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2022 , Vol. 10 >Issue 3: 233 - 243

DOI: https://doi.org/10.3969/j.issn.2095-560X.2022.03.007

Research Progress on Copper-Based Perovskite Materials

  • Ya-jie ZHAO 1, 2, 3, 4 ,
  • Gui-zhang SHENG 1, 2, 3, 5 ,
  • Jie-yuan ZHENG 1, 2, 3, 5 ,
  • Xue-song CAI 1, 2, 3, 6 ,
  • Li-rong CHEN 1, 2, 3, 6 ,
  • Xiu-di XIAO , †, 1, 2, 3 ,
  • Gang XU 1, 2, 3
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  • 1. Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China
  • 2. CAS Key Laboratory of Renewable Energy, Guangzhou 510640, China
  • 3. Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, China
  • 4. Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215123, Jiangsu, China
  • 5. University of Chinese Academy of Sciences, Beijing 100049, China
  • 6. University of Science and Technology of China, Hefei 230026, China

Received date: 2022-03-01

  Revised date: 2022-04-12

  Online published: 2022-06-30

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版权所有 © 《新能源进展》编辑部
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Abstract

Lead-based perovskites have the advantages of suitable band gap, wide spectral absorption range, high carrier diffusion length, etc, while the problems of toxicity and poor stability also limit the commercial development of lead-based perovskites. Based on this, the use of other non-toxic metal elements instead of leading elements to prepare lead-free perovskite with high stability in air is of great significance. Copper storage is rich and environmentally friendly, copper-based perovskite materials can solve the problems of toxicity and instability of Lead-based perovskites to a certain extent, and can be used in many fields such as photovoltaics, thermochromism, and photodetectors. In this paper, the types of lead-free copper-based perovskites and their research status in solar cells, thermochromism, luminescence, photodetectors, and catalysis, and indicates possible future research directions were reviewed, and the potential research direction in the future was pointed out.

Key words： copper-based perovskites; structure; applications

Cite this article

Ya-jie ZHAO , Gui-zhang SHENG , Jie-yuan ZHENG , Xue-song CAI , Li-rong CHEN , Xiu-di XIAO , Gang XU . Research Progress on Copper-Based Perovskite Materials[J]. Advances in New and Renewable Energy, 2022 , 10(3) : 233 -243 . DOI: 10.3969/j.issn.2095-560X.2022.03.007

0 引言

钙钛矿是一类通式为ABO3或ABX3的复合金属化合物,其中A位是半径较大的阳离子,主要起支撑骨架的作用;B位为半径较小的金属阳离子,是钙钛矿结构的中心部位;O是氧离子,X是卤素离子（如Cl-、Br-、I-）。按结构类型划分,一般有简单的钙钛矿结构、双钙钛矿结构和层状钙钛矿结构,具有钙钛矿结构类型的化合物所属晶系主要有正交、立方、四方、单斜和三斜晶系。常规钙钛矿材料具有Pm$\bar{3}$m空间群立方晶体结构,占据A位的阳离子有12个阴离子配位,形成最密立方堆积;占据B位的阳离子有6个阴离子配位,占据立方密堆积中的八面体中心,最终可以长成三维（3D）、二维（2D）、一维（1D）或零维（0D）晶体结构[1,2]。
钙钛矿成分和元素价态的多变性通常是决定其结构及性质的主要因素[3,4]。与简单化合物相比,钙钛矿结构可以使一些元素以非正常价态存在,具有非化学计量比的氧或活性金属以混合价态存在可以使钙钛矿呈现出某些特殊的性质。在满足离子半径和电中性要求的前提下,钙钛矿的A位和B位能够被其他不同的离子部分取代,从而生成多组分化合物。被部分取代后的钙钛矿能够保持晶体结构基本不变,并不会产生离子结构缺陷,不同位置的离子取代及结构调控使其化学成分和形貌具有很高的灵活性,同时也赋予了其优异的光学、电学等物理化学性质,进而能够在太阳能电池、发光、光电探测等多个领域[5,6,7,8,9,10,11,12]都有较为广泛的研究和应用。
钙钛矿中的铅基卤化物钙钛矿由于具有可调的光学带隙、高载流子迁移率、较长的载流子扩散长度和载流子寿命、高光电转换效率、大吸收系数[13,14,15]等优点,使其在光伏发电领域被广泛研究,而且目前单结钙钛矿太阳能电池已经实现了25.7%的美国国家可再生能源实验室（National Renewable Energy Laboratory, NREL）认证效率[16]（图1）,与硅基太阳能电池效率相当[17]。此外,铅基卤化物钙钛矿在光致发光、光电探测、晶体管和激光器等领域也迅发展[18,19,20,21]。然而,铅基钙钛矿也因其缓慢降解带来的毒性问题以及卤化铅钙钛矿材料对湿度、氧气、紫外线和热不稳定性等问题,给其商业化应用带来了巨大的挑战[22,23,24]。大量研究工作旨在开发新的无铅钙钛矿材料,锡（Sn）、锗（Ge）、铋（Bi）、锑（Sb）和铜（Cu）等元素是有望替代铅的候选者[25,26,27,28,29]。然而,Sn和Ge基钙钛矿材料暴露于周围环境时表现出较差的化学稳定性;Bi和Sb元素已被应用于构建三价金属阳离子小尺寸结构的无铅钙钛矿或者双钙钛矿[30]等,但是这些低维钙钛矿和双钙钛矿通常具有较大的激子结合能和较宽的带隙,不利于光电转换。
Fig. 1 Best research-cell efficiencies of emerging photovoltaics[16]

图1 新兴光伏研究的最佳电池效率[16]

铜是一种含量丰富、成本低且对环境友好的元素,甚至在人体中都存在一定量的铜离子。铜基钙钛矿主要可分为氧化物型结构和卤化物型结构。目前在常见的ACuO3型氧化铜基钙钛矿中,A位主要为La、Ce、K、Ca、Mg和Sr等,该类型的晶体结构能够允许组成元素A:Cu:O的化学计量比偏离1:1:3,形成具有非化学计量比的A1-xA'xCuO3±δ多组分氧化铜基钙钛矿结构,金属离子和晶格氧是主要活性位,决定着钙钛矿的氧化还原性能,在催化过程中起关键作用[31]。而在卤化铜基钙钛矿中,A位阳离子既可以是有机铵阳离子,也可以是铯离子。对于有机-无机杂化卤化铜基钙钛矿,由于铜离子半径较小而有机铵阳离子尺寸较大,因此这种结构一般不受常规钙钛矿容忍因子和八面体因子的限制,可以形成二维层状结构,二维无机层[CuX4]2-与A位阳离子交替存在,这种二维结构为构建有机无机杂化钙钛矿材料提供了较大的灵活性[32,33],在热致变色和太阳能电池等领域研究较多。此外,具有深度自陷激子的全无机卤化铜基钙钛矿（Cs3Cu2X5和Cs2CuX3）由于其无毒、有良好的量子光电转换效率和量子效率等特点在光电应用中也显示出了广阔的前景[34]。
铜基钙钛矿除了具有一般钙钛矿的光学和电学等方面的性质外,还有优于铅基和锡基等钙钛矿的低毒性和稳定性。本文根据铜基钙钛矿的不同性质,总结其在太阳能电池、热致变色、发光、光电探测器、催化等方面的应用。

1 铜基钙钛矿材料的应用

1.1 太阳能电池

作为第三代太阳能电池吸收材料之一的钙钛矿,在2009年首次[35]被尝试应用于光伏发电领域之后,光电转换效率已经实现了较大提升,因其性能优异、成本低廉、商业价值巨大而掀起了全球范围内的研究热潮。目前用于实验研究的铜基钙钛矿基本上是二维层状结构,这种二维杂化铜基钙钛矿主要是以通式为(A')2(A)n-1CuX3n+1的Ruddlesden-Popper（RP）型钙钛矿结构为主（其中A'为有机单铵根阳离子）,而随着研究的不断深入,Dion-Jacobson（DJ）型钙钛矿(A'')(A)n-1CuX3n+1也较受关注。RP型层状钙钛矿的有机层之间存在较弱的范德华作用力,而DJ型层状钙钛矿的间隔组分A''通常为有机二铵阳离子,两端直接以氢键与无机层相连,没有范德华力作用,因此相较而言具有更强的稳定性[36,37,38]。
CUI等[39]早期报道了(p-FC6H5C2H4NH3)2CuBr4（P1）和[CH3(CH2)3NH3]2CuBr4（P2）这两种溴化铜基钙钛矿的合成,其带隙分别是1.74 eV和1.76 eV。进而使用这两种材料作为光吸收剂,Spiro-OMeTAD（2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9'-螺二芴）作为空穴传输材料,在介孔TiO2异质结太阳能电池中初步探究了光电性能：P1在短路电流Jsc = 1.46 mA/cm2、开路电压Voc = 0.87 V、填充因子FF = 0.40时实现了0.51%的光电转换效率,而P2在Jsc = 1.78 mA/cm2、Voc = 0.88 V、FF = 0.40时实现了0.63%的光电转换效率（图2a）。
Fig. 2 J-V curves (a) and incident photon-to-current efficiency (IPCE) curves (b) for the P1- or P2- based devices[39]; (c) J-V curves of solar cells sensitized with MA2CuCl2Br2 and MA2CuCl0.5Br3.5 under 1 sun of light illumination; (d) photocurrent measurement performed on a device sensitized with MA2CuCl2Br2 (upper) compared to the perovskite absorption spectrum[40]; (e) current-voltage curves and (f) external quantum efficiency (EQE) spectra of the solar cells consisting of (CH3NH3)2CuCl4, (CH3NH3)2CuCl2I2 and (CH3NH3)2CuCl2Br2 perovskites as absorber materials[41]

图2 基于P1和P2器件的J-V曲线（a）和入射单色光子-电子转化效率（incident photon-to-current efficiency, IPCE）曲线（b）[39];（c）MA2CuCl2Br2和MA2CuCl0.5Br3.5太阳能电池在 1 个太阳光照下的 J-V 曲线;（d）与钙钛矿吸收光谱相比,在MA2CuCl2Br2（上图）器件上进行的光电流测量[40];（e）电流-电压曲线和（f）由(CH3NH3)2CuCl4、(CH3NH3)2CuCl2I2和 (CH3NH3)2CuCl2Br2组成的太阳能电池的外量子效率（external quantum efficiency, EQE）光谱[41]

2016年,CORTECCHIA等[40]详细研究了具有(CH3NH3)2CuClxBr4-x结构的混合铜基卤化物钙钛矿及其光电特性,由于铜离子半径较小,这种钙钛矿具有二维结构,并且可以通过改变卤化物成分来调节钙钛矿的带隙（图3）。当钙钛矿阴离子仅由溴离子组成时,获得的钙钛矿纯度低,对大气水分非常敏感;当加入少量氯离子后可以显著增加结晶程度,且增大了混合铜基卤化物钙钛矿在潮湿环境中的稳定性。基于Spiro-OMeTAD和介孔TiO2功能层所制备的光伏器件经过优化后,(CH3NH3)2CuCl2Br2的光电转换效率为0.017%,此时Jsc = 216 μA∙cm2、Voc = 256 mV、FF = 0.32,同时还观察到了较大的暗电流（图2c）,高漏电流的存在可能是由于钙钛矿覆盖不均匀导致介孔TiO2与空穴传输层之间直接接触所引起,而且较低的光伏效率也与二维钙钛矿材料中载流子朝向 (001) 方向的不利扩散有较大关系。
Fig. 3 Absorption coefficient for perovskites of the series (CH3NH3)2CuClxBr4-x (inset: broad d-d transitions between 650 nm and 900 nm) [40]

图3 (CH3NH3)2CuClxBr4-x系列钙钛矿的吸收系数（插图为650 ~ 900 nm之间的宽d-d跃迁）[40]

2018年,ELSEMAN课题组[41]通过调整卤素的组成研究了(CH3NH3)2CuX4系列铜基钙钛矿的光电性质。该研究主要对(CH3NH3)2CuCl4、(CH3NH3)2CuCl2I2、(CH3NH3)2CuCl2Br2三种材料进行讨论,也再次证实该系列铜基钙钛矿中Cl元素存在对结构稳定至关重要,这类钙钛矿材料显示出一定吸收特性,可扩展到近红外区,同时具有适当的带隙。在FTO/TiO2/(CH3NH3)2CuCl4[(CH3NH3)2CuCl2I2或(CH3NH3)2CuCl2Br2]/Spiro-OMeTAD/Au光伏器件中,(CH3NH3)2CuCl4、(CH3NH3)2CuCl2I2、(CH3NH3)2CuCl2Br2作为吸收层时效率分别可以达到2.41%、1.75%和0.99%（图2e）。尽管优化了钙钛矿材料的带隙,但由于(CH3NH3)2CuCl2Br2中较高的陷阱密度引起Cu2+ 减少导致太阳能电池光电转换效率仍然不理想。
DJ型钙钛矿pPDACuBr4[42][pPDA2+为(H3NC6H4NH3)2+]具有1.43 eV的带隙,接近用于单结太阳能电池的GaAs半导体（约1.42eV）。在相对湿度为40% ~ 50%环境中连续暴露1 200 h,并在充满氮气的手套箱中受紫外照射1 008 h后,pPDACuBr4薄膜仍表现出优异的稳定性（图4）。此外,通过热铸技术还能实现大面积（大于20 cm2）制备无针孔、光滑的pPDACuBr4薄膜,这也是目前报道的最大的铜基钙钛矿薄膜,为进一步开发潜在光电应用的低带隙、高稳定性无铅钙钛矿材料奠定了基础。
Fig. 4 (a) UV-vis spectra of the pPDACuBr4 film and that after storage in ambient air (relative humidity of 40% - 50%) for 120, 240, 480, and 1 200 h (inset: the image of the pPDACuBr4 film used for the humidity stability test); (b) UV-vis spectra of the pPDACuBr4 film and that after storage under UV light (395 nm) for 72 h, 168 h, 504 h, and 1 008 h (inset: the image of the pPDACuBr4 film under UV light); (c) UV-vis spectra of the pPDACuBr4 film before and after heating at 90°C in ambient air for 180 h; (d) TGA curve of the pPDACuBr4 materials[42]

图4 （a）pPDACuBr4薄膜在环境空气中分别储存（相对湿度为40% ~ 50%）120 h、240 h、480 h和1 200 h后的紫外-可见光谱（插图为用于湿度稳定性测试的pPDACuBr4薄膜）;（b）pPDACuBr4薄膜在紫外光（395 nm）下分别储存72 h、168 h、504 h和1 008 h后的紫外-可见光谱（插图为在紫外光下拍摄的pPDACuBr4薄膜）;（c）pPDACuBr4薄膜在环境空气中90℃加热180 h之前和之后的紫外-可见光谱;（d）pPDACuBr4的热重曲线[42]

到目前为止,铜基钙钛矿太阳能电池的光电转换效率都远低于铅基或锡基钙钛矿太阳能电池的效率,电荷传输时较强的各向异性[40]、较多的缺陷[41]以及较短的载流子寿命[43]等是限制效率的主要因素。但同时2D铜基钙钛矿材料作为光吸收材料所展示出的一定效率和稳定性[44],也为进一步开发基于过渡金属的钙钛矿以及探索新型高稳定无毒的光伏材料提供了崭新的思路。

1.2 热致变色

二维有机-无机杂化铜基钙钛矿材料由于姜-泰勒效应（Jahn-Taller effect）[45]而使其结构具有较强的灵活性,当这类材料在所处的温度条件变化时,钙钛矿容易发生相变,这种相变过程主要是铜离子周围的配位构型改变,进而改变了材料颜色。
ELATTAR等[46]报道了通过机械剥离法合成(CH3NH3)2CuClxBr4-x 2D铜基混合卤化物钙钛矿薄膜,并研究了其结构、热学、光学和热致变色性质。随着Br含量的增加,混合卤化物铜基钙钛矿表现出可调的带隙能量,范围为2.24 ~ 1.43 eV。在温度变化时,富氯钙钛矿表现出可逆的热致变色行为,颜色在黄色、橙色、红色和棕色之间变化,但富溴钙钛矿却没有观察到可逆的颜色变化（图5）。
Fig. 5 Color changes of (CH3NH3)2CuClxBr4-x crystals at room temperature (a) and elevated temperature (b) (where the x values in the ① - ⑧ perovskite structures are 4, 3.63, 2.55, 2.20, 1.79, 0.78, 0.31, 0, respectively)[ 46]

图5 (CH3NH3)2CuClxbr4-x 晶体分别在室温（a）和高温（b）时的颜色变化（其中 ① ~ ⑧钙钛矿结构中的x值分别为4、3.63、2.55、2.20、1.79、0.78、0.31、0）[46]

LI等[47]对铜基钙钛矿的结构相变和热致变色进行了深入研究（图6）,发现二维铜基钙钛矿材料A2CuCl4（A = CnH2n+1NH3, n = 1 ~ 6）中的有机组分A对材料的变色温度起到了一定的调控作用,随着有机组分碳原子数目的增加,材料的变色温度先升高后降低。该研究工作利用同步辐射的变温X射线吸收精细结构（X-ray absorption fine structure, XAFS）测试,获得了在室温和高温下Cu2+ 周围的局域结构信息,升高温度会导致铜氯原子四配位结构中的Cu-Cl键长的变化并改变Cu2+ 周围的化学环境,影响了其中电荷结构转移过程进而引起材料宏观上颜色的变化。铜基钙钛矿的热致变色行为源于无机组分 [CuCl4]2- 几何构型的变化,而有机组分则通过影响其几何构型进而改变变色温度：长链有机组分的热运动变得迟缓导致变色温度升高,同时长链有机组分与无机组分的相互作用（N—H…Cl氢键）变弱又会导致变色温度降低。这项工作证明了杂化钙钛矿中有机组分对材料性质带来的影响,为分析材料的变色机理提供了最直接的实验证据,同时也为开发新型的光电功能杂化材料提供了有益的借鉴。
Fig. 6 Photograph images of color change in (MA)2CuCl4, (EA)2CuCl4, (HA)2CuCl4 upon temperature change[47] (MA = CH3NH3, EA = C2H5NH3, HA = C6H13NH3)

图6 (MA)2CuCl4、(EA)2CuCl4、(HA)2CuCl4晶体在温度变化时的颜色变化[47]（MA = CH3NH3,EA = C2H5NH3,HA = C6H13NH3）

此外,PAREJA-RIVERA等[48]发现了(CEA)2CuCl4和 (BEA)2CuCl4（CEA为2-氯乙基铵,BEA为2-溴乙基铵）两种钙钛矿也具有一定的热致变色行为（图7）。不同的是,由于 (BEA)2CuCl4有机铵阳离子中溴元素的存在,当温度发生改变后,溴元素会和X位中的氯元素发生部分交换,从而破坏了原来的(BEA)2CuCl4结构,导致即便再回到加热前的室温后,钙钛矿的颜色仍不能复原。该工作展示了一种调节铜基卤化物钙钛矿中热致变色的新方法,根据有机配体控制颜色变化使这些材料有望设计为不可逆的热致变色传感器。
Fig. 7 (a) Reversible thermochromic phenomenon of (CEA)2CuCl4; (b) irreversible thermochromic phenomenon of (BEA)2CuCl4[48]

图7 （a）(CEA)2CuCl4晶体的可逆热致变色现象;（b） (BEA)2CuCl4晶体的不可逆热致变色[48]

铜基层状钙钛矿由于带隙可调、组分可控、丰富的相变和热致变色行为有望成为无铅钙钛矿热致变色智能窗[49,50]的候选材料[51,52]。较为成熟的热致变色智能窗要求变色材料更稳定、更高效,对环境更友好,变色温度更接近室温,但目前研究所发现的这些铜基钙钛矿晶体变色差异仍不够明显,变色温度也远高于室温,若要将其投入智能窗的实际应用或者结合其光伏特性实现建筑光伏一体化的目标仍有不小的难度。

1.3 发光

作为智能发光材料领域的新材料,金属卤化物钙钛矿量子点因其具有低成本、高吸收系数、高荧光量子产率、窄的荧光发射半峰宽、可调的能带结构、长载流子寿命等诸多优点在发光领域引起了持续的关注[53,54,55]。
YANG等[56]在室温下通过改进配体辅助再沉积的技术合成了一系列全无机铜基钙钛矿的纳米晶体Cs2CuX4（X = Cl、Br和Br/I）,具有蓝绿色发光的Cs2CuX4纳米晶体荧光发射波长可以通过改变原材料的摩尔比进行调节（图8）。卤素诱导的可调性是由于能带结构的直接调制,由于卤化物轨道对卤化物钙钛矿纳米晶体中的前沿轨道贡献最大。这种现象也与卤化物电负性一致,即Cl使带隙增加,而Br和I使带隙逐渐减小。
Fig. 8 PL spectra of mixed halide perovskite QDs obtained via anion-exchange reactions (from left to right, Cs2CuClxBr4-x, Cs2CuBr4, and Cs2CuBr4-xIx) [56]

图8 通过阴离子交换反应获得的混合卤化物铜基钙钛矿量子点的PL光谱[56],从左到右依次为Cs2CuClxX4-x、Cs2CuBr4、Cs2CuBr4-xIx

除此之外,单价铜基[Cu(I)]类钙钛矿材料由于具有优异的光电性能和环境友好性,也被广泛应用于发光领域。JUN等[57]通过反溶剂蒸汽饱和旋涂法分别制备了0D Cs3Cu2I5单晶和薄膜。5 mm的Cs3Cu2I5单晶显示出445 nm的荧光发射,具有高达90%的荧光量子产率（photoluminescence quantum yield, PLQY）;而稳定的Cs3Cu2I5薄膜具有62%的PLQY。
这种具有高PLQY的单价铜基[Cu(I)]类钙钛矿材料在发光二极管[58]（light emitting diode, LED）中显示出巨大的应用前景。LIU等[59]采用环境友好、稳定性高的CsCu2I3作为发光层,使用真空沉积法制备了CsCu2I3发光二极管,实现了10 cd∙m2的最大发光亮度和0.02%的最佳外部量子效率（图9）。CsCu2I3的“软”晶格特性使其具有很强的光声耦合作用,其受激发后产生的电子-空穴对很容易引起晶格畸变从而被晶格捕获,形成自陷域态激子（self-trapped exciton, STE）。CsCu2I3是首次通过真空沉积技术成功实现了基于STE 的电致发光材料。相比于目前常用来制备钙钛矿层的溶液加工法,真空沉积技术有着制备环境可控、重复性高和可大面积制备的优点,是更有希望实现钙钛矿商业化应用批量生产的制备技术。该研究为钙钛矿材料的制备提供了另外一种新颖可靠的工艺路线,其制备的黄光LED也有望为产业界的黄光照明和显示应用提供新方向。
Fig. 9 (a) Current density-voltage (J-V) and luminance-voltage (L-V) curves of the CsCu2I3 Pe-LED; (b) EQE curve of the CsCu2I3 Pe-LED; (c) the CIE color coordinate of the CsCu2I3 Pe-LED[59]

图9 （a）CsCu2I3 Pe-LED的电流密度-电压（J-V）和亮度-电压（L-V）曲线;（b）CsCu2I3 Pe-LED的EQE曲线;（c）CsCu2I3 Pe-LED的CIE颜色坐标[59]

除了具有高的荧光量子效率外,通过改变化学组成来调整钙钛矿量子点的发光波长,或许可以探究将其应用于防伪或显示器的电致发光器件[37]中,在今后相关材料和技术方面的研究中都需要更多关注。

1.4 光电探测器

光电探测器的工作原理是基于半导体材料的光电效应,进一步将光信号转换为电信号,可以实现射线测量和探测、工业自动化控制、光度计量等[60]。在过去的几年中,全无机金属卤化物钙钛矿由于其优异的光电性能,包括优异的载流子传输能力、良好的热稳定性、可调发射和吸收性能,在光电器件领域引起了较大的关注[61,62]。其中,CsCu2I3相和Cs3Cu2I5相的铯铜碘基钙钛矿由于其无铅和高稳定性而备受关注,表1中总结了部分具有不同结构的铯铜碘光电探测器的性能。
Table 1 Performance comparisons of Cs-Cu-I copper-based perovskite photodetector

表1 Cs-Cu-I铜基钙钛矿光电探测器性能对比

Device structure Wavelength / nm Responsivity / (A/W) Detectivity / (cm·Hz1/2/W) On/Off ration Ref.
In/GaN/Cs3Cu2I5/Au 320 0.28@0V 1.4 × 1012 120 000 [63]
Cs3Cu2I5/Si-core/shell NWs 265 0.13@0V 3.1 × 1012 2 500 [64]
ITO/Cs3Cu2I5/ITO 265 0.0649@1V 6.9 × 1011 127 [65]
Au/CsCu2I3 nanowires/Au 325 32.2@5V 1.89 × 1012 2 600 [66]
Au/CsCu2I3 films/Au 265 22.1@3V 1.2 × 1011 22 [67]
Ag/CsCu2I3 single crystal/Ag 350 0.052@3V 9.3 × 1010 188 [68]
然而,由于CsCu2I3和Cs3Cu2I5两相通常共存,很难通过溶液法获得纯CsCu2I3。ZHOU等[69]通过真空热蒸发生长CuI缓冲层的CsCu2I3薄膜的无溶剂生长策略,获得了更高纯度的CsCu2I3材料,通过CuI缓冲层提高了CsCu2I3薄膜的纯度和光电特性。此外,基于高纯CsCu2I3薄膜制造的金属-半导体-金属（metal-semiconductor-metal, MSM）光电探测器在340 nm单色光连续照射下,Ag/CsCu2I3薄膜/Au探测器在5 V偏压下获得了6.6 × 10-4 A/W的响应率,相比基于不纯的CsCu2I3薄膜探测器其光电响应性能得到了较大的增强,而且响应度和比检测率也分别比没有CuI缓冲层的器件大了近74倍和138倍（图10）。该工作所获得的紫外光电探测器具有非常快的响应速度、出色的重现性和稳定性,这些优点为制备纯相CsCu2I3薄膜及相关高性能光电器件提供了可行的策略。
Fig. 10 Typical I-V curves for two devices under dark and UV illumination (340 nm): (a) Au/Cs-Cu-I (without CuI)/Au. (b) Au/Cs-Cu-I (with CuI)/Au; spectral responsivity (c) and detectivity (d) of Au/Cs-Cu-I (without CuI)/Au and Au/Cs-Cu-I (with CuI)/Au devices under 2 V[69]

图10 两种器件分别在黑暗和紫外光（340 nm）下的I-V 曲线：（a）Au/Cs-Cu-I（无CuI）/Au;（b）Au/Cs-Cu-I (含CuI)/Au;Au/Cs-Cu-I (不含 CuI)/Au和Au/Cs-Cu-I (含 CuI)/Au 器件在2 V下的光谱响应度（c）和检测率（d）[69]

1.5 催化

钙钛矿催化剂的催化机制主要从晶格氧的氧化作用和金属阳离子的反应性来解释。钙钛矿中的晶格氧能够氧化目标物质,参与气体的重整反应,从而抑制催化剂积碳;水对晶格氧的再生作用使得钙钛矿格外适用于生物质水蒸气气化和蒸气重整过程。此外钙钛矿的特殊结构能够促进活性金属的反应性能,有效缓解高温金属烧结。因此钙钛矿在生物质热化学领域表现出了优异的催化活性和稳定性。RAMKIRAN等[70]通过使用柠檬酸盐的溶胶凝胶法合成了LaCuO3钙钛矿,该催化剂能够催化乙醇生成氢气和一氧化碳等还原性气体,且具有较低的还原温度、较高的比表面积和结晶度、较多活性位点、良好的表面形貌,在生产合成气方面具有较大优势。
利用可再生能源将二氧化碳通过电还原转化为增值化工原料和燃料,是解决二氧化碳排放和缓解能源危机等问题最有潜力的技术之一。在各种流行的催化剂中,铜基催化剂能够在电还原中产生可观的高阶产物,如CH4、C2H4、C2H5OH等,其中Ruddlesden-Popper（RP）氧化钙钛矿因其组成灵活、结构多样、物理化学性质可控、活性位点多等独特的优点已被证明是重要的电化学反应潜在催化剂。用于电还原的铜基RP钙钛矿氧化物的研究尚处于起步阶段,但其催化性能仍有很大的提升空间。朱佳伟教授团队[71]通过使用La2-xCuO4-δ（x = 0, 0.1, 0.2, 0.3）系列作为概念验证催化剂,不仅系统地研究了铜基RP钙钛矿氧化物的A位阳离子缺陷与二氧化碳电还原性能之间的结构-活性关系（图11）,而且证明了调控A位阳离子缺陷是优化二氧化碳电还原性能的有效策略。在引入La位缺陷后,一方面,RP晶体结构中产生了一定数量的氧空位,几乎不随La位缺陷量而改变;另一方面,在较高的x值（即x = 0.2, 0.3）下,构建了CuO/RP杂化物,其中CuO含量随着La位缺陷的增加而增加。实验和理论计算都表明该强化的二氧化碳电还原性能主要归因于阳离子缺陷引起的氧空位或CuO/RP杂化体带来的显著优势,包括促进关键反应物种的吸附和活化以及控制CO* 中间体的二聚和氢化。这项工作为合理设计用作二氧化碳电还原高效催化剂的铜基RP钙钛矿氧化物提供了一条有效途径。
Fig. 11 Relationship between structure and activity of La2-xCuO4-δ series perovskites[71]

图11 La2-xCuO4-δ系列钙钛矿结构与活性关系[71]

2 总结与展望

电子器件行业的无铅化浪潮风靡全球,各种无毒的钙钛矿材料也将成为研究的重要对象。当前,铜基钙钛矿除了在太阳能电池、热致变色、发光、光电探测器、催化等方面的应用研究外,也拓展了关于湿度传感器、铁电材料等方面的初步探索,但将铜基钙钛矿材料应用于这些领域并实现量产化和商业化还有很大的距离。未来在铜基钙钛矿的发展上,以下几个方向仍具有研究价值：
（1）对于RP型或DJ型铜基钙钛矿,虽然较大的有机官能团可以提高材料的稳定性,但同时在一定程度上也会阻碍载流子的传输,影响光电性能。可以选择合适的界面修饰层和修饰物质来改善钙钛矿吸收层的形貌,减小界面间的非辐射复合,提高光吸收系数、载流子的寿命和传输能力,从而优化材料和器件性能;
（2）在Cs-Cu-X型钙钛矿发光材料中,可以通过掺杂或者钝化对材料进行尺寸调控,提高发光效率和稳定性;而基于Cs-Cu-I型的铜基钙钛矿光电探测器则可以在器件工程方面,通过活性层形貌调控、器件结构设计等进一步提高器件的光响应性能和比探测率;
（3）目前对氧化物型铜基钙钛矿作为催化剂的研究尚处于起步阶段,可催化的反应类型也比较单一。今后可以结合具有较高催化活性的元素,设计出成分和结构更加丰富的B位混合型钙钛矿,以提高催化剂的比表面积和催化性能,并深入了解其催化机制和规律。

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