Low-dimensional Metal Halide Perovskites Research Articles

Anion Exchange and Lateral Heterostructure Formation in Ferromagnetic PEA2Cr(Cl,Br)4 Two-Dimensional Perovskites.

Postsynthetic vapor-phase anion exchange in the ferromagnetic two-dimensional (2D) hybrid metal-halide perovskite, PEA2CrCl4 (PEA+ = phenethylammonium), is reported. Anion exchange using vaporous trimethylsilyl bromide (TMS-Br) is shown to drive complete conversion of solution-processed PEA2CrCl4 polycrystalline thin films to PEA2CrBr4. Low-temperature magnetic circular dichroism spectroscopy indicates ferromagnetic ordering in these PEA2CrCl4 and PEA2CrBr4 films. Via partial anion exchange of exfoliated flakes of PEA2CrCl4 single crystals, we demonstrate that it is possible to generate abrupt lateral PEA2CrCl4/PEA2CrBr4 magneto-heterointerfaces. Kinetic studies reveal that lateral heterostructure formation is dictated by rapid edge-site halide exchange followed by slower intralayer bromide diffusion, and there is negligible interlayer (3D) bromide or TMS-Br diffusion. The importance of the bulky PEA+ interlayer cation in suppressing 3D diffusion is highlighted by parallel anion-exchange experiments on MA2CrCl4 (MA+ = methylammonium), which instead show 3D exchange. Comparison of anion-exchange reactions in PEA2CrCl4, PEA2MnCl4, and PEA2PbCl4 shows that 2D bromide diffusion is slowest in PEA2CrCl4, attributed to the antiferrodistortive ordering found in this composition. In addition to demonstrating both postsynthetic composition control and heterostructure formation in ferromagnetic Cr-based 2D perovskites for the first time, these results also advance our fundamental understanding of ion-exchange processes in this relatively unexplored family of 2D perovskites, broadening opportunities for investigation and control of novel spin effects in low-dimensional metal-halide perovskites.

Origin of Dopant-Carrier Exchange Coupling and Excitonic Zeeman Splitting in Mn2+-Doped Lead Halide Perovskite Nanocrystals.

Low-dimensional metal halide perovskites have unique optical and electrical properties that render them attractive for the design of diluted magnetic semiconductors. However, the nature of dopant-exciton exchange interactions that result in spin-polarization of host-lattice charge carriers as a basis for spintronics remains unexplored. Here, we investigate Mn2+-doped CsPbCl3 nanocrystals using magnetic circular dichroism spectroscopy and show that Mn2+ dopants induce excitonic Zeeman splitting which is strongly dependent on the nature of the band-edge structure. We demonstrate that the largest splitting corresponds to exchange interactions involving the excited state at the M-point along the spin-orbit split-off conduction band edge. This splitting gives rise to an absorption-like C-term excitonic MCD signal, with the estimated effective g-factor (geff) of ca. 70. The results of this work help resolve the assignment of absorption transitions observed for metal halide perovskite nanocrystals and allow for a design of new diluted magnetic semiconductor materials for spintronics applications.

Narrow-Band Green-Emitting Hybrid Organic-Inorganic Eu (II)-Iodides for Next-Generation Micro-LED Displays.

Low-dimensional metal halide perovskites are an emerging class of light-emitting materials for LED-based displays; however, their B-site cations are confined to ns2, d5, and d10 metals. Here, the design of divalent rare earth ions at B-site is presented and a novel Eu(II)-based iodide hybrid is reported with efficient (PLQY≈98%) narrow-band (FWHM≈43nm) green emission and high thermal stability (97%@150°C). Owing to reduced lattice vibrations and shrunken average distance of Eu(II)-iodide bonds in the face-sharing 1D-structure, photoluminescence from Eu(II) 4f-5d transition appears along with elevated crystal-field splitting of 5d energy level. The Eu(II)-based iodide hybrid is further demonstrated for color-pure green phosphor-converted LEDs with a maximum brightness of ≈396000cdm-2 and photoelectric efficiency of 29.2%. High-resolution micrometer-scale light-emitting diode (micro-LED) displays (2540PPI) via the solution-processed screen is also presented. This work thus showcases a compelling narrow-band green emitter for commercial micro-LED displays.

Synthesis and Photoluminescence Modulation of Cs4Cd1-xMnxBi2Cl12-Based Two-Dimensional Layered Double Perovskites.

Two-dimensional (2D) layered double perovskites have attracted much attention because of their excellent photoelectric properties. However, few reports have been published on the synthesis of 2D layered double perovskites from halide perovskites as precursors. Here, we report that CsCdCl3 and Cs3Bi2Cl9 were synthesized by the coprecipitation method, and a two-dimensional layered double perovskite Cs4CdBi2Cl12 was readily synthesized by mixing the two halide perovskites. We doped different amounts of Mn2+ into CsCdCl3 to form CsCd1-xMnxCl3, which introduced impurity states into the energy level and exhibited an orange-red light emission that is characteristic of Mn2+. A series of 2D layered double perovskites Cs4Cd1-xMnxBi2Cl12 were synthesized from CsCd1-xMnxCl3 and Cs3Bi2Cl9, which showed a bright orange-yellow luminescence under ultraviolet excitation. The presence of high concentrations of Cd2+ in the two-dimensional layered double perovskites weakened the strong Mn-Mn coupling and suppressed the energy transfer to defects, thus minimizing nonradiative decay and promoting efficient energy transfer. Our work provides a new concept for the synthesis of low-dimensional metal halide perovskites with unique optical properties.

Origin of Broad Emission Induced by Rigid Aromatic Ditopic Cations in Low-Dimensional Metal Halide Perovskites.

The development of broadband emitters based on metal halide perovskites (MHPs) requires the elucidation of structure-emission property correlations. Herein, we report a combined experimental and theoretical study on a series of novel low-dimensional lead chloride perovskites, including ditopic aromatic cations. Synthesized lead chloride perovskites and their bromide analogues show both narrow and broad photoluminescence emission properties as a function of their cation and halide nature. Structural analysis shows a correlation between the rigidity of the ditopic cations and the lead halide octahedral distortions. Density functional theory calculations reveal, in turn, the pivotal role of octahedral distortions in the formation of self-trapped excitons, which are responsible for the insurgence of broad emission and large Stokes shifts together with a contribution of halide vacancies. For the considered MHP series, the use of conventional octahedral distortion parameters allows us to nicely describe the trend of emission properties, thus providing a solid guide for further materials design.

Orange-emitting zero-dimensional Te4+-Doped Cs2ScCl5·H2O perovskite microcrystals

Low-dimensional metal halide perovskites have gained the favor of many researchers for their potential applications in solid-state lighting due to their excellent optoelectronic properties. Herein, Te4+ doped Cs2ScCl5·H2O, a novel orange-emitting zero-dimensional scandium halide perovskite microcrystal was synthesized by hydrothermal method. Cs2ScCl5·H2O is isomorphic to Cs2InCl5·H2O with the space group Pnma. Under UV excitation, Cs2ScCl5·H2O:Te4+ exhibits a bright orange emission at 620 nm with a full width at half maximum (FWHM) of 170 nm, which is related to the formation of self-trapping excitons (STEs) in the zero-dimensional Te4+ doped Cs2ScCl5·H2O soft lattice. The fluorescence lifetime of Cs2ScCl5·H2O:Te4+ microcrystals are highly temperature-dependent with significant changes from microseconds (5.352 μs) at 110 K to nanoseconds (252 ns) at 298 K. The microcrystal-based white LED and thin film were initially explored for their potential application. These findings provide new insights into the excited state dynamics of Te4+ in Cs2ScCl5·H2O and demonstrate the potential application prospect for lead-free scandium halides doped by ns2 metal ions.

Expanding the absorption and photoresponse of 1D lead-halide perovskites via ultrafast charge transfer.

Low-dimensional metal halide perovskites are attracting extensive attention due to their enhanced quantum confinement and stability compared to three-dimensional perovskites. However, low dimensional connectivity in the inorganic frameworks leads to strongly bounded excitons with limited absorption properties, which impedes their application in photovoltaic devices. Here, we show that, by incorporating a strong electron accepting methylviologen cation, charge transfer (CT) at the organic/inorganic interface can effectively tune the optical properties in one-dimensional (1D) lead-halide perovskites. Both 1D MVPb2I6 and MVPb2Br6 display expanded absorption and photoresponse activity compared to CT inactive cations. The photoinduced CT process in MVPb2I6 was further characterized by transient absorption spectroscopy, which shows an ultrafast CT process within 1ps, generating charge separated states. Our work unveils the interesting photophysics of these unconventional 1D perovskites with functional organic chromophores.

Perovskite superlattices with efficient carrier dynamics.

Compared with their three-dimensional (3D) counterparts, low-dimensional metal halide perovskites (2D and quasi-2D; B2An-1MnX3n+1, such as B = R-NH3+, A = HC(NH2)2+, Cs+; M = Pb2+, Sn2+; X = Cl-, Br-, I-) with periodic inorganic-organic structures have shown promising stability and hysteresis-free electrical performance1-6. However, their unique multiple-quantum-well structure limits the device efficiencies because of the grain boundaries and randomlyoriented quantum wells in polycrystals7. In single crystals, the carrier transport through the thickness direction is hindered by the layered insulating organic spacers8. Furthermore, the strong quantum confinement from the organic spacers limits the generation and transport of free carriers9,10. Also, lead-free metal halide perovskites have been developed but their device performance is limited by their low crystallinity and structural instability11. Here we report a low-dimensional metal halide perovskite BA2MAn-1SnnI3n+1 (BA, butylammonium; MA, methylammonium; n = 1, 3, 5) superlattice by chemical epitaxy. The inorganic slabs are aligned vertical to the substrate and interconnected in a criss-cross 2D network parallel to the substrate, leading to efficient carrier transport in three dimensions. A lattice-mismatched substrate compresses the organic spacers, which weakens the quantum confinement. The performance of a superlattice solar cell has been certified under the quasi-steady state, showing a stable 12.36% photoelectric conversion efficiency. Moreover, an intraband exciton relaxation process may have yielded an unusually high open-circuit voltage (VOC).

Pressure Tuning of Optical Properties and Structures in All-Inorganic Halide Perovskite Rb7Sb3Cl16.

All lead-free inorganic halide perovskites, as efficient solid-state light emission materials, have become ideal green optoelectronic materials to replace lead halide perovskites for diversified lighting and display applications with their excellent stability. Here, we investigated the pressure-derived optical and structural response of a zero-dimensional lead-free perovskite Rb7Sb3Cl16 through applying controllable pressure. A pressure-induced blue shift of the broadband emission was achieved, and it was followed by the emission color transformation from yellow to green, which was ascribed to the electron-phonon coupling weakening and the suppression of structural deformation upon lattice contraction. In parallel, the band gap was narrowed by about 0.5 eV as a result of enhanced metal halide orbital overlap under high pressure. This work provides a fundamental understanding for modulating the optical properties of the low-dimensional metal halide perovskites.

Temperature-Responsive Photoluminescence and Elastic Properties of 1D Lead Halide Perovskites R- and S-(Methylbenzylamine)PbBr3.

Low-dimensional metal halide perovskites (MHPs) have received much attention due to their striking semiconducting properties tunable at a molecular level, which hold great potential in the development of next-generation optoelectronic devices. However, the insufficient understanding of their stimulus-responsiveness and elastic properties hinders future practical applications. Here, the thermally responsive emissions and elastic properties of one-dimensional lead halide perovskites R- and S-MBAPbBr3 (MBA+ = methylbenzylamine) were systematically investigated via temperature-dependent photoluminescence (PL) experiments and first-principles calculations. The PL peak positions of both perovskites were redshifted by about 20 nm, and the corresponding full width at half maximum was reduced by about 40 nm, from ambient temperature to about 150 K. This kind of temperature-responsive self-trapped exciton emission could be attributed to the synergistic effect of electron–phonon coupling and thermal expansion due to the alteration of hydrogen bonding. Moreover, the elastic properties of S-MBAPbBr3 were calculated using density functional theory, revealing that its Young’s and shear moduli are in the range of 6.5–33.2 and 2.8–19.5 GPa, respectively, even smaller than those of two-dimensional MHPs. Our work demonstrates that the temperature-responsive emissions and low elastic moduli of these 1D MHPs could find use in flexible devices.

Ultrasensitive Near-Infrared Circularly Polarized Light Detection Using 3D Perovskite Embedded with Chiral Plasmonic Nanoparticles.

Chiral organic ligand‐incorporated low‐dimensional metal‐halide perovskites have received increasing attention for next‐generation photodetectors because of the direct detection capability of circularly polarized light (CPL), which overcomes the requirement for subsidiary optical components in conventional CPL photodetectors. However, most chiral perovskites have been based on low‐dimensional structures that confine chiroptical responses to the ultraviolet (UV) or short‐wavelength visible region and limit photocurrent due to their wide bandgap and poor charge transport. Here, chiroptical properties of 3D Cs0.05FA0.5MA0.45Pb0.5Sn0.5I3 polycrystalline films are achieved by incorporating chiral plasmonic gold nanoparticles (AuNPs) into the mixed Pb—Sn perovskite, without sacrificing its original optoelectronic properties. CPL detectors fabricated using chiral AuNP‐embedded perovskite films can operate without external power input; they exhibit remarkable chirality in the near‐infrared (NIR) region with a high anisotropy factor of responsivity (g res) of 0.55, via giant plasmon resonance shift of chiral plasmonic AuNPs. In addition, a CPL detector array fabricated on a plastic substrate demonstrates highly sensitive self‐powered NIR detection with superior flexibility and durability.

Phase-Pure Quasi-2D Perovskite by Protonation of Neutral Amine.

Phase control of low-dimensional metal-halide perovskites (LDPs) greatly affects their optoelectronic properties, and phase-pure LDPs are desirable to achieve efficient perovskite optoelectronic devices such as solar cells and light-emitting diodes. Herein, we introduce a method to obtain phase-pure LDP by using a neutral amine, cyclohexylmethyl amine (CHMA). The incorporation of CHMA into a formamidinium lead bromide (FAPbBr3) precursor solution leads to the protonation of the amine that allows the phase transition of 3D FAPbBr3 to phase-pure quasi-2D perovskite (n = 2). For comparison, cyclohexylmethylammonium bromide (CHMABr), which is a conventional form of ammonium halide salt with the same organic moiety to the amine, is used, which resulted in a 2D perovskite (n = 1). The perovskite films fabricated by the two different methodologies are characterized. This study paves the way for further research on the realization of phase-pure perovskites and their relevant optoelectronic devices.

Low-Dimensional Metal Halide Perovskite Crystal Materials: Structure Strategies and Luminescence Applications.

Replacing methylammonium (MA+), formamidine (FA+), and/or cesium (Cs+) in 3D metal halide perovskites by larger organic cations have built a series of low‐dimensional metal halide perovskites (LDMHPs) in which the inorganic metal halide octahedra arranging in the forms of 2D layers, 1D chains, and 0D points. These LDMHPs exhibit significantly different optoelectronic properties from 3D metal halide perovskites (MHPs) due to their unique quantum confinement effects and large exciton binding energies. In particular, LDMHPs often have excellent broadband luminescence from self‐trapped excitons. Chemical composition, hydrogen bonding, and external factors (temperature and pressure etc.) determine structures and influence photoelectric properties of LDMHPs greatly, and especially it seems that there is no definite regulation to predict the structure and photoelectric properties when a random cation, metal, and halide is chosen to design a LDMHP. Therefore, this review discusses the construction strategies of the recent reported LDMHPs and their application progress in the luminescence field for a better understanding of these factors and a prospect for LDMHPs’ development in the future.

Cation Engineering for Resonant Energy Level Alignment in Two-Dimensional Lead Halide Perovskites.

Low-dimensional metal halide perovskites are being intensively investigated because of their higher stability and chemical versatility in comparison to their 3D counterparts. Unfortunately, this comes at the expense of the electronic and charge transport properties, limited by the reduced perovskite dimensionality. Cation engineering can be envisaged as a solution to tune and possibly further improve the material's optoelectronic properties. In this work, we screen and design new electronically active A-site cations that can promote charge transport across the inorganic layers. We show that hybridization of the valence band electronic states of the perovskite inorganic sublattice and the highest occupied molecular orbitals of the A-site organic cations can be tuned to exhibit a variety of optoelectronic properties. A significant interplay of A-cation size, electronic structure, and steric constraints is revealed, suggesting intriguing means of further tuning the 2D perovskite electronic structure toward achieving stable and efficient solar cell devices.

Nonlinear Photonics Using Low‐Dimensional Metal‐Halide Perovskites: Recent Advances and Future Challenges

Low-dimensional metal-halide perovskites have exhibited significantly superior nonlinear optical properties compared to traditional semiconductor counterparts, thanks to their peculiar physical and electronic structures. Their exceptional nonlinear optical characteristics make them excellent candidates for revolutionizing widespread applications. However, the research of nonlinear photonics based on low-dimensional metal-halide perovskites is in its infancy. There is a lack of comprehensive and in-depth summary of this research realm. Here, the state-of-the-art research progress related to third-and higher-order nonlinear optical properties of low-dimensional metal-halide perovskites with diverse crystal structures from 3D down to 0D, together with their practical applications, is summarized comprehensively. Critical discussions are offered on thefundamental mechanisms beneath their exceptional nonlinear optical performancefrom the physics viewpoint, attempting to disclose the role of intrinsic attributes (e.g., composition, bandgap, size, shape, and structure) and external modulation strategies (e.g., developing core-shell structures, transition metal ion doping, and hybridization with dielectric microspheres) in tuning the response. Additionally, their potential applications in nonlinear photonics, nonlinear optoelectronics, and biophotonics are systematically and thoroughly summed up and categorized. Lastly, insights into the current technical challenges and future research opportunities of nonlinear photonics based on low-dimensional metal-halide perovskites are provided.

Resolving buried optoelectronic features in metal halide perovskites via modulation spectroscopy studies

As research on both bulk and low dimensional metal halide perovskites (MHPs) continues to grow, the tools necessary to gain insights into their exotic and highly convoluted optoelectronic features must also expand.

Dual Self-Trapped Exciton Emission with Ultrahigh Photoluminescence Quantum Yield in CsCu2I3 and Cs3Cu2I5 Perovskite Single Crystals

Low-dimensional metal halide perovskites possessing a large exciton binding energy have shown great promise in achieving efficient photonic emission required in the fields of lighting sources and d...

Pressure Effects on the Electronic and Optical Properties in Low-Dimensional Metal Halide Perovskites.

Metal halide perovskites have shown enormous potential in perovskite solar cells and light-emitting diodes and made unprecedented progress in the past decade. Pressure engineering as an effective technique can systematically modify the electronic structures and physical properties of functional materials. Low-dimensional metal halide perovskites (0D, 1D, and 2D) with a variety of compositions have soft lattices that allow pressure to drastically modulate their structures and properties. High-pressure investigations have obtained a comprehensive understanding of their structure-property relationships. Simultaneously, discoveries of novel pressure-driven properties, such as metallization and partially retained band gap narrowing have contributed significantly to the further development of such materials. In this Perspective, we mainly highlight the effect of pressure on the properties and structures of low-dimensional metal halide perovskites, which is essential for designing new perovskite materials and advancing applications.

High charge carrier mobility in solution processed one-dimensional lead halide perovskite single crystals and their application as photodetectors.

Organic inorganic hybrid metal halide perovskites have emerged as promising candidates for photovoltaics and light-emitting diodes. Recently, interest has been growing in the properties of low-dimensional metal halide perovskites, and one-dimensional versions with strong quantum confinement have demonstrated highly efficient broadband luminescence. Nevertheless, the charge transport mechanism in these low dimensional perovskites remains unclear. In this work, we characterised the charge mobility in one-dimensional perovskite single crystals using a space charge limited current method. Temperature dependent charge mobility measurements indicated that localized polarons at high temperature are replaced by delocalized polarons at low temperature with extended states in the polaronic band. A minimum mobility of 4.51 cm2 V-1 s-1 was measured at room temperature. UV photodetectors based on these crystals show an ultrahigh photoresponsivity of 132.3 A W-1. These findings show the promise of high mobility low dimensional perovskite materials for optoelectronic applications.

Atomistic Mechanism of Broadband Emission in Metal Halide Perovskites.

Broadband emission is attributed to the formation of self-trapped excitons (STEs) due to the strong electron-phonon coupling. Interestingly, it has been observed in only certain three-dimensional and low-dimensional metal halide perovskites. Here, we show by density functional theory calculation that a low electronic dimensionality is a prerequisite for the formation of STE and, therefore, broadband emission. We further show that multiple STE structures exist in each perovskite exhibiting broadband emission. However, only the STE with Jahn-Teller-like octahedral distortion is mainly responsible for the observed broadband emission, though it may not be the lowest-energy structure. Our results provide important insights for designing perovskite materials for broadband emissions with preferred chromaticity coordinator or color temperature.