Welcome to visit Advances in New and Renewable Energy!

Advances in New and Renewable Energy >

2021 , Vol. 9 >Issue 3: 186 - 197

DOI: https://doi.org/10.3969/j.issn.2095-560X.2021.03.002

Antimony-Based Chalcogenide Semiconductors and Solar Cells

  • Cong LIU ,
  • Jian-zha ZHENG ,
  • Kai SHEN , † ,
  • Yao-hua MAI , †
Expand
  • Institute of New Energy Technology, College of Information Science and Technology, Jinan University, Guangzhou 510632, China

Received date: 2021-03-05

  Revised date: 2021-04-08

Copyright

版权所有 © 《新能源进展》编辑部
Fold

Abstract

Antimony-based chalcogenides are a class of semiconductor materials with stable properties, environmentally friendly, rich element content, continuous adjustable band gap and excellent photoelectric properties, including antimony selenide (Sb2Se3), antimony sulfide (Sb2S3) and antimony selenosulfide [Sb2(S,Se)3]. Among them, the band gap of Sb2(S,Se)3 matches well with the solar spectrum, so it is more suitable to be used as the absorber layer of solar cells. The solar cell with Sb2(S,Se)3 absorber has achieved a certified power conversion efficiency of 10%, showing the great potential of antimony-based chalcogenide solar cells. In this paper, the material and photoelectric properties, films preparation technology and defect characteristics of antimony-based chalcogenide were described in detail. Based on the research progress of antimony-based chalcogenide solar cells in recent years, the direction and strategy of further improving the device performance were proposed.

Key words： antimony-based chalcogenide; antimony selenide; antimony sulfide; antimony selenosulfide; solar cells

Cite this article

Cong LIU , Jian-zha ZHENG , Kai SHEN , Yao-hua MAI . Antimony-Based Chalcogenide Semiconductors and Solar Cells[J]. Advances in New and Renewable Energy, 2021 , 9(3) : 186 -197 . DOI: 10.3969/j.issn.2095-560X.2021.03.002

开放科学（资源服务）标识码（OSID）:

0 引言

当前,我国社会经济正处于快速发展的过程中,对能源的需求很大。能源问题已经上升到国家的重大战略问题,为此我国政府出台一系列政策支持新能源产业的发展。其中,太阳能凭借环境友好、资源分布广泛和使用安全可靠等优势成为可再生能源中的佼佼者。太阳能光伏组件在太阳光的照射下可产生直流电,将太阳能转化为电能应用到社会生产当中,对人类社会的可持续发展具有重要意义。光伏产业在过去几年里取得了巨大进展,2019年全国新增光伏发电装机30.11 GW,2020年新增光伏发电装机48.45 GW。2019年中国太阳能发电量为1 172亿kW∙h,同比增长13.3%。
晶硅太阳电池凭借高效率和高工作稳定性实现了商业化应用,并占据了绝大部分太阳能光伏市场。然而,其生产成本较高,对材料纯度的要求非常严格。而且,刚性的晶硅电池板也不能满足日益流行的柔性可穿戴电子设备的要求。在薄膜太阳电池中,铜铟镓硒[Cu(In,Ga)Se2]和碲化镉（CdTe）太阳电池已经取得了超过22%的能量转换效率[1,2],但不利的是铟、镓的稀缺性和镉的毒性。有机太阳电池以低成本、质量轻、可大面积制备以及柔性制备等优势而引起光伏研究者的强烈兴趣,其能量转换效率达到了18.2%[3]。但是,聚合物分子价格昂贵,合成步骤繁琐,并且在光热条件下的稳定性差,这些缺点限制了其商业化的进程。钙钛矿太阳电池作为一种新型太阳电池,凭借其低成本、溶液加工和优异的光电性能等优势迅速发展起来,能量转换效率达到了25.5%,但人们对其稳定性仍有些疑虑,大面积制备技术也不够成熟。
为了满足光伏产业多元化、高效率、高稳定性和低成本的需求,开展基于锑基硫属化合物的新型太阳电池是非常必要的。锑基硫属化合物主要包括硒化锑（Sb2Se3）、硫化锑（Sb2S3）以及硒硫化锑[Sb2(S1-xSex)3或Sb2(S,Se)3]。从2013年以来,锑基硫属化合物太阳电池的研究文献逐年递增,引起了国内外科研工作者的广泛关注。此外,锑基硫属化合物材料还应用于光电探测器、热电、锂离子电池和光解水制氢等领域[4,5,6,7,8],显示出其在光电、能源方面的巨大应用潜力。本文阐述了锑基硫属化合物材料及光电特性,薄膜制备方法及缺陷特性。结合近年来锑基硫属化合物太阳电池的研究进展,提出进一步提高锑基硫属化合物太阳电池性能的研究策略和方向。

1 锑基硫属化合物材料及光电性质

1.1 材料性质

硒化锑和硫化锑是一种无机化合物材料,化学式分别为Sb2Se3和Sb2S3,分子量分别为480.38和339.68。Sb2Se3属于正交晶系,空间群为Pnma 62,晶格常数为a = 1.162 nm、b = 1.177 nm和c = 0.396 2 nm,其晶格结构如图1所示。Sb2Se3具有一维晶体结构,在[001]方向上通过Sb-Se共价键连接形成[Sb4Se6]n纳米带,每条带由三棱锥Sb1Se2Se3和四棱锥Sb2Se2Se3交替构成,而在[100]、[010]方向上则是[Sb4Se6]n纳米带通过范德华力堆叠而成[9]。Sb2S3同属正交晶系,空间群为Pnma 62,晶格常数a = 1.131 nm、b = 0.383 6 nm、c = 1.123 nm[10]。Sb2Se3和Sb2S3近乎同晶形,S2- 和Se2- 可以相互替代,形成Sb2(S,Se)3。
Fig. 1 The crystal structure diagram of Sb2Se3

图1 硒化锑的晶体结构示意图

锑基硫属化合物材料的优势在于其光电性能优异、性质稳定、组分和物相简单、元素含量丰富、环境友好。如表1所示,Sb、Se和S元素丰度分别为0.20 g/t、0.05 g/t和260.00 g/t,原材料价格低廉[10]。同时,制备锑基硫属化合物光伏薄膜所需材料用量较少。
Table 1 The elemental abundance, output and price of antimony chalcogenide[10]

表1 锑基硫属化合物元素丰度、产量和价格[10]

元素 丰度 / (g/t) 年产量 / t 价格 / (元/kg)
Sb 0.20 53 000 47
Se 0.05 600 110
S 260.00 54 000 000 2

1.2 光电性质

锑基硫属化合物具有优异的光电性能,非常有潜力作为新型太阳电池的吸光材料[11,12,13,14,15]。
1.2.1 光学性质
Sb2Se3间接带隙为1.03 eV,直接带隙为1.17 eV,接近硅的带隙（1.12 eV）。根据肖克利-奎伊瑟极限（Shockley-Queisser limit）理论计算[16],Sb2Se3太阳电池的理论极限效率可达30%以上。Sb2Se3在紫外可见光范围内的吸光系数可达约1 × 105 cm-1,几百纳米厚（约500 nm）的薄膜就可以吸收足够的太阳光。Sb2S3为直接带隙半导体,光学带隙约为1.7 ~ 1.8 eV。其电子结构被广泛研究[17,18,19,20,21],一般认为价带顶由Sb-5p、Sb-5s和S-3p电子态组成,后者起主导作用。导带主要由Sb-5p和S-3p反键电子态构成。根据Shockley-Querisser理论计算此带隙制备出的单结太阳电池的理论能量转换效率可以超过28.64%。Sb2S3的光吸收系数在1 × 104 ~ 1 × 105 cm-1之间,吸收边可以达到750 nm,只需几百纳米厚度的薄膜就可以对入射太阳光进行充分吸收。Sb2(S,Se)3中的Sb2S3和Sb2Se3可以形成均匀的合金,通过调节Se/S比例可以对Sb2(S,Se)3的带隙在1.1 ~ 1.8 eV范围内进行调控。
1.2.2 电学特性
根据热电功率测试,Sb2Se3表现为p型导电性,Sb2S3表现n型导电性[22]。Sb2Se3的相对介电常数为15,电子和空穴迁移率分别为15 cm2/(V·s) 和42 cm2/(V·s)。化学水浴法制备的Sb2S3薄膜的霍尔迁移率是 9.8 cm2/(V·s),载流子浓度大于1 × 1012 cm-3。电子扩散长度较长,在290 ~ 900 nm之间[23]。Sb2Se3和Sb2S3的一维晶体结构使其具有高度的各向异性,制备的薄膜具有多种取向。电荷载流子在沿着(Sb4X6)n方向上具有较高的迁移率,在(Sb4X6)n纳米带间跳跃传输效率就低得多。

2 锑基硫属化合物薄膜的制备

2.1 硒化锑

Sb2Se3具有较高的饱和蒸汽压（550℃时约为1 200 Pa）和较低的熔点（611℃）,并且其组分和物相单一,适用于多种方法制备。目前文献报道的制备方法主要分为真空法和非真空法。如图2 所示,真空法主要包括快速热蒸发（rapid thermal evaporation, RTE）、近空间升华（close-space sublimation, CSS）、载气输运沉积（vapor transport deposition, VTD）、磁控溅射沉积和脉冲激光沉积（pulsed laser deposition, PLD）。非真空法包括电化学沉积、水热沉积、溶液旋涂法、喷雾热解等。
Fig. 2 (a) Rapid thermal evaporation[24]; (b) close-space sublimation[25]; (c) vapor transport deposition[26]; (d) magnetron sputtering[27]; (e) pulsed laser deposition[28]

图2 （a）快速热蒸发[24];（b）近空间升华[25];（c）载气输运沉积[26];（d）磁控溅射[27];（e）脉冲激光沉积[28]

2.2 硫化锑

在基于敏化结构和平面结构的Sb2S3太阳电池中,化学水浴沉积（chemical bath deposition, CBD）是最常用的制备方法。CBD法除了成本低、操作简单外,还具有以下优势:在化学浴中加入不同浓度的掺杂剂,可以很容易地实现膜的掺杂;在合成过程中,溶液可以渗透到多孔结构中,薄膜可以在多孔结构中共沉积,这是敏化太阳电池的关键。此外,溶液旋涂法、水热沉积、原子层沉积（atomic layer deposition, ALD）也常用来制备Sb2S3薄膜。由于Sb2S3的熔点较低（约550℃）,可以在较低温度下制备高结晶质量的薄膜。

2.3 硒硫化锑

Sb2(S,Se)3光吸收层可通过对Sb2Se3后硫化处理得到,以及对单源Sb2(Se1-xSx)3粉末通过RTE、VTD法制备得到。目前,高质量的Sb2(S,Se)3光吸收层是通过水热沉积法制备而来。在水热体系中,以酒石酸锑钾为锑源,硫代硫酸钠为硫源,硒脲为硒源,125℃下水热沉积2 ~ 3 h,在惰性气体氛围下经过350℃退火得到高度结晶、大晶粒的Sb2(S,Se)3薄膜[59]。

3 锑基硫属化合物薄膜缺陷特性及检测

3.1 缺陷特性

锑基硫属半导体点缺陷主要包括空位缺陷、替位缺陷和间隙缺陷。硒化锑只有硒和锑两种元素,因此只有6种可能的点缺陷,分别是阳离子空位（VSb）、阴离子空位（VSe）、阳离子间隙（Sbi）、阴离子间隙（Sei）、阳离子取代阴离子反位缺陷（SbSe）和阴离子取代阳离子反位缺陷（SeSb）。与铜锌锡硫、铜锌锡硫硒等多元化合物相比[29,30],硒化锑可能的点缺陷要少很多。在这种情况下,硒化锑中的点缺陷更为良性,并且缺陷更加容易控制。因此,通过缺陷钝化可以获得更高的能量转换效率。
然而,第一性原理计算的结果表明硒化锑的本征缺陷非常复杂。在硒化锑分子体系中,不同位点的Sb原子周围键合的Se原子数目不同,这就造成两个Sb原子和三个Se原子的成键环境不同,是不等价的。相同类型的缺陷位于非等价原子位点,具有不同的性质,即使在只有几种点缺陷的情况下,点缺陷的性质也很复杂[31]。这些缺陷在带隙中产生一系列的受体和施主能级,会对光生载流子的传输、复合与收集产生不利影响,进而限制了太阳电池的器件性能。
Fig. 3 The intrinsic point defects of Sb2Se3[31]

图3 硒化锑的本征点缺陷[31]

3.2 检测手段

3.2.1 深能级瞬态谱
深能级瞬态光谱（deep-level transient spectroscopy, DLTS）是一种研究光伏薄膜的缺陷能级、缺陷类型和浓度的有效工具[32,33,34]。通过探测不同温度下p-n结的瞬态电容来监测深能级缺陷复合中心电荷态的变化。给器件施加一个脉冲电压,器件中的缺陷态将会被载流子填充,就会改变与p-n结相关的电容[35]。在不同温度下,ΔC/C0的变化可以反映出DLTS的信号。基于缺陷放电过程中的电容变化,空穴缺陷和电子缺陷可以通过ΔC的正负来区分。
WEN等[26]采用深能级瞬态谱比较了VTD和RTE制备的硒化锑太阳电池的缺陷水平。在这两种器件中,一个负的、两个正的DLTS信号同时出现,表明硒化锑薄膜中存在着一种电子缺陷（E1）和两种空穴缺陷（H1和H2）。根据DLTS信号做出阿伦尼乌斯曲线,缺陷活化能可从曲线斜率计算得到,俘获截面可从与y轴的截距得到。他们将H1和H2缺陷归于锑空位（VSb）和硒反位缺陷（SeSb）,将E1缺陷归于锑反位缺陷（SbSe）,计算得到的缺陷态浓度在1.1 × 1014 ~ 2.3 × 1015 cm-3范围内。
Fig. 4 (a) DLTS signals of VTD-fabricated and RTE-fabricated devices; (b) Arrhenius plots obtained from DLTS signals[26]

图4 （a）载气输运沉积和快速热蒸发制备的硒化锑太阳电池的DLTS信号;（b）从DLTS信号获得的阿伦尼乌斯图[26]

3.2.2 导纳谱
导纳光谱学涉及复导纳的测量:Y(ω,T) = G(ω,T) + iωC(ω,T),为角频率ω和温度T的函数。其中,G(ω,T)为电导,C(ω,T)为电容。在这里只讨论电容光谱。除了半导体结的空间电荷区（space charge region, SCR）的电容外,该结的SCR中的电子活性缺陷或陷阱也可能在较低频率或较高温度下影响电容谱[36]。这是由于电子（空穴）的缺陷能级Et与准费米能级EFn（EFp）交叉时,缺陷会被捕获和释放。
HU等[37]采用导纳谱确定了硒化锑光吸收层内部的三种缺陷。图5显示了效率分别为5.91%的Sb2Se3太阳电池在不同温度下（从180 K到334 K,以4 ~ 5 K增量）测量的电容谱。在不同频率下,所有谱的低频区（20 ~ 105 Hz）均表现出三个明显的电容阶跃。这种电容响应归因于Sb2Se3带隙中的三种缺陷,分别为D1、D2和D3。利用高斯函数对三种缺陷的分布进行拟合,得到的高斯分布的面积作为缺陷密度。同样,从阿伦尼乌斯曲线得到活化能。结果显示,三种缺陷的密度分别为2.46 × 1014 cm-3、1.36 × 1015 cm-3、1.15 × 1016 cm-3,活化能分别为286 meV、188 meV、570 meV。
Fig. 5 (a) Derivative -dC/dlnf versus frequency for various temperatures for the 5.91%-cell sample; (b) Arrhenius plots of ω0/T2 versus 1000/T for the three defects measured from the 5.91%-cell sample; (c) defect distribution of D1, D2, and D3 for the 5.91%-cell sample[37]

图5 能量转换效率为5.91%的Sb2Se3太阳电池:（a）不同温度下的 -dC/dlnf与频率的比;（b）三种缺陷的阿伦尼乌斯曲线;（c）D1、D2和D3的缺陷分布[37]

4 锑基硫属化合物太阳电池效率发展

4.1 硒化锑太阳电池

图6展示了近年来硒化锑太阳电池能量转换效率的发展情况。2009年,NGO等[38]制备了器件结构为FTO/TiO2/Sb2Se3/CuSCN/Au的敏化太阳电池,实现了18 mA/cm2的短路电流密度。MESSINA等[39]首次以化学水浴沉积硒化锑作为太阳电池的光吸收层,获得了0.13%的能量转换效率。2014年,CHOI等[40]在介孔TiO2上旋涂Sb、Se前驱体,由此制备的敏化太阳电池取得了3.21%的能量转换效率。随后国内外多个团队开展了相关研究。WEN等[26]采用载气输运沉积制备了平面异质结硒化锑太阳电池,能量转换效率快速提升至7.6%。LI等[41]制备了基于纳米棒核壳结构的Sb2Se3太阳电池,效率达到9.2%,是目前已知的硒化锑太阳电池的世界最高能量转换效率。此外,SHEN等[42]发展了基于三方晶系硒结构的顶衬Sb2Se3薄膜太阳电池,可有效钝化吸收层表面缺陷,促进界面空穴传输和抑制载流子界面复合,能量转换效率达到7.5%。LIU等[43]采用氧化钨空穴传输层进行背接触修饰,形成良好的能级匹配并提高器件的内建电势,基于n-i-p结构的Sb2Se3太阳电池的能量转换效率达到了7.1%。TANG等[27]提出了一种两步法,即先磁控溅射Sb2Se3薄膜和后硒化处理制备Sb2Se3太阳电池,可以同时优化Sb2Se3薄膜质量和Sb2Se3/CdS异质结界面。通过调整硒化参数,制备的Sb2Se3薄膜太阳电池的效率达到了6.06%,开路电压高达494 mV。而后,LIANG等[44]采用溅射和硒化锑前驱体薄膜的组合工艺制备Sb2Se3太阳电池。在适当的Sb前驱体薄膜厚度和优化的硒化方案下,成功地实现了具有大晶粒、择优取向和精确化学成分的Sb2Se3薄膜的自组装生长。由此制备的太阳电池效率达到了6.84%,开路电压高达504 mV,这与Sb2Se3吸收层缺陷密度降低、Sb2Se3/CdS异质结界面缺陷钝化以及异质结热处理引起的Cd和S互扩散密切相关。
Fig. 6 The efficiency development of Sb2Se3 solar cells

图6 Sb2Se3太阳电池能量转换效率的进展

4.2 硫化锑太阳电池

Sb2S3最早应用于介孔太阳电池。2010年, SEOK课题组[45]通过化学水浴法制备了结构为FTO/TiO2/Sb2S3/P3HT/Au的介孔太阳电池,能量转换效率为5.13%。2014年,该课题组制备了器件结构为Au/PCPDTBT/Sb2S3/mp-TiO2/BL/FTO的电池,通过后硫化处理获得了7.5% 的能量转换效率[46],是目前Sb2S3太阳电池的最高效率。之后,陆续有学者报道了不同方法制备Sb2S3薄膜太阳电池。
2014年,ESCORCIA-GARCÍA等[47]在FTO/CdS上蒸发沉积Sb2S3获得1.27% 的能量转换效率。2015年,MAYON等[48]在TiO2上蒸发沉积Sb2S3,器件能量转换效率达1.69%。ZHANG等[49]及DENG等[50]采用VTD和RTE工艺,通过调控Sb2S3晶向生长分别获得4.5% 和5.4% 的能量转换效率。ZENG等[51]同样通过VTD工艺获得4.73%的能量转换效率。基于Mo电极的底衬Sb2S3太阳电池,PAN等及LIU等采用RTE法分别获得了1.75%[52]和1.86%[53]的能量转换效率。LUO等[54]利用射频磁控溅射的方法获得0.95%的能量转换效率。
JIANG等[55]采用旋涂法研究了碱金属（Li、Na、K、Rb、Cs）、氯化锌（ZnCl2）对Sb2S3薄膜太阳电池的影响,发现重碱金属铯掺杂Sb2S3对载流子浓度、结晶度和成膜性能都有显著提高,器件能量转换效率达6.56%。ZnCl2则可以调节薄膜的生长以提高结晶度,器件能量转换效率达6.35%[56]。此外,通过一种快速化学方法（fast chemical approach, FCA）,以Sb2O3为锑源制备高性能Sb2S3平面异质结太阳电池,以Spiro-OMeTAD为空穴传输层获得4.3% 的能量转换效率[57],以V2O5为空穴传输层获得4.8% 的能量转换效率[58]。TANG等[59]通过水热法以酒石酸锑钾为锑源、五水合硫代硫酸钠为硫源制备Sb2S3薄膜,能量转换效率达6.02%。此外,JIN等[60]在溶液引入额外镉源,促进Sb2S3垂直取向生长从而获得6.4% 的能量转换效率。HAN等[61]采用卤化锌无机盐修饰TiO2电子传输层,改善TiO2的电学性能,促进了Sb2S3薄膜的生长,使其具有更大的晶粒尺寸和更高的结晶度。实验结果和理论计算进一步揭示,卤化锌可与TiO2相互作用,同时与上层Sb2S3膜形成强烈的键合,形成独特的电子转移途径,钝化陷阱态,有效地缓解复合损失。引入ZnCl2后,器件能量转换效率达到7.08%。HAN等[62]采用无机盐SbCl3对Sb2S3薄膜进行表面钝化,可以减少缺陷和抑制非辐射复合。结果显示,引入SbCl3层可以将开路电压提升至0.72 V,能量转换效率达到7.1%。图7为硫化锑太阳电池能量转换效率的进展。
Fig. 7 The efficiency development of Sb2S3 solar cells

图7 Sb2S3太阳电池能量转换效率的进展

4.3 硒硫化锑太阳电池

Sb2S3具有较大的带隙,可以实现高开路电压,但也限制了光吸收范围。Sb2Se3带隙小,可以利用较长波段的太阳光,但实际Voc损失严重。Sb2(S,Se)3是为了利用Sb2S3、Sb2Se3两者的优点而衍生的吸收层材料。2008年,EL-SAYAD[63]采用热蒸发制备了Sb2(S,Se)3非晶薄膜,通过调节Se/S含量,发现随着S含量增加,其光带隙能量呈二次增长。2015年,YANG等[64]通过旋涂Sb-S-Se肼溶液得到了单相多晶Sb2(S1-xSex)3膜,得出带隙与Se/S含量的关系式Eg (x) = 0.118x2 - 0.662x + 1.62 eV。这些发现证明了Sb2(S,Se)3带隙及能带水平的可调性,有望能成为除Sb2S3、Sb2Se3之外的高效光伏材料。2016年,YANG等[65]通过在快速热蒸发Sb2Se3中引入硫化步骤制备了均匀Sb2(Se0.8S0.2)3薄膜,器件效率达到5.79%,有力证明了Sb2(S,Se)3可以成为优异的太阳电池光吸收材料。之后,ISHAQ等[66]采用单源Sb2(Se1-xSx)3粉末通过RTE制备吸收层薄膜,电池能量转换效率为5.73%。LU等[67]采用单源Sb2(Se1-xSx)3粉末通过VTD制备吸收层薄膜,电池能量转换效率为6.30%。LI等[68]采用双源Sb2Se3、Sb2S3粉末通过VTD法获得了7.27%的效率。NIE等[69]在Sb2(SxSe1-x)3前驱体中掺入BiI3,更大的Bi和I离子可分别替换Sb和S,从而调节晶格之间的应变关系并降低缺陷态能级,获得了7.05%的器件能量转换效率。WANG等[70]采用一步水热法,以酒石酸锑钾为锑源,以硫代硫酸钠为硫源,在120℃下水热沉积12 h制备Sb2S3,再经硒化后得到Sb2(S,Se)3薄膜,以此制备的太阳电池获得了5.73%的能量转换效率,后来通过工艺改进获得了6.14%的器件效率[71]。TANG等[59]采用化学水热法沉积硒硫化锑光吸收层薄膜,由此制备器件结构为FTO/CdS/Sb2(S,Se)3/Spiro-OMeTAD/Au的太阳电池,取得了10%的认证效率,成为又一个能量转换效率可以达到10%的光伏材料。在水热体系中,以酒石酸锑钾为锑源,硫代硫酸钠为硫源,硒脲为硒源,通过改变Se/S的比例和后退火的温度,改善了薄膜形貌,增大了晶粒尺寸,并减小了缺陷的数量。研究发现,提高Se/S的比例可以使一维纳米带择优生长。在此基础上,WANG等[72]在水热体系中引入乙二胺四乙酸（ethylenediaminetetra-acetic acid, EDTA）添加剂控制晶体成核和生长过程,将器件效率进一步提升至10.5%。此外,HAN等[73]通过水热沉积技术制备了大面积、化学成分和表面形貌都较均匀的Sb2(S,Se)3薄膜。利用激光划线技术,获得了串联的Sb2(S,Se)3光伏组件,效率达到了7.43%,活性面积为15.66 cm2。图8展示了硒硫化锑太阳电池能量转换效率的进展。
Fig. 8 The efficiency development of Sb2(S,Se)3 solar cells

图8 Sb2(S,Se)3太阳电池效率进展

5 结论与展望

近年来,锑基硫属化合物太阳电池发展迅速,表2总结了锑基硫属化合物太阳电池的器件性能。其中,Sb2S3太阳电池取得了7.5%的能量转换效率,Sb2Se3太阳电池取得了9.2%的能量转换效率,Sb2(S,Se)3太阳电池能量转换效率更是突破了10.5%,成为又一个效率可以达到10%的光伏材料。但是,这尚不能满足产业化的要求,需要进一步提高锑基硫属化合物太阳电池的器件效率。
Table 2 Summary of antimony chalcogenide solar cells

表2 锑基硫属化合物太阳电池汇总

锑基硫属 化合物 方法 器件结构 能量转换效率/ % 开路电压 / mV 短路电流 密度 / (mA/cm2) 填充因子/ % 文献
Sb2Se3 TE FTO/CdS/Sb2Se3/Au 1.90 300 13.20 48.0 [74]
FTO/CdS/Sb2Se3/Au 3.70 335 24.40 46.8 [75]
ITO/ZnO/CdS/Sb2Se3/Au 3.50 339 20.70 49.0 [76]
RTE FTO/CdS/Sb2Se3/Au 5.60 400 25.14 55.7 [24]
ITO/CdS/Sb2Se3/PbS CQDs/Au 6.50 427 25.5 59.3 [89]
FTO/TiO2/Sb2Se3/PbS CQDs/Au 7.62 386 32.60 60.6 [77]
VTD ITO/CdS/Sb2Se3/Au 7.60 420 29.90 60.4 [26]
ITO/CdS/Sb2Se3/CuSCN/Au 7.50 423 30.10 57.0 [78]
Spin-coating FTO/TiO2/CdS/Sb2Se3/Spiro-OMeTAD/Au 3.90 340 27.20 41.9 [79]
PLD FTO/CdSe/Sb2Se3/Au 3.65 357 20.18 50.7 [80]
CSS Mo/Sb2Se3/CdxZn1-xS/ZnO/AZO 6.71 403 25.69 64.8 [81]
Mo/MoSe2/Sb2Se3/TiO2/CdS/ZnO/AZO 9.20 400 32.58 70.3 [41]
FTO/CdS:O/Sb2Se3/graphite/Ag 7.01 432 29.87 54.0 [82]
FTO/TiO2/Sb2Se3/Au 7.30 434 31.70 52.6 [83]
FTO/SnO2/CdS/Sb2Se3/t-Se/Au 7.45 413 28.90 62.3 [42]
FTO/CdS/Sb2Se3/WO3-x/Au 7.10 420 28.81 58.8 [43]
Sputtering FTO/CdS/Sb2Se3/CuSbSe2/Au 5.87 377 27.86 55.9 [84]
Mo/Sb2Se3/CdS/ITO/Ag 6.84 504 24.91 54.5 [44]
Sb2S3 TE FTO/CdS/Sb2S3/C-Ag 1.27 600 6.10 35.0 [47]
FTO/TiO2/Sb2S3/Spiro-OMeTAD/Au 1.69 599 6.43 44.0 [48]
VTD ITO/CdS/Sb2S3/Au 4.50 730 10.90 56.0 [49]
ITO/CdS/Sb2S3/Au 4.73 710 15.70 43.2 [51]
RTE FTO/TiO2/Se-Sb2S3/Au 5.40 690 11.53 51.2 [50]
Mo/Sb2S3/CdS/i-ZO/AZO/Ni:Al 1.75 658 7.09 37.6 [52]
Mo(MoSe2)/Sb2S3/CdS/iZO/AZO/Ni:Al 1.86 466 13.60 31.1 [53]
Sputtering Mo/Sb2S3/CdS/ITO/Ag 0.95 308 10.33 30.8 [54]
FCA FTO/CdS/Sb2S3/Spiro-OMeTAD/Au 4.30 632 12.93 52.4 [57]
FTO/TiO2/Sb2S3/V2O5/Au 4.80 590 15.29 52.9 [58]
Hydrothermal FTO/CdS/Sb2S3/Spiro-OMeTAD/Au 6.02 707 15.20 55.9 [59]
Spin-coating FTO/c-TiO2/Cs-Sb2S3/Spiro-OMeTAD/Au 6.56 690 17.30 55.2 [55]
FTO/c-TiO2/Zn-Sb2S3/Spiro-OMeTAD/Au 6.35 647 17.19 57.1 [56]
FTO/TiO2/CdS/Sb2S3/Spiro-OMeTAD/Au 6.40 760 15.11 56.1 [60]
FTO/TiO2/ZnCl2/Sb2S3/Spiro-OMeTAD/Au 7.08 650 17.69 61.6 [61]
FTO/TiO2/Sb2S3/SbCl3/Spiro-OMeTAD/Au 7.10 720 17.24 57.2 [62]
FTO/TiO2-bl/TiO2-mp/Sb2S3/PCPDTBT/Au 6.40 596 16.10 66.5 [92]
Sb2(S,Se)3 RTE ITO/CdS/Sb2(Se1-xSx)3/Au 5.79 500 22.30 52.2 [65]
FTO/ZnO/CdS/Sb2(Se1-xSx)3/Au 5.73 480 21.89 54.5 [66]
VTD ITO/CdS/Sb2(Se1-xSx)3/Au 6.30 534 20.90 56.6 [67]
ITO/CdS/Sb2(S,Se)3/Au 7.27 460 29.60 54.2 [68]
Spin-coating FTO/TiO2/BiI3:Sb2(S,Se)3/PEDOT:PSS/Au 7.05 521 21.50 63.0 [69]
FTO/c-TiO2/Sb2(S1-xSex)3/Spiro-OMeTAD/Au 7.42 491 25.40 59.5 [85]
FTO/c-TiO2/In:CdS/Sb2(S1-xSex)3/Spiro-OMeTAD/Au 6.63 590 18.14 62.4 [86]
CBD FTO/c-TiO2/Sb2(S1-xSex)3/Spiro-OMeTAD/Au 5.71 560 19.48 52.3 [87]
Hydrothermal FTO/TiO2/CdS/Sb2(Se1-xSx)3/Spiro-OMeTAD/Au 5.73 792 12.03 60.9 [70]
FTO/CdS/Sb2(S,Se)3/Spiro-OMeTAD/Au 6.14 733 14.60 60.8 [71]
FTO/CdS/Sb2(S,Se)3/DTPThMe-ThTPA/Au 9.69 638 23.19 65.5 [88]
FTO/CdS/Sb2(S,Se)3/Spiro-OMeTAD/Au 10.10 630 23.70 67.7 [59]
FTO/CdS/Sb2(S,Se)3/Spiro-OMeTAD/Au 10.50 664 23.80 66.3 [72]
锑基硫属化合物太阳电池是一个复杂的系统,涉及器件结构的设计、缓冲层及窗口层的选择和光吸收层的结构及质量等。钝化吸收层本征缺陷态和界面修饰是提升器件性能的关键。关于本征缺陷态,可以利用第一性原理计算锑基硫属化合物半导体点缺陷性质,开发新的缺陷检测手段,识别缺陷的类型、位点及分布。在此基础上,可以针对性地进行后钝化处理以降低缺陷态密度。此外,可探索缺陷态的产生原因及形成过程,在生长动力学模拟指导下抑制缺陷的产生。通过对器件前接触和背接触的界面修饰,可优化界面结构和能级排列,促进载流子的传输和收集,是制备高效率锑基硫属化合物太阳电池的必要手段。
锑基硫属化合物性质稳定,元素含量丰富,环境友好,带隙连续可调,非常有潜力实现低成本、高效率的太阳电池。此外,锑基硫属化合物还应用于光电探测器、热电、锂离子电池和光解水等领域。相信在未来的科学研究中,锑基硫属化合物将会成为一个明星材料,太阳电池效率也会不断取得突破。

References

Publishing order | Descend order by publishing year | Descend order by cited within
[1]
GREEN M A, HISHIKAWA Y, DUNLOP E D, et al.Solar cell efficiency tables (version 52)[J]. Progress in photovoltaics: research and applications, 2018, 26(7): 427-436. DOI: 10.1002/pip.3040.

[2]
CARRON R, NISHIWAKI S, FEURER T, et al.Advanced alkali treatments for high-efficiency Cu(In,Ga)Se2 solar cells on flexible substrates[J]. Advanced energy materials, 2019, 9(24): 1900408. DOI: 10.1002/aenm.201900408.

[3]
LIU Q S, JIANG Y F, JIN K, et al.18% efficiency organic solar cells[J]. Science bulletin, 2020, 65(4): 272-275. DOI: 10.1016/j.scib.2020.01.001.

[4]
LI G, LI Z Q, CHEN J W, et al.Self-powered, high-speed Sb2Se3/Si heterojunction photodetector with close spaced sublimation processed Sb2Se3 layer[J]. Journal of alloys and compounds, 2018, 737: 67-73. DOI: 10.1016/j.jallcom.2017.12.039.

[5]
WEN X X, LU Z H, VALDMAN L, et al.High-crystallinity epitaxial Sb2Se3 thin films on mica for flexible near-infrared photodetectors[J]. ACS applied materials & interfaces, 2020, 12(31): 35222-35231. DOI: 10.1021/acsami.0c08467.

[6]
AN D C, CHEN S P, LU Z X, et al.Low thermal conductivity and optimized thermoelectric properties of p-type Te-Sb2Se3: synergistic effect of doping and defect engineering[J]. ACS applied materials & interfaces, 2019, 11(31): 27788-27797. DOI: 10.1021/acsami.9b07313.

[7]
XUE M Z, FU Z W.Pulsed laser deposited Sb2Se3 anode for lithium-ion batteries[J]. Journal of alloys and compounds, 2008, 458(1/2): 351-356. DOI: 10.1016/j.jallcom.2007.03.109.

[8]
YANG W, LEE S, KWON H C, et al.Time-resolved observations of photo-generated charge-carrier dynamics in Sb2Se3 photocathodes for photoelectrochemical water splitting[J]. ACS nano, 2018, 12(11): 11088-11097. DOI: 10.1021/acsnano.8b05446.

[9]
薛丁江, 石杭杰, 唐江. 新型硒化锑材料及其光伏器件研究进展[J]. 物理学报, 2015, 64(3): 038406. DOI: 10.7498/aps.64.038406.

[10]
WANG X M, TANG R F, WU C Y, et al.Development of antimony sulfide-selenide Sb2(S,Se)3-based solar cells[J]. Journal of energy chemistry, 2018, 27(3): 713-721. DOI: 10.1016/j.jechem.2017.09.031.

[11]
OU C Z, SHEN K, LI Z Q, et al.Bandgap tunable CdS:O as efficient electron buffer layer for high-performance Sb2Se3 thin film solar cells. Solar Energy Materials and Solar Cells 2019, 194, 47-53. DOI: 10.1016/j.solmat.2019.01.043

[12]
HU X B, TAO J H, CHEN S M, et al.Improving the efficiency of Sb2Se3 thin-film solar cells by post annealing treatment in vacuum condition[J]. Solar energy materials and solar cells, 2018, 187: 170-175. DOI: 10.1016/j.solmat.2018.08.006.

[13]
YUAN C C, ZHANG L J, LIU W F, et al.Rapid thermal process to fabricate Sb2Se3 thin film for solar cell application[J]. Solar energy, 2016, 137: 256-260. DOI: 10.1016/j.solener.2016.08.020.

[14]
BIRKETT M, LINHART W M, STONER J, et al.Band gap temperature-dependence of close-space sublimation grown Sb2Se3 by photo-reflectance[J]. APL materials, 2018, 6(8): 084901. DOI: 10.1063/1.5027157.

[15]
YAO S, WANG J S, CHENG J, et al.Improved performance of thermally evaporated Sb2Se3 thin-film solar cells via substrate-cooling-speed control and hydrogen- sulfide treatment[J]. ACS applied materials & interfaces, 2020, 12(21): 24112-24124. DOI: 10.1021/acsami.0c03674.

[16]
SHOCKLEY W, QUEISSER H J.Detailed balance limit of efficiency of p-n junction solar cells[J]. Journal of applied physics, 1961, 32(3): 510-519. DOI: 10.1063/1.1736034.

[17]
CARACAS R, GONZE X.First-principles study of the electronic properties of A2B3 minerals, with A=Bi, Sb and B=S, Se[J]. Physics and chemistry of minerals, 2005, 32(4): 295-300. DOI: 10.1007/s00269-005-0470-y.

[18]
FILIP M R, PATRICK C E, GIUSTINO F.Quasiparticle band structures of stibnite, antimonselite, bismuthinite, and guanajuatite[J]. Physical review B, 2013, 87(20): 205125. DOI: 10.1103/PhysRevB.87.205125.

[19]
BEN NASR T, MAGHRAOUI-MEHERZI H, BEN ABDALLAH H, et al.Electronic structure and optical properties of Sb2S3 crystal[J]. Physica B: condensed matter, 2011, 406(2): 287-292. DOI: 10.1016/j.physb.2010.10.070.

[20]
KOC H, MAMEDOV A M, DELIGOZ E, et al.First principles prediction of the elastic, electronic, and optical properties of Sb2S3 and Sb2Se3 compounds[J]. Solid state sciences, 2012, 14(8): 1211-1220. DOI: 10.1016/j.solidstatesciences.2012.06.003.

[21]
VADAPOO R, KRISHNAN S, YILMAZ H, et al.Self-standing nanoribbons of antimony selenide and antimony sulfide with well-defined size and band gap[J]. Nanotechnology, 2011, 22(17): 175705. DOI: 10.1088/0957-4484/22/17/175705.

[22]
SAVADOGO O, MANDAL K C.Fabrication of low-cost n-Sb2S3/p-Ge heterojunction solar cells[J]. Journal of physics D: applied physics, 1994, 27(5): 1070-1075. DOI: 10.1088/0022-3727/27/5/028.

[23]
ENGLMAN T, TERKIELTAUB E, ETGAR L.High open circuit voltage in Sb2S3/metal oxide-based solar cells[J]. The journal of physical chemistry C, 2015, 119(23): 12904-12909. DOI: 10.1021/acs.jpcc.5b04231.

[24]
ZHOU Y, WANG L, CHEN S Y, et al.Thin-film Sb2Se3 photovoltaics with oriented one-dimensional ribbons and benign grain boundaries[J]. Nature photonics, 2015, 9(6): 409-415. DOI: 10.1038/nphoton.2015.78.

[25]
SHEN K, OU C Z, HUANG T L, et al.Mechanisms and modification of nonlinear shunt leakage in Sb2Se3 thin film solar cells[J]. Solar energy materials and solar cells, 2018, 186: 58-65. DOI: 10.1016/j.solmat.2018.06.022.

[26]
WEN X X, CHEN C, LU S C, et al.Vapor transport deposition of antimony selenide thin film solar cells with 7.6% efficiency[J]. Nature communications, 2018, 9(1): 2179. DOI: 10.1038/s41467-018-04634-6.

[27]
TANG R, ZHENG Z H, SU Z H, et al.Highly efficient and stable planar heterojunction solar cell based on sputtered and post-selenized Sb2Se3 thin film[J]. Nano energy, 2019, 64: 103929. DOI: 10.1016/j.nanoen.2019.103929.

[28]
CHEN C, YIN Y W, LIAN W T, et al.Pulsed laser deposition of antimony selenosulfide thin film for efficient solar cells[J]. Applied physics letters, 2020, 116(13): 133901. DOI: 10.1063/1.5139467.

[29]
CHEN S Y, GONG X G, WALSH A, et al.Defect physics of the kesterite thin-film solar cell absorber Cu2ZnSnS4[J]. Applied physics letters, 2010, 96(2): 021902. DOI: 10.1063/1.3275796.

[30]
CHEN S Y, WALSH A, GONG X G, et al.Classification of lattice defects in the kesterite Cu2ZnSnS4 and Cu2ZnSnSe4 earth-abundant solar cell absorbers[J]. Advanced materials, 2013, 25(11): 1522-1539. DOI: 10.1002/adma.201203146.

[31]
HUANG M L, XU P, HAN D, et al.Complicated and unconventional defect properties of the quasi-one- dimensional photovoltaic semiconductor Sb2Se3[J]. ACS applied materials & interfaces, 2019, 11(17): 15564-15572. DOI: 10.1021/acsami.9b01220.

[32]
HEO S, SEO G, LEE Y, et al.Deep level trapped defect analysis in CH3NH3PbI3 perovskite solar cells by deep level transient spectroscopy[J]. Energy & environmental science, 2017, 10(5): 1128-1133. DOI: 10.1039/C7EE00303J.

[33]
LANG D V.Deep-level transient spectroscopy: a new method to characterize traps in semiconductors[J]. Journal of applied physics, 1974, 45(7): 3023-3032. DOI: 10.1063/1.1663719.

[34]
AURET F D, NEL M.Detection of minority-carrier defects by deep level transient spectroscopy using Schottky barrier diodes[J]. Journal of applied physics, 1987, 61(7): 2546-2549. DOI: 10.1063/1.337931.

[35]
NGUYEN T P.Defects in organic electronic devices[J]. Physica status solidi (a), 2008, 205(1): 162-166. DOI: 10.1002/pssa.200776805.

[36]
JASENEK A, RAU U, NADENAU V, et al.Electronic properties of CuGaSe2-based heterojunction solar cells. Part II. Defect spectroscopy[J]. Journal of applied physics, 2000, 87(1): 594-602. DOI: 10.1063/1.371904.

[37]
HU X B, TAO J H, WENG G E, et al.Investigation of electrically-active defects in Sb2Se3 thin-film solar cells with up to 5.91% efficiency via admittance spectroscopy[J]. Solar energy materials and solar cells, 2018, 186: 324-329. DOI: 10.1016/j.solmat.2018.07.004.

[38]
NGO T T, CHAVHAN S, KOSTA I, et al.Electrodeposition of antimony selenide thin films and application in semiconductor sensitized solar cells[J]. ACS applied materials & interfaces, 2014, 6(4): 2836-2841. DOI: 10.1021/am405416a.

[39]
MESSINA S, NAIR M T S, NAIR P K. Antimony selenide absorber thin films in all-chemically deposited solar cells[J]. Journal of the electrochemical society, 2009, 156(5): H327-H332. DOI: 10.1149/1.3089358

[40]
CHOI Y C, MANDAL T N, YANG W S, et al.Sb2Se3-sensitized inorganic-organic heterojunction solar cells fabricated using a single-source precursor[J]. Angewandte chemie, 2014, 126(5): 1353-1357. DOI: 10.1002/ange.201308331.

[41]
LI Z Q, LIANG X Y, LI G, et al.9.2%-efficient core-shell structured antimony selenide nanorod array solar cells[J]. Nature communications, 2019, 10(1): 125. DOI: 10.1038/s41467-018-07903-6.

[42]
SHEN K, ZHANG Y, WANG X Q, et al.Efficient and stable planar n-i-p Sb2Se3 solar cells enabled by oriented 1D trigonal selenium structures[J]. Advanced science, 2020, 7(16): 2001013. DOI: 10.1002/advs.202001013.

[43]
LIU C, SHEN K, LIN D X, et al.Back contact interfacial modification in highly-efficient all-inorganic planar n-i-p Sb2Se3 solar cells[J]. ACS applied materials & interfaces, 2020, 12(34): 38397-38405. DOI: 10.1021/acsami.0c10629.

[44]
LIANG G X, LUO Y D, CHEN S, et al.Sputtered and selenized Sb2Se3 thin-film solar cells with open-circuit voltage exceeding 500 mV[J]. Nano energy, 2020, 73: 104806. DOI: 10.1016/j.nanoen.2020.104806.

[45]
CHANG J A, RHEE J H, IM S H, et al.High- performance nanostructured inorganic-organic heterojunction solar cells[J]. Nano letters, 2010, 10(7): 2609-2612. DOI: 10.1021/nl101322h.

[46]
CHOI Y C, LEE D U, NOH J H, et al.Highly improved Sb2S3 sensitized-inorganic-organic heterojunction solar cells and quantification of traps by deep-level transient spectroscopy[J]. Advanced functional materials, 2014, 24(23): 3587-3592. DOI: 10.1002/adfm.201304238.

[47]
ESCORCIA-GARCÍA J, BECERRA D, NAIR M T S, et al. Heterojunction CdS/Sb2S3 solar cells using antimony sulfide thin films prepared by thermal evaporation[J]. Thin solid films, 2014, 569: 28-34. DOI: 10.1016/j.tsf.2014.08.024.

[48]
MAYON Y O, WHITE T P, WANG R P, et al.Evaporated and solution deposited planar Sb2S3 solar cells: a comparison and its significance[J]. Physica status solidi (A), 2016, 213(1): 108-113. DOI: 10.1002/pssa.201532438.

[49]
ZHANG H, YUAN S J, DENG H, et al.Controllable orientations for Sb2S3 solar cells by vertical VTD method[J]. Progress in photovoltaics: research and applications, 2020, 28(8): 823-832. DOI: 10.1002/pip.3278.

[50]
DENG H, ZENG Y Y, ISHAQ M, et al.Quasiepitaxy strategy for efficient full-inorganic Sb2S3 solar cells[J]. Advanced functional materials, 2019, 29(31): 1901720. DOI: 10.1002/adfm.201901720.

[51]
ZENG Y Y, SUN K W, HUANG J L, et al.Quasi-vertically-orientated antimony sulfide inorganic thin-film solar cells achieved by vapor transport deposition[J]. ACS applied materials & interfaces, 2020, 12(20): 22825-22834. DOI: 10.1021/acsami.0c02697.

[52]
PAN G X, WANG D X, GAO S S, et al.Substrate structured Sb2S3 thin film solar cells fabricated by rapid thermal evaporation method[J]. Solar energy, 2019, 182: 64-71. DOI: 10.1016/j.solener.2019.02.014.

[53]
LIU L, ZHANG S L, WU J Y, et al.Current improvement in substrate structured Sb2S3 solar cells with MoSe2 interlayer[J]. Chinese physics B, 2020, 29(5): 058801. DOI: 10.1088/1674-1056/ab8220.

[54]
LUO J T, XIONG W, LIANG G X, et al.Fabrication of Sb2S3 thin films by magnetron sputtering and post-sulfurization/selenization for substrate structured solar cells[J]. Journal of alloys and compounds, 2020, 826: 154235. DOI: 10.1016/j.jallcom.2020.154235.

[55]
JIANG C H, TANG R F, WANG X M, et al.Alkali metals doping for high-performance planar heterojunction Sb2S3 solar cells[J]. Solar RRL, 2019, 3(1): 1800272. DOI: 10.1002/solr.201800272.

[56]
TANG R F, WANG X M, JIANG C H, et al.n-type doping of Sb2S3 light-harvesting films enabling high-efficiency planar heterojunction solar cells[J]. ACS applied materials & interfaces, 2018, 10(36): 30314-30321. DOI: 10.1021/acsami.8b08965.

[57]
WANG X M, LI J M, LIU W F, et al.A fast chemical approach towards Sb2S3 film with a large grain size for high- performance planar heterojunction solar cells[J]. Nanoscale, 2017, 9(10): 3386-3390. DOI: 10.1039/C7NR00154A.

[58]
ZHANG L J, JIANG C H, WU C Y, et al.V2O5 as hole transporting material for efficient all inorganic Sb2S3 solar cells[J]. ACS applied materials & interfaces, 2018, 10(32): 27098-27105. DOI: 10.1021/acsami.8b09843.

[59]
TANG R F, WANG X M, LIAN W T, et al.Hydrothermal deposition of antimony selenosulfide thin films enables solar cells with 10% efficiency[J]. Nature energy, 2020, 5(8): 587-595. DOI: 10.1038/s41560-020-0652-3.

[60]
JIN X, FANG Y N, SALIM T, et al.In situ growth of [hk1]-oriented Sb2S3 for solution-processed planar heterojunction solar cell with 6.4% efficiency[J]. Advanced functional materials, 2020, 30(35): 2002887. DOI: 10.1002/adfm.202002887.

[61]
HAN J, PU X Y, ZHOU H, et al.Synergistic effect through the introduction of inorganic zinc halides at the interface of TiO2 and Sb2S3 for high-performance Sb2S3 planar thin-film solar cells[J]. ACS applied materials & interfaces, 2020, 12(39): 44297-44306. DOI: 10.1021/acsami.0c11550.

[62]
HAN J, WANG S J, YANG J B, et al.Solution- processed Sb2S3 planar thin film solar cells with a conversion efficiency of 6.9% at an open circuit voltage of 0.7 v achieved via surface passivation by a SbCl3 interface layer[J]. ACS applied materials & interfaces, 2020, 12(4): 4970-4979. DOI: 10.1021/acsami.9b15148.

[63]
EL-SAYAD E A. Compositional dependence of the optical properties of amorphous Sb2Se3-xSx thin films[J]. Journal of non-crystalline solids, 2008, 354(32): 3806-3811. DOI: 10.1016/j.jnoncrysol.2008.05.004.

[64]
YANG B, XUE D J, LENG M Y, et al.Hydrazine solution processed Sb2S3, Sb2Se3 and Sb2(S1-xSex)3 film: molecular precursor identification, film fabrication and band gap tuning[J]. Scientific reports, 2015, 5: 10978. DOI: 10.1038/srep10978.

[65]
YANG B, QIN S K, XUE D J, et al.In situ sulfurization to generate Sb2(Se1-xSx)3 alloyed films and their application for photovoltaics[J]. Progress in photovoltaics: research and applications, 2017, 25(1): 113-122. DOI: 10.1002/pip.2819.

[66]
ISHAQ M, DENG H, YUAN S J, et al.Efficient double buffer layer Sb2 (SexS1-x)3 thin film solar cell via single source evaporation[J]. Solar RRL, 2018, 2(10): 1800144. DOI: 10.1002/solr.201800144.

[67]
LU S C, ZHAO Y, WEN X X, et al.Sb2(Se1-xSx)3 thin-film solar cells fabricated by single-source vapor transport deposition[J]. Solar RRL, 2019, 3(4): 1800280. DOI: 10.1002/solr.201800280.

[68]
LI K H, LU Y, KE X X, et al.Over 7% efficiency of Sb2(S,Se)3 solar cells via v-shaped bandgap engineering[J]. Solar RRL, 2020, 4(9): 2000220. DOI: 10.1002/solr.202000220.

[69]
NIE R M, LEE K S, HU M M, et al.Strain tuning via larger cation and anion codoping for efficient and stable antimony-based solar cells[J]. Advanced science, 2021, 8(1): 2002391. DOI: 10.1002/advs.202002391.

[70]
WANG W H, WANG X M, CHEN G L, et al.Promising Sb2(S,Se)3 solar cells with high open voltage by application of a TiO2/CdS double buffer layer[J]. Solar RRL, 2018, 2(11): 1800208. DOI: 10.1002/solr.201800208.

[71]
WANG W H, WANG X M, CHEN G L, et al.Over 6% certified Sb2(S,Se)3 solar cells fabricated via in situ hydrothermal Growth and postselenization[J]. Advanced electronic materials, 2019, 5(2): 1800683. DOI: 10.1002/aelm.201800683.

[72]
WANG X M, TANG R F, JIANG C H, et al.Manipulating the electrical properties of Sb2(S,Se)3 film for high-efficiency solar cell[J]. Advanced Energy Materials, 2020, 10(40): 2002341. DOI: 10.1002/aenm.202002341.

[73]
HAN W H, GAO D, TANG R F, et al.Efficient Sb2(S,Se)3 solar modules enabled by hydrothermal deposition[J]. Solar RRL, 2021, 5(3): 2000750. DOI: 10.1002/solr.202000750.

[74]
LUO M, LENG M Y, LIU X S, et al.Thermal evaporation and characterization of superstrate CdS/Sb2Se3 solar cells[J]. Applied physics letters, 2014, 104(17): 173904. DOI: 10.1063/1.4874878.

[75]
LENG M Y, LUO M, CHEN C, et al.Selenization of Sb2Se3 absorber layer: an efficient step to improve device performance of CdS/Sb2Se3 solar cells[J]. Applied physics letters, 2014, 105(8): 083905. DOI: 10.1063/1.4894170.

[76]
KUMAR V, ARTEGIANI E, KUMAR A, et al.Effects of post-deposition annealing and copper inclusion in superstrate Sb2Se3 based solar cells by thermal evaporation[J]. Solar energy, 2019, 193: 452-457. DOI: 10.1016/j.solener.2019.09.069.

[77]
LI K H, CHEN C, LU S C, et al.Orientation engineering in low-dimensional crystal-structural materials via seed screening[J]. Advanced materials, 2019, 31(44): 1903914. DOI: 10.1002/adma.201903914.

[78]
LI K H, WANG S Y, CHEN C, et al.7.5% n-i-p Sb2Se3 solar cells with CuSCN as a hole-transport layer[J]. Journal of materials chemistry A, 2019, 7(16): 9665-9672. DOI: 10.1039/C9TA01773A.

[79]
WANG X M, TANG R F, YIN Y W, et al.Interfacial engineering for high efficiency solution processed Sb2Se3 solar cells[J]. Solar energy materials and solar cells, 2019, 189: 5-10. DOI: 10.1016/j.solmat.2018.09.020.

[80]
YANG Y J, GUO T Z, WANG D, et al.Preparation and characterization of pulsed laser deposited CdSe window layer for Sb2Se3 thin film solar cell[J]. Journal of materials science: materials in electronics, 2020, 31(16): 13947-13956. DOI: 10.1007/s10854-020-03954-y.

[81]
LI G, LI Z Q, LIANG X Y, et al.Improvement in Sb2Se3 solar cell efficiency through band alignment engineering at the buffer/absorber interface[J]. ACS applied materials & interfaces, 2019, 11(1): 828-834. DOI: 10.1021/acsami.8b17611.

[82]
GUO L P, ZHANG B Y, RANJIT S, et al.Interface engineering via sputtered oxygenated CdS:O window layer for highly efficient Sb2Se3 thin-film solar cells with efficiency above 7%[J]. Solar RRL, 2019, 3(10): 1900225. DOI: 10.1002/solr.201900225.

[83]
HOBSON T D C, PHILLIPS L J, HUTTER O S, et al. Isotype heterojunction solar cells using n-type Sb2Se3 thin films[J]. Chemistry of materials, 2020, 32(6): 2621-2630. DOI: 10.1021/acs.chemmater.0c00223.

[84]
CANG Q F, GUO H F, JIA X G, et al.Enhancement in the efficiency of Sb2Se3 solar cells by adding low lattice mismatch CuSbSe2 hole transport layer[J]. Solar energy, 2020, 199: 19-25. DOI: 10.1016/j.solener.2020.02.008.

[85]
WU C Y, LIAN W T, ZHANG L J, et al.Water additive enhanced solution processing of alloy Sb2(S1-xSex)3-based solar cells[J]. Solar RRL, 2020, 4(5): 1900582. DOI: 10.1002/solr.201900582.

[86]
WU C Y, JIANG C H, WANG X M, et al.Interfacial engineering by indium-doped CdS for high efficiency solution processed Sb2(S1-xSex)3 solar cells[J]. ACS applied materials & interfaces, 2019, 11(3): 3207-3213. DOI: 10.1021/acsami.8b18330.

[87]
ZHANG Y, LI J M, JIANG G S, et al.Selenium-graded Sb2(S1-xSex)3 for planar heterojunction solar cell delivering a certified power conversion efficiency of 5.71%[J]. Solar RRL, 2017, 1(5): 1700017. DOI: 10.1002/solr.201700017.

[88]
JIANG C H, ZHOU J, TANG R F, et al.9.7%-efficient Sb2(S,Se)3 solar cells with a dithieno[3,2-b: 2′3′-d]pyrrole- cored hole transporting material[J]. Energy & environmental science, 2021, 14(1): 359-364. DOI: 10.1039/D0EE02239J.

[89]
CHEN C, WANG L, GAO L, et al.6.5% Certified Efficiency Sb2Se3 Solar Cells Using PbS Colloidal Quantum Dot Film as Hole-Transporting Layer[J]. ACS Energy Letters, 2017, 2(9), 2125-2132. DOI: 10.1021/acsenergylett.7b00648.

[90]
LIU C P, WANG H E, NG T W, et al.Hybrid photovoltaic cells based on ZnO/Sb2S3/P3HT heterojunctions[J]. Physica Status Solidi (B) 2012, 249(3), 627-633. DOI: 10.1002/pssb.201147393.

[91]
KIM D H, LEE S J, PARK M S, et al.Highly reproducible planar Sb2S3-sensitized solar cells based on atomic layer deposition[J]. Nanoscale 2014, 6(23), 14549-14554. DOI: 10.1039/c4nr04148h.

[92]
CHOI Y C, SEOK S I.Efficient Sb2S3-Sensitized Solar Cells Via Single-Step Deposition of Sb2S3 Using S/Sb- Ratio-Controlled SbCl3-Thiourea Complex Solution[J]. Advanced Functional Materials 2015, 25(19), 2892-2898. DOI: 10.1002/adfm.201500296.

Options
Outlines

/

〈 〉

Superintendent: Chinese Academy of Sciences
Sponsored by: Guangzhou Institute of Energy Conversion (GIEC), Chinese Academy of Sciences
ISSN 2095-560X　
CN 44-1698/TK
Tel: +86-20-87057066　
E-mail：xnyjz@ms.giec.ac.cn
粤ICP备11089167号-2　 Copyright © Advances in New and Renewable Energy