Colorless to black switching with high contrast ratio via the electrochemical process of a hybrid organic-inorganic perovskite

Colorless‐to‐black switching has attracted widespread attention for smart windows and multifunctional displays because they are more useful to control solar energy.However,it still remains a challenge owing to the tremendous difficulties in the design of completely reverse absorptions in transmissive and colored states.Herein,we report on an electrochemical device that can switch between colorless and black by using the electrochemical process of hybrid organic–inorganic perovskite MAPbBr_(3),which shows a high integrated contrast ratio of up to 73%from 400 to 800 nm.The perovskite solution can be used as the active layer to assemble the device,showing superior transmittance over the entire visible region in neutral states.By applying an appropriate voltage,the device undergoes reversible switching between colorless and black,which is attributed to the formation of lead and Br_(2)in the redox reaction induced by the electron transfer process in MAPbBr_(3).In addition,the contrast ratio can be modulated over the entire visible region by changing the concentration and the applied voltage.These results contribute toward gaining an insightful understanding of the electrochemical process of perovskites and greatly promoting the development of switchable devices.

Giant magneto field effect in up-conversion amplified spontaneous emission via spatially extended states in organic-inorganic hybrid perovskites

Up-conversion lasing actions are normally difficult to realize in light-emitting materials due to small multi-photon absorp-tion cross section and fast dephasing of excited states during multi-photon excitation.This paper reports an easily ac-cessible up-conversion amplified spontaneous emission(ASE)in organic-inorganic hybrid perovskites(MAPbBr3)films by optically exciting broad gap states with sub-bandgap laser excitation.The broad absorption was optimized by adjust-ing the grain sizes in the MAPbBr3 films.At low sub-bandgap pumping intensities,directly exciting the gap states leads to 2-photon,3-photon,and 4-photon up-conversion spontaneous emission,revealing a large optical cross section of multi-photon excitation occurring in such hybrid perovskite films.At moderate pumping intensity(1.19 mJ/cm2)of 700 nm laser excitation,a significant spectral narrowing phenomenon was observed with the full width at half maximum(FWHM)de-creasing from 18 nm to 4 nm at the peak wavelength of 550 nm,simultaneously with a nonlinear increase on spectral peak intensity,showing an up-conversion ASE realized at low threshold pumping fluence.More interestingly,the up-con-version ASE demonstrated a giant magnetic field effect,leading to a magneto-ASE reaching 120%.In contrast,the up-conversion photoluminescence(PL)showed a negligible magnetic field effect(<1%).This observation provides an evid-ence to indicate that the light-emitting states responsible for up-conversion ASE are essentially formed as spatially exten-ded states.The angular dependent spectrum results further verify the existence of spatially extended states which are polarized to develop coherent in-phase interaction.Clearly,using broad gap states with spatially extended light-emitting states presents a new approach to develop up-conversion ASE in organic-inorganic hybrid perovskites.

Recent advances in atomic imaging of organic-inorganic hybrid perovskites

Three-dimensional organic-inorganic hybrid perovskites(OHPs)hold a great prospect for photovoltaic applications due to their outstanding electronic and optical properties.These fascinating properties of OHPs in combination with their scalable and low-cost production make OHPs promising candidates for next-generation optoelectronic devices.The ability to obtain atomistic insights into physicochemical properties of this class of materials is crucial for the future development of this field.Recent advances in various scanning probe microscopy techniques have demonstrated their extraordinary capability in real-space imaging and spectroscopic measurements of the structural and electronic properties of OHPs with atomic-precision.Moreover,these techniques can be combined with light illumination to probe the structural and optoelectronic properties of OHPs close to the real device operation conditions.The primary focus of this review is to summarize the recent progress in atomic-scale studies of OHPs towards a deep understanding of the phenomena discovered in OHPs and OHP-based optoelectronic devices.

Preparation and Optical Patterning of Organic-Inorganic Hybrid Color-Filter Films Using Latent Pigments by Utilizing Photo-Acid-Generator and Microwave Irradiation

Preparation and photo-patterning characteristics of organic-inorganic hybrid thin film containing latent pigment by using photo-acid-generator (PAG) and microwave irradiation have been investigated. The acrylic thin film modified with methoxysilane containing PAG was formed on a glass substrate and irradiated with ultraviolet rays to promote sol-gel reaction by catalytic action of acid which was generated from PAG. And then the film was hardened with microwave irradiation, yielding organic-inorganic hybrid polymer film having hardness, highly transparency and strong adhesion with a glass substrate. Since this reaction only occurred in the optically (UV) irradiated regions, by exploiting the difference between the adhesivenesses of these regions photo-irradiated through photomask with a glass substrate, it was possible to form a patterned film with pitch of 100 to 50 μm by a simple lift-off method. A pigment-containing film using latent pigments (with subtractive three primary colors of coloring materials) and a patterned film were prepared, and it was possible to make these films multi-colored by varying the mixing ratio of the pigments. This multi-colored film-preparation method is effective for simply and efficiently forming a color-filter film by applying optical and microwave irradiation.

Crystal engineering regulation achieving inverse temperature symmetry breaking ferroelasticity in a cationic displacement type hybrid perovskite system

Ferroelastic hybrid perovskite materials have been revealed the significance in the applications of switches,sensors,actuators,etc.However,it remains a challenge to design high-temperature ferroelastic to meet the requirements for the practical applications.Herein,we reported an one-dimensional organicinorganic hybrid perovskites(OIHP)(3-methylpyrazolium)CdCl_(3)(3-MBCC),which possesses a mmmF2/m ferroelastic phase transition at 263 K.Moreover,utilizing crystal engineering,we replace-CH_(3) with-NH_(2) and-H,which increases the intermolecular force between organic cations and inorganic frameworks.The phase transition temperature of(3-aminopyrazolium)CdCl_(3)(3-ABCC),and(pyrazolium)CdCl_(3)(BCC)increased by 73 K and 10 K,respectively.Particularly,BCC undergoes an unconventional inverse temperature symmetry breaking(ISTB)ferroelastic phase transition around 273 K.Differently,it transforms from a high symmetry low-temperature paraelastic phase(point group 2/m)to a low symmetry high-temperature ferroelastic phase(point group ī)originating from the rare mechanism of displacement of organic cations phase transition.It means that crystal BCC retains in ferroelastic phase above 273 K until melting point(446 K).Furthermore,characteristic ferroelastic domain patterns on crystal BCC are confirmed with polarized optical microscopy.Our study enriches the molecular mechanism of ferroelastics in the family of organic-inorganic hybrids and opens up a new avenue for exploring high-temperature ferroic materials.

Robust hybrid bismuth perovskites as potential photocatalysts for overall water splitting

Organic-inorganic hybrid perovskites have gained great attention as promising photocatalysts for hydrogen generation.However,due to their poor stability in water,the use of aqueous hydrohalic acid solutions is specifically required for an efficient hydrogen evolution.Herein,three novel photoactive lead-free hybrid perovskites based on bismuth and triazolium cations(denoted as IEF-15,IEF-16,and IEF-17(IEF stands for IMDEA energy frameworks))were synthesized and fully characterized(structural,compositional,optical,etc.).Further,these solids were proposed as photocatalysts for the challenging gas phase overall water splitting(OWS)reaction.Accordingly,IEF-16 thin films exhibited a remarkable photocatalytic activity in both H_(2) and O_(2) evolution,as a consequence of its appropriate bandgap and energy-band alignment,achieving hydrogen evolution rates ofμmol·g_(H_(2))^(-)1846 and 360 after 24 h under ultraviolet-visible(UV-vis)irradiation or simulated solar irradiation,respectively.This study additionally highlights the remarkable structural and photochemical stability of IEF-16 under different operational conditions(i.e.water volume,irradiation and temperature),paving the way for green hydrogen production from OWS using perovskite-based photocatalysts.

Advanced Strategies of Passivating Perovskite Defects for High-Performance Solar Cells

Organic–inorganic halide perovskite(OIHP)solar cells have garnered great attention in the last decade since they continuously approach the Shockley–Queisser Limit.Compared with conventional organic and inorganic semiconductors,OIHPs possess the high tolerance on defects due to the dominated intrinsically shallow-level carrier-trapping centers.However,the existence of defects still causes the ion migration,produces the hysteresis effect,and accelerates the film degradation,eventually suppressing the device efficiency and stability.In this Review Article,we summarize recent impressive advance on passivating OIHP defects and discuss the future horizon of exploiting high-efficiency and long-stability OIHP solar cells in terms of defect managements.

Charge Localization Induced by Reorientation of FA Cations Greatly Suppresses Nonradiative Electron-Hole Recombination in FAPbI3 Perovskites:a Time-Domain Ab Initio Study

Recent experiments report the rotation of FA(FA=HC[NH2]2+)cations significantly influence the excited-state lifetime of FAPbI3.However,the underlying mechanism remains unclear.Using ab initio nonadiabatic(NA)molecular dynamics combined with time-domain density functional simulations,we have demonstrated that reorientation of partial FA cations significantly inhibits nonradiative electron-hole recombination with respect to the pristine FAPbI3 due to the decreased NA coupling by localizing electron and hole in different positions and the suppressed atomic motions.Slow nuclear motions simultaneously increase the decoherence time,which is overcome by the reduced NA coupling,extending electron-hole recombination time scales to several nanoseconds and being about 3.9 times longer than that in pristine FAPbI3,which occurs within sub-nanosecond and agrees with experiment.Our study established the mechanism for the experimentally reported prolonged excited-state lifetime,providing a rational strategy for design of high performance of perovskite solar cells and optoelectronic devices.

Recent advances on organic-inorganic hybrid perovskite photodetectors with fast response

In the last decade,optoelectronic devices based on organic-inorganic hybrid perovskite(OIHP)materials,which have unique advantages of direct bandgap,large absorption coefficient,low density of defects,long charge carrier lifetime,diffusion length,and solution processability,have traveled with traditional inorganic semiconductor devices.The state-of-the-art OIHP photodetectors have contributed a comparable performance with Si and III-V compound semiconductor based photodetectors.Large amount of efforts have been focused on improving sensitivity,broadening detection spectra,enlarging linear dynamic range.However,few reports emphasized the important parameter of response speed.In this review,we summarize the progress and applications of OIHP photodetectors with fast response.Based on photovoltaic and photoconductive-type OIHP photodetectors,the working principle and key factors on determining response speed are systematically mentioned.Then,the research progress of response speed,which is composed of resistance-capacitance(RC)time constant and charge carrier transit time is discussed in detail.Subsequently,considering the intrinsic flexibility of perovskite materials,we briefly discuss the flexible photodetectors.Finally,an outlook and potential rules for designing fast-response OIHP photodetectors are further proposed.

Transmission electron microscopy of organic-inorganic hybrid perovskites:myths and truths

Organic-inorganic hybrid perovskites(OIHPs)have attracted extensive research interest as a promising candidate for efficient and inexpensive solar cells.Transmission electron microscopy(TEM)characterizations that can benefit the fundamental understanding and the degradation mechanism are widely used for these materials.However,their sensitivity to the electron beam illumination and hence structural instabilities usually prevent us from obtaining the intrinsic information or even lead to significant artifacts.Here,we systematically investigate the structural degradation behaviors under different experimental factors to reveal the optimized conditions for TEM characterizations of OIHPs by using low-dose electron diffraction and imaging techniques.We find that a low temperature(-180°C)does not slow down the beam damage but instead induces a rapid amorphization for OIHPs.Moreover,a less severe damage is observed at a higher accelerating voltage.The beam-sensitivity is found to be facetdependent that a(100)exposed CH3NH3PbI3(MAPbI3)surface is more stable than a(001)surface.With these guidance,we successfully acquire the atomic structure of pristine MAPbI3 and identify the characterization window that is very narrow.These findings are helpful to guide future electron microscopy characterizations of these beam-sensitive materials,which are also useful for finding strategies to improve the stability and performance of the perovskite solar cells.

Organic-inorganic hybrid Sn-based perovskite photodetectors with high external quantum efficiencies and wide spectral responses from 300 to 1000 nm

Organic-inorganic hybrid perovskites are ideal materials for photodetection owing to their high charge carrier mobility, long charge carrier diffusion length, low dark current density and sharp absorption edge. However, a relatively small band gap(1.6 e V) limits their photonharvesting efficiency in the near-infrared region. In the present work, we demonstrate a hybrid methylamine iodide and Pb-Sn binary perovskite as the light absorption layer in photodetectors. Experimentally, the wavelength of photoresponse onset for the photodetectors can be extended to as great as 1,000 nm when the Sn content of the hybrid perovskite is increased to 30 mol%. In addition, the photodetectors exhibit a photoresponsivity of 0.39 A W^-1, a specific detectivity of 7×10^12 Jones, a fast photoresponse with rise and decay time constants and an external quantum efficiency greater than 50% in the wavelength range of350–900 nm, with a maximum value of about 80% at 550 nm.

Progress in organic-inorganic hybrid halide perovskite single crystal:growth techniques and applications

As a new generation of solution-processable optoelectronic materials, organic-inorganic hybrid halide perovskites have attracted a great deal of interest due to their high and balanced carrier mobility, long carrier dif- fusion length and large light absorption coefficient. These materials have demonstrated wide applications in solar cell, light-emitting diode, laser, photodetector, catalysis and other fields. Comparing with their polycrystalline film counter- part, perovskite single crystals have low trap density and no grain boundaries and thus are anticipated to possess much better optoelectronic performances. Herein, we review the key progress in the development of organic-inorganic halide perovskite single crystals. Particularly, the crystal growth techniques and applications of these advanced materials are highlighted.

Research progress on hybrid organic-inorganic perovskites for photo-applications

Hybrid organic-inorganic perovskite materials have attracted significant atte ntion of most re searchers in recently years,which is ascribed to the superior photoelectric properties,such as the suitable band gaps for harvesting sunlight,and exhibit high optical adsorption,high charge-carrier lifetimes and long diffusion lengths.The photodetectors,light-emitting diodes,solar cells and photocatalysts represent the remarkable applications for the hybrid organic-inorganic perovskite materials.Herein,we review the recent progress of hybrid organic-inorganic perovskite-based photodetectors,light-emitting diodes,solar cells and photocatalysts.The challenges and outlook for the hybrid organic-inorganic perovskitebased photodetectors,light-emitting diodes,solar cells and photocatalysts are considered.

Unconventional solution-phase epitaxial growth of organic-inorganic hybrid perovskite nanocrystals on metal sulfide nanosheets

Epitaxial heterostructures based on organicinorganic hybrid perovskites and two-dimensional materials hold great promises in optoelectronics, but they have been prepared only via solid-state methods that restricted their practical applications. Herein, we report cubic-phased MAPbBr3(MA=CH3NH3+) nanocrystals were epitaxially deposited on trigonal/hexagonal-phased MoS2 nanosheets in solution by facilely tuning the solvation conditions. In spite of the mismatched lattice symmetry between the square MAPbBr3(001) overlayer and the hexagonal MoS2(001) substrate, two different aligning directions with lattice mismatch of as small as 1% were observed based on the domainmatching epitaxy. This was realized most likely due to the flexible nature and absence of surface dangling bonds of MoS2 nanosheets. The formation of the epitaxial interface affords an effective energy transfer from MAPbBr3 to MoS2, and as a result, paper-based photodetectors facilely fabricated from these solution-dispersible heterostructures showed better performance compared to those based on MoS2 or MAPbBr3 alone. In addition to the improved energy transfer and light adsorption, the use of MoS2 nanosheets provided flexible and continuous substrates to connect the otherwise discrete MAPbBr3 nanocrystals and achieved the better film forming ability. Our work suggests that the scalable preparation of heterostructures based on organic-inorganic hybrid perovskites and 2D materials via solution-phase epitaxy may bring about more opportunities for expanding their optoelectronic applications.

The chemistry and physics of organic-inorganic hybrid perovskite quantum wells

Organic-inorganic hybrid two dimensional(2D)lead halide perovskites(LHPs)are tunable quantum wells that exhibit a set of intriguing structural and physical properties including soft and dynamic lattices,organic-inorganic epitaxial heterointerfaces,quantum and dielectric confinements,strong light-matter interactions,and large spin-orbit coupling,which enable promising perspectives for optoelectronics,ferroelectrics,and spintronics.While the properties of 2D LHPs bear some resemblance of the3D LHPs,they are often drastically altered due to the reduced dimensionality and the complex interactions between organic and inorganic components.In this review,we discuss the influences of the reduced dimensionality and the organic-inorganic interplays on the structural stability and distortion of the inorganic lattices,inversion symmetry of the crystal structure,electronic band structures,excitonic physics,and carrier-phonon interactions in 2D LHPs.An emphasis is placed on the relationships between the crystal structures and photophysical properties.Future perspectives on the opportunities of hybrid quantum wells are provided.

基于模板剥离法制备高性能钙钛矿单晶薄膜光电探测器

近年来,杂化钙钛矿半导体材料由于其带隙可调、吸收系数高、载流子迁移率高、成本低廉等诸多优点,在光电器件领域备受青睐,如太阳能电池、电致发光器件、光电探测器等。其中,钙钛矿单晶薄膜因其无晶界、杂质和缺陷含量低等特点,展现出更为优异的光学、电学特性,成为制备高性能光电器件的理想材料体系。然而,钙钛矿单晶薄膜常采用空间限域法直接生长在空穴传输层上,不可避免地将导致界面缺陷和载流子层间输运等问题,严重制约了钙钛矿单晶薄膜光电探测器的性能。为此,本文通过引入模板剥离法工艺技术,在钙钛矿单晶薄膜两侧分别蒸镀功能层材料,制备了结构为Cu/BCP/C_(60)/MAPbBr_(3)/MoO_(3)/Ag的钙钛矿单晶薄膜光电探测器。基于模板剥离法,两侧蒸镀的功能层与钙钛矿单晶薄膜接触紧密,将有效改善载流子的注入和传输;同时,优化的器件结构以及考虑能带匹配等因素可实现高灵敏、响应快速的钙钛矿单晶薄膜光电探测器。改进后器件的开关比高达3.1×10^(3),响应度可达7.15 A/W,探测率为5.39×10^(12)Jones,外量子效率达到1794%。该工作为进一步改善和提升钙钛矿单晶薄膜光电探测器的探测性能提供了一种可行性技术方案。

溶液空间限域法制备有机-无机杂化卤化铅钙钛矿单晶薄膜及其器件应用研究进展

近年来,有机-无机杂化卤化铅钙钛矿材料因其出色的光电特性在国际上备受瞩目,并已成功应用于太阳能光伏、光电探测、电致发光等多个领域。目前绝大部分器件研究都集中在钙钛矿多晶材料上,但钙钛矿单晶材料拥有更低的缺陷态密度、更高的载流子迁移率、更长的载流子复合寿命、更宽的光吸收范围,以及更高的稳定性等优异的性质,可有效减少载流子传输过程中的散射损失,以及在晶界处的非辐射复合,并抑制离子迁移所引起的迟滞效应。采用钙钛矿单晶薄膜作为器件有源层有望制备性能更高效且更稳定的钙钛矿光电器件。目前,已报道的多种钙钛矿单晶薄膜制备方法包括溶液空间限域法、化学气相沉积法、自上而下加工法等,其中溶液空间限域法的发展和应用最为广泛。本文聚焦利用溶液空间限域法制备高质量钙钛矿单晶薄膜的相关方法,以及钙钛矿单晶薄膜在光电探测器、太阳能电池、场效应晶体管和发光二极管等相关器件应用中的研究进展,并对钙钛矿单晶薄膜及其光电器件的未来发展趋势进行了展望。

Targeted Management of Perovskite Film by Co(Ⅱ)Sulfophenyl Porphyrin for Efficient and Stable Solar Cells

In the lead halide perovskite solar cells(PSCs),the redox reaction of I-and Pb^(2+) ions in perovskite materials under the fabrication and operation processes causes the formation of defects to destroy the cell efficiency and long-term stability.Herein,we have employed a Co(Ⅱ)sulfophenyl porphyrin(CoTPPS)to modify the perovskite film.The sulfonic group could coordinate with Pb2+to efficiently passivate the uncoordinated Pb^(2+).Additionally,Co^(2+) ions in CoTPPS could react with I^(2) generated under the thermal and light stress to yield the Co^(3+) and I^(-),thus achieving the regeneration of I^(-) in perovskite film.Therefore,the CoTPPS could realize the targeted management of the imperfections in perovskite film.As a result,the modified PSCs reveal the remarkably enhanced cell perfor-mance.More importantly,the CoTPPS modified device retains 75%of its initial efficiency value storing at 85℃for 2000 h and about 70%of its efficiency when being continuously illuminated at a simulated sunlight for 1200 h.This strategy tackles the chemical reaction and inhibits the defect generation,thus improving the operational stability and efficiency of PSCs.

The first 2D organic-inorganic hybrid relaxor-ferroelectric single crystal

Inorganic relaxor ferroelectric solid solution single crystals are spurring new generations of high performance electromechanical devices,including transducers,sensors,and actuators,due to their ultrahigh electric field induced strain,large piezoelectric constant,high electromechanical coupling factor and low dielectric loss.However,relaxor ferroelectric single crystals found in organic-inorganic hybrid perovskites are very limited,but achieving these superior properties in them will be of great significance in the design of modern functional materials.Fortunately,here the first two-dimensional(2D)organic-inorganic hybrid relaxor ferroelectric single crystal,[Br(CH_(2))_(3)NH_(3)]_(2)PbBr_(4)(BPA_(2)-PbBr_(4),BPA=3-bromopropylamine),achieves some of superior properties.Interestingly,BPA_(2)-PbBr_(4)reveals a successive relaxor ferroelectric-ferroelectric-paraelectric phase transitions accompanying by a large degree of relaxationΔT_(relax)=61 K and ultralow energy loss(tanδ<0.001).Meanwhile,it exhibits a superior second harmonic generation(SHG)effect with maximum value accounts for 95%of the standard KDP due to great deformation of structure(3.2302×10^(-4)).In addition,temperature dependent luminescence spectra(80-415 K)exhibit fluorescence and phosphorescence overlapping emission originated from inorganic and organic components with the nanosecond-scale short lifetime and the millisecond-scale long lifetime,respectively,and the color of the emitted light is continuously adjustable,which is the first to achieve luminescence and relaxor ferroelectricity compatibility.

Ferroelectric perovskite-type films with robust in-plane polarization toward efficient room-temperature chemiresistive sensing

Ferroelectric materials have become key components for versatile device applications,and their thin films are highly desirable for integrating the miniaturized devices.Despite substantial endeavors,it is still challenging to achieve effective chemiresistive sensing in the ferroelectric films.Here,for the first time,we have exploited ferroelectric thin films of 2D hybrid perovskite BA_(2)EA_(2)Pb_(3)I_(10)(1),to fabricate the high-performance chemiresistor gas sensors.The spin-coated films of 1 exhibit high orientation and good crystallinity,thus preserving robust in-plane spontaneous polarization(P_(s)~2.0μC/cm^(2))and low electric coercivity.Notably,such ferroelectric filmbased sensors after electric poling enable the dramatic room-temperature sensing responses to NO_(2) gas,including high sensitivity(0.05 ppm^(-1)),extremely low detection limit(1 ppm)and fast responding rate(~6 s).Besides,the chemiresistive responses are remarkably enhanced by threefold(up to 320%)through electric poling.It is proposed that this behavior closely involves with strong in-plane ferroelectric polarization of 1 that generates a built-in electric field inhibiting the recombination of charge carriers.As far as we know,this ferroelectric-based film chemiresisor is one of the best room-temperature sensors for NO_(2) gas among all the existing candidate materials.These findings highlight great potential of ferroelectrics toward effective chemiresistive performances,and also establish a bright direction to explore their future device applications.