Aqueous Phase Exfoliating Quasi‐2D CsPbBr3 Nanosheets with Ultrahigh Intrinsic Water Stability

All‐inorganic cesium lead halide perovskite nanocrystals (NCs) have emerged as attractive optoelectronic materials due to the excellent optical and electronic properties. However, their environmental stability, especially in the presence of water, is still a significant challenge for their further commercialization. Here, ultrahigh intrinsically water‐stable all‐inorganic quasi‐2D CsPbBr₃ nanosheets (NSs) via aqueous phase exfoliation method are reported. Compared to conventional perovskite NCs, these unique quasi‐2D CsPbBr₃ nanosheets present an outstanding long‐term water stability with 87% photoluminescence (PL) intensity remaining after 168 h under water conditions. Moreover, the photoluminescence quantum yields (PLQY) of quasi‐2D CsPbBr₃ NSs is up to 82.3%, and these quasi‐2D CsPbBr₃ NSs also present good photostability of keeping 85% PL intensity after 2 h under 365 nm UV light. Evidently, such quasi‐2D perovskite NSs will open up a new way to investigate the intrinsic stability of all‐inorganic perovskites and further promote the commercial development of perovskite‐based optoelectronic and photovoltaic devices.     

Efficient and Stable Inverted Perovskite Solar Cells Incorporating Secondary Amines

Large‐bandgap perovskites offer a route to improve the efficiency of energy capture in photovoltaics when employed in the front cell of perovskite–silicon tandems. Implementing perovskites as the front cell requires an inverted (p–i–n) architecture; this architecture is particularly effective at harnessing high‐energy photons and is compatible with ionic‐dopant‐free transport layers. Here, a power conversion efficiency of 21.6% is reported, the highest among inverted perovskite solar cells (PSCs). Only by introducing a secondary amine into the perovskite structure to form MA_1?xDMA_xPbI₃ (MA is methylamine and DMA is dimethylamine) are defect density and carrier recombination suppressed to enable record performance. It is also found that the controlled inclusion of DMA increases the hydrophobicity and stability of films in ambient operating conditions: encapsulated devices maintain over 80% of their efficiency following 800 h of operation at the maximum power point, 30 times longer than reported in the best prior inverted PSCs. The unencapsulated devices show record operational stability in ambient air among PSCs.     

Inorganic lead-based halide perovskites: From fundamental properties to photovoltaic applications

Compared with organic–inorganic hybrid halide perovskites (OIHPs), inorganic cesium lead halide perovskites (CsPbX₃) possess superior intrinsic stability for high temperatures and are considered one of the most attractive research hotspots in the perovskite photovoltaic (PV) field in the past several years. The PCE of CsPbX₃ inorganic perovskite solar cells (IPSCs) has increased from 2.9% in 2015 to more than 20% with excellent stability. There are still many on-going studies on the properties of perovskite materials and their applications in PV technology, thereby needing a thorough understanding. Here, the progress of inorganic perovskites is systematically introduced, including the fundamental properties of CsPbX₃ materials and CsPbX₃-based PV devices. The origins of stability and instability of CsPbX₃ and defects in CsPbX₃ are discussed. CsPbI₃-, CsPbI₂Br-, CsPbIBr₂- and CsPbBr₃-based PV devices and performance are comprehensively reviewed. The stabilization methods and mechanism for the photoactive phases of inorganic perovskites with low bandgap are emphasized. Reported strategies to boost the performance of CsPbX₃-based IPSCs are summarized. In the end, the potential of inorganic perovskites is evaluated, which opens up new prospects for the commercialization of IPSCs.     

Structural and Functional Diversity in Lead‐Free Halide Perovskite Materials

Lead halide perovskites have emerged as promising semiconducting materials for different applications owing to their superior optoelectronic properties. Although the community holds different views toward the toxic lead in these high‐performance perovskites, it is certainly preferred to replace lead with nontoxic, or at least less‐toxic, elements while maintaining the superior properties. Here, the design rules for lead‐free perovskite materials with structural dimensions from 3D to 0D are presented. Recent progress in lead‐free halide perovskites is reviewed, and the relationships between the structures and fundamental properties are summarized, including optical, electric, and magnetic‐related properties. 3D perovskites, especially A₂B⁺B³⁺X₆‐type double perovskites, demonstrate very promising optoelectronic prospects, while low‐dimensional perovskites show rich structural diversity, resulting in abundant properties for optical, electric, magnetic, and multifunctional applications. Furthermore, based on these structure–property relationships, strategies for multifunctional perovskite design are proposed. The challenges and future directions of lead‐free perovskite applications are also highlighted, with emphasis on materials development and device fabrication. The research on lead‐free halide perovskites at Linköping University has benefited from inspirational discussions with Prof. Olle Inganäs.     

Fluorinated 2D Lead Iodide Perovskite Ferroelectrics

Hybrid perovskite materials are famous for their great application potential in photovoltaics and optoelectronics. Among them, lead‐iodide‐based perovskites receive great attention because of their good optical absorption ability and excellent electrical transport properties. Although many believe the ferroelectric photovoltaic effect (FEPV) plays a crucial role for the high conversion efficiency, the ferroelectricity in CH₃NH₃PbI₃ is still under debate, and obtaining ferroelectric lead iodide perovskites is still challenging. In order to avoid the randomness and blindness in the conventional method of searching for perovskite ferroelectrics, a design strategy of fluorine modification is developed. As a demonstration, a nonpolar lead iodide perovskite is modified and a new 2D fluorinated layered hybrid perovskite material of (4,4‐difluorocyclohexylammonium)₂PbI₄, 1 , is obtained, which possesses clear ferroelectricity with controllable spontaneous polarization. The direct bandgap of 2.38 eV with strong photoluminescence also guarantees the direct observation of polarization‐induced FEPV. More importantly, the 2D structure and fluorination are also expected to achieve both good stability and charge transport properties. 1 is not only a 2D fluorinated lead iodide perovskite with confirmed ferroelectricity, but also a great platform for studying the effect of ferroelectricity and FEPV in the context of lead halide perovskite solar cells and other optoelectronic applications.     

Highly Oriented Thin Films of 2D Ruddlesden‐Popper Hybrid Perovskite toward Superfast Response Photodetectors

2D hybrid perovskites have shown great promise in the photodetection field, due to their intriguing attributes stemming from unique structural architectures. However, the great majority of detectors based on this 2D system possess a relatively low response speed (≈ms), making it extremely urgent to develop new candidates for superfast photodetection. Here, a new organic–inorganic hybrid perovskite, (PA)₂(FA)Pb₂I₇ (EFA, where PA is n‐pentylaminium and FA is formamidine), which features the 2D Ruddlesden–Popper type perovskite framework that is composed of the corner‐sharing PbI₆ octahedra is reported. Significantly, photodetectors fabricated on highly oriented thin films, which exhibit a perfect orientation parallel to 2D inorganic perovskite layers, exhibit a superfast response time up to ≈2.54 ns. To the best of the knowledge, this figure‐of‐merit catches up with that of the top‐ranking commercial materials, and sets a new record for 2D hybrid perovskite photodetectors. Moreover, extremely high photodetectivity (≈1.73 × 10¹⁴ Jones, under an incident power intensity of ≈46 µW cm^?2), considerable switching ratios (>10³), and low dark current (≈10 pA) are also achieved in the detector, indicating its great potential for high‐efficiency photodetection. These results shed light on the possibilities to explore new 2D candidates for assembling future high‐performance optoelectronic devices.     

Amide‐Catalyzed Phase‐Selective Crystallization Reduces Defect Density in Wide‐Bandgap Perovskites

Wide‐bandgap (WBG) formamidinium–cesium (FA‐Cs) lead iodide–bromide mixed perovskites are promising materials for front cells well‐matched with crystalline silicon to form tandem solar cells. They offer avenues to augment the performance of widely deployed commercial solar cells. However, phase instability, high open‐circuit voltage (V_oc) deficit, and large hysteresis limit this otherwise promising technology. Here, by controlling the crystallization of FA‐Cs WBG perovskite with the aid of a formamide cosolvent, light‐induced phase segregation and hysteresis in perovskite solar cells are suppressed. The highly polar solvent additive formamide induces direct formation of the black perovskite phase, bypassing the yellow phases, thereby reducing the density of defects in films. As a result, the optimized WBG perovskite solar cells (PSCs) (E_g ≈ 1.75 eV) exhibit a high V_oc of 1.23 V, reduced hysteresis, and a power conversion efficiency (PCE) of 17.8%. A PCE of 15.2% on 1.1 cm² solar cells, the highest among the reported efficiencies for large‐area PSCs having this bandgap is also demonstrated. These perovskites show excellent phase stability and thermal stability, as well as long‐term air stability. They maintain ≈95% of their initial PCE after 1300 h of storage in dry air without encapsulation.     

Boosting Perovskite Photodetector Performance in NIR Using Plasmonic Bowtie Nanoantenna Arrays

Triple‐cation mixed metal halide perovskites are important optoelectronic materials due to their high photon to electron conversion efficiency, low exciton binding energy, and good thermal stability. However, the perovskites have low photon to electron conversion efficiency in near‐infrared (NIR) due to their weak intrinsic absorption at longer wavelength, especially near the band edge and over the bandgap wavelength. A plasmonic functionalized perovskite photodetector (PD) is designed and fabricated in this study, in which the perovskite ((Cs_0.06FA_0.79MA_0.15)Pb(I_0.85Br_0.15)₃) active materials are spin‐coated on the surface of Au bowtie nanoantenna (BNA) arrays substrate. Under 785 nm laser illumination, near the bandedge of perovskite, the fabricated BNA‐based plasmonic PD exhibits ≈2962% enhancement in the photoresponse over the Si/SiO₂‐based normal PD. Moreover, the detectivity of the plasmonic PD has a value of 1.5 × 10¹² with external quantum efficiency as high as 188.8%, more than 30 times over the normal PD. The strong boosting in the plasmonic PD performance is attributed to the enhanced electric field around BNA arrays through the coupling of localized surface plasmon resonance. The demonstrated BNA‐perovskite design can also be used to enhance performance of other optoelectronic devices, and the concept can be extended to other spectral regions with different active materials.     

Perovskite-Derivative Valleytronics

Halide perovskites are revolutionizing the renewable energy sector owing to their high photovoltaic efficiency, low manufacturing cost, and flexibility. Their remarkable mobility and long carrier lifetime are also valuable for information technology, but fundamental challenges like poor stability under an electric field prevent realistic applications of halide perovskites in electronics. Here, it is discovered that valleytronics is a promising route to leverage the advantages of halide perovskites and derivatives for information storage and processing. The synthesized all-inorganic lead-free perovskite derivative, Cs₃Bi₂I₉, exhibits strong light–matter interaction and parity-dependent optically addressable valley degree of freedom. Robust optical helicity in all odd-layer-number crystals with inversion symmetry breaking is observed, indicating excitonic coherence extending well beyond 11 layers. The excellent optical and valley properties of Cs₃Bi₂I₉ arise from the unique parallel bands, according to first principles calculations. This discovery points to new materials design principles for scalable valleytronic devices and demonstrates the promise of perovskite derivatives beyond energy applications.     

Space‐Confined Growth of Individual Wide Bandgap Single Crystal CsPbCl3 Microplatelet for Near‐Ultraviolet Photodetection

Perovskite photodetectors (PDs) with tunable detection wavelength have attracted extensive attention due to the potential application in the field of imaging, machine vision, and artificial intelligence. Most of the perovskite PDs focus on I‐ or Br‐based materials due to their easy preparation techniques. However, their main photodetection capacity is situated in the visible region because of their narrower bandgap. Cl‐based wide bandgap perovskites, such as CsPbCl₃, are scarcely reported because of the bad film quality of the spin‐coated Cl‐based perovskite, due to the poor solubility of the precursor. Therefore, ultraviolet detection using high‐quality full inorganic perovskite films, especially with high thermal stability of materials and devices, is still a big challenge. In this work, high‐quality single crystal CsPbCl₃ microplatelets (MPs) synthesized by a simple space‐confined growth method at low temperature for near‐ultraviolet (NUV) PDs are reported. The single CsPbCl₃ MP PDs demonstrate a decent response to NUV light with a high on/off ratio of 5.6 × 10³ and a responsivity of 0.45 A W^?1 at 5 V. In addition, the dark current is as low as pA level, leading to detectivity up to 10¹¹ Jones. Moreover, PDs possess good stability and repeatability.     

Manipulating Crystallographic Orientation via Cross-Linkable Ligand for Efficient and Stable Perovskite Solar Cells

The crystallographic orientation of polycrystalline perovskites is found to be strongly correlated with their intrinsic properties; therefore, it can be used to effectively enhance the performance of perovskite-based devices. Here, a facile way of manipulating the facet orientation of polycrystalline perovskite films in a controllable manner is reported. By incorporating a cross-linkable organic ligand into the perovskite precursor solution, the crystal orientation disorder can be reduced in the resultant perovskite films to exhibit the prominent (001) orientation with a preferred stacking mode. Moreover, the as-formed low-dimensional perovskites (LDPs) between the organic ligand and the excess lead iodide can passivate the defects around the grain boundaries. Consequently, highly efficient p-i-n structured perovskite solar cells (PSCs) can be made in both rigid and flexible forms from modified perovskites to show high power conversion efficiencies (PCE) of 24.12% and 23.23%, respectively. The devices also exhibit superior long-term stability in a humid environment (with T₉₀ > 1000 h) and under thermal stress (retaining 87% of its initial PCE after 1000 h). More importantly, the ligand enables the derived LDPs to be crosslinked (under 254 nm UV illumination) to demonstrate excellent mechanical bending durability in flexible devices.     

In Situ Grazing-Incidence Wide-Angle Scattering Reveals Mechanisms for Phase Distribution and Disorientation in 2D Halide Perovskite Films

2D hybrid halide perovskites with the formula (A′)₂(A)_n-1Pb_nI_3n+1 have remarkable stability and promising efficiency in photovoltaic and optoelectronic devices, yet fundamental understanding of film formation, key to optimizing these devices, is lacking. Here, in situ grazing-incidence wide-angle X-ray scattering (GIWAXS) is used to monitor film formation during spin-coating. This elucidates the general film formation mechanism of 2D halide perovskites during one-step spin-coating. There are three stages of film formation: sol–gel, oriented 3D, and 2D. Three precursor phases form during the sol–gel stage and transform to perovskite, first giving a highly oriented 3D-like phase at the air/liquid interface followed by subsequent nucleations forming slightly less oriented 2D perovskite. Furthermore, heating before crystallization leads to fewer nucleations and faster removal of the precursors, improving orientation. This outlines the primary causes of phase distribution and perpendicular orientation in 2D perovskite films and paves the way for rationally designed film fabrication techniques.     

Dual‐Phase CsPbBr3–CsPb2Br5 Perovskite Thin Films via Vapor Deposition for High‐Performance Rigid and Flexible Photodetectors

Inorganic perovskites with special semiconducting properties and structures have attracted great attention and are regarded as next generation candidates for optoelectronic devices. Herein, using a physical vapor deposition process with a controlled excess of PbBr₂, dual‐phase all‐inorganic perovskite composite CsPbBr₃–CsPb₂Br₅ thin films are prepared as light‐harvesting layers and incorporated in a photodetector (PD). The PD has a high responsivity and detectivity of 0.375 A W^?1 and 10¹¹ Jones, respectively, and a fast response time (from 10% to 90% of the maximum photocurrent) of ≈280 µs/640 µs. The device also shows an excellent stability in air for more than 65 d without encapsulation. Tetragonal CsPb₂Br₅ provides satisfactory passivation to reduce the recombination of the charge carriers, and with its lower free energy, it enhances the stability of the inorganic perovskite devices. Remarkably, the same inorganic perovskite photodetector is also highly flexible and exhibits an exceptional bending performance (>1000 cycles). These results highlight the great potential of dual‐phase inorganic perovskite films in the development of optoelectronic devices, especially for flexible device applications.     

Highly Efficient and Ultrasensitive Large‐Area Flexible Photodetector Based on Perovskite Nanowires

Hybrid organic–inorganic perovskites have shown exceptional semiconducting properties and microstructural versatility for inexpensive, solution‐processable photovoltaic and optoelectronic devices. In this work, an all‐solution‐based technique in ambient environment for highly sensitive and high‐speed flexible photodetectors using high crystal quality perovskite nanowires grown on Kapton substrate is presented. At 10 V, the optimized photodetector exhibits a responsivity as high as 0.62 A W^?1, a maximum specific detectivity of 7.3 × 10¹² cm Hz^1/2 W^?1, and a rise time of 227.2 µs. It also shows remarkable photocurrent stability even beyond 5000 bending cycles. Moreover, a deposition of poly(methyl methacrylate) (PMMA) as a protective layer on the perovskite yields significantly better stability under ambient air operation: the PMMA‐protected devices are stable for over 30 days. This work demonstrates a cost‐effective fabrication technique for high‐performance flexible photodetectors and opens opportunities for research advancements in broadband and large‐scale flexible perovskite‐based optoelectronic devices.     

Strongly Coupled Tin‐Halide Perovskites to Modulate Light Emission: Tunable 550–640 nm Light Emission (FWHM 36–80 nm) with a Quantum Yield of up to 6.4%

Colloidal perovskite quantum dots represent one of the most promising materials for applications in solar cells and photoluminescences. These devices require a low density of crystal defects and a high yield of photogenerated carriers, which are difficult to realize in tin‐halide perovskite because of the intrinsic instability of tin during nucleation. Here, an enhancement in the luminescent property of tin‐halide perovskite nanoplates (TPNPs) that are composed of strongly coupled layered structures with the chemical formula of PEA₂SnX₄ (PEA = C₆H₅(CH₂)₂NH₃, X = Br, I) is reported. TPNPs (X = I) show an emission at a wavelength of 640 nm, with high quantum yield of 6.40 ± 0.14% and full width at half maximum (FWHM) as small as 36 nm. The presence of aliphatic carboxylic acid is found to play a key role in reducing the tin perovskite defect density, which significantly improves the emission intensity and stability of TPNPs. Upon mixing iodo‐ and bromo‐ precursors, the emission wavelength is successfully tuned from 640 nm (PEA₂SnI₄) to 550 nm (PEA₂SnBr₄), with a corresponding emission quantum yield and FWHM of 0.16–6.40% and 36–80 nm, respectively. The results demonstrate a major advance for the emission yield and tunability of tin‐halide perovskites.     

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.     

Intrinsic Instability of Inorganic–Organic Hybrid Halide Perovskite Materials

Hybrid lead halide perovskite materials are used in solar cells and show efficiencies greater than 23%. Furthermore, they are applied in light‐emitting diodes, X‐ray detectors, thin‐film transistors, thermoelectrics, and memory devices. Lead trihalide hybrid materials contain methylammonium (MA) or formamidinium (FA) (or a mixture), or long alkylammonium halides, as alternative organic cations. However, the intrinsic stability of hybrid lead halide perovskites is not very high, and they are chemically unstable when exposed to moisture, light, or heat because of their organic contents and low formation energies. Therefore, although improvements in the chemical stability are crucial, changing the material composition is challenging because it is directly related to the desired application requirements. Fortunately, hybrid lead halide perovskites have a very high tolerance toward changes in physical properties arising from doping or addition of different cations and anions, in many cases showing improved properties. Here, the intrinsic instability of hybrid lead halide perovskites is reviewed in relation to the crystal phase and chemical stability. It is suggested that FA should be used for lead halide perovskites for chemical stability instead of MA. Furthermore, additives that stabilize the crystal phase with α‐FAPbI₃ should eschew MA.     

A Highly Sensitive Single Crystal Perovskite–Graphene Hybrid Vertical Photodetector

Organolead trihalide perovskites have attracted significant attention for optoelectronic applications due to their excellent physical properties in the past decade. Generally, both grain boundaries in perovskite films and the device structure play key roles in determining the device performance, especially for horizontal‐structured device. Here, the first optimized vertical‐structured photodetector with the perovskite single crystal MAPbBr₃ as the light absorber and graphene as the transport layer is shown. The hybrid device combines strong photoabsorption characteristics of perovskite and high carrier mobility of flexible graphene, exhibits excellent photoresponse performance with high photoresponsivity (≈1017.1 A W^?1) and high photodetectivity (≈2.02 × 10¹³ Jones) in a low light intensity (0.66 mW cm^?2) under the actuations of 3 V bias and laser irradiation at 532 nm. In particular, an ultrahigh photoconductive gain of ≈2.37 × 10³ is attained because of fast charge transfer in the graphene and large recombination lifetime in the perovskite single crystal. The vertical architecture combining perovskite crystal with highly conductive graphene offers opportunities to fulfill the synergistic effect of perovskite and 2D materials, is thus promising for developing high‐performance electronic and optoelectronic devices.     

Engineering the Phases and Heterostructures of Ultrathin Hybrid Perovskite Nanosheets

Low-dimensional perovskites have gained increasing attention recently, and engineering their material phases, structural patterning and interfacial properties is crucial for future perovskite-based applications. Here a phase and heterostructure engineering on ultrathin perovskites, through the reversible cation exchange of hybrid perovskites and efficient surface functionalization of low-dimensional materials, is demonstrated. Using PbI₂ as precursor and template, perovskite nanosheets of varying thickness and hexagonal shape on diverse substrates is obtained. Multiple phases, such as PbI₂, MAPbI₃ and FAPbI₃, can be flexibly designed and transformed as a single nanosheet. A perovskite nanosheet can be patterned using masks made of 2D materials, fabricating lateral heterostructures of perovskite and PbI₂. Perovskite-based vertical heterostructures show strong interfacial coupling with 2D materials. As a demonstration, monolayer MoS₂/MAPbI₃ stacks give a type-II heterojunction. The ability to combine the optically efficient perovskites with versatile 2D materials creates possibilities for new designs and functionalities.     

Two‐Dimensional Materials for Halide Perovskite‐Based Optoelectronic Devices

Halide perovskites have high light absorption coefficients, long charge carrier diffusion lengths, intense photoluminescence, and slow rates of non‐radiative charge recombination. Thus, they are attractive photoactive materials for developing high‐performance optoelectronic devices. These devices are also cheap and easy to be fabricated. To realize the optimal performances of halide perovskite‐based optoelectronic devices (HPODs), perovskite photoactive layers should work effectively with other functional materials such as electrodes, interfacial layers and encapsulating films. Conventional two‐dimensional (2D) materials are promising candidates for this purpose because of their unique structures and/or interesting optoelectronic properties. Here, we comprehensively summarize the recent advancements in the applications of conventional 2D materials for halide perovskite‐based photodetectors, solar cells and light‐emitting diodes. The examples of these 2D materials are graphene and its derivatives, mono‐ and few‐layer transition metal dichalcogenides (TMDs), graphdiyne and metal nanosheets, etc. The research related to 2D nanostructured perovskites and 2D Ruddlesden–Popper perovskites as efficient and stable photoactive layers is also outlined. The syntheses, functions and working mechanisms of relevant 2D materials are introduced, and the challenges to achieving practical applications of HPODs using 2D materials are also discussed.