层状类钙钛矿结构有机-无机杂合物的结构与性能

层状类钙钛矿结构有机-无机杂合物是由有机、无机组元在分子尺度上组装而成的一类新材料,其结构和能带具有可设计可控性,因此应用前景广阔.综述了层状类钙钛矿杂合物的结构形成规则和组成、结构变化对能带及其电子学性能的影响.     

有机-无机分子组装层状类钙钛矿结构与特性

有机-无机分子组装层状类钙钛矿材料在分子水平上结合了有机组分和无机组分的优点，无机组分通过强的共价键或离子键形成扩展的骨架，并将有机组分填入框架中形成有机层与无机层交替的结构，具有某些电学、光学、磁学等特性。在此主要介绍了有机-无机分子组装层状类钙钛矿材料的结构及相关的性能研究。     

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。     

有机/无机层状类钙钛矿(C12 H25 NH3)2 PbI4晶体及薄膜的制备与结构表征

介绍了有机/无机类钙钛矿(C12H25NH3)2PbI4的晶体和薄膜的制备,并采用了XRD、SEM、AFM和PL表征材料的结构、形貌及光学特性等.XRD实验表明制备的(C12 H25NH3)2PbI4晶体结晶度高.探索旋涂法制备工艺参数对薄膜结构的影响,在薄膜XRD中几乎只能观察到(0021)晶面的衍射峰,表明有机/无机类钙钛矿层沿平行与基片方向择优生长,SEM和AFM表明薄膜致密性较好,表面粗糙度较小.     

倒置结构全无机钙钛矿太阳能电池的界面层研究进展

铯基无机钙钛矿(CsPbX3)因其耐热性好、低成本和带隙可调等优点,近年来备受关注,并广泛用于制备新型薄膜太阳能电池。目前,虽然具有倒置结构的无机钙钛矿太阳能电池(PSC)更稳定且有望应用于构筑叠层电池的顶电池,其性能仍落后于正置结构的电池。因此,倒置电池的结构,特别是其界面层亟待进一步优化。近年来,研究者们设计和开发了一系列有机、无机界面层(包括空穴传输层和电子传输层),尝试优化基于无机钙钛矿的倒置电池。本综述针对这一现状,从材料和制备工艺的角度出发,综述了基于有机、无机材料体系的多种界面层的制备和应用进展,总结各类界面层材料的特点,讨论目前界面层的瓶颈问题和潜在的解决方案。     

醋酸铅添加剂在印刷钙钛矿太阳能电池中的应用

印刷钙钛矿太阳能电池采用无机介孔骨架包覆有机无机杂化钙钛矿材料的器件结构,制备工艺简单,原材料成本低廉,且稳定性优异.然而,在介孔骨架中均匀沉积高质量的钙钛矿材料存在一定困难.本研究通过在典型钙钛矿材料甲胺铅碘(MAPbI3)前驱液中引入醋酸铅(Pb(Ac)2)作为添加剂,加快钙钛矿晶体的成核从而改善其在介孔骨架中的生...     

用于神经形态学计算的低能耗、高稳定性2D-3D钙钛矿忆阻器（英文）

近年来,有机-无机卤化物钙钛矿在忆阻器和人工突触器件等电子器件中的应用取得了快速进展.由于其离子迁移特性和制造上的优势,有机-无机卤化物钙钛矿有望成为下一代计算设备的候选材料.本文采用ITO/FA_1-yMA_yPbI_3-xCl_x/(PEA)₂PbI₄/Au的叠层结构,研究了2D-3D有机-无机杂化钙钛矿忆阻器.结果表明,这种新型忆阻器具有新颖的电阻开关特性,如扫描速率相关的电流开关特性、良好的电流-电压曲线重复性和超低能耗.利用p-i-n结模型证实了缺陷调制电子隧穿机制,并证明了忆阻器件的电导状态由电极侧附近钙钛矿薄膜中的缺陷浓度决定.除了良好的忆阻特性外,这种2D-3D钙钛矿型忆阻器还可以很好地用作人工突触,其内部缺陷运动可以真实地模拟生物突触中Ca²⁺的流入和挤出.此外,由于有机-无机卤化物钙钛矿中的可切换p-i-n结构,这种基于钙钛矿的人工突触具有超低功耗.我们的发现展示了2D-3D钙钛矿忆阻器在未来神经形态计算系统中的巨大应用潜...     

自组装制备有机/无机层状复合材料

自然界中形成的生物材料在结构和性能上具有优异的配备性。模仿生物矿化的形成机制,利用自组装原理能够仿生合成出性能优良和具有多级结构特点的有机/无机界面层状复合材料。本文在总结近年来最新研究的成果上,简要介绍了自组装和生物矿化的机理,重点阐述了基于无机相层的自组装和以有机大分子为模板自组装制备有机／无机层状复合材料两种合成连径,并对未来的发展趋势做了展望。     

有机-无机杂化一维磁性自组装聚合物纳米链的研究进展

随着纳米科技的发展,有机-无机杂化一维磁性自组装聚合物纳米链的设计合成与应用成为新的研究热点。综述了有机-无机杂化一维磁性自组装聚合物纳米链的磁场诱导自组装、模板诱导自组装和偶极诱导自组装等制备方法,并介绍了其在光学、生物医学和水处理等领域的应用。最后指出有机-无机杂化一维磁性自组装聚合物纳米材料制备技术存在的不足,并对其应用前景进行展望。     

稀土配合物-无机杂化发光材料研究进展

稀土元素独特的4f亚层电子在一定的激发条件下具有丰富的能级跃迁,表现出优异的磁、光、电等性能,但稀土三价离子4f组态内跃迁是宇称禁戒的。将稀土离子引入某些晶格中或者结合有机配体形成稀土配合物,可提高其发光强度。稀土配合物易受外界环境影响,稳定性较差,将有机配体与无机基质连接制备高性能稀土杂化发光材料,应用潜力巨大。本文从结构组成、发光机理和合成方法等方面详细综述多种无机基质和稀土配合物杂化材料的研究现状,包括介孔二氧化硅、沸石、锂皂石、石墨烯及其衍生物、二氧化钛等。其次,介绍稀土无机杂化材料在硅太阳能电池、LED发光材料、信息防伪加密发光传感器和生物应用等不同领域的应用进展。最后,对稀土无机杂化工艺的发展趋势进行了展望,未来应探究稀土离子有机配体和无机基质的微观结构组成及作用机理,研究敏化性能良好有机配体的设计和组装,从而实现稀土无机杂化材料的高效利用和功能化发展,并实现工业化生产。     

Inorganic and Layered Perovskites for Optoelectronic Devices

Organic–inorganic halide perovskites are making breakthroughs in a range of optoelectronic devices. Reports of >23% certified power conversion efficiency in photovoltaic devices, external quantum efficiency >21% in light‐emitting diodes (LEDs), continuous‐wave lasing and ultralow lasing thresholds in optically pumped lasers, and detectivity in photodetectors on a par with commercial GaAs rivals are being witnessed, making them the fastest ever emerging material technology. Still, questions on their toxicity and long‐term stability raise concerns toward their market entry. The intrinsic instability in these materials arises due to the organic cation, typically the volatile methylamine (MA), which contributes to hysteresis in the current–voltage characteristics and ion migration. Alternative inorganic substitutes to MA, such as cesium, and large organic cations that lead to a layered structure, enhance structural as well as device operational stability. These perovskites also provide a high exciton binding energy that is a prerequisite to enhance radiative emission yield in LEDs. The incorporation of inorganic and layered perovskites, in the form of polycrystalline films or as single‐crystalline nanostructure morphologies, is now leading to the demonstration of stable devices with excellent performance parameters. Herein, key developments made in various optoelectronic devices using these perovskites are summarized and an outlook toward stable yet efficient devices is presented.     

Mix and Match: Organic and Inorganic Ions in the Perovskite Lattice

Materials science evolves to a state where the composition and structure of a crystal can be controlled almost at will. Given that a composition meets basic requirements of stoichiometry, steric demands, and charge neutrality, researchers are now able to investigate a wide range of compounds theoretically and, under various experimental conditions, select the constituting fragments of a crystal. One intriguing playground for such materials design is the perovskite structure. While a game of mixing and matching ions has been played successfully for about 150 years within the limits of inorganic compounds, the recent advances in organic–inorganic hybrid perovskite photovoltaics have triggered the inclusion of organic ions. Organic ions can be incorporated on all sites of the perovskite structure, leading to hybrid (double, triple, etc.) perovskites and inverse (hybrid) perovskites. Examples for each of these cases are known, even with all three sites occupied by organic molecules. While this change from monatomic ions to molecular species is accompanied with increased complexity, it shows that concepts from traditional inorganic perovskites are transferable to the novel hybrid materials. The increased compositional space holds promising new possibilities and applications for the universe of perovskite materials.     

Uncovering the Mechanism Behind the Improved Stability of 2D Organic–Inorganic Hybrid Perovskites

2D organic–inorganic hybrid perovskites (OIHPs) may resolve the stability problem of bulk OIHPs. First‐principles calculations are employed to investigate the mechanism behind their favorable material properties. Two processes are identified to play a critical role: First, the 2D structure supports additional distortions that enhance the intrinsic structural stability. Second, the surface terminations of 2D OIHPs suppress degradation effects due to humidity. Having uncovered the stabilization mechanism, 2D OIHPs are designed with optimal stability and favorable electronic properties.     

Nonconfinement Structure Revealed in Dion–Jacobson Type Quasi‐2D Perovskite Expedites Interlayer Charge Transport

Dion–Jacobson (DJ) type 2D perovskites with a single organic cation layer exhibit a narrower distance between two adjacent inorganic layers compared to the corresponding Ruddlesden–Popper perovskites, which facilitates interlayer charge transport. However, the internal crystal structures in 2D DJ perovskites remain elusive. Herein, in a p‐xylylenediamine (PDMA)‐based DJ perovskite bearing bifunctional NH₃⁺ spacer, the compression from confinement structure (inorganic layer number, n = 1, 2) to nonconfinement structure (n > 3) with the decrease of PDMA molar ratio is unraveled. Remarkably, the nonconfined perovskite displays shorter spacing between 2D quantum wells, which results in a lower exciton binding energy and hence promotes exciton dissociation. The significantly diminishing quantum confinement promotes interlayer charge transport leading to a maximum photovoltaic efficiency of ≈11%. Additionally, the tighter interlayer packing arising from the squeezing of inorganic octahedra gives rise to enhanced ambient stability.     

3D Nanoprinting of Perovskites

As competing with the established silicon technology, organic–inorganic metal halide perovskites are continually gaining ground in optoelectronics due to their excellent material properties and low‐cost production. The ability to have control over their shape, as well as composition and crystallinity, is indispensable for practical materialization. Many sophisticated nanofabrication methods have been devised to shape perovskites; however, they are still limited to in‐plane, low‐aspect‐ratio, and simple forms. This is in stark contrast with the demands of modern optoelectronics with freeform circuitry and high integration density. Here, a nanoprecision 3D printing is developed for organic–inorganic metal halide perovskites. The method is based on guiding evaporation‐induced perovskite crystallization in mid‐air using a femtoliter ink meniscus formed on a nanopipette, resulting in freestanding 3D perovskite nanostructures with a preferred crystal orientation. Stretching the ink meniscus with a pulling process enables on‐demand control of the nanostructure's diameter and hollowness, leading to an unprecedented tubular‐solid transition. With varying the pulling direction, a layer‐by‐layer stacking of perovskite nanostructures is successfully demonstrated with programmed shapes and positions, a primary step for additive manufacturing. It is expected that the method has the potential to create freeform perovskite nanostructures for customized optoelectronics.     

Review on Recent Progress of All‐Inorganic Metal Halide Perovskites and Solar Cells

All‐inorganic perovskites are considered to be one of the most appealing research hotspots in the field of perovskite photovoltaics in the past 3 years due to their superior thermal stability compared to their organic–inorganic hybrid counterparts. The power‐conversion efficiency has reached 17.06% and the number of important publications is ever increasing. Here, the progress of inorganic perovskites is systematically highlighted, covering materials design, preparation of high‐quality perovskite films, and avoidance of phase instabilities. Inorganic perovskites, nanocrystals, quantum dots, and lead‐free compounds are discussed and the corresponding device performances are reviewed, which have been realized on both rigid and flexible substrates. Methods for stabilization of the cubic phase of low‐bandgap inorganic perovskites are emphasized, which is a prerequisite for highly efficient and stable solar cells. In addition, energy loss mechanisms both in the bulk of the perovskite and at the interfaces of perovskite and charge selective layers are unraveled. Reported approaches to reduce these charge‐carrier recombination losses are summarized and complemented by methods proposed from our side. Finally, the potential of inorganic perovskites as stable absorbers is assessed, which opens up new perspectives toward the commercialization of inorganic perovskite solar cells.     

Electro‐Optic Modulation in Hybrid Metal Halide Perovskites

Rapid and efficient conversion of electrical signals to optical signals is needed in telecommunications and data network interconnection. The linear electro‐optic (EO) effect in noncentrosymmetric materials offers a pathway to such conversion. Conventional inorganic EO materials make on‐chip integration challenging, while organic nonlinear molecules suffer from thermodynamic molecular disordering that decreases the EO coefficient of the material. It has been posited that hybrid metal halide perovskites could potentially combine the advantages of inorganic materials (stable crystal orientation) with those of organic materials (solution processing). Here, layered metal halide perovskites are reported and investigated for in‐plane birefringence and linear electro‐optic response. Phenylmethylammonium lead chloride (PMA₂PbCl₄) crystals are grown that exhibit a noncentrosymmetric space group. Birefringence measurements and Raman spectroscopy confirm optical and structural anisotropy in the material. By applying an electric field on the crystal surface, the linear EO effect in PMA₂PbCl₄ is reported and its EO coefficient is determined to be 1.40 pm V^?1. This is the first demonstration of this effect in hybrid metal halide perovskites, materials that feature both highly ordered crystalline structures and solution processability. The in‐plane birefringence and electro‐optic response reveal that layered perovskite crystals could be further explored for potential applications in polarizing optics and EO modulation.     

Morphology-Dependent Charge Carrier Dynamics and Ion Migration Behavior of CsPbBr3 Halide Perovskite Quantum Dot Films

Exceptional electronic, optoelectronic, and sensing properties of inorganic Cs-based perovskites are significantly influenced by the defect chemistry of the material. Although organic halide perovskites that have a polycrystalline structure are heavily studied, understanding of the defect properties at the grain boundaries (GB) of inorganic Cs-based perovskite quantum dots (QDs) is still limited. Here, morphology-dependent charge carrier dynamics of CsPbBr₃ quantum dots at the nanoscale by performing scanning probe microscopy of thermally treated samples are investigated. The grain boundaries of defect-engineered samples show higher surface potential than the grain interiors under light illumination, suggesting an effective role of GBs as charge collection and transport channels. The lower density of crystallographic defects and lower trap density at GBs specifically of heat-treated samples cause insignificant dark current, lower local current hysteresis, and higher photocurrent, than the control samples. It is also shown that the decay rate of surface photovoltage of the heated sample is quicker than the control sample, which implies a considerable impact of ion migration on the relaxation dynamic of photogenerated charge carriers. These findings reveal that the annealing process is an effective strategy to control not only the morphology but also the optoelectrical properties of GB defects, and the dynamic of ion migration. Understanding the origin of photoelectric activity in this material allows for designing and engineering optoelectronic QD devices with enhanced functionality.     

Preparation and performance of organic–inorganic halide perovskites

Layered organic–inorganic perovskites have potential application in solar cells because of their unique electrical and optical properties. These materials can also overcome the instability of organic sensitizers and the disorder of metal oxides. A preliminary study on the preparation of organic–inorganic halide perovskites (CH₃NH₃PbI _x Cl_3?x ) was conducted in this paper. The synthesis temperature and thermal stability in air were analyzed by thermogravimetric analysis and differential scanning calorimetry. The structure and morphology of the products were investigated by X-ray diffraction and scanning electron microscopy. UV–visible spectroscopy revealed that the material had good absorption within the range of 350–750 nm and can be used as the active light-absorbing layer of solar cells. Hybrid solar cells of FTO/TiO₂–CH₃NH₃PbI _x Cl_3?x /Spiro-MeOTAD/Ag were found to have a high fill factor of 0.5 but low power conversion efficiency of 0.28 %.