溶胶-凝胶法制备铜锌锡硫材料的研究进展

四元硫化物铜锌锡硫(CZTS)是一种新型薄膜太阳电池材料,具有锌黄锡矿结构,呈p型导电性,带隙约为1.5eV,光学吸收系数高于10~4cm~(-1),这些特性与太阳光谱相匹配。基于上述原因,CZTS薄膜是一种有望能低成本、可规模化开发利用的新型薄膜太阳电池材料。简要阐述了CZTS性质及其薄膜太阳能电池的器件结构,详细介绍了溶胶-凝胶方法制备CZTS薄膜及其相应器件效率的研究进展。最后,总结了此方法制备CZTS薄膜及其相关电池性能难以突破的关键技术问题,并提出了有效的改进措施,对CZTS薄膜太阳电池未来的研究进行了展望。     

阳离子部分取代Cu2ZnSnS4的研究进展

P型半导体Cu_2ZnSnS_4(CZTS)由于具有最佳的直接带隙(1.0~1.5eV)、高的光吸收系数(超过104 cm~(-1))以及丰富、无毒的元素组成,使其成为商业化低成本太阳能电池最有希望的候选材料之一。然而,材料本身的一些缺陷制约了CZTS薄膜太阳能电池效率的提高。为了提高CZTS薄膜太阳能电池的效率,研究者们使用其他阳离子部分取代Cu、Zn或Sn来改善CZTS的缺陷。从CZTS的3种不同取代位置出发,综述了近年来各种阳离子部分取代CZTS的研究进展,同时对阳离子部分取代CZTS材料的发展前景进行了展望。     

Mg掺杂Cu2ZnSnS4的第一性原理研究

采用基于密度泛函理论(DFT)的第一性原理对光伏材料Cu₂ZnSnS₄ (CZTS)掺Mg进行了研究。通过建立Mg取代CZTS中Cu、Zn和Sn的点缺陷结构, 计算Mg掺杂缺陷的生成能及对CZTS电子结构的影响。计算结果表明掺Mg不引入深能级缺陷也不改变材料的禁带宽度; 并且富Sn条件更有利于Mg取代Cu形成施主缺陷, 使p型转变为n型。本研究可为CZTS太阳能电池掺Mg的应用研究提供理论基础。     

磁控溅射制备Cu2ZnSnS4薄膜的研究进展

Cu_2ZnSnS_4(CZTS)薄膜由于其合适的禁带宽度、高的光吸收系数以及组分无毒、储量丰富等特性,被视为薄膜太阳能电池最佳的吸收层材料之一。磁控溅射是制备CZTS薄膜的主要方法之一,因为其制备过程相对简单且可以产业化,一直是太阳能电池领域的研究热点。从磁控溅射制备CZTS薄膜的3种路径出发,综述了近年来各种路径在制备CZTS薄膜方面的研究进展,比较了3种路径的优缺点,同时对磁控溅射制备CZTS薄膜的发展前景进行了展望。     

电沉积法制备铜锌锡硫薄膜太阳能电池吸收层的研究进展

直接禁带半导体材料铜锌锡硫(CZTS)四元硫化物是近年来研究较多的具有锌黄锡矿结构的化合物半导体,由于其光吸收系数较高,禁带宽度适中,是太阳能电池理想的候选材料,使其在薄膜太阳能电池中迅速崛起。由于目前报道的最高转换效率距离其理论转换效率还存在相当差距,因此,研究CZTS(Se)四元硫(硒)化物半导体仍然是当前的研究热点之一。简单介绍了CZTS薄膜太阳能电池的结构组成,并详细介绍了3种主要制备CZTS薄膜的电沉积方法,即分步沉积Cu/Sn/Zn金属层、连续沉积Cu-Zn-Sn金属层、一步沉积Cu-Zn-Sn-S(Se)制备CZTS薄膜太阳能电池吸收层的电化学技术及相应器件,对其研究进展进行了综述,指出了相应方法存在的问题。还将3种电沉积方法进行了分析比较,提出了优化方法,展望了未来的发展趋势。     

溶胶-凝胶法制备铜锌锡硫薄膜及其太阳能电池的研究进展

原料丰富价廉的铜锌锡硫(Cu2ZnSnS4,CZTS)材料与非真空、低成本绿色溶胶-凝胶法相结合在产业化制造高性价比CZTS薄膜太阳能电池方面的应用引人关注。为了了解未来发展方向,综述了溶胶-凝胶法制备CZTS薄膜与器件的研究进展,讨论了不同溶胶-凝胶工艺途径、不同溶剂、硫化等对CZTS薄膜制备与器件特性的影响,分析了Na掺杂及硫化退火对CZTS薄膜的作用,并结合绿色制造的要求探讨了其发展趋势。     

CZTS薄膜太阳能电池无镉缓冲层材料的研究进展

Cu(In,Ga) Se_2(CIGS)薄膜太阳能电池是单结转换效率最高(～22. 6%)的光伏器件,但In、Ga是稀缺元素,从而限制了CIGS电池的产业化。新型材料Cu_2ZnSnS_4(CZTS)是结构与光电性能均与CIGS十分相似的直接带隙半导体材料,它在CIGS器件结构中可替代CIGS吸收层,并得到新型CZTS薄膜太阳能电池。与CIGS相反,CZTS的原料丰富、无毒。大量研究表明,CZTS薄膜太阳能电池具有较高的转换效率和良好的稳定性,且可采用低成本、非真空的溶液法薄膜沉积技术来制造,因此CZTS器件是一种低成本、环境友好、极具产业化前景的薄膜太阳能电池。CZTS器件具有与CIGS器件一样的堆层结构{SLG/Mo/CZTS/CdS/i-ZnO/n-ZnO},目前转换效率最高(～12. 6%)的CZTS器件仍沿用CIGS器件的CdS缓冲层,因而大规模生产与应用中存在高毒重金属镉污染的危险,寻找能替代CdS的无镉缓冲层材料来消除潜在的镉污染问题十分必要。此外,与高效率的{CIGS/CdS}器件相比,{CZTS/CdS}器件界面的能带匹配可能并不是最优,CZTS器件的转换效率还远不如CIGS器件,因此需要寻找新的无镉缓冲层材料。在确定新缓冲层材料时,必须考虑{CZTS/新缓冲层}界面的能级对齐效应。CIGS和CZTS器件的缓冲层新材料基本上可归纳为3种半导体材料:硫化物、硫氧化物、氧化物。这些材料的薄膜均可用化学浴(CBD)法等多种方法来制备。材料选取很大程度上取决于其与CZTS或CIGS吸收层接触所形成界面上的导带带阶情况,因为导带带阶对器件性能参数有很大的影响。大的正导带带阶(尖刺状带阶)对少子(电子)收集存在一个势垒而降低短路电流密度J_(sc);相反,负导带带阶(断崖状带阶)导致缓冲层与吸收层界面上的复合增大而降低了开路电压V_(oc);理想情况是器件有一个小(0～0. 4 eV)的正导带带阶(尖刺状带阶),正如在使用CdS缓冲层的CIGSSe器件中所发现的那样。为了研发低成本、环境友好的CZTS电池器件的新型缓冲层材料,本文综述了CZTS和CIGS器件的无镉缓冲层材料的研究进展,讨论了无镉缓冲层材料的选用条件,以及多种硫化物(如ZnS和In_2S_3)、硫氧化物(如Zn(S,O)和In(S,O,OH))、氧化物(如ZnO、TiO_2、Zn_(1-x)Mg_xO_y和Zn_(1-x)Sn_xO_y等)薄膜作为CZTS缓冲层的性能特点(特别是它们的导带带阶)以及存在的问题,探讨了其发展方向。对于含硒CZTSSe器件,In2S3、Zn(S,O)是良好的无镉缓冲层材料,而对于更环保、低成本的全硫CZTS器件,Zn_(1-x)Mg_xO_y和Zn_(1-x)Sn_xO_y可提供良好性能的缓冲层。     

新型铜硫系薄膜太阳能电池材料制备的研究进展

薄膜太阳能电池提供了低成本、大面积的无碳发电应用前景,迅猛发展的纳米科技为高转换效率薄膜太阳能电池的低成本制造提供了新途径。新型铜硫系半导体Cu_2ZnSnS_4(CZTS)薄膜材料具有禁带宽度与太阳辐射匹配性好、光吸收系数大、元素丰度大、价格便宜、无毒等优点,因此将成为最具发展前景的薄膜太阳能电池材料。讨论与分析了CZTS薄膜和纳米晶材料的制备及由这些材料制备绿色、低成本、高效率新型太阳能电池的研究进展。     

溶胶-凝胶法制备CZTS太阳能电池吸收层薄膜

Cu2ZnSnS4(CZTS)具有与CIGS相似的结构,其直接带隙宽度为1.45~1.6eV,吸收系数则高于104cm-1,构成元素丰富且无毒,因此其作为一种P型半导体材料,被认为是最有希望替代CIGS的材料之一。以去离子水和无水乙醇作为溶剂,采用溶胶-凝胶法(Sol-gel)在玻璃基底上制得了CZTS薄膜,利用X射线衍射仪、拉曼光谱仪、扫描电镜和紫外可见光谱对样品进行了表征,并讨论了烘焙温度对薄膜结构和形貌的影响。结果表明当热处理温度达到200℃时得到了黑色的CZTS薄膜,其禁带宽度为1.45eV,经过EDS分析制得的薄膜的元素比Cu∶Zn∶Sn∶S接近2∶1∶1∶4,这与CZTS的理论值是一致的,但是薄膜中存在少量的氯元素,同时适当降低前期的烘焙温度可以提高薄膜的致密性。     

Cu2ZnSnS4纳米颗粒及其薄膜的制备与表征

采用热注入法,在油胺(OLA)中合成出Cu2ZnSnS4(CZTS)纳米颗粒,并在玻璃衬底上制备了薄膜,研究了不同合成温度对纳米颗粒生成的影响.通过X射线衍射仪、拉曼光谱仪、透射电子显微镜、扫描电子显微镜、紫外可见分光光度计对所得纳米晶材料的结构与成分、颗粒大小与形貌、光吸收谱进行了测试分析.研究结果表明:采用热注入法的最佳合成温度在260℃左右,该温度下生成的多晶CZTS纳米颗粒尺寸约10 nm,分散性良好,光学禁带宽度约1.5 eV.     

Low-cost fabrication of Cu2ZnSnS4 thin films for solar cell absorber layers

A new and low-cost chemical method is used to fabricate Cu₂ZnSnS₄ (CZTS) thin films by annealing Cu–Sn metallic inks with spin-coating ZnO layers under H₂S. The obtained pure phase and smooth CZTS thin films are characterized by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). Further, the CZTS thin films are grown on n-type Si substrates to form proto-type CZTS/Si heterojunction solar cells that have photovoltaic properties, indicating the promising application of CZTS as the absorber layers in Si-based heterojunction solar cells.     

Cu2ZnSnS4 films by paste coating and their optoelectronic properties

Cu₂ZnSnS₄ (CZTS) thin films were prepared by a paste coating method as the absorb layer of solar cells. This method is more eco-friendly using ethanol as solvent and more convenient than traditional sol–gel method. The effects of sulfurization temperature on properties of thin film were studied. The results of X-ray diffraction and Raman spectroscopy showed the formation of kesterite structure of CZTS films. The scanning electron microscopy images revealed that CZTS thin film obtained at 550 °C were compact and uniform. The optical band gap of the CZTS film was about 1.5 eV, and the CZTS film had an obvious optoelectronic response. Moreover, CZTS solar cell was prepared with a conversion efficiency of 0.47 %.     

Development of CZTS-based thin film solar cells

The low cost, environmental harmless Cu₂ZnSnS₄ (CZTS)-based thin film solar cells are fabricated by using abundant materials. The CZTS film possesses promising characteristic optical properties; band-gap energy of about 1.5 eV and large absorption coefficient in the order of 10⁴ cm^− 1. All constituents of this CZTS film, which are abundant in the crust of the earth, are non-toxic. Therefore, if we can use CZTS film practically as the absorber of solar cells, we will be free from both of the resource saving problem and the environmental pollution.In our CZTS project, CZTS absorber films were prepared by two independent techniques. One is three rf sources co-sputtering followed by annealing in sulfurized atmosphere. The latest conversion efficiency of over 6.7% was achieved by this technique. The other is co-evaporation technique. CZTS films were grown on Si (100) by vacuum co-evaporation using elemental Cu, Sn, S and binary ZnS as sources. XRD patterns indicated that the polycrystalline growth was suppressed and the orientational growth was relatively induced in a film grown at higher temperatures.In this presentation, the development of CZTS-based thin film solar cells will be surveyed.     

溶剂热法制备Cu2ZnSnS4粉末及其表征

采用溶剂热法, 以CuCl₂·2H₂O、Zn(Ac)₂·2H₂O、SnCl₄·5H₂O作金属源, 硫脲作硫源, 乙二醇作溶剂, PVP作表面活性剂, 制备了Cu₂ZnSnS₄(CZTS)粉末。利用XRD、SEM、Raman、TEM、EDS、UV-Vis吸收光谱探讨了反应温度和反应时间对制备CZTS粉末的相结构、成分、形貌以及光学性能的影响。结果表明: 反应温度和反应时间对CZTS粉末的颗粒形貌和光学性能影响较大, 最佳合成温度为230℃, 反应时间24 h。该条件下生成的CZTS粉末相较为纯净、结晶完全, 形貌为表面嵌有薄片的微球, 各元素原子比接近化学计量比, 光学带隙为1.52 eV, 与太阳能电池所需的最佳带隙接近。并对其形成机理进行了初步探讨。     

CZTS synthesis in aqueous media by microwave irradiation

Copper zinc tin sulfide (Cu₂ZnSnS₄, CZTS), a p-type semiconductor composed of non-toxic earth abundant elements, is a promising material for absorber layer application in thin film solar photovoltaics. The present work describes a relatively faster and reliable microwave irradiation technique to prepare CZTS powder in aqueous media. The CZTS phase of the as-synthesized powder was confirmed by X-ray diffraction and Raman spectroscopy. Optical properties i.e. band gap determined from Tauc plot of the optical absorption spectrum measured by UV–Vis spectroscopy was 1.27 eV, which is suitable for absorbing the solar radiation. The particle morphology studied under SEM and TEM analysis was found to be a 3D flower-like nanostructure formed from 2D layers of CZTS crystals. Further, the most probable mechanism for the formation of CZTS phase is explained.     

Control of metal salt ratio and MoS2 layer thickness in a Cu2ZnSnS4 thin film solar cell

Cu₂ZnSnS₄ (CZTS) absorber layers were prepared from copper acetate, zinc acetate, tin chloride, and thiourea in a solution of methanol, ethylenediamine, and ethanolamine using a sol–gel spin-coating method. Sol–gel precursor solutions were prepared with different metal salt ratios, and the effects on film growth, optical properties, and crystal properties of CZTS films were investigated. In addition, the role of sulfurization temperature on grain size of CZTS and formation of the MoS₂ layer at the CZTS and Mo interface were investigated. By changing the metal salt ratio in the precursor solution, a Zn-rich and Cu-poor condition in the CZTS film was obtained. By preparing Zn-rich and Cu-poor CZTS film with a thinner MoS₂ layer at a lower sulfurization temperature, the CZTS cell efficiency was improved, and a conversion efficiency of 1.22 % was obtained.     

Na2S2O3浓度对共电沉积制备Cu2ZnSnS4薄膜性能的影响

采用电化学沉积的方法在SnO2透明导电玻璃基底上沉积Cu2ZnSnS4(CZTS)薄膜,在氮气保护下对其进行进一步硫化,研究了溶液中不同Na2S2O3浓度对沉积薄膜性质的影响。运用X射线衍射、扫描电镜、紫外-可见光分光光度计和拉曼光谱等手段分别对薄膜进行表征。实验结果表明:随着浓度的增加,薄膜的结构和光学特性逐渐变好。当Na2S2O3的浓度为0.11 mol/L时,制得理想的具有类黝锡矿结构的CZTS薄膜,光学带隙1.51 eV。     

Optimization of Cu<Subscript>2</Subscript>ZnSnS<Subscript>4</Subscript> thin film absorber layer growth without sulphurization using triethanolamine as complexing agent for thin film solar cells applications

Quaternary kesterite Cu₂ZnSnS₄ (CZTS) thin films have been prepared via a simple spin-coating technique based on a sol–gel precursor of 2-methoxyethanol solution with metal salts and thiourea. Solution processed CZTS thin film growth parameters using complexing agent triethanolamine (TEA) have been investigated. Effects of complexing agent TEA on structural, morphological, optical, electrical and photovoltaic properties of CZTS thin films were systematically investigated. X-ray diffraction and Raman spectroscopy studies reveal that amorphous nature of CZTS thin film changes into polycrystalline with kesterite crystal structure with optimized TEA concentartion. Surface morphology of CZTS films were analyzed by field emission scanning electron microscope and atomic force microscope, which revealed the smooth, uniform, homogeneous and densely packed grains and systematic grain growth formation with varying TEA concentrations. UV–Vis spectra revealed a direct energy band gap ranging from 1.78 to 1.50 eV, which was found to depend upon the TEA concentration. X-ray photoelectron spectroscopy demonstrated stoichiometric atomic ratios of multicationic quaternary CZTS thin film grown without sulphurization. p-type conductivity was confirmed using Hall measurements and the effect of varying concentartion of TEA on electrical and photovoltaic properties are studied. The SLG/FTO/ZnO/CZTS/Al thin film solar cell is fabricated with the CZTS absorber layer grown at optimized TAE concentration of 0.06 M. It shows a power conversion efficiency of 0.87% for a 0.16 cm² area with V_oc = 0.257 mV, J_sc = 8.95 mA/cm² and FF?=?38%.     

Fabrication and characterization of Cu2ZnSnS4 thin films deposited by spray pyrolysis technique

We have investigated synthesis conditions and some properties of sprayed Cu₂ZnSnS₄ (CZTS) thin films in order to determine the best preparation conditions for the realization of CZTS based photovoltaic solar cells. The thin films are made by means of spraying of aqueous solutions containing copper chloride, zinc chloride, tin chloride and thiourea on heated glass substrates at various temperatures. In order to optimize the synthesis conditions of the CZTS films, two series of experiments are performed. In the first series the sprayed duration was fixed at 30 min and in the second it is fixed at 60 min. In each series, the substrate temperature was changed from 553°K to 633°K. The X-ray diffraction shows, on one hand, that the best crystallinity was obtained for 613°K as substrate temperature and 60 min as sprayed duration. On the other hand, these CZTS films exhibit the kesterite structure with preferential orientation along the [112] direction. Atomical Force Microscopy was used to determine the grain sizes and the roughness of these CZTS thin film. After the annealing treatment, we estimated the optical band-gap energy of the CZTS thin film exhibiting the best crystallinity as 1.5 eV which is quite close to the optimum value for a solar cell.