Imaging Light-Induced Migration of Dislocations in Halide Perovskites with 3D Nanoscale Strain Mapping
Kieran W. P. Orr, Jiecheng Diao, Muhammad Naufal Lintangpradipto, Darren J. Batey, Affan N. Iqbal, Simon Kahmann, Kyle Frohna, Milos Dubajic, Szymon J. Zelewski… 展开作者
Kieran W. P. Orr, Jiecheng Diao, Muhammad Naufal Lintangpradipto, Darren J. Batey, Affan N. Iqbal, Simon Kahmann, Kyle Frohna, Milos Dubajic, Szymon J. Zelewski, Alice E. Dearle, Thomas A. Selby, Peng Li, Tiarnan A. S. Doherty, Stephan Hofmann, Osman M. Bakr, Ian K. Robinson, Samuel D. Stranks
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Main text and Supplementary Information. Main text: 15 pages, 4 figures. Supplementary Information: 16 pages, 27 figures, 1 table
In recent years, halide perovskite materials have been used to make high performance solar cell and light-emitting devices. However, material defects still limit device performance and stability. Here, we use synchrotron-based Bragg Coherent Diffraction Imaging to visualise nanoscale strain fields, such as those local to defects, in halide perovskite microcrystals. We find significant strain heterogeneity within MAPbBr$_{3}$ (MA = CH$_{3}$NH$_{3}^{+}$) crystals in spite of their high optoelectronic quality, and identify both $\langle$100$\rangle$ and $\langle$110$\rangle$ edge dislocations through analysis of their local strain fields. By imaging these defects and strain fields in situ under continuous illumination, we uncover dramatic light-induced dislocation migration across hundreds of nanometres. Further, by selectively studying crystals that are damaged by the X-ray beam, we correlate large dislocation densities and increased nanoscale strains with material degradation and substantially altered optoelectronic properties assessed using photoluminescence microscopy measurements. Our results demonstrate the dynamic nature of extended defects and strain in halide perovskites and their direct impact on device performance and operational stability.
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…
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…
Electronic structure and optical properties of halide double perovskites from a Wannier-localized optimally-tuned screened range-separated hybrid functional
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…
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…
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…
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…
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…
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…
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…
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 …
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…
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…
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…
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…
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…
Metal halide perovskite semiconductors have outstanding optoelectronic properties. Although these perovskites are defect-tolerant electronically, defects hamper their long-term stability and cause degradation. Density functional theory (DFT) calculations are an important tool to unravel the microscopic structures of defects, but results suffer from the different approximations used in the DFT functionals. In the case of metal halide perovskites, qualitatively different results have been reported with different functionals, either predicting vacancy or interstitial point defects to be most domi…
Naturals and synthetic perovskites are widely used functional materials thanks to their particular physical properties, such as superconductivity, ferroelectricity and photo-activity. Many of these properties are related to static or dynamic motion of octahedral units; Yet a full understanding of the relationships between perovskite crystal structure, chemical bonding and physical properties is currently missing. Several studies indicate the existence of dynamic disorder generated by anharmonic motion of octahedral units e.g. in halide perovskite structures. In this work, we derive all possibl…
Two critical limitations of organic-inorganic lead halide perovskite materials for solar cells are their poor stability in humid environments and inclusion of toxic lead. In this study, high-throughput density functional theory (DFT) methods are used to computationally model and screen 1845 halide perovskites in search of new materials without these limitations that are promising for solar cell applications. This study focuses on finding materials that are comprised of nontoxic elements, stable in a humid operating environment, and have an optimal bandgap for one of single junction, tandem Si-…
Charge transport is crucial to the performance of hybrid halide perovskite solar cells. A theoretical model based on large polarons is proposed to elucidate charge transport properties in the perovskites. Critical new physical insights are incorporated into the model, including the recognitions that acoustic phonons as opposed to optical phonons are responsible for the scattering of the polarons; these acoustic phonons are fully excited due to the "softness" of the perovskites, and the temperature-dependent dielectric function underlies the temperature dependence of charge carrier mobility. Th…
A method for improving the efficiency of solar cells is combining a low-bandgap semiconductor with a singlet fission material (which converts one high energy singlet into two low energy triplets following photoexcitation). Here we present a study of the interface between singlet fission molecules and low-bandgap halide pervoskites. We briefly show a range of experiments screening for triplet transfer into a halide perovskite. However, in all cases triplet transfer was not observed. This motivated us to understand the halide perovskite/singlet fission interface better by carrying out first-prin…
The high-symmetry pseudocubic init cell is often used for modelling the electronic structure of halide perovskites. However, direct comparison of the band structure with more realistic low-symmetry phases is impeded by the zone folding. We utilize a spectral density technique in order to reduce the supercell band structure to a common Bloch basis. This allows us to compare the electronic structure of high- and low-symmetry phases as well as investigate effects of structural and compositional disorder on states near to the band edges that govern transport, dissociation and recombination of opti…
Organometal halide perovskites are promising solar-cell materials for next-generation photovoltaic applications. The long carrier lifetime and diffusion length of these materials make them very attractive for use in light absorbers and carrier transporters. While these aspects of organometal halide perovskites have attracted the most attention, the consequences of the Rashba effect, driven by strong spin-orbit coupling, on the photovoltaic properties of these materials are largely unexplored. In this work, taking the electronic structure of methylammonium lead iodide as an example, we propose …
Organic-inorganic coupling in the hybrid lead-halide perovskite is a central issue in rationalizing the outstanding photovoltaic performance of these emerging materials. Here we compare and contrast the evolution of structure and dynamics of the hybrid CH3NH3PbBr3 and the inorganic CsPbBr3 lead-halide perovskites with temperature, using Raman spectroscopy and single-crystal X-ray diffraction. Results reveal a stark contrast between their order-disorder transitions, abrupt for the hybrid whereas smooth for the inorganic perovskite. X-ray diffraction observes an intermediate incommensurate phase…
Favorable optoelectronic properties and ease of fabrication make NiO a promising hole transport layer for perovskite solar cells. To achieve maximum efficiency, the electronic levels of NiO need to be optimally aligned with those of the perovskite absorber. Applying surface modifiers by adsorbing species on the NiO surface, is one of the most widespread strategies to tune its energy levels. Alkali halides are simple inorganic surface modifiers that have been extensively used in organic optoelectronics, however, rarely studied in perovskite solar cells. Using density functional theory (DFT) cal…
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.
Organic-inorganic halide perovskite solar cells have attracted much attention due to their low-cost fabrication, flexibility, and high-power conversion efficiency. More recent efforts show that the reduction from three- to two-dimensions (2D) of organic-inorganic halide perovskites promises an exciting opportunity to tune their electronic properties. Here, we explore the effect of reduced dimensionality and heterostructure engineering on the intrinsic material properties, such as energy stability, bandgap and transport properties of 2D hybrid organic-inorganic halide perovskites using first-pr…
The centrosymmetric halide perovskites undergo a continuous phase transition from a normal insulator to a topological insulator at the critical value of strain. Contrarily, in noncentrosymmetric halide perovskites, this phase transition is discontinuous. The noncentrosymmetry does not stabilize the gapless state, causing a discontinuity in the bandgap. We have employed the density functional theory and Slater-Koster formalism-based tight-binding Hamiltonian studies to understand the evolution of band topology under the compressive strain in the halide perovskites. Our study shows that both cub…
Halide perovskites make efficient solar cells due to their exceptional optoelectronic properties, but suffer from several stability issues. The characterization of the degradation processes is challenging because of the limitations in the spatio-temporal resolution in experiments and the absence of efficient computational methods to study the reactive processes. Here, we present the first effort in developing reactive force fields for large scale molecular dynamics simulations of the phase instability and the defect-induced degradation reactions in inorganic CsPbI$_{3}$. We find that the phase…
Hybrid halide perovskites are currently under intense investigation due to their potential applications in optoelectronics and solar cells. Among them, MAPbI$_3$ where MA stands for the methylammonium cation, exhibits ideal properties for solar cells. In attempt to identify new lead-free halide perovskites we have studied using \textit{ab-initio} electronic structure calculations in conjunction with hybrid functionals a series of MABX$_3$ compounds where B is a divalent cation and X a halogen atom. Our results suggest that the compounds under study exhibit a variety of lattice constants and en…
