.4.2能量散佈光譜儀 33
3.4.3 X光繞射分析儀 34
3.4.4拉曼光譜儀 35
3.4.5紫外-可見光穿透光譜儀 37
3.4.6光致發光量測 38
3.4.7 霍爾量側系統 39
第四章、結果與討論 41
4.1 SEM圖分析 41
4.2成份比例分析 45
4.3 X光繞射分析 47
4.4拉曼光譜分析 49
4.5光學特性分析 52
4.6 PL光譜分析 54
4.7電性分析 56
第五章、結論 58
參考文獻 59

[1]顧鴻壽, “太陽能電池元件導論,” 全威圖書有限公司, 台北市 (2008)
[2]邱秋燕, 廖曰淳, 郭豐綱, “低成本銅銦鎵硒(CIGS)太陽能電池技術發展,”工業材料, 276, 58-68 (2009)
[3] K.Ito, T. Nakazawa, “Electrical and optical properties of stannite-type quaternary semiconductor thin films,” Jpn. J. Appl. Phys. 27, 2094 (1988)
[4] Hironori Katagiri, et al., “Preparation and evaluation of Cu2ZnSnS4 thin films by sulruzation of E-B evaporated precursors,” Sol. Energy Mater. Sol. Cells, 49, 407-414 (1997)
[5] Hironori Katagiri, et al., “Development of thin &;quot;lm solar cell based on Cu2ZnSnS4 thin films,” Sol. Energy Mater. Sol. Cells, 65, 141-148 (2001)
[6] Jae-Seung Seol, et al., “Electrical and optical properties of Cu2ZnSnS4 thin films prepared by rf magnetron sputtering process,” Sol. Energy Mater. Sol. Cells, 75, 155-165 (2003)
[7] Tooru Tanaka, et al., “Preparation of Cu2ZnSnS4 thin films by hybrid sputtering,” J. Phys. Chem. Solids, 66, 1978-1981 (2005)
[8] Katsuhiko MORIYA, Kunihiko TANAKA, Hisao UCHIKI, ” Fabrication of Cu2ZnSnS4 Thin-Film Solar Cell Prepared by Pulsed Laser Deposition,” Jpn. J. Appl. Phys. Vol. 46, 5780-5781 (2007)
[9] Hironori Katagiri, et al., “Cu2ZnSnS4 -type thin film solar cells using abundant materials,” Thin Solid Films, 515, 5997-5999 (2007)
[10] Supratik Guha, et al., “Thin film solar cell with 8.4% power conversion efficiency using an earth-abundant Cu2ZnSnS4 absorber,” Prog. Photovolt: Res. Appl. 21, 72-76 (2013)
[11]P.A. Fernandes, P.M.P. Salomé, A.F. da Cunha, “Growth and Raman scattering characterization of Cu2ZnSnS4 thin films,” Thin Solid Films, 517, 2519-2523 (2009)
[12] Bjo¨ rn-Arvid Schubert, et al., “Cu2ZnSnS4 thin film solar cells by fast coevaporation,” Prog. Photovolt: Res. Appl. 19, 93-96 (2011)
[13] S.M. Pawar, et al., “Effect of laser incident energy on the structural, morphological and optical properties of Cu2ZnSnS4 (CZTS) thin films,” Curr. Appl. Phys. 10, 565-569 (2010)
[14] Hironori Katagiri, et al., “Characterization of Cu2ZnSnS4 Thin Films Prepared by Vapor Phase Sulfurization,” Jpn. J. Appl. Phys. Vol. 40, 500-504 (2001)
[15] Kunihiko Tanaka, et al., “Cu2ZnSnS4 thin film solar cells prepared by non-vacuum processing ,” Sol. Energy Mater. Sol. Cells, 93, 583-587 (2009)
[16] M.S. Aida, et al., “Cu2ZnSnS4 thin films deposition by ultrasonic spray pyrolysis,” J. Alloys Compd. 542, 22-27 (2013)
[17] Fangyang Liu, et al., “Preparation of Cu2ZnSnS4 thin films by sulfurizing stacked precursor thin films via successive ionic layer adsorption and reaction method,” Appl. Surf. Sci. 258, 7678-7682 (2012)
[18] Li Maio-maio, et al., “First-principles of calculation of electronic structure and optical properties of Cu2ZnSnS4/Cu2ZnSnSe4,” Chin. J. Nonfer. Metals, Vol. 22, 1413-1420 (2012)
[19] Andrew Fairbrother, et al., “On the formation mechanisms of Zn-rich Cu2ZnSnS4 films prepared by sulfurization of metallic stacks,” Sol. Energy Mater. Sol. Cells, 112, 97-105 (2013)