Size- and shape- dependent unique properties of the metal halide perovskite nanocrystals make them promising building blocks for constructing various electronic and optoelectronic devices. These unique properties together with their easy colloidal synthesis render them efficient nanoscale functional components for multiple applications ranging from light emission devices to energy conversion and storage devices. Recently, two-dimensional (2D) metal halide perovskites in the form of nanosheets (NSs) or nanoplatelets (NPls) are being intensively studied due to their promising 2D geometry which is more compatible with the conventional electronic and optoelectronic device structures where film-like components are employed. In particular, 2D perovskites exhibit unique thickness-dependent properties due to the strong quantum confinement effect, while enabling the bandgap tuning in a wide spectral range. In this review the synthesis procedures of 2D perovskite nanostructures will be summarized, while the application-related properties together with the corresponding applications will be extensively discussed. In addition, perovskite nanocrystals/2D material heterostructures will be reviewed in detail. Finally, the wide application range of the 2D perovskite-based structures developed to date, including pure perovskites and their heterostructures, will be presented while the improved synergetic properties of the multifunctional materials will be discussed in a comprehensive way.
Photo-induced phase-segregation in mixed halide perovskite MAPb(BrxI1-x)3 is investigated in the full compositional range by correlative X-ray diffraction and photo-luminescence experiments.
Lead-free double perovskite halides are emerging optoelectronic materials that are alternatives to lead-based perovskite halides. Recently, single-crystalline double perovskite halides were synthesized, and their intriguing functional properties were demonstrated. Despite such pioneering works, lead-free double perovskite halides with better crystallinity are still in demand for applications to novel optoelectronic devices. Here, we realized highly crystalline Cs2AgBiBr6 single crystals with a well-defined atomic ordering on the microscopic scale. We avoided the formation of Ag vacancies and t…
Halide perovskites are promising semiconductor materials for optoelectronics. One of their unique features is the synthesis, that could be performed by the crystallization from the solution. This method is fast, but practically couldn't be optimized due to the strongly non-equilibrium conditions of crystal growth. Another quality limitation is the typical incorporation of organic solvent molecules into crystals when perovskite crystallization is performed from solution with organic solvent. Here we report an alternative method of perovskite single crystal growth based on the counterdiffusion o…
Under continuous light illumination, it is known that localized domains with segregated halide compositions form in semiconducting mixed-halide perovskites, thus severely limiting their optoelectronic applications due to the negative changes in bandgap energies and charge-carrier characteristics. Here we deposit mixed-halide perovskite CsPbBr1.2I1.8 nanocrystals onto an indium tin oxide substrate, whose temperature can be rapidly changed by ~10 degree in a few seconds by applying or removing an external voltage. Such a sudden temperature change induces a temporary transition of CsPbBr1.2I1.8 n…
The MAPbI$_3$ halide perovskite single crystals are studied at 5 K temperature using the photoluminescence excitation spectroscopy. Two non-interacting types of states are determined: bound excitons and defect-related states. Excitation of the crystal with light energy below the bound exciton resonance reveals the complex low-density defects emission, otherwise hidden by the emission of bound excitons. A way to separate these defect-related luminescence spectra is proposed, and the thorough study of this emission regime is carried out. The results of this study opens an area of low-density def…
Two-dimensional (2D) halide perovskites are emerging as promising candidates for nano-electronics and optoelectronics. To realize their full potential, it is important to understand the role of those defects that can strongly impact material properties. In contrast to other popular 2D semiconductors (e.g. transition metal dichalcogenides MX2) for which defects typically induce harmful traps, we show that the electronic activities of defects in 2D perovskites are significantly tunable. For example, even with a fixed lattice orientation, one can change the synthesis conditions to convert a line …
Halide perovskites exhibit giant photostriction, that is, volume or shape changes upon illumination. However, the microscopic origin of this phenomenon remains unclear and there are experimental reports of both light-induced lattice expansion and contraction. In this paper we establish a general method, based on first-principles calculations and molecular orbital theory, which provides a microscopic picture of photostriction in insulators based on the orbital characters of their electronic bands near the Fermi level. For lead-halide perovskites, we find that different valence states have diffe…
Perovskite solar cells with record power conversion efficiency are fabricated by alloying both hybrid and fully inorganic compounds. While the basic electronic properties of the hybrid perovskites are now well understood, key electronic parameters for solar cell performance, such as the exciton binding energy of fully inorganic perovskites, are still unknown. By performing magneto transmission measurements, we determine with high accuracy the exciton binding energy and reduced mass of fully inorganic CsPbX$_3$ perovskites (X=I, Br, and an alloy of these). The well behaved (continuous) evolutio…
Epitaxial III-V semiconductor heterostructures are key components in modern microelectronics, electro-optics and optoelectronics. With superior semiconducting properties, halide perovskite materials are rising as promising candidates for coherent heterostructure devices. In this report, spinodal decomposition is proposed and experimentally implemented to produce epitaxial double heterostructures in halide perovskite system. Pristine epitaxial mixed halide perovskites rods and films were synthesized via Van der Waals epitaxy by chemical vapor deposition method. At room temperature, photon was a…
We theoretically study the optical absorption of an angulon in the metal halide perovskites (MHP) based on the improved Devreese-Huybrechts-Lemmens model, where the formation of quasiparticle angulon states originates from the organic cation rotating in the inorganic octahedral cage of MHP. We find that the resonance optical absorption peaks are appeared when the energy of incident photon matches the quantum levels of angulon. Moreover, the intensity of absorption depends on the quantum states of phonon angular momentum. These theoretical results provide significant insight to study the redist…
Instability of hybrid organic-inorganic halide perovskites hinders their development for photovoltaic applications. First-principle calculations are used for evaluation of a decomposition reaction enthalpy of hybrid halide perovskites, which is linked to experimentally observed degradation of device characteristics. However, simple criteria for predicting stability of halide perovskites are lacking since Goldschmidt's tolerance and octahedral geometrical factors do not fully capture formability of those perovskites. In this paper, we extend the Born-Haber cycle to partition the reaction enthal…
Using density-functional theory calculations, we analyze the optical absorption properties of lead (Pb)-free metal halide perovskites (AB$^{2+}$X$_3$) and double perovskites (AB$^+$B$^{3+}$X$_6$) (A = Cs or monovalent organic ion, B$^{2+}$ = non-Pb divalent metal, B$^+$ = monovalent metal, B$^{3+}$ = trivalent metal, X = halogen). We show that, if B$^{2+}$ is not Sn or Ge, Pb-free metal halide perovskites exhibit poor optical absorptions because of their indirect bandgap nature. Among the nine possible types of Pb-free metal halide double perovskites, six have direct bandgaps. Of these six typ…
Two-dimensional (2D) halide perovskites feature a versatile structure, which not only enables the fine-tuning of their optoelectronic properties but also makes them appealing as model systems to investigate the fundamental properties of hybrid perovskites. In this study, we analyzed the changes in the optical absorption of 2D Dion-Jacobson mixed halide perovskite thin films (encapsulated) based on (PDMA)Pb(I0.5Br0.5)4 (PDMA: 1,4-phenylenedimethanammonium spacer) exposed to a constant illumination. We demonstrate that these 2D mixed-halide perovskites undergo photo de-mixing with direct transfo…
With the rapid evolution of lead halide perovskite solar cells, there are considerable evidences that the mobile ions strongly impact their properties. However, except the activation energy, the other properties of ionic migration are mostly explored with first principle calculations. Here we investigate the migration of halide ion (vacancy) in lead bromide perovskite single crystalline microplates. In contrast to conventional studies with external bias voltages, we introduce built-in potentials into the microplates via low-energy electron beams and study the corresponding ionic migrations. By…
Single crystals of Cs2BiAgBr6 lead-free perovskite were grown by crystallization from supersaturated solution. According to characterization by XRD and EBSD methods the double perovskite single crystal are of the cubic Fm-3m symmetry with the lattice constant a = 11.20 Å. DFT predictions based on the single crystal X-ray diffraction analysis reveal that the material is an indirect band gap semiconductor. Low temperature (1.4 K) photoluminescence spectra demonstrate three broadened bands that correspond to two lowest computed indirect and one direct band-to-band transitions.
Understanding the intrinsic charge transport in organolead halide perovskites is essential for the development of high-efficiency photovoltaics and other optoelectronic devices. Despite the rapid advancement of the organolead halide perovskite in photovoltaic and optoelectronic applications, the intrinsic charge carrier transport in these materials remains elusive partly due to the difficulty of fabricating electrical devices and obtaining good electrical contact. Here, we report the fabrication of organolead halide perovskite microplates with monolayer graphene as low barrier electrical conta…
Perovskite stability is of the core importance and difficulty in current research and application of perovskite solar cells. Nevertheless, over the past century, the formability and stability of perovskite still relied on simplified factor based on human knowledge, such as the commonly used tolerance factor t. Combining machine learning (ML) with first-principles density functional calculations, we proposed a strategy to firstly calculate the decomposition energies, considered to be closely related to thermodynamic stability, of 354 kinds halide perovskites, establish the machine learning rela…
The bandgap tunability of mixed-halide perovskites makes them promising candidates for light emitting diodes and tandem solar cells. However, illuminating mixed-halide perovskites results in the formation of segregated phases enriched in a single-halide. This segregation occurs through ion migration, which is also observed in single-halide compositions, and whose control is thus essential to enhance the lifetime and stability. Using pressure-dependent transient absorption spectroscopy, we find that the formation rates of both iodide- and bromide-rich phases in MAPb(BrxI1-x)3 reduce by two orde…
Electronic structure and optical properties of halide double perovskites from a Wannier-localized optimally-tuned screened range-separated hybrid functional
One of the most significant features of lead-halide perovskites are their ability to have comparably slow recombination despite the fact that these materials are mostly processed from solution at room temperature. The slow recombination allows achieving high open-circuit voltages when the lead-halide perovskite layers are used in solar cells. This perspective discusses the state of the art of our understanding and of experimental data with regard to recombination and open-circuit voltages in lead-halide perovskites. A special focus is put onto open questions that the community has to tackle to…
Organic-inorganic halide perovskite solar cells have recently attracted much attention due to their low-cost fabrication, flexibility, and high-power conversion efficiency. The reduction from three- to two-dimension (2D) promises an exciting opportunity to tune the electronic properties of organic-inorganic halide perovskites. Here, we propose first-principles density-functional theory based route to study the effect of reduced dimensionality, impurity doping, and heterostructure engineering on energy stability, band-gap and transport properties of 2D hybrid organic-inorganic halide perovskite…
Based on first-principles calculations, we show that chemically active metal ns2 lone pairs play an important role in exciton relaxation and dissociation in low-dimensional halide perovskites. We studied excited-state properties of several recently discovered luminescent all-inorganic and hybrid organic-inorganic zero-dimensional (0D) Sn and Pb halides. The results show that, despite the similarity in ground-state electronic structure between Sn and Pb halide perovskites, the chemically more active Sn2+ lone pair leads to stronger excited-state structural distortion and larger Stokes shift in …
In recent years, metal halide perovskites have generated tremendous interest for optoelectronic applications and their underlying fundamental properties. Due to the large electron-phonon coupling characteristic of soft lattices, self-trapping phenomena are expected to dominate hybrid perovskite photoexcitation dynamics. Yet, while the photogeneration of small polarons was proven in low dimensional perovskites, the nature of polaron excitations in technologically relevant 3D perovskites, and their influence on charge carrier transport, remain elusive. In this study, we used a combination of fir…
Cui et al. describe the fabrication and characterization of planar pn-junction solar cells based on lead-halide perovskites. The doping densities measured using Hall effect measurements vary from $N_D = 10^{12} cm^{-3}$ to $8\times 10^{12} cm^{-3}$ for the solution-processed n-type layer and $N_A = 8\times 10^9 cm^{-3}$ for the evaporated p-type layer. While these devices outperform their counterparts, that are supposedly un-doped, the results raise three important questions: (i) Are the reported doping densities high enough to change the electrostatic potential distribution in the device from…
Halide perovskites have attracted increasing research attention regarding their outstanding optoelectronic applications. Owing to its low activation energy, ion migration is implicated in the long-term stability and many unusual transport behaviors of halide perovskite devices. However, precise control of the ionic transport in halide perovskite crystals remains challenging. Here we visualized and quantified the electric-field-induced halide ion migration in an axial CsPbBr$_3$-CsPbCl$_3$ nanowire heterostructure and demonstrated a solid-state ionic rectification, which is due to the non-unifo…
Using first principles calculations we show that several alkali lead halides potentially present collective ferroelectric polarization. This should occur at least at the nanoscale; it could be detected macroscopically provided it is not concealed by lattice vibrations in the temperature range of stability of the cubic perovskite phase. For potassium lead halides and for alkali lead fluorides, remarkably, the ferroelectric behavior turns hyper-ferroelectric, suggesting a more robust ferroelectric polarization in spite of depolarization potentials induced by charge accumulation on surfaces or in…
We use path integral molecular dynamics simulations and theory to elucidate the interactions between charge carriers, as mediated by a lead halide perovskite lattice. We find that the charge-lattice coupling of MAPbI$_3$ results in a repulsive interaction between electrons and holes at intermediate distances. The effective interaction is understood using a Gaussian field theory, whereby the underlying soft, polar lattice contributes a nonlocal screening between quasiparticles. Path integral calculations of this nonlocal screening model are used to rationalize the small exciton binding energy a…
Halide perovskites are semiconductors that exhibit sharp optical absorption edges and small Urbach energies allowing for efficient collection of sunlight in thin-film photovoltaic devices. However, halide perovskites also exhibit large nuclear anharmonic effects and disorder, which is unusual for efficient optoelectronic materials and difficult to rationalize in view of the small Urbach energies that indicate a low amount of disorder. To address this important issue, the disorder potential induced for electronic states by the nuclear dynamics in various paradigmatic halide perovskites is studi…
We develop techniques to study the temperature dependent localization, thermalization, and the effects of phonon scattering on the excitons in halide perovskites from the analysis of the emission spectra. The excitonic Urbach edge, when inferred from the low energy tails of the temperature dependent luminescence spectra, is shown to be sensitive to the electron distribution and thermalization. A method to observe the Urbach focus is devised for halide perovskites where the temperature dependence of the excitonic gap is anomalous. The value of the zero-point bandgap renormalization is inferred …
Surface-defect passivation is key to achieving high photoluminescence quantum yield in lead halide perovskite nanocrystals. However, in perovskite light-emitting diodes these surface ligands also have to enable balanced charge injection into the nanocrystals to yield high efficiency and operational lifetime. In this respect, alkaline halides have been reported to passivate surface trap states and increase the overall stability of perovskite light emitters. On the one side, the incorporation of alkaline ions into the lead halide perovskite crystal structure is considered to counterbalance catio…
Halide perovskites exhibit slow rates of non-radiative electron-hole recombination upon illumination. Chu et al. [Sci. Adv. 6 7, eaaw7453 (2020)] use the results of first-principles simulations to argue that this arises from the nature of the crystal vibrations and leads to a breakdown of Shockley-Read-Hall theory. We highlight flaws in their methodology and analysis of carrier capture by point defects in crystalline semiconductors.
The discovery of double perovskites A2B(I)B(III)X6 (A=monovalent cation; B(I)/B(III) = metal cation; X = halogen) as Pb(II)-free alternatives has attracted widespread attention, making it possible to introduce d-block metal cations (e.g., d0 and d10) into halide perovskites. However, at present, there are quite limited insights into the underlying bonding orbitals for d-block metal cation-based halide perovskites. Here, we present an orbital engineering strategy to construct two-dimensional (2D) electronic structures in three-dimensional (3D) halide perovskites by rationally controlling the d …
Despite their puzzling vibrational characteristics that include strong signatures of anharmonicity and thermal disorder already around room temperature, halide perovskites exhibit favorable optoelectronic properties for applications in photovoltaics and beyond. Whether these vibrational properties are advantageous or detrimental to their optoelectronic properties remains, however, an important open question. Here, this issue is addressed by investigation of the {finite-temperature optoelectronic properties} in the prototypical cubic CsPbBr$_3$, using first-principles molecular dynamics based o…
Here we develop a microscopic approach aimed at the description of a suite of physical effects related to carrier transport in, and the optical properties of, halide perovskites. Our theory is based on the description of the nuclear dynamics to all orders and goes beyond the common assumption of linear electron-phonon coupling in describing the carrier dynamics and band gap characteristics. When combined with first-principles calculations and applied to the prototypical MAPbI$_{3}$ system, our theory explains seemingly disparate experimental findings associated with both the charge-carrier mob…
Bulk quantum materials based on zero-dimensional (0D) lead-free organic tin halide perovskites have been developed for the first time, which give broadband Gaussian-shaped and strongly Stokes shifted emissions with quantum efficiencies of up to near-unity at room temperature due to excited state structural reorganization.
The low ionization energy of an $A$ site molecule is a very important factor, which determines the thermodynamical stability of $A$PbI$_3$ hybrid halide perovskites, while the size of the molecule governs the stable phase at room temperature and, eventually, the bandgap. It is challenging to achieve both a low ionization energy and the reasonable size for the PbI$_3$ cage to circumvent the stability issue inherent to hybrid halide perovskites. Here we propose a new three-membered charged ring radical, which demonstrates a low ionization energy that renders a good stability for its correspondin…
Ni et al. report minimum bulk trap densities of 10^11 cm-3 and 1-4 orders change in interfacial trap densities derived from drive-level capacitance profiling of lead halide perovskites. From basic electrostatic arguments, we show that such bulk trap densities cannot be resolved for a p-i-n perovskite solar cell for the reported layer thicknesses, while the apparent interfacial charge densities are a consequence of the geometrical capacitance and of charge injection into the perovskite layer.
The electronic structure evolution of deficient halide perovskites with a general formula $(A,A')_{1+x}M_{1-x}X_{3-x}$ was investigated using the density functional theory. The focus is placed on characterization of changes in the band gap, band alignment, effective mass, and optical properties of deficient perovskites at various concentrations of defects. We uncover unusual electronic properties of the defect corresponding to a $M\!-\!X$ vacancy filled with an $A'$ cation. This defect "repels" electrons and holes producing no trap states and, in moderate quantities ($x\le0.1$), does not hinde…
Halide perovskites are promising materials for light-emitting and light-harvesting applications. In this context, two-dimensional perovskites such as nanoplatelets or Ruddlesden-Popper and Dion-Jacobson layered structures are important because of their structural flexibility, electronic confinement, and better stability. This review article brings forth an extensive overview of the recent developments of two-dimensional halide perovskites both in the colloidal and non-colloidal forms. We outline the strategy to synthesize and control the shape and discuss different crystalline phases and optoe…
Instabilities relating to cooperative octahedral tilting is common in materials with perovskite structures, and in particular in the sub class of halide perovskites. In this work, the energetics of octahedral tilting in the inorganic metal halide perovskites CsPbI$_3$ and CsSnI$_3$ are investigated using first-principles density functional theory calculations. Several low energy paths between symmetry equivalent variants of the stable orthorhombic (\textit{Pnma}) perovskite variant are identified and investigated. The results are in favor of the presence of dynamic disorder in the octahedral t…
Bulk CsEuBr$_3$ and CsEuCl$_3$ are experimentally shown to be magnetic semiconductors that order antiferromagnetically at Neel temperatures of 2.0 K and 1.0 K respectively. Given that nanoparticles and thin films of CsEuCl$_3$ have been reported to order ferromagnetically at a similar temperature, our observation of antiferromagnetic ordering in CsEuBr$_3$ and CsEuCl$_3$ expands the possible applications of halide perovskites to now include spintronic devices where both ferromagnetic and antiferromagnetic devices can be fabricated from a single material. The conclusion that CsEuCl$_3$ can be u…
Lead-based halide perovskites are emerging as the most promising class of materials for next generation optoelectronics. However, despite the enormous success of lead-halide perovskite solar cells, the issues of stability and toxicity are yet to be resolved. Here we report on the computational design and the experimental synthesis of a new family of Pb-free inorganic halide double-perovskites based on bismuth or antimony and noble metals. Using first-principles calculations we show that this hitherto unknown family of perovskites exhibits very promising optoelectronic properties, such as tunab…
We use general symmetry-based arguments to construct an effective model suitable for studying optical properties of lead-halide perovskites. To build the model, we identify an atomic-level interaction between electromagnetic fields and the spin degree of freedom that should be added to a minimally-coupled $\mathbf{k\cdot p}$ Hamiltonian. As a first application, we study two basic optical characteristics of the material: the Verdet constant and the refractive index. Beyond these linear characteristics of the material the model is suitable for calculating non-linear effects such as the third-ord…
Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that inhibit carrier recombination. We combine low frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in both hybrid (CH$_3$NH$_3$PbBr$_3$) and all-inorganic (CsPbBr$_3$) lead-halide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead…
