Perovskite solar cells (PSCs) with an inverted structure (often referred to as the p-i-n architecture) are attractive for future commercialization owing to their easily scalable fabrication, reliable ...operation and compatibility with a wide range of perovskite-based tandem device architectures
. However, the power conversion efficiency (PCE) of p-i-n PSCs falls behind that of n-i-p (or normal) structure counterparts
. This large performance gap could undermine efforts to adopt p-i-n architectures, despite their other advantages. Given the remarkable advances in perovskite bulk materials optimization over the past decade, interface engineering has become the most important strategy to push PSC performance to its limit
. Here we report a reactive surface engineering approach based on a simple post-growth treatment of 3-(aminomethyl)pyridine (3-APy) on top of a perovskite thin film. First, the 3-APy molecule selectively reacts with surface formamidinium ions, reducing perovskite surface roughness and surface potential fluctuations associated with surface steps and terraces. Second, the reaction product on the perovskite surface decreases the formation energy of charged iodine vacancies, leading to effective n-type doping with a reduced work function in the surface region. With this reactive surface engineering, the resulting p-i-n PSCs obtained a PCE of over 25 per cent, along with retaining 87 per cent of the initial PCE after over 2,400 hours of 1-sun operation at about 55 degrees Celsius in air.
High-quality metal halide perovskite single crystals have low defect densities and excellent photophysical properties, yet thin films are the most sought after material geometry for optoelectronic ...devices. Perovskite single-crystal thin films (SCTFs) would be highly desirable for high-performance devices, but their growth remains challenging, particularly for inorganic metal halide perovskites. Herein, we report the facile vapor-phase epitaxial growth of cesium lead bromide perovskite (CsPbBr3) continuous SCTFs with controllable micrometer thickness, as well as nanoplate arrays, on traditional oxide perovskite SrTiO3(100) substrates. Heteroepitaxial single-crystal growth is enabled by the serendipitous incommensurate lattice match between these two perovskites, and overcoming the limitation of island-forming Volmer–Weber crystal growth is critical for growing large-area continuous thin films. Time-resolved photoluminescence, transient reflection spectroscopy, and electrical transport measurements show that the CsPbBr3 epitaxial thin film has a slow charge carrier recombination rate, low surface recombination velocity (104 cm s–1), and low defect density of 1012 cm–3, which are comparable to those of CsPbBr3 single crystals. This work suggests a general approach using oxide perovskites as substrates for heteroepitaxial growth of halide perovskites. The high-quality halide perovskite SCTFs epitaxially integrated with multifunctional oxide perovskites could open up opportunities for a variety of high-performance optoelectronics devices.
A remarkable PL enhancement by 12 fold is achieved using pressure to modulate the structure of a recently developed 2D perovskite (HA)2(GA)Pb2I7 (HA=n‐hexylammonium, GA=guanidinium). This structure ...features a previously unattainable, extremely large cage. In situ structural, spectroscopic, and theoretical analyses reveal that lattice compression under a mild pressure within 1.6 GPa considerably suppresses the carrier trapping, leading to significantly enhanced emission. Further pressurization induces a non‐luminescent amorphous yellow phase, which is retained and exhibits a continuously increasing band gap during decompression. When the pressure is released to 1.5 GPa, emission can be triggered by above‐band gap laser irradiation, accompanied by a color change from yellow to orange. The obtained orange phase could be retained at ambient conditions and exhibits two‐fold higher PL emission compared with the pristine (HA)2(GA)Pb2I7.
A remarkably enhanced emission (by 12‐fold) is achieved using pressure to modulate the structure of a highly distorted 2D halide perovskite (HA)2(GA)Pb2I7. In situ structural, spectroscopic, and theoretical analyses reveal that lattice compression under a mild pressure within 1.6 GPa considerably suppresses the carrier trapping, leading to the significantly improved performance.
Lead halide perovskite quantum dots (QDs) possess color‐tunable and narrow‐band emissions and are very promising for lighting and display applications, but they suffer from lead toxicity and ...instability. Although lead‐free Bi‐based and Sn‐based perovskite QDs (CsSnX3, Cs2SnX6, and (CH3NH3)3Bi2X9) are reported, they all show low photoluminescence quantum yield (PLQY) and poor stability. Here, the synthesis of Cs3Bi2Br9 perovskite QDs with high PLQY and excellent stability is reported. Via a green and facile process using ethanol as the antisolvent, as‐synthesized Cs3Bi2Br9 QDs show a blue emission at 410 nm with a PLQY up to 19.4%. The whole series of Cs3Bi2X9 (X = Cl, Br, and I) QDs by mixing precursors can cover the photoluminescence emission range from 393 to 545 nm. Furthermore, Cs3Bi2Br9 QDs show excellent photostability and moisture stability due to the all‐inorganic nature and the surface passivation by BiOBr, which enables the one‐pot synthesis of Cs3Bi2Br9 QD/silica composite. A lead‐free perovskite white light‐emitting diode is fabricated by simply combining the composite of Cs3Bi2Br9 QD/silica with Y3Al5O12 phosphor. As a new member of lead‐free perovskite QDs, Cs3Bi2Br9 QDs open up a new route for the fabrication of optoelectronic devices due to their excellent stability and photophysical characteristics.
A simple and environmentally benign synthetic method, combined with good crystallization, high photoluminescence quantum yields in the blue wavelength region, and excellent moisture stability, makes Cs3Bi2Br9 quantum dots (QDs) very competitive for various optoelectronic applications. Finally, the first lead‐free perovskite white light‐emitting diode is successfully made by simply combining the composite of Cs3Bi2Br9 QD/silica with Y3Al5O12 phosphor.
The development of highly stable and efficient wide-bandgap (WBG) perovskite solar cells (PSCs) based on bromine-iodine (Br-I) mixed-halide perovskite (with Br greater than 20%) is critical to create ...tandem solar cells. However, issues with Br-I phase segregation under solar cell operational conditions (such as light and heat) limit the device voltage and operational stability. This challenge is often exacerbated by the ready defect formation associated with the rapid crystallization of Br-rich perovskite chemistry with antisolvent processes. We combined the rapid Br crystallization with a gentle gas-quench method to prepare highly textured columnar 1.75-electron volt Br-I mixed WBG perovskite films with reduced defect density. With this approach, we obtained 1.75-electron volt WBG PSCs with greater than 20% power conversion efficiency, approximately 1.33-volt open-circuit voltage (
), and excellent operational stability (less than 5% degradation over 1100 hours of operation under 1.2 sun at 65°C). When further integrated with 1.25-electron volt narrow-bandgap PSC, we obtained a 27.1% efficient, all-perovskite, two-terminal tandem device with a high
of 2.2 volts.
Two-dimensional-on-three-dimensional (2D/3D) halide perovskite heterostructures have been extensively utilized in optoelectronic devices. However, the labile nature of halide perovskites makes it ...difficult to form such heterostructures with well-defined compositions, orientations, and interfaces, which inhibits understanding of the carrier transfer properties across these heterostructures. Here, we report solution growth of both horizontally and vertically aligned 2D perovskite (PEA)2PbBr4 (PEA = phenylethylammonium) microplates onto 3D CsPbBr3 single crystal thin films, with well-defined heterojunctions. Time-resolved photoluminescence (TRPL) transients of the heterostructures exhibit the monomolecular and bimolecular dynamics expected from exciton annihilation, dissociation, and recombination, as well as evidence for carrier transfer in these heterostructures. Two kinetic models based on Type-I and Type-II band alignments at the interface of horizontal 2D/3D heterostructures are applied to reveal a shift in balance between carrier transfer and recombination: Type-I band alignment better describes the behaviors of heterostructures with thin 2D perovskite microplates but Type-II band alignment better describes those with thick 2D microplates (>150 nm). TRPL of vertically aligned 2D microplates is dominated by directly excited PL and is independent of the height above the 3D film. Electrical measurements reveal current rectification behaviors in both heterostructures with vertical heterostructures showing better electrical transport. As the first systematic study on comparing models of 2D/3D perovskite heterostructures with controlled orientations and compositions, this work provides insights on the charge transfer mechanisms in these perovskite heterostructures and guidelines for designing better optoelectronic devices.
Fabrication of heterostructures using two-dimensional (2D) materials with different bandgaps creates opportunities for exploring new properties and device applications. Ruddlesden–Popper (RP) layered ...halide perovskites have recently emerged as a new class of solution-processable 2D materials that demonstrate exotic optoelectronic properties. However, heterostructures using 2D halide perovskites have not been achieved. Here, we report a simple solution growth method for making vertically stacked double heterostructures and complex multilayer heterostructures of 2D lead iodide perovskites (PEA)2(MA) n–1Pb n I3n+1, PEA = C6H5(CH2)2NH3 +, MA = CH3NH3 + via van der Waals epitaxy. These heterostructures present atomically sharp interfaces and display distinct photoluminescence that allow fingerprinting the RP phases. Time-resolved photoluminescence measurements reveal internal energy transfer from higher energy bandgap (lower n value) perovskite layers to lower energy bandgap (higher n value) perovskite layers on the time scale of hundreds of picoseconds due to natural type I band alignments. These results offer new strategies to fabricate perovskite–perovskite heterojunctions by taking advantage of surface-bound ligands as spatial barriers to prevent ion migration across the junctions. These heterostructures capable of multicolor emission with high spectral purity are promising for light-emitting applications.
Nanostructures of inorganic semiconductors have revolutionized many areas of electronics, optoelectronics and photonics. The controlled synthesis of semiconductor nanostructures could lead to novel ...physical properties, improved optoelectronic device performance and new areas for exploration. Lead halide perovskites have recently excited the photovoltaic research community owing to their high solar-conversion efficiencies and ease of solution processing; they also hold great promise for optoelectronic applications, such as light-emitting diodes and lasers. In this Review, we summarize recent developments in the synthesis and characterization of metal halide perovskite nanostructures with controllable compositions, dimensionality, morphologies and orientations. We examine the advantageous optical properties, improved stability and potential optoelectronic applications of these 1D and 2D single-crystal perovskite nanostructures and compare them with those of bulk perovskites and nanostructures of conventional semiconductors. Studies in which perovskite nanostructures have been used to study the fundamental physical properties of perovskites are also highlighted. Finally, we discuss the challenges in realizing halide perovskite nanostructures for optoelectronic and photonic applications and offer our perspectives on future opportunities and research directions.Metal halide perovskite nanostructures are promising materials for optoelectronic applications. In this Review, we discuss the synthesis and properties of 1D and 2D single-crystal perovskite nanostructures, examine potential optoelectronic applications and highlight recent studies in which these nanostructures have been used to study the fundamental properties of perovskites.
Heterostructures of three-dimensional (3D) halide perovskites are unstable because of facile anion interdiffusion at halide interfaces. Two-dimensional (2D) Ruddlesden–Popper halide perovskites ...(RPPs) show suppressed and anisotropic ion diffusion that could enable stable RPP heterostructures, yet the direct and general growth of lateral RPP heterostructures remains challenging. Here, we show that halide miscibility in RPPs decreases with perovskite layer thickness (n), enabling the formation of sharp halide lateral heterostructures from n = 1 and 2 RP lead iodide microplates via anion exchange with hydrogen bromide vapor. In contrast, RPPs with n ≥ 3 form more diffuse lateral heterojunctions, more similar to those in 3D perovskites. The anion exchange behaviors are further modulated by the spacer and A-site cations in the RPP structures. These new insights, and kinetic studies of the exchange reactions, enable the preparation of lateral heterostructures from various n = 2 RPPs that are more stable against anion interdiffusion and degradation for potential optoelectronic device applications.
The stability and formation of a perovskite structure is dictated by the Goldschmidt tolerance factor as a general geometric guideline. The tolerance factor has limited the choice of cations (A) in ...3D lead iodide perovskites (APbI3), an intriguing class of semiconductors for high-performance photovoltaics and optoelectronics. Here, we show the tolerance factor requirement is relaxed in 2D Ruddlesden–Popper (RP) perovskites, enabling the incorporation of a variety of larger cations beyond the methylammonium (MA), formamidinium, and cesium ions in the lead iodide perovskite cages for the first time. This is unequivocally confirmed with the single-crystal X-ray structure of newly synthesized guanidinium (GA)-based (n-C6H13NH3)2(GA)Pb2I7, which exhibits significantly enlarged and distorted perovskite cage containing sterically constrained GA cation. Structural comparison with (n-C6H13NH3)2(MA)Pb2I7 reveals that the structural stabilization originates from the mitigation of strain accumulation and self-adjustable strain-balancing in 2D RP structures. Furthermore, spectroscopic studies show a large A cation significantly influences carrier dynamics and exciton–phonon interactions through modulating the inorganic sublattice. These results enrich the diverse families of perovskite materials, provide new insights into the mechanistic role of A-site cations on their physical properties, and have implications to solar device studies using engineered perovskite thin films incorporating such large organic cations.
PDF
