有机无机杂化太阳能电池中常见无机缓冲层材料的研究进展

有机无机杂化太阳能电池中, 电极缓冲层的选择对光电转换效率有着重要的影响. 理想的负极缓冲层兼具传输电子和阻挡空穴的作用, 而理想的正极缓冲层兼具传输空穴和阻挡电子的作用. 常见的无机电子传输材料主要有TiO₂和ZnO等, 而常见的无机空穴传输材料主要有CuI、CuSCN和NiO等. 本文就这些常见的无机缓冲层材料在有机无机杂化太阳能电池中的应用作一简要回顾, 并对其可能存在的问题进行了分析和评述.     

杂化太阳电池中异质结界面的修饰及其对电池光电性能的影响

有机-无机杂化太阳电池综合了有机、无机材料的优点,成本低、理论效率高,受到人们的广泛关注.杂化太阳电池的光活性层由无机半导体和有机共轭聚合物复合而成.当光照射到活性层上时,共轭聚合物吸收光子产生激子(电子-空穴对);激子迁移到有机给体-无机受体的异质结界面处发生解离而产生自由电子和空穴;自由电子和空穴分别向无机半导体和有机聚合物传输,从而实现电荷的分离和传导.激子在有机-无机异质结界面处的分离效率是影响电池性能的一个重要因素.有机、无机两相材料往往因为接触面积小以及相容性差使此两相材料接触不佳,激子迁移到此界面不能有效分离,从而严重影响了杂化太阳电池的效率.这个问题可以通过此界面的修饰加以改善.本文即综述了有机-无机异质结界面修饰的方法、作用和意义,并展望了杂化太阳电池未来的发展趋势和应用前景.     

无机-有机杂化光催化剂:合成、机理及应用（英文）

由无机与有机组分组成的无机-有机杂化材料因其优异的性能及良好的物理化学性质在光催化领域得到了广泛的关注.目前,已经开发的单相光催化剂有很多种,但其很难同时满足宽的光激发范围以及高的光吸收能力和强的氧化还原能力等需求,因此,科研人员开发了很多方法去解决上述问题,主要包括以下两大类.第一类,修饰光催化剂扩大光激发范围以及增强可见光吸收.例如构建固溶体、引入表面缺陷、杂质掺杂、染料敏化和表面等离子体共振等策略.第二类,构建半导体异质结,通过界面处的协同作用有效促进光生电子空穴对的转移与分离.例如type II型、直接Z型以及S型异质结等.有机成分与无机成分的杂化是有效解决上述问题的方法之一.大部分有机材料具有成本低、吸光系数高以及比表面积大等优点;但低的强度以及宽的带隙限制了有机材料在光催化上的应用.而大部分无机材料具有高强度、窄带隙以及良好的光学性能.但低韧性和较差的分散性限制了无机材料在光催化上的应用.无机-有机杂化材料不仅保留了无机与有机组分的原有性质,而且界面处组分之间的协同作用会产生新的性质,如高的载流子传输能力和高的光吸收能力等.无机-有机杂化材料是多相材料,其中的一相是纳米材料...     

Ni纳米粒子作为电子转移剂和NiSx作为产氢界面活性位协同增强 TiO2光催化制氢性能

作为一种传统的半导体光催化材料, TiO_2因具有低价易得、无毒性及稳定性好等优势而一直受到研究者的关注.理论上, TiO_2的能带结构可满足分解水制氢的条件.然而,研究发现TiO_2本身的光催化制氢性能较低,主要是由于TiO_2被光激发后生成的电子和空穴尚未到达材料表面参与反应,就在其体相内发生复合,导致电子参与有效光催化制氢反应的几率较低.近年来,为提高TiO_2的制氢性能,研究者主要通过半导体耦合、元素掺杂、形貌调控和助剂修饰等方式对TiO_2进行改性.其中,助剂表面修饰由于用量少、条件温和并且对主体材料结构影响很小而成为一种常见和有效的改性手段.最常用的电子助剂是贵金属如Au, Ag, Pt和Pd.当TiO_2表面沉积微量的贵金属纳米粒子时,导带上的光生电子被贵金属捕获并迅速转移,将H~+在贵金属表面发生界面还原反应生成H_2,从而有效提高了制氢效率.除了贵金属电子助剂外,还有一些价格较低、产量丰富的非贵金属如Co, Cu, Ni和Bi等也可以作为电子助剂应用于光催化制氢,在提高制氢性能的同时也降低了光催化剂的成本.但在大多数情况下,这些金属材料(除贵金属Pt以外)本身都不能作为有效的界面催化活性位点,表现出较低的界面析氢速率,导致金属-半导体光催化材料的产氢活性低.因此,进一步对金属表面进行改性、增加界面催化活性位点、促进其界面产氢催化反应,对于提高金属-半导体光催化材料的制氢性能非常重要.在金属作为电子传输介质修饰半导体材料的制氢过程中,电子传输介质快速转移光生电子和有效捕获溶液中的H+直接进行界面催化还原反应生成H_2这两个步骤都十分关键.在制备金属-半导体光催化材料时,对于通常的金属材料本身都不能作为界面催化活性位点、缺乏有效的界面产氢活性位点的问题,可通过在金属表面进一步修饰作为界面催化活性位点的基团或离子来解决.本文采用先将Ni纳米粒子光沉积在TiO_2表面、再在水热条件下在Ni纳米粒子表面生成NiS_x的两步法合成了以Ni作为电子转移介质、以NiS_x作为界面催化活性位点共修饰的高效TiO_2光催化剂(称为TiO_2/Ni-NiS_x).研究结果表明,优化后的TiO_2/Ni-NiS_x光催化的最高制氢速率(223.74μmolh~(-1))分别是纯TiO_2, TiO_2/Ni和TiO_2/NiS_x样品的22.2, 8.0和2.2倍.性能增强的原因是Ni纳米粒子作为电子传输体、NiS_x作为界面催化活性位点同时提高了光生电子的转移速率和界面催化反应速率,即Ni和NiS_x两者协同作用增强了TiO_2光催化制氢性能.这种非贵金属助剂和界面活性位点协同作用的方法为设计高制氢性能催化剂提供了新的思路,并有望在光催化领域得到应用.     

多维CsPbX3无机钙钛矿材料的制备及其在太阳能电池中的应用

近年来全无机CsPbX3(X=Cl、Br、I)型钙钛矿材料由于其高吸光系数、低激子束缚能、长的载流子扩散长度等优点使其在太阳能电池(PSC)器件应用方面备受关注.高效的合成方法和精准的形貌控制对无机钙钛矿的光学性质及其太阳能电池光电性能及稳定性至关重要.本文系统介绍了不同维度无机钙钛矿材料包括零维量子点、一维纳米线/棒...     

染料敏化太阳电池中双层结构TiO2薄膜空间的电子分布与接触界面转移过程

采用电化学阻抗谱(EIS)研究了双层结构TiO2薄膜的电子积累和与电解液接触界面的电子转移过程. 通过制备纳米颗粒单层和纳米颗粒/亚微米颗粒双层2种不同微结构的TiO2薄膜电极, 对其电容分布、 局域态密度、 薄膜内部电子传输和固/液界面电子转移过程进行了研究. 分析了纳米颗粒/亚微米颗粒双层结构电极对染料敏化太阳电池(DSC)性能的影响. 结果表明, 一定数量的电子会积累在亚微米颗粒层中引起薄膜电极化学电容的增加. 在纳米颗粒层上端覆盖亚微米颗粒后降低了界面复合电阻, 但对薄膜电极的传输性能影响较小. 因此在筛选和制备DSC散射层材料时除应具有良好的光散射性能外, 还应考虑材料的化学电容和界面转移电阻等因素.     

阴极界面修饰层改善平面p-i-n型钙钛矿太阳能电池的光伏性能

有机/无机杂化金属卤化物钙钛矿半导体材料结合了有机材料良好的溶液可加工性以及无机材料优越的光电特性,近几年受到了热捧,成为太阳能电池领域一颗耀眼的明星. 伴随着钙钛矿薄膜结晶过程和形貌的优化、器件结构的改进以及电极界面材料的开发,这类有机/无机杂化金属卤化物钙钛矿太阳能电池的光电转换效率从最初的3.8%迅速提高到目前最高的22.1%. 其中界面工程在提升器件性能上发挥着极其重要的作用. 本文总结了平面p-i-n型钙钛矿太阳能电池中阴极界面修饰层（CBL）的研究进展. CBL从材料上讲可分为无机金属氧化物、金属或金属盐以及有机材料,从构成上讲可分为单层CBL、双层CBLs以及共混型CBL. 本文对这些类型的CBL分别给予详细的介绍. 最后,我们归纳出CBL在改善器件效率和稳定性上所起的作用以及理想CBL所应满足的要求,希望能为以后阴极界面修饰材料的设计提供一定的借鉴.     

无机纳米晶-生物界面作用的分子机制

无机纳米晶材料以其独特的光、电、磁、力学性质,成为疾病诊断与治疗功能的关键材料.本文总结了无机纳米晶的表面化学活性、离子释放性、晶相结构、晶格缺陷、表面吸附和表面修饰等与尺寸相关的理化性质与生物效应之间的关系.综述了无机纳米晶与蛋白质、磷脂生物膜间的界面相互作用,探讨了纳米晶-生物界面作用的分子机理.这有助于理解无机纳米晶的生物行为和毒理性质,指导设计安全、高效的纳米晶生物医学材料.     

金属氧化物/聚(N,N-二甲基苯胺)界面相互作用的ESR研究

共轭聚合物在电、光、磁等方面有很大的应用价值［１～３］,利用其研制各种实用性电子器件时,往往会涉及到它与其它材料尤其是无机半导体材料的界面复合问题［４～７］．在这些界面间,除形成一定的化学键外［８］,更多的则是伴随着电子的转移和电荷的重新分配［９,１...     

水/醇溶共轭聚合物界面材料及其在光电器件中的应用

相对于传统的无机半导体器件,以有机半导体(特别是聚合物半导体)材料为基础的有机光电器件,可采用与传统印刷技术(例如喷墨打印、卷对卷印刷等)相结合的溶液加工方式制备低成本、大面积、柔性光电器件,因而成为广泛关注的焦点,并得到了快速发展.实现溶液加工的高效有机光电器件的一个关键问题是界面问题——如何避免溶液加工时有机层间的互溶以及如何实现可印刷稳定金属电极的高效电子注入等.水/醇溶性共轭聚合物的迅速发展为解决溶液加工多层有机光电器件所面临的界面问题提供了有效手段.研究发现,水/醇溶共轭聚合物不但可以有效避免溶液加工多层器件中的界面互溶,而且还可与高功函数的稳定金属发生界面偶极相互作用而增强其电子注入,从而解决了高功函数稳定金属电子注入的难题,为实现全溶液加工的高效印刷有机光电器件提供了可行的方案.本文介绍了近年来本课题组在水/醇溶共轭聚合物阴极界面材料及器件应用方面的研究进展,并对水/醇溶共轭聚合物阴极界面材料在聚合物发光二极管和聚合物太阳电池中的工作机理进行了探讨.     

A mini review: Constructing perovskite p-n homojunction solar cells

Organic metal halide perovskite materials have excellent photoelectric properties, and the power conversion efficiency(PCE) of the perovskite solar cells(PSCs) has increased from 3.8% to more than 25%. In the development of PSCs, innovative architectures were being proposed constantly. However, the use of the electron transport layer(ETL) and hole transport layer(HTL) increases manufacturing costs and process complexity. Perovskite material has ambipolar charge transport characteristics, so it c...     

Mixed-phase Mesoporous TiO2 Film for High Efficiency Perovskite Solar Cells

Mesoporous scaffold structures have played great roles in halide perovskite solar cells(PSCs),due to the excellent photovoltaic performance and commercial perspective of mesoporous PSCs.Here,we reported a mixed-phase TiO2 mesoporous film as an efficient electron transport layer(ETL)for mesoporous perovskite solar cells.Due to the improved crystal phase,fihn thickness and nanopartMe size of TiO2 layer,which were controlled by varying the one-step hydrothermal reaction time and annealing time,the PSCs exhibited an outstanding short circuit photocurrent density of 25.27 mA/cm^2,and a maximum power conversion efficiency(PCE)of 19.87%.It is found that the ultra-high Jsc attributes to the excellent film quality,light capturing and excellent electron transport ability of mixed-phase TiO2 mesoporous film.The results indicate that mix-phase mesoporous metal oxide fihns could be a promising candidate for producing effective ETLs and high efficiency PSCs.     

Suppressing Interfacial Charge Recombination in Electron-Transport-Layer-Free Perovskite Solar Cells to Give an Efficiency Exceeding 21 %

The performances of electron-transport-layer (ETL)-free perovskite solar cells (PSCs) are still inferior to ETL-containing devices. This is mainly due to severe interfacial charge recombination occurring at the transparent conducting oxide (TCO)/perovskite interface, where the photo-injected electrons in the TCO can travel back to recombine with holes in the perovskite layer. Herein, we demonstrate for the first time that a non-annealed, insulating, amorphous metal oxyhydroxide, atomic-scale thin interlayer (ca. 3 nm) between the TCO and perovskite facilitates electron tunneling and suppresses the interfacial charge recombination. This largely reduced the interfacial charge recombination loss and achieved a record efficiency of 21.1 % for n-i-p structured ETL-free PSCs, outperforming their ETL-containing metal oxide counterparts (18.7 %), as well as narrowing the efficiency gap with high-efficiency PSCs employing highly crystalline TiO₂ ETLs.     

Recent advancement in inorganic-organic electron transport layers in perovskite solar cell: current status and future outlook

Organic-inorganic lead halide perovskite solar cells have captured significant attention in recent years due to low processing costs and unprecedented development in power conversion efficiency (PCE). It has appeared from 2009 with PCE of 3.8% to being claimed more than 25.2% PCE in a very short span of time, showing their future prospective toward the fabrication of less expensive and stable solar cells. The incredible advancement in this technology encourages at one end, whereas several hurdles restricting its complete utilization for commercial purposes at another end. Although the selection of perovskite structure is limited with planar and mesoporous electron transport layers (ETLs), but identification of appropriate ETLs necessitates excellent effort to improve the surface morphology of absorber and obtain enhanced PCE with higher stability. In the present review, we have investigated various inorganic-organic ETLs with different device configurations of PSCs, primarily focusing on crystallization and morphology control techniques of ETL thin films. Numerous strategies such as surface functionalization, doping, and addition of interfacial layer are adopted for ETLs, and their effect on device efficiency, performance, and hysteresis is also discussed in detail. Additionally, designs of PSCs with different device configurations are discussed as well, providing future guidelines for significant progress in PSCs structure with different ETLs.     

TiO_2 nanoparticle-based electron transport layer with improved wettability for efficient planar-heterojunction perovskite solar cell

The electron transport layer(ETL) plays an important role in planar heterojunction perovskite solar cell(PSCs),by affecting the light-harvesting, electron injection and transportation processes, and especially the crystallization of perovskite absorber. In this work, we utilized a commercial TKD-TiO_2 nanoparticle with a small diameter of 6 nm for the first time to prepare a compact ETL by spin coating. The packing of small-size particles endowed TKD-TiO_2 ETL an appropriate surface-wettability, which is beneficial to the crystallization of perovskite deposited via solution-processed method. The uniform and high-transmittance TKD-TiO_2 films were successfully incorporated into PSCs as ETLs. Further careful optimization of ETL thickness gave birth to a highest power conversion efficiency of 11.0%, which was much higher than that of PSC using an ETL with the same thickness made by spray pyrolysis. This TKD-TiO_2 provided a universal solar material suitable for the further large-scale production of PSCs. The excellent morphology and the convenient preparation method of TKD-TiO_2 film gave it an extensive application in photovoltaic devices.     

Eliminating Hysteresis of Perovskite Solar Cells with Hollow TiO2 Mesoporous Electron Transport Layer

Current density-voltage(J-V) hysteresis issue caused by unbalanced charge transport has greatly limited the improvement of power conversion efficiency(PCE) of halide perovskite solar cells(PSCs). Herein, hollow TiO₂ mesoporous electron transport layer(ETL) was used to fabricate PSCs. The structure-dependent charge collection as well as its effect on PCE and hysteresis impactor(HI) of PSC were investigated. The results demonstrate that TiO₂ hollow spheres in a size of around 50 nm (HS-50) can form a high quality perovskite/ETL interface with a less trap density. Moreover, the hollow TiO₂ with the thin shell can help promote the extraction of electrons from perovskite layer to ETL, so as to reduce the charge accumulation and recombination at the perovskite/ETL interface and alleviate the hysteresis behavior. As a result, PSCs with HS-50 TiO₂ delivered a champion PCE of 16.81% with a small HI of 0.0297, indicating a better performance than the commercial P25(PCE of 15.87%, HI of 0.2571).     

SnO2表面卤化提高钙钛矿太阳能电池光伏性能

钙钛矿太阳能电池(PSCs)成为近几年来迅速发展的新型太阳能电池,其中将SnO₂纳米粒子层用作电子传输层(ETL)的钙钛矿太阳能电池器件得到了广泛的关注。SnO₂有着更低的制备温度,使其具备应用于柔性器件的潜力,但与钙钛矿层能级不匹配等问题限制着其发展。而在界面处加入钝化层,尤其是表面卤化的方法或可解决这一问题。本文综合研究了SnO₂表面卤化对钙钛矿太阳能电池光伏性能的影响,选用四丁基氯化铵(TBAC)、四丁基溴化铵(TBAB)和四丁基碘化铵(TBAI)三种钝化材料对SnO₂表面进行钝化处理,并对钝化材料溶液进行了浓度梯度研究。通过材料形貌、结构和光学性能表征以及电池器件性能测试分析等方法,证明了SnO₂表面卤化可提高钙钛矿层的质量和PSCs光伏性能,并从器件内部电荷传输动力学等角度解释了器件性能改善的原因。为进一步说明其性能改善的机理,采用基于密度泛函理论(DFT)的第一性原理计算方法对材料表面性质进行了深入研究,从能量、结构、电荷密度、态密度、功函数等角度解释了表面卤化提高SnO₂/钙钛矿界面处电子传输特性的原因。实验和理论计算均表明TBAC对于SnO₂具有较好的钝化效果,并随着溶液浓度的提升钝化作用越明显。SnO₂表面卤化作用的深入研究不仅对提高电池器件性能具有实际意义,还能够帮助理解太阳能电池界面现象,为界面改性提供新的研究思路。     

碳基钙钛矿太阳能电池的研究进展

由于具有成本低、工艺简单等优点,有机-无机杂化太阳能电池(PSCs)的研究和发展受到了广泛的关注,光电转换效率也快速提升到与传统晶体硅太阳能电池相当的水平。 然而,PSCs稳定性差的问题严重限制了其商业化。 在各种PSCs中,基于碳电极的无空穴传输层器件(C-PSCs)去除了影响稳定性的有机空穴传输层和金属电极,使得器件稳定性得到了明显的提高,是最具有应用前景的电池器件之一。 自从2013年首次报道以来,C-PSCs的各方面研究取得了很大的进展,效率也从最初的6.6%提高到现在的15.9%。 本综述将系统地介绍C-PSCs的最新研究进展,包括器件结构和工作原理、各部分研究进展(电子传输层、钙钛矿薄膜和碳电极),以及存在的问题和解决方案。     

Materials and structures for the electron transport layer of efficient and stable perovskite solar cells

The electron transport layer plays a vital function in extracting and transporting photogenerated electrons, modifying the interface, aligning the interfacial energy level and minimizing the charge recombination in perovskite solar cells. This review summarizes the recent research progress on electron transport materials of metal oxides, organic molecules and multilayers. The doped metal oxides as electron transport materials in regular perovskite solar cells show improved device performance relative to their non-doped counterpart due to enhanced electron mobility and energy level alignment. The non-fullerene organic electron transport materials with better electron mobility and tunable energy level alignment need to be further designed and developed despite their advantages of mechanical flexibility and wide range tunability. The multilayer electron transport materials are suggested to be an important direction of research for efficient and stable perovskite solar cells because of their favorable synergistic interaction.     

低成本富勒烯衍生物电子传输层在钙钛矿太阳能电池的应用

Organic-inorganic hybrid perovskite solar cells (PSCs) have attracted significant attention owing to their high absorption coefficient and ambipolar charge transport properties. With only several years of development, the power conversion efficiency (PCE) has increased from 3.8% to 22.7%. In general, PSCs have two types of structural architecture: mesoporous and planar. The latter possesses higher potential for commercialization due to its simpler structure and fabrication process, especially the inverted planar structure, which possesses negligible hysteresis. In an inverted PSC, the electron transport materials (ETM) are deposited on a perovskite film. Only a few ETMs can be used for inverted PSCs as the perovskite film is easily damaged by the solvent used to dissolve the ETM. Furthermore, the energy levels of the ETM should be well aligned with that of the perovskites. Normally it is difficult to use inorganic ETMs as they require high temperatures for the annealing process to improve the electron conductivity; the perovskite film cannot sustain these high temperatures. To date, the fullerene derivative, [6, 6]-phenyl-C61-butyric acid methyl ester (PCBM), is the most commonly used organic ETM for high efficiency inverted planar PSCs. However, the high manufacturing cost due to its complex synthesis retards the industrialization of the PSCs. Here, we introduce a fullerene pyrrolidine derivative, N-methyl-2-pentyl-[60]fullerene pyrrolidine (NMPFP), synthesized via the Prato reaction of C₆₀ directly with cheap hexanal and sarcosine. Then the NMPFP electron transport layer (ETL) was prepared by a simple solution process. The properties of the resulting NMPFP ETLs were characterized using UV-Vis absorption spectroscopy, cyclic voltammetry measurements, atomic force microscopy, and conductivity test. From the results of the UV-Vis absorption spectroscopy and cyclic voltammetry measurements, the LUMO level of NMPFP ETL was calculated to be 0.2 eV higher than that of the PCBM ETL. This contributes to a higher open-circuit photovoltage. In addition, the NMPFP film presented higher conductivity than the PCBM film. Thus, the photo-generated charge carriers in the perovskite films should be transported more efficiently to the NMPFP electron transport layer (ETL) than to the PCBM ETL. This was confirmed by the results of the steady-state photoluminescence spectroscopy. Finally, the NMPFP as an alternative low-cost ETL was employed in an inverted planar PSC to evaluate the device performance. The device made with the NMPFP ETL yielded an efficiency of 13.83% with negligible hysteresis, which is comparable to the PCBM counterpart devices. Moreover, since stability is another important parameter retarding the commercialization of PSCs, the stability of the PCBM and NMPFP base PSCs were investigated and compared. It was found that the NMPFP devices possessed significantly improved stability due to the higher hydrophobicity of the NMPFP. In conclusion, this research demonstrates that NMPFP is a promising ETL to replace PCBM for the industrialization of cheap, efficient and stable inverted planar PSCs.