倒置钙钛矿太阳能电池的空穴传输层的研究进展

倒置钙钛矿太阳能电池(PSCs)具有器件结构简单、吸光系数高、迟滞效应小、良好的缺陷容忍性等优点,受到了广泛的关注。但倒置器件光电转换效率(PCE)尚有待提高,究其原因是空穴传输层(HTL)和钙钛矿层界面处的能量损失表现出相对较小的开路电压。文章综述了包括有机聚合物、无机物、尖晶石氧化物等作为空穴传输材料的相关研究进展,进一步分析了通过调节电极/空穴传输层能级使之与钙钛矿价带匹配,及通过界面修饰促进器件对载流子的注入与收集,从而提高光电转换效率的研究现状。对提高倒置钙钛矿太阳能电池性能的研究具有一定的指导意义,最后对倒置器件的应用前景进行了展望。     

SnO2退火温度对钙钛矿太阳能电池性能的影响

电子传输层是钙钛矿太阳能电池的关键部分, 起到阻挡空穴、传输电子和减少电子空穴复合的作用。本研究采用低温溶液法制备SnO₂薄膜作为钙钛矿电池的电子传输层, 研究SnO₂的退火温度对电子传输层微观形貌、物理性能以及钙钛矿太阳能电池性能的影响。结果表明: 当退火温度为60、90、120和240 ℃时, SnO₂薄膜表面存在较多的孔隙; 而退火温度为150、180和210 ℃时, 薄膜表面孔隙较少。在实验温度下, 制备的SnO₂薄膜为四方相, FTO玻璃上涂覆SnO₂薄膜后其透过率要优于空白FTO玻璃的透过率。当SnO₂退火温度为180 ℃时, 薄膜的电子迁移率最高, 钙钛矿电池具有最佳的传输电阻和复合电阻, 所得电池的性能最优, 其光电转换效率为17.28%, 开路电压为1.09 V, 短路电流为20.91 mA/cm², 填充因子为75.91%。     

钙钛矿太阳能电池界面工程优化研究

有机-无机杂化钙钛矿太阳能电池(PSCs)具有高能量转换效率、低能耗和低成本等优点,但PSCs界面缺陷引起的非辐射复合严重阻碍了其光电转换性能提升。本研究通过降低氧化镍空穴传输层的粒径尺寸,提高粒径均匀性,实现了光生空穴在电池界面的高效传输;并通过优化钙钛矿薄膜的反溶剂作用时间提升结晶质量,降低界面非辐射复合,改善空穴传输层和钙钛矿的界面问题,使钙钛矿太阳能电池的能量转换效率(PCE)从10.11%提高到18.37%。开尔文探针力显微镜(KPFM)研究表明,界面优化后的钙钛矿薄膜在亮态下的表面接触电位差相比于暗态下增加了120.39 mV。采用压电力原子力显微镜(PFM)分析钙钛矿薄膜明暗态铁电性能,发现界面优化后的钙钛矿铁电极化变化微弱,说明优化界面有效降低了电池界面缺陷和迟滞效应。该研究结果表明,优化氧化镍空穴传输层,提高钙钛矿薄膜质量,减少了界面缺陷,降低了非辐射复合和电池迟滞效应,提高了钙钛矿太阳能电池的能量转换效率。     

空穴传输材料在高效钙钛矿太阳能电池中的发展演变

钙钛矿太阳能电池(PSCs)转换效率已从2009年的3.8%上升到2017年的22.7%,其快速的发展可能使光伏工业进入革命新阶段。空穴传输材料(HTM)是构成高效钙钛矿太阳能电池的重要组成部分,开发和设计导电性好、成本低、稳定性好的空穴传输层材料对钙钛矿太阳能电池的研究显得非常重要。本文将近几年应用于钙钛矿太阳能电池中较高效的空穴传输材料归纳为有机小分子类、有机聚合物类和无机材料类,同时也介绍了无空穴传输层的钙钛矿电池。详细评述了基于各类空穴传输材料的钙钛矿太阳能电池的光电性能及稳定性,重点讨论了HOMO能级、空穴迁移率、添加剂的掺杂等因素对钙钛矿太阳能电池的影响。最后指出了空穴传输材料未来的研究重点和发展趋势。     

NiO层作为空穴传输层的钙钛矿太阳能电池的制备和性能研究

有机-无机杂化钙钛矿太阳能电池因具有光吸收强、载流子扩散长度长等优点,近年来在光伏领域吸引了广泛的关注,其中,无机NiO薄膜在电池结构中作为空穴传输层已发展成为钙钛矿电池研究的重要方向。采用溶液旋涂法制备了NiO薄膜,系统优化了不同烧结温度和不同浓度条件下NiO薄膜对钙钛矿电池性能的影响。采用扫描电镜、X射线衍射、紫外-可见分光光度计、电流-电压测试、光量子效率等方法分别观察和分析了NiO薄膜以及相应电池的光电性能。结果表明:溶液旋涂法制备的NiO薄膜具有良好的覆盖性、非常低的表面粗糙度,当制备NiO的预制溶液浓度为0.05mol/L,NiO的烧结温度为500℃时,获得了最优的电池性能,最高电池转换效率为14.62%。     

无机电荷传输层在有机-无机杂化钙钛矿太阳能电池中的应用及研究进展

近年来,基于有机-无机杂化钙钛矿材料为光活性层构建的太阳能电池由于具有直接带隙、吸光系数高、激子束缚能低、激子和载流子扩散距离长,以及成本低、制备工艺简单、光电转换率高、易于实现大面积柔性器件等优点,而成为当今新型光伏技术中一颗耀眼的新星。在钙钛矿太阳能电池中,电荷传输层在提高光电转换效率、稳定性及寿命等方面扮演着非常重要的角色,其中无机电荷传输层因具有载流子迁移率高、稳定性好、制备工艺简单等优势越来越受到人们的关注。本文总结了无机电荷传输层在钙钛矿太阳能电池中的应用,详细介绍了各种无机电子/空穴传输层在钙钛矿太阳能电池中的研究进展,并对其发展趋势进行了展望。     

埋底界面修饰对钙钛矿太阳能电池的影响

经过十多年的发展,钙钛矿太阳能电池（PSCs）迅速实现了能量转换效率（PCE）从3.8%提高到25.7%的突破,在新一代光伏产业中具有显著的竞争力。钙钛矿太阳能电池的蓬勃发展不仅源于钙钛矿材料具有高光吸收系数、优异的载流子迁移率和可调节的直接带隙,还源于其简便且成本低廉的制造工艺。但是钙钛矿电池内部的缺陷问题,特别是钙钛矿层与底层界面处的缺陷是限制钙钛矿电池效率与稳定性进一步提升的一个瓶颈。通过有效的界面修饰,一方面可以提高钙钛矿的效率,另一方面可以提高器件的稳定性。本文从界面工程对钙钛矿性能的影响出发,着重介绍了埋底界面的修饰工作对钙钛矿电池效率与稳定性的影响,包含电子传输层（ETL）/钙钛矿界面与空穴传输层（HTL）/钙钛矿界面这两部分,通过对这两类埋底界面的有效改性修饰,器件的效率与稳定性显著提高。通过对比分析了各种材料与实验方法对钙钛矿器件整体性能和稳定性的影响,探索了一条有效改善器件性能的路径。最后,本文还对钙钛矿太阳能电池的前景进行了展望。     

复合钙钛矿太阳能电池电荷传输层材料研究进展

有机无机复合钙钛矿太阳能电池因具有适合的载流子扩散长度而成为备受关注的有望获得高效率的光伏器件。复合钙钛矿材料本身不含贵金属元素,可以采用液相法或物理气相法低温制备,成本低廉,但目前应用最多的电子传输层材料TiO2需400~500℃煅烧,与柔性基底及低温制备技术适应性差;空穴传输层材料SpiroOMeTAD合成工艺复杂,价格高昂,限制了复合钙钛矿太阳能电池的开发应用。开发和研究导电性好、成本低、稳定性好的电子和空穴传输层材料是复合钙钛矿太阳能电池研究中的一个非常重要的方面。综述了复合钙钛矿太阳能电池中电荷传输层材料的研究进展及发展方向。电子传输层材料方面通过对TiO2的改性以及与石墨烯的复合,采用ZnO、石墨烯或PCBM作为电子传输层材料,以与柔性基底及低温制备技术相适应。空穴传输层材料方面,采用其它低成本、导电性高的有机p型半导体替代spiro-OMeTAD;采用无机空穴传输层材料以避免有机空穴传输层材料的老化问题,提高电池的长期稳定性;利用复合钙钛矿材料兼作吸收层与空穴传输层,制备无空穴传输层材料结构电池以降低成本,提高稳定性。     

酞菁类聚合物／硅太阳能电池的制备与研究

用熔融法和溶剂法合成了聚酞菁铜，聚酞菁氧钒等可溶性有机半导体。研究表明：酞菁类聚合物／硅太阳能电池具有良好的整流特性和光伏效应，整流比为１７。经过掺杂处理，光电转换性能有明显提高，当入射光强为０．８８ｍＷ／ｃｍ２时，开路电压为２１０ｍＶ，短路电流密度为０．７５ｍＡ／ｃｍ２，光电转换效率达３．９％（填充因子为０．２２），掺杂处理后的酞菁聚合物／硅太阳能电池有较好的稳定性。     

聚苯乙烯和聚乙二醇对TiO2薄膜微观结构及DSSC性能的影响

用水热法制备了多孔TiO2光电薄膜;分析了聚苯乙烯和聚乙二醇对纳米TiO2晶体薄膜微观结构的影响;用紫外-可见-近红外分光光度计和场发射扫描电镜对纳米TiO2薄膜进行了表征;并对组装的染料敏化太阳能电池进行了光电性能测试,发现用聚苯乙烯处理后的TiO2薄膜提高了染料敏化太阳能电池(DSSC)的开路电压、短路电流密度、填充因子和光电转换效率.     

Methylammonium cation deficient surface for enhanced binding stability at TiO<Subscript>2</Subscript>/CH<Subscript>3</Subscript>NH<Subscript>3</Subscript>PbI<Subscript>3</Subscript> interface

Heterojunction interfaces in perovskite solar cells play an important role in enhancing their photoelectric properties and stability.Till date,the precise lattice arrangement at TiO2/CH3NH3PbI3 heterojunction interfaces has not been investigated clearly.Here,we examined a TiO2/CH3NH3PbI3 interface and found that a heavy atomic layer exists in such interfaces,which is attributed to the vacancies of methylammonium (MA) cation groups.Further,first-principles calculation results suggested that an MA cation-deficient surface structure is beneficial for a strong heterogeneous binding between TiO2 and CH3NH3PbI3 to enhance the interface stability.Our research is helpful for further understanding the detailed interface atom arrangements and provides references for interfacial modification in perovskite solar cells.     

Efficient light harvesting from flexible perovskite solar cells under indoor white light-emitting diode illumination

This is the first report of an investigation on flexible perovskite solar cells for artificial light harvesting by using a white light-emitting diode (LED) lamp as a light source at 200 and 400 lx,values typically found in indoor environments.Flexible cells were developed using either low-temperature sol-gel or atomiclayer-deposited compact layers over conducting polyethylene terephthalate (PET)substrates,together with ultraviolet (UV)-irradiated nanoparticle TiO2 scaffolds,a CH3NH3PbI3-xClx perovskite semiconductor,and a spiro-MeOTAD hole transport layer.By guaranteeing high-quality carrier blocking (via the 10-40 nm-thick compact layer) and injection (via the nanocrystalline scaffold and perovskite layers) behavior,maximum power conversion efficiencies (PCE) and power densities of 10.8％ and 7.2 μW.cm-2,respectively,at 200 lx,and 12.1％ and 16.0 μW·cm-2,respectively,at 400 lx were achieved.These values are the state-of-the-art,comparable to and even exceeding those of flexible dye-sensitized solar cells under LED lighting,and significantly greater than those for flexible amorphous silicon,which are currently the main flexible photovoltaic technologies commercially considered for indoor applications.Furthermore,there are significant margins of improvement for reaching the best levels of efficiency for rigid glass-based counterparts,which we found was a high of PCE ～24％ at 400 lx.With respect to rigid devices,flexibility brings the advantages of being low cost,lightweight,very thin,and conformal,which is especially important for seamless integration in indoor environments.     

High-Efficiency Perovskite Quantum Dot Hybrid Nonfullerene Organic Solar Cells with Near-Zero Driving Force

To take advantages of the intense absorption and fluorescence, high charge mobility, and high dielectric constant of CsPbI₃ perovskite quantum dots (PQDs), PQD hybrid nonfullerene organic solar cells (OSCs) are fabricated. Addition of PQDs leads to simultaneous enhancement of open-circuit voltage (V_OC), short-circuit current density (J_SC), and fill factor (FF); power conversion efficiencies are boosted from 11.6% to 13.2% for PTB7-Th:FOIC blend and from 15.4% to 16.6% for PM6:Y6 blend. Incorporation of PQDs dramatically increases the energy of the charge transfer state, resulting in near-zero driving force and improved V_OC. Interestingly, at near-zero driving force, the PQD hybrid OSCs show more efficient charge generation than the control device without PQDs, contributing to enhanced J_SC, due to the formation of cascade band structure and increased molecular ordering. The strong fluorescence of the PQDs enhances the external quantum efficiency of the electroluminescence of the active layer, which can reduce nonradiative recombination voltage loss. The high dielectric constant of the PQDs screens the Coulombic interactions and reduces charge recombination, which is beneficial for increased FF. This work may open up wide applicability of perovskite quantum dots and an avenue toward high-performance nonfullerene solar cells.     

染料敏化太阳能电池中CuO/TiO2薄膜制备及应用

采用普通直流电沉积和超声直流电沉积制备Cu∕TiO2纳米管阵列∕Ti基复合薄膜,而后在NaOH溶液中用电氧化的方法将Cu单质氧化成CuO,制备了CuO∕TiO2纳米管阵列∕Ti基复合薄膜。利用扫描电子显微镜(SEM)和X射线衍射仪(XRD)对两种复合薄膜电极的形貌和结构进行了表征,详细考察了电镀工艺参数(电流密度)和超声波对复合薄膜形貌的影响。同时通过稳态光电响应技术对复合薄膜电极组成的染料敏华太阳能电池(DSSC)的光电性能进行了研究,结果表明:通过普通直流电沉积在工艺参数(3mA/cm2、5min)处制备的复合薄膜组装的DSSC具有该体系下的最佳光电性能(Jsc=9.00mA/cm2、Voc=0.664V、FF=0.512、η=3.06%);在同等条件下通过超声辅助直流电沉积制备的复合薄膜组装的DSSC的最佳光电性能(Jsc=15.50mA/cm2、Voc=0.688V、FF=0.505、η=5.39%)出现在工艺参数为(6mA/cm2、5min)处。对比可知超声条件下的光电性能较好,且最佳光电性能工艺参数发生了后移。     

A Strategy to Produce High Efficiency,High Stability Perovskite Solar Cells Using Functionalized Ionic Liquid‐Dopants

Functionalized imidazolium iodide salts (ionic liquids) modified with ? CH₂? CH?CH₂, ? CH₂C?CH, or ? CH₂C?N groups are applied as dopants in the synthesis of CH₃NH₃PbI₃‐type perovskites together with a fumigation step. Notably, a solar cell device prepared from the perovskite film doped with the salt containing the ? CH₂? CH?CH₂ side‐chain has a power conversion efficiency of 19.21%, which is the highest efficiency reported for perovskite solar cells involving a fumigation step. However, doping with the imidazolium salts with the ? CH₂C?CH and ? CH₂C?N groups result in perovskite layers that lead to solar cell devices with similar or lower power conversion efficiencies than the dopant‐free cell.     

Synergistic Ionic Liquid in Hole Transport Layers for Highly Stable and Efficient Perovskite Solar Cells

Perovskite solar cells (PSCs) with n-i-p structures often utilize an organic 2,2′,7,7′-tetrakis (N, N-di-p-methoxyphenyl-amine) 9,9′-spirobifluorene (spiro-OMeTAD) along with additives of lithium bis(trifluoromethanesulfonyl)imide salt (LiTFSI) and tert-butylpyridine as the hole transporting layer (HTL). However, the HTL lacks stability in ambient air, and numerous defects are often present on the perovskite surface, which is not conducive to a stable and efficient PSC. Therefore, constructive strategies that simultaneously stabilize spiro-OMeTAD and passivate the perovskite surface are required. In this work, it is demonstrated that a novel ionic liquid of dimethylammonium bis(trifluoromethanesulfonyl)imide (DMATFSI) could act as a bifunctional HTL modulator in n-i-p PSCs. The addition of DMATFSI into spiro-OMeTAD can effectively stabilize the oxidized spiro-OMeTAD⁺ cation radicals through the formation of spiro-OMeTAD⁺TFSI⁻ because of the excellent charge delocalization of the conjugated CF₃SO₂⁻ moiety within TFSI⁻. In addition, DMA⁺ cations could move toward the perovskite from the HTL, resulting in the passivation of defects at the perovskite surface. Accordingly, a power conversion efficiency of 23.22% is achieved for PSCs with DMATFSI and LiTFSI co-doped spiro-OMeTAD. Moreover, benefiting from the improved ion migration barrier and hydrophobicity of the HTL, still retained nearly 80% of their initial power conversion efficiency after 36 days of exposure to ambient air.     

How To Quantify the Efficiency Potential of Neat Perovskite Films: Perovskite Semiconductors with an Implied Efficiency Exceeding 28%

Perovskite photovoltaic (PV) cells have demonstrated power conversion efficiencies (PCE) that are close to those of monocrystalline silicon cells; however, in contrast to silicon PV, perovskites are not limited by Auger recombination under 1-sun illumination. Nevertheless, compared to GaAs and monocrystalline silicon PV, perovskite cells have significantly lower fill factors due to a combination of resistive and non-radiative recombination losses. This necessitates a deeper understanding of the underlying loss mechanisms and in particular the ideality factor of the cell. By measuring the intensity dependence of the external open-circuit voltage and the internal quasi-Fermi level splitting (QFLS), the transport resistance-free efficiency of the complete cell as well as the efficiency potential of any neat perovskite film with or without attached transport layers are quantified. Moreover, intensity-dependent QFLS measurements on different perovskite compositions allows for disentangling of the impact of the interfaces and the perovskite surface on the non-radiative fill factor and open-circuit voltage loss. It is found that potassium-passivated triple cation perovskite films stand out by their exceptionally high implied PCEs > 28%, which could be achieved with ideal transport layers. Finally, strategies are presented to reduce both the ideality factor and transport losses to push the efficiency to the thermodynamic limit.     

Wet chemical synthesis and self-assembly of SnS2 nanoparticles on TiO2 for quantum dot-sensitized solar cells

SnS2 nanoparticles were synthesized through a simple wet chemical process at room temperature. The SnS2 nanoparticles were approximately spherical in shape and had diameter about 3-4 nm. SnS2-sensitized TiO2 electrodes were fabricated by the immersion of chemically modified TiO2 to well-dispersed SnS2 solution for 72 h (i.e., self-assembly method.) SnS2-sensitized TiO2 electrodes were applied in quantum dot-sensitized solar cells (QDSSCs). Under AM1.5 irradiation with 100 mW/cm2 light intensity (at 1 sun), the short-circuit current density (J(sc)), the open-circuit voltage (V(oc)), the fill factor (FF), and the energy conversion efficiency (eta) were 0.47 mA/cm2, 0.29 V, 0.58 and 0.081%, respectively.     

不同炭黑对钙钛矿太阳能电池性能的影响

本文研究了四种炭黑(Cabot Vulan XC-72(CVXC-72),XFI15,Ketjen EC-300J(EC300J),Ketjen EC-300JD(EC300JD))对碳对电极及其制备的电池性能的影响。研究结果表明:以EC-300J为基础制备的碳对电极导电性最好且其与CH3NH3PbI3前驱体溶液具有较好的润湿性,基于这种炭黑制备的电池器件得到了4.88%的光电转换效率,并具有较好的稳定性。     

An integrated power pack of dye-sensitized solar cell and Li battery based on double-sided TiO2 nanotube arrays

We present a new approach to fabricate an integrated power pack by hybridizing energy harvest and storage processes. This power pack incorporates a series-wound dye-sensitized solar cell (DSSC) and a lithium ion battery (LIB) on the same Ti foil that has double-sided TiO(2) nanotube (NTs) arrays. The solar cell part is made of two different cosensitized tandem solar cells based on TiO(2) nanorod arrays (NRs) and NTs, respectively, which provide an open-circuit voltage of 3.39 V and a short-circuit current density of 1.01 mA/cm(2). The power pack can be charged to about 3 V in about 8 min, and the discharge capacity is about 38.89 μAh under the discharge density of 100 μA. The total energy conversion and storage efficiency for this system is 0.82%. Such an integrated power pack could serve as a power source for mobile electronics.