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  本文關(guān)鍵詞：銅鋅錫硫薄膜太陽電池材料和器件的制備與性質(zhì)研究　出處：《華東師范大學(xué)》2014年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 溶膠-凝膠法 薄膜太陽能電池 Cu_2ZnSnS_4 Cu_2ZnSn(S Se)_4 硫化 硒化 預(yù)退火 后退火

【摘要】：Cu2ZnSnS4(CZTS)系太陽能薄膜電池是在Cu(In,Ga)Se2(CIGS)薄膜太陽電池基礎(chǔ)上發(fā)展起來的新型化合物半導(dǎo)體光伏器件。CZTS系半導(dǎo)體材料,由于其光電性質(zhì)與CIGS類似,并且所用元素在地殼中的含量均較豐富,避免了像CIGS所用的稀有金屬元素In、Ga,因而可作為一種低成本、高效率太陽薄膜電池的吸收層材料,也因此吸引了全球科技工作者的興趣。目前已開發(fā)了基于真空和非真空的多種方法制備CZTS薄膜和電池,并取得了較好的電池效率。針對目前各種制備方法存在的問題,本課題提出一種低成本、綠色環(huán)保的溶膠-凝膠法制備CZTS和Cu2ZnSn(S,Se)4(CZTSSe)薄膜及電池器件,論文所得主要創(chuàng)新性結(jié)果如下： 1.選用無毒或低毒有機物乙二醇為溶劑,以金屬有機鹽為原料,采用溶膠-凝膠非硫化法(后退火過程中不使用硫源)制備CZTS薄膜。制備的CZTS薄膜表面平整、致密、沒有孔洞；不過,薄膜均貧硫,但通過調(diào)節(jié)退火工藝可以提高薄膜中硫組分的含量到符合化學(xué)計量比。 選用乙二醇為溶劑,采用金屬有機鹽制備CZTS薄膜,制備過程中避免硫化(簡化工藝、降低對設(shè)備的要求以及減少對環(huán)境的污染)；有機鹽制備的CZTS薄膜較致密、表面沒有孔洞；通過預(yù)退火對CZTS前驅(qū)膜組分影響的分析,尋找到最佳的預(yù)退火溫度250℃和預(yù)退火時間50s；通過后退火對CZTS薄膜組分影響的分析,尋找到最佳的后退火溫度530℃和后退火時間30Os; CZTS前驅(qū)體溶膠中S/Cu的摩爾比在4.0左右時,可以制備硫組分符合化學(xué)計量比的CZTS薄膜,同時制備的CZTS薄膜表面平整、致密。 2.溶膠-凝膠后硫化法制備的CZTS薄膜電池效率最高達4.28%；同時探索了非硫化法制備CZTS薄膜電池,其效率為2.1%,說明其方法是可行的,但效率低,需優(yōu)化制備工藝。 制備并優(yōu)化了電池其它各層薄膜,采用凝膠-凝膠后硫化法制備CZTS薄膜電池,吸收層CZTS在570℃C硫化20min、CdS薄膜厚度～50nm時制備的器件效率達到最大值,為4.28%；同時探索了凝膠-凝膠非硫化法制備CZTS薄膜電池,其電池效率為2.1%,說明這樣的工藝路線是可行的,只是還有很多需要優(yōu)化改進的地方。 3.溶膠-凝膠后硒化法可以實現(xiàn)制備CZTSSe薄膜,此方法較傳統(tǒng)工藝節(jié)省了硫化過程；在制備CZTSSe薄膜的基礎(chǔ)上,制得CZTSSe電池,其轉(zhuǎn)換效率為2.92%。 通過CZTS溶膠制備CZTS前驅(qū)體薄膜,然后經(jīng)過預(yù)退火,最后在硒化爐中硒化,可以制備出CZTSSe薄膜。后退火過程中沒用硫化,簡化了制備工藝；隨著硒化時間的延長及用硒量的增加,x=Se/(S+Se)從0增加到0.91,薄膜的帶隙呈現(xiàn)減小趨勢,光學(xué)帶隙(Eg)從1.51減小到1.14eV；制備CZTSSe電池器件的條件較苛刻,尤其是對硒化氣壓的要求比較高,通過實驗得到較好的硒化氣壓條件：硒化前,硒化爐的石英管內(nèi)充N2、并使氣壓達到200Torr,然后關(guān)閉石英管兩端的氣閥、進行硒化；本課題制備的CZTSSe電池器件效率為2.92%,說明這樣的工藝路線是可行的,但效率比較低,因此還有很多需要優(yōu)化改進的地方。
[Abstract]:Cu2ZnSnS4 (CZTS), thin film solar cell is in Cu (In, Ga) Se2 (CIGS) model of compound semiconductor photovoltaic devices.CZTS semiconductor materials based on the development of thin film solar cells, because of its photoelectric properties similar to CIGS, and the content of elements in the crust are relatively abundant, avoided a rare the metal elements used by CIGS In Ga, which can be used as a low cost, high efficiency absorption layer of film solar battery, has also attracted interest in the field of global science and technology. It has developed a legal vacuum and non vacuum deposition of CZTS films and a variety of battery based on, and achieved good efficiency of the battery. At present, various preparation methods of the existing problems, this paper puts forward a kind of low cost, green CZTS prepared by sol-gel method and Cu2ZnSn (S, Se) 4 (CZTSSe) thin film and battery device, the main innovative results are as follows: :
1. selection of non-toxic or low toxic organic compounds with ethylene glycol as solvent, organic metal salts as raw materials by sol gel method (do not use non sulfide sulfur source annealing process) for the preparation of the CZTS film. CZTS film surface roughness, the preparation of dense, no holes; however, films are sulfur deficient, but improved stoichiometric ratio. Content of sulfur components in the films can be adjusted by the annealing process
Using ethylene glycol as solvent, the CZTS thin films prepared by metal organic salt curing system, avoid the preparation process (simplify process and reduce the requirement on equipment and reduce the pollution of the environment); CZTS thin films prepared by organic salt is dense, no voids; through the analysis of the impact of pre annealing on CZTS precursor film components and find the pre annealing temperature of 250 DEG C and pre annealing time optimal 50s; through the analysis after annealing on CZTS thin films. The influence, to find the best annealing temperature of 530 DEG C after the annealing time and the molar ratio of S/Cu 30Os; CZTS precursor sol in 4, sulfur component can be prepared in accordance with CZTS the film stoichiometry, and CZTS thin films were prepared with smooth surface and compact.
2., the efficiency of CZTS thin film cell prepared by sol-gel vulcanization is up to 4.28%. Meanwhile, the CZTS thin film battery prepared by non sulfurization method is explored, and its efficiency is 2.1%. It shows that the method is feasible, but the efficiency is low, so it is necessary to optimize the preparation process.
Preparation and optimization of the battery the other layers of films by sol-gel after vulcanization of CZTS films prepared by cell absorption layer CZTS at 570 DEG C sulfide 20min, CdS thin film thickness to 50nm preparation device efficiency reaches the maximum value, 4.28%; at the same time to explore the sol-gel method to prepare CZTS films of nonsulfide the battery, the battery efficiency is 2.1%, indicating that the process is feasible, but there are many places need to be improved.
3., after sol-gel selenization, CZTSSe thin films can be prepared. This method saves sulphide process than traditional process. Based on the preparation of CZTSSe thin films, CZTSSe battery is obtained, and its conversion efficiency is 2.92%..
Preparation of CZTS precursor film by CZTS sol, and then through the pre annealing furnace, finally in selenium selenium, can be prepared CZTSSe films. In the process of annealing without vulcanization, simplifies the preparation process; with selenium extension and by increasing the amount of Se time, x=Se/ (S+Se) from 0 increased to 0.91, the band gap of the films decreases, the optical band gap (Eg) decreases from 1.51 to 1.14eV; preparation of CZTSSe battery device condition is more severe, especially for selenium pressure requirements are relatively high, the better selenium pressure conditions: selenium, selenium quartz furnace tube filling and N2, so that the pressure is up to 200Torr, and then close the valve at both ends of the quartz tube, by selenium; the CZTSSe battery device preparation efficiency is 2.92%, indicating that the process is feasible, but the efficiency is relatively low, so there are a lot of places need to be improved.

【學(xué)位授予單位】：華東師范大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2014
【分類號】：TM914.4

【參考文獻】

相關(guān)期刊論文 前6條

1 鄔恒前;;金屬氧化物納米顆粒溶膠—凝膠合成概述[J];廣東化工;2011年01期

2 黎立桂;魯廣昊;楊小牛;周恩樂;;聚合物太陽能電池研究進展[J];科學(xué)通報;2006年21期

3 張松;肖可嫻;;紫外/可見/近紅外分光光度計測量玻璃可見光透射比的不確定度分析與表示[J];深圳土木與建筑;2010年01期

4 孫云,王俊清,杜兆峰,舒保健,于剛,溫國忠,周禎華,孫健,李長健,張麗珠;CIS和CIGS薄膜太陽電池的研究[J];太陽能學(xué)報;2001年02期

5 李鳳巖;李長健;熊紹珍;;薄膜太陽電池系列講座(8) CIGS薄膜太陽電池(下)[J];太陽能;2012年01期

6 鄭春滿;郭宇杰;謝凱;韋永滔;;薄膜太陽能電池光電轉(zhuǎn)換材料研究進展[J];宇航材料工藝;2010年04期

，

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