多元硫族化合物的湿化学制备及光电性能研究
摘要
薄膜太阳能电池以其成本低,质量轻等优势成为目前太阳能电池研究的主流方向,多元化合物薄膜太阳能电池材料成为当今纳米材料领域的研究热点。
本论文主要研究内容归纳如下：
(1)我们采用原位生长法在不锈钢和FTO基底上制备出CZTS和CZTSe两种四元化合物光电薄膜材料。在CZTS的研究工作中,我们研究了反应温度、时间、合金厚度、基底等因素对CZTS薄膜形成的影响。并对各种实验条件下产物做了XRD和Raman测试。我们得到以下结论：FTO基底更加适于CZTS晶体的形成,温度是CZTS晶体形成的主要控制因素。我们对以FTO为基底的CZTS做了FETEM测试,并对其生长机理进行简单推测。以FTO为基底的产物做了TEM和HRTEM测试,测试结果更加定性说明我们的产物,以FTO为基底的产物的UV-Vis测试和光电响应测试证明我们的产物可以进行光学器件的组装。我们在CZTS研究的基础上对CZTSe进行了研究。我们研究了反应温度、时间、基底等因素对CZTSe薄膜形成的影响。并对各种实验条件下产物做了XRD和Raman测试。得出以下结论：由于Se的活性较低,CZTSe的合成条件较CZTS难,反应温度270℃和反应时间24h我们可以得到CZTSe,提高温度和延长反应时间有利于CZTSe的合成。
(2)我们采用湿化学的合成方法,利用NaOH和S粉等简单易得的原料在没有任何表面活性剂的条件下采用简单的合成方法合成出了三维花状结构的NaInS2。我们在NaInS2合成的基础上,采用同样的方法合成出CZTS粉末。在NaInS2的工作中,我们对晶体形成的各种影响因素S粉和NaOH的比例、时间、温度等进行了对比试验,得出产物形成的最佳条件是S:NaOH=1:3,反应温度为160℃,反应时间为12h。我们对其生长机理进行了推测,发现整个过程是一种自组装过程。我们对其光学活性进行测试,该物质在可见光的条件下,一个小时就可以降解罗丹明B,具有很好的光学活性。我们在此基础上合成了四元硫化物粉末CZTS。我们研究了晶体形成的各种影响因素：S粉的用量,S粉和NaOH的比例、时间、温度等,得出产物形成的最佳条件,我们对不同合成条件下的所的产物进行XRD测试进行对比分析。
本论文针对目前制备出的CZTS纳米晶材料的方法中存在基底温度较高、工艺复杂、反应条件苛刻和形貌不理想等缺点。提供一种不需要任何模板,不需要添加任何表面活性剂,不必经过除杂等繁琐的后处理操作,在较低的温度下即可制得高纯度的纳米网状结构的Cu2ZnSnS4四元化合物光电薄膜材料的方法,对于CZTS的工业化生产具有重要意义。
The development of thin film solar cells is to reduce the quality of the battery in order to reduce the cost of the battery. Thin film solar cell solar battery direction research focus with its unique advantages, Multiple compound thin film solar cell materials become a hot research field of nanomaterials today.
The main contents are summarized as follows:
(1) We obtained the CZTS and CZTSe thin film photovoltaic material on stainless steel and FTO substrate by in-situ growth method..In the work about CZTS, we have studied the effects of reaction temperature, time, alloy thickness, substrate and other factors on the formation of CZTS film. The products under various experimental conditions were Characterization by XRD and Raman test. We get the following conclusions:The FTO substrate was more suitable for the formation of CZTS crystal, the temperature is the main controlling factor for the formation of CZTS crystal. The products on FTO substrate were Characterization by FETEM test and the growth mechanism were guessed. The TEM and HRTEM test results are more qualitative description of our product, the FTO substrate UV-Vis product testing and optical response test prove that our products can be the assembly of the optics. We make the research about CZTSe based on the CZTS. We studied the effects of reaction temperature and time for the formation of CZTSe film. We take the XRD and Raman test for the product under various experimental conditions. The conclusions are as follows:we can obtain the CZTSe under the condtion24h and270℃. Increasing temperature and reaction time is a good way for the synthesis of CZTSe.
(2)We obtained a three-dimensional flower-shaped structure NaInS2by using wet chemical synthesis methods. The materials NaOH and S are low-cost. We use the same method to synthesis the CZTS powder. We investigative various factors for the formation of crystals, including the proportion of S and NaOH, time, temperature. The optimum conditions obtained product formation is S:NaOH=1:3, the reaction temperature is160℃, the reaction time for12h. We speculate that the growth mechanism and found that the whole process is a self-assembly process. Its optically active testing, the substance under the conditions of the visible light, an hour can Degradation of RhB, having good optical activity. We were synthesized the quaternary sulfides powder of CZTS based on the NaInS2. We studied the various factors affecting the formation of crystals:an amount of S powder, the ratio of S and NaOH, time, temperature, etc. We obtained the best conditions for product formation.
This thesis focuses on CZTS nanocrystalline materials prepared substrate temperature is higher, the process is complicated and harsh reaction conditions and morphology. Provided which does not require any templates do not need to add any surface active agents, having to go through the tedious post-processing operation in the impurity in a lower temperature to obtain high-purity nano-sheet structure Cu2ZnSnS4quaternary compound photoelectric method of thin film material, for CZTS industrialized production has important significance.
本论文主要研究内容归纳如下：
(1)我们采用原位生长法在不锈钢和FTO基底上制备出CZTS和CZTSe两种四元化合物光电薄膜材料。在CZTS的研究工作中,我们研究了反应温度、时间、合金厚度、基底等因素对CZTS薄膜形成的影响。并对各种实验条件下产物做了XRD和Raman测试。我们得到以下结论：FTO基底更加适于CZTS晶体的形成,温度是CZTS晶体形成的主要控制因素。我们对以FTO为基底的CZTS做了FETEM测试,并对其生长机理进行简单推测。以FTO为基底的产物做了TEM和HRTEM测试,测试结果更加定性说明我们的产物,以FTO为基底的产物的UV-Vis测试和光电响应测试证明我们的产物可以进行光学器件的组装。我们在CZTS研究的基础上对CZTSe进行了研究。我们研究了反应温度、时间、基底等因素对CZTSe薄膜形成的影响。并对各种实验条件下产物做了XRD和Raman测试。得出以下结论：由于Se的活性较低,CZTSe的合成条件较CZTS难,反应温度270℃和反应时间24h我们可以得到CZTSe,提高温度和延长反应时间有利于CZTSe的合成。
(2)我们采用湿化学的合成方法,利用NaOH和S粉等简单易得的原料在没有任何表面活性剂的条件下采用简单的合成方法合成出了三维花状结构的NaInS2。我们在NaInS2合成的基础上,采用同样的方法合成出CZTS粉末。在NaInS2的工作中,我们对晶体形成的各种影响因素S粉和NaOH的比例、时间、温度等进行了对比试验,得出产物形成的最佳条件是S:NaOH=1:3,反应温度为160℃,反应时间为12h。我们对其生长机理进行了推测,发现整个过程是一种自组装过程。我们对其光学活性进行测试,该物质在可见光的条件下,一个小时就可以降解罗丹明B,具有很好的光学活性。我们在此基础上合成了四元硫化物粉末CZTS。我们研究了晶体形成的各种影响因素：S粉的用量,S粉和NaOH的比例、时间、温度等,得出产物形成的最佳条件,我们对不同合成条件下的所的产物进行XRD测试进行对比分析。
本论文针对目前制备出的CZTS纳米晶材料的方法中存在基底温度较高、工艺复杂、反应条件苛刻和形貌不理想等缺点。提供一种不需要任何模板,不需要添加任何表面活性剂,不必经过除杂等繁琐的后处理操作,在较低的温度下即可制得高纯度的纳米网状结构的Cu2ZnSnS4四元化合物光电薄膜材料的方法,对于CZTS的工业化生产具有重要意义。
The development of thin film solar cells is to reduce the quality of the battery in order to reduce the cost of the battery. Thin film solar cell solar battery direction research focus with its unique advantages, Multiple compound thin film solar cell materials become a hot research field of nanomaterials today.
The main contents are summarized as follows:
(1) We obtained the CZTS and CZTSe thin film photovoltaic material on stainless steel and FTO substrate by in-situ growth method..In the work about CZTS, we have studied the effects of reaction temperature, time, alloy thickness, substrate and other factors on the formation of CZTS film. The products under various experimental conditions were Characterization by XRD and Raman test. We get the following conclusions:The FTO substrate was more suitable for the formation of CZTS crystal, the temperature is the main controlling factor for the formation of CZTS crystal. The products on FTO substrate were Characterization by FETEM test and the growth mechanism were guessed. The TEM and HRTEM test results are more qualitative description of our product, the FTO substrate UV-Vis product testing and optical response test prove that our products can be the assembly of the optics. We make the research about CZTSe based on the CZTS. We studied the effects of reaction temperature and time for the formation of CZTSe film. We take the XRD and Raman test for the product under various experimental conditions. The conclusions are as follows:we can obtain the CZTSe under the condtion24h and270℃. Increasing temperature and reaction time is a good way for the synthesis of CZTSe.
(2)We obtained a three-dimensional flower-shaped structure NaInS2by using wet chemical synthesis methods. The materials NaOH and S are low-cost. We use the same method to synthesis the CZTS powder. We investigative various factors for the formation of crystals, including the proportion of S and NaOH, time, temperature. The optimum conditions obtained product formation is S:NaOH=1:3, the reaction temperature is160℃, the reaction time for12h. We speculate that the growth mechanism and found that the whole process is a self-assembly process. Its optically active testing, the substance under the conditions of the visible light, an hour can Degradation of RhB, having good optical activity. We were synthesized the quaternary sulfides powder of CZTS based on the NaInS2. We studied the various factors affecting the formation of crystals:an amount of S powder, the ratio of S and NaOH, time, temperature, etc. We obtained the best conditions for product formation.
This thesis focuses on CZTS nanocrystalline materials prepared substrate temperature is higher, the process is complicated and harsh reaction conditions and morphology. Provided which does not require any templates do not need to add any surface active agents, having to go through the tedious post-processing operation in the impurity in a lower temperature to obtain high-purity nano-sheet structure Cu2ZnSnS4quaternary compound photoelectric method of thin film material, for CZTS industrialized production has important significance.
引文
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[2]Fritts C E.On a new form of selenium photocell [J].American Journal Science,1883,26:245
[3]孟庆巨,刘海波,孟庆辉.半导体器件物理[M].北京：科学出版社,2005,58-59
[4]彭英才,于威.纳米太阳电池技术[M].北京：化学工业出版社,2010,1-12
[5]Chung B C,Virshup G F, Werthen J G High-efficiency one-sun (22.3%at air mass 0; 23.9%at air mass 1.5) monolithic two-junction cascade solar cell grown by metalorganic vapor phase epitaxy [J].Applied Physics Letters,1988,52:1889
[6]Olson J M, Kurtz S R, Friedman D J, et al. A 27.3%efficient Gao.5In0.5P/GaAs tandem solar cell[J]. Applied Physics Letters,1990,56:623
[7]Bertness K A, Kurtz S R, Friedman D J, et al.29.5%-efficient GalnP/GaAs tandem solar cells [J].Applied Physics Letters,1994,65:989
[8]Ermer J. Validation in pharmaceutical analysis. Part I:An integrated approach [J]. Journal of Pharmaceutical and Biomedical Analysis,2001,24,755～767
[9]King R R,Karam N H, Ermer J H, et al. Next-generation, high-efficiency Ⅲ-V multijunction solar cells [C].Proc.28th IEEE Photovoltaic Specialists Conference,2000:998～1001
[10]King R R, Law D C,Edmondson K M, et al. Advances in high-efficiency III-V multijunction solar cells [J]. Applied Physics Letters,2007,90:183516
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