Stable Halide Perovskite Research Articles

Utilizing Strain-Engineered Stable Halide Perovskite for Interfacial Interaction with Molecular Dipoles To Enhance Ferroelectric Switching and Piezoresponse in Polymer Composite Nanofibers.

Mechanical and solar to electrical energy conversion using piezo- and ferroelectric and photovoltaic effects may be a practical answer to the rising energy demand. In this quest, piezoelectric polymer poly(vinylidene fluoride-hexafluoroproylene) (P(VDF-HFP)) has gained interest due to its superior piezo- and ferroelectricity. In photovoltaic applications, inorganic halide perovskite (IHP) of CsPbI3 is considered a prime model compound. However, its application is limited because of the photoactive perovskite phase instability at ambient conditions. Here, we report the in situ synthesis of the stable perovskite γ-CsPbI3 through an electrospinning process at room temperature, encapsulated within a ferroelectric copolymer poly(vinylidene fluoride-hexafluoroproylene) (P(VDF-HFP)) as a composite nanofiber. Computational calculation using density functional theory (DFT) reveals that tensile strain plays a critical role in the dynamical stabilization of γ-CsPbI3. This tensile strain is triggered by the electrospinning process, which aids in the formation and growth of γ-CsPbI3. In the CsPbI3-P(VDF-HFP) composite nanofiber, γ-CsPbI3 nucleates the polar β-crystalline phase in P(VDF-HFP), which results in the intrinsic piezo- and ferroelectric characteristics. The γ-CsPbI3 aids in preferable molecular dipole orientation, resulting in improved nanoscale piezo- and ferroelectric properties. The composite nanofiber features a higher piezoelectric d33 magnitude (∼30 pm/V) and lower decay constant for polarized domains (τcomposite ≈ 17). The composite was utilized as a piezoelectric nanogenerator to demonstrate human physiological motion monitoring in self-power mode. The relevant pressure sensitivities of 81 and 40 mV/kPa for the low-pressure (<0.6 kPa) and high-pressure (>0.6 to 12 kPa) ranges, respectively, promise its suitability in the health care sector.

Lead-Free Copper-Based Perovskite Nanonets for Deep Ultraviolet Photodetectors with High Stability and Better Performance.

Considering practical application and commercialization, the research of non-toxic and stable halide perovskite and its application in the field of photoelectric detection have received great attention. However, there are relatively few studies on deep ultraviolet photodetectors, and the perovskite films prepared by traditional spin-coating method have disadvantages such as uneven grain size and irregular agglomeration, which limit their device performance. Herein, uniform and ordered Cs3Cu2I5 nanonet arrays are fabricated based on monolayer colloidal crystal (MCC) templates prepared with 1 μm polystyrene (PS) spheres, which enhance light-harvesting ability. Furthermore, the performance of the lateral photodetector (PD) is significantly enhanced when using Cs3Cu2I5 nanonet compared to the pure Cs3Cu2I5 film. Under deep ultraviolet light, the Cs3Cu2I5 nanonet PD exhibits a high light responsivity of 1.66 AW−1 and a high detection up to 2.48 × 1012 Jones. Meanwhile, the unencapsulated PD has almost no response to light above 330 nm and shows remarkable stability. The above results prove that Cs3Cu2I5 nanonet can be a great potential light-absorbing layer for solar-blind deep ultraviolet PD, which can be used as light absorption layer of UV solar cell.

Component Engineering to Tailor the Structure and Optical Properties of Sb-Doped Indium-Based Halides.

Controlling the structure of halide perovskites through component engineering, and thus revealing the changes in luminescence properties caused by the conversion of crystal structure, is of great significance. Herein, we report a controllable synthetic strategy of three-dimensional (3D) Cs2KInCl6 and zero-dimensional (0D) (Cs/K)2InCl5(H2O) halide perovskites by changing the Cs/K feed ratio. 3D Cs2KInCl6 double perovskites are obtained at the Cs/K feed ratio of 1:1, while 0D (Cs/K)2InCl5(H2O) perovskites are formed at the Cs/K feed ratio of 2:1. Further, a reversible crystal structure transformation between 3D Cs2KInCl6 double perovskites and 0D (Cs/K)2InCl5(H2O) perovskites can be achieved by subsequent addition of metal-salt precursors. In addition, the emission efficiency of two perovskite structures can be greatly boosted by breaking the forbidden transition through Sb doping, and as a result, a novel green/yellow reversible emission switch is generated. Meanwhile, the relationship between perovskite structure and luminescence mechanism has been systematically revealed. These environmentally stable halide perovskites have great potential to be applied in optoelectronic devices.

Partial replacement of B-site cation to stabilize the optically active cubic phase of FAPbI3 for optoelectronic applications

Due to the unique and indispensable electronic, physical and chemical properties, halide perovskites are being widely used in optoelectronic applications like solar cells and LEDs. However, the stability of halide perovskites has always been an alarming issue towards the development of these devices on an industrial scale. Specifically, Formamidinium Lead Iodide (FAPbI3), the most suitable organic halide perovskite for solar cells is very unstable due to environmental factors like humidity, temperature and ultraviolet radiation which led to poor-performing devices. Moreover, FAPbI3 is more stable in its photo-inactive hexagonal (δ-FAPbI3) phase. For photovoltaic devices, only the optically active cubic phase (α-FAPbI3) is suitable due to its proper band gap (∼1.45 eV). In this communication, we have partially substituted the Pb2+ cation in FAPbI3 with Tin (Sn2+) and Manganese (Mn2+). The structural and optical properties are analyzed using X-Ray Diffraction, Ultra-violet Diffuse Reflectance Spectroscopy and Photoluminescence (PL) spectroscopy. The results show that the α-FAPbI3 phase can be retained with successful incorporation of Sn2+ and Mn2+ at the B-site of FAPbI3 structure.

Balanced change in crystal unit cell volume and strain leads to stable halide perovskite with high guanidinium content.

Up-to-date studies propose that strain in halide perovskites is one of the key factors that determine a device's efficiency and stability. Here, we show a systematic approach to characterize the phenomenon in the standard methylammonium lead iodine (MAPbI3) perovskite system by: (i) the substitution of some MA by guanidinium (Gu); (ii) the incorporation of PbS quantum dot (QD) additives and (iii) addition of both Gu and PbS at the same time. We studied the effect of these incorporations on the film strain and crystal cell unit volume, and on the solar cell device efficiency and stability. Gu cations and PbS QDs affect the strain, the former due to the relatively large dimensions of Gu, and the latter due to the lattice matching parameters. With the control of Gu and PbS QD content, higher performance and longer solar cell stability are obtained. We demonstrated that the presence of Gu and PbS QDs alters the structure of perovskite, in terms of modification of the unit cell volume and strain. The greater size of Gu cations produces a MAPbI3 unit cell volume expansion as Gu is incorporated, modifying the strain from compressive to tensile. PbS QDs aid Gu incorporation, producing a unit cell volume expansion. In the case of 15% mol Gu incorporation, the addition of PbS QDs modifies strain from compressive to tensile, limiting the deleterious effect. At the same time the unit cell volume is less affected, increasing the solar cell stability. Our work shows that the control of compressive strain and the unit cell volume expansion lead to a 50% increase in T 80, the time in which the PCE decreases to 80% of its original value, increasing the T 80 value from 120 to 187 days under air conditions. Moreover it highlights the importance of exploiting not only the control of the strain induced by internal component, the cation, but also the strain induced by the external component, the QD, associated instead with critical volume variation of metastable perovskite unit cell volume.

First-Principles Characterization of Surface Phonons of Halide Perovskite CsPbI3 and Their Role in Stabilization.

The stability of halide perovskites has been a long-standing issue for their real-world application. Approaches to improve stability include nanostructuring, dimensionality reduction, and strain engineering, where surfaces play an important role in the formation of a stable structure. To understand the mechanism we compute the lattice dynamics of the surface of CsPbI3 using density functional theory. We demonstrate, for the first time, that CsPbI3 crystals exhibit surface phonons that are localized on the outermost layers of the slabs, and we perform a complete symmetry characterization including an identification of the Raman/IR active modes. These surface phonons are present in the optically active cubic phase but are absent in the optically inactive "yellow" phase. Furthermore, we show that the surface suppresses bulk instabilities by hardening soft modes of the bulk cubic phase, resulting in phase stabilization and quenching of dynamical disorder. This study is fundamental for understanding the structural behavior of halide perovskite materials with high surface area-to-volume ratios, and for guiding stabilization strategies.

Material, Phase, and Interface Stability of Photovoltaic Perovskite: A Perspective

The past decade has witnessed the unprecedented boost of power conversion efficiency (PCE) of photovoltaics based on halide perovskite materials since its early discovery. Despite its remarkably good performance, long-term stability is yet one of the last barriers before commercializing halide perovskite photovoltaics is possible. In this perspective, we discuss the challenges and concurrently the strategies regarding the stability of the perovskite materials, photoactive crystal phases, and the performance as well as stability limiting interfaces. Future perspectives of stable halide perovskite and perovskite solar cells are also proposed to shine light on letting perovskite technology satisfy long-term operation warranty.

Deactivating grain boundary defect by bifunctional polymer additive for humid air-synthesized stable halide perovskite solar cells

At present, the inferior stability compared to the high power conversion efficiency (PCE) for halide perovskite solar cells (PSCs) is the foremost drawback to impede their potential applications. Here, our work incorporate bifunctional polycaprolactone (PCL) agent into perovskite precursors in order to enhance the performance and stability of the humid air-fabricated perovskite solar cells (PSCs). The mechanism of efficiency and stability improvement can be resulted from assist in growth of perovskite grain and passivation of trap states in grain boundaries. The proved reduction of defect-state density can be ascribed to the cross-link function of PCL agent with CO bond, which was distributed along the grain boundaries and could play the synthetic role of Lewis base and acid, consequently resulting in the suppressed carrier recombination both in the bulk perovskite films and interfaces. The corresponding best performance device generates a conversion efficiency of 19.78%, 26.6% higher than that of the pristine device and retains ~88% of the initial values after 21 days’ storage without any encapsulation in ambient air. The proposed bifunctional adding strategy and the mechanism study could probe into the improvement of both efficiency and stability of the PSCs fabricated under fully open air conditions.

Highly stable halide perovskite with Na incorporation for efficient photocatalytic degradation of organic dyes in water solution.

To overcome water instability and low photocatalytic activity of lead-free halide perovskite for the degradation of organic dyes, we report a novel photocatalyst of lead-free halide perovskite with Na incorporation and employ it for the photocatalytic degradation of organic dyes in water solution under visible light irradiation. The main purpose of this work is to confirm the feasibility of lead-free halide perovskite with Na incorporation for improving the photocatalytic efficiency and recyclability in water solution and further to explore the mechanism behind the enhancement of photocatalytic performance after Na incorporation. The results show that Cs2Ag0.60Na0.40InCl6 can increase the dye degradation rate by at least 50% than the lead-free halide perovskite (Cs2AgInCl6) and the photocatalyst of Ag substituted by Na (Cs2NaInCl6). The degradation efficiency of rhodamine 6G catalyzed by Cs2Ag0.60Na0.40InCl6 reaches 94.94% over 60 min, which is 72% higher than that catalyzed by Cs2NaInCl6 and 27% higher than that catalyzed by Cs2AgInCl6. What's more, the degradation efficiency of methyl orange catalyzed by Cs2Ag0.60Na0.40InCl6 is 90.39% within 150 min, which is 66% higher than that catalyzed by Cs2NaInCl6 and 54% higher than that catalyzed by Cs2AgInCl6. Moreover, the photocatalyst of Cs2Ag0.60Na0.40InCl6 exhibits a desirable recyclability by water exposure, retaining the degradation efficiency over 90% after five cycles. The strengthened photocatalytic performance in the presence of Cs2Ag0.60Na0.40InCl6 is ascribed to an increase of radiative recombination rate and an improvement of average lifetime to 204 ns since an appropriate Na incorporation at the atomic ratio of Na/Ag=4:6 breaks the original crystal lattice and meanwhile increases the electron and hole overlap. The work proves a great potential of halide perovskite with Na incorporation for the highly efficient photocatalytic degradation of organic dyes in water solution.

Decoupling the effects of defects on efficiency and stability through phosphonates in stable halide perovskite solar cells

Summary Understanding defects is of paramount importance for the development of stable halide perovskite solar cells (PSCs). However, isolating their distinctive effects on device efficiency and stability is currently a challenge. We report that adding the organic molecule 3-phosphonopropionic acid (H3pp) to the halide perovskite results in unchanged overall optoelectronic performance while having a tremendous effect on device stability. We obtained PSCs with ∼21% efficiency that retain ∼100% of the initial efficiency after 1,000 h at the maximum power point under simulated AM1.5G illumination. The strong interaction between the perovskite and the H3pp molecule through two types of hydrogen bonds (H…I and O…H) leads to shallow point defect passivation that has a significant effect on device stability but not on the non-radiative recombination and device efficiency. We expect that our work will have important implications for the current understanding and advancement of operational PSCs.

In data science we trust: Machine learning for stable halide perovskites

The exploration of the compositional space of halide perovskites is prohibitively costly using traditional experimental research strategies. Sun and colleagues demonstrated a physics-informed, machine-learning-guided, experimental approach that overturns this limitation enabling a rapid and efficient maximization of stability in mixed-cation perovskites.

Shallow Iodine Defects Accelerate the Degradation of α-Phase Formamidinium Perovskite

Summary Shallow defects are mostly benign in covalent semiconductors, such as silicon, given that they do not constitute non-radiative recombination sites. In contrast, the existence of shallow defects in ionic perovskite crystals might have significant repercussions on the long-term stability of perovskite solar cells (PSCs) because of the metastability of the ubiquitous formamidinium lead triiodide (FAPbI3) perovskite and the migration of charged point defects. Here, we show that shallow iodine interstitial defects ( I i ) can be generated unintentionally during commonly used post-fabrication treatments, which can lower the cubic-to-hexagonal transformation barrier of FAPbI3-based perovskites to accelerate its phase degradation. We demonstrate that concurrently avoiding the generation of I i and the more effective passivation of iodine vacancies ( V I ) can improve the thermodynamic stability of the films and operational stability of the PSCs. Our most stable PSC retained 92.1 % of its initial performance after nearly 1,000 h of continuous illumination operational stability testing.

Machine learning for halide perovskite materials

Halide perovskite materials serve as excellent candidates for solar cell and optoelectronic devices. Recently, the design of the halide perovskite materials is greatly facilitated by machine learning techniques, which effectively identify suitable halide perovskite candidates and unveil hidden relationships by algorithms that mimic the human cognitive functions. In this manuscript, we review recent progresses on the machine learning studies of the halide perovskite materials, including the prediction and understanding of lead-free and stable halide perovskite materials. The structural descriptors to describe the property and performance of the halide perovskite materials are discussed. In addition, the design strategy of the additive species for the halide perovskite materials via the machine learning technique is provided. Suggestions to further develop the halide perovskite-based systems via the machine learning methods in the future are provided.

N-Substituted Phenothiazines as Environmentally Friendly Hole-Transporting Materials for Low-Cost and Highly Stable Halide Perovskite Solar Cells.

Most of the high-performing halide perovskite solar cells (PSCs) leverage toxic chlorinated solvents (e.g., o-dichlorobenzene or chlorobenzene) for the hole-transporting material (HTM) processing and/or antisolvents in the perovskite film fabrication. To minimize the environmental and health-related hazards, it is highly desirable, yet at the same time demanding, to develop HTMs and perovskite deposition processes relying on nonhalogenated solvents. In this work, we designed two small molecules, AZO-III and AZO-IV, and synthesized them via simple and environmentally friendly Schiff base chemistry, by condensation of electron-donating triarylamine and phenothiazine moieties connected through an azomethine bridge. The molecules are implemented as HTMs in PSCs upon processing in a nonchlorinated (toluene) solvent, rendering their synthesis and film preparation eco-friendly. The enhancement in the power conversion efficiency (PCE) was achieved when switching from AZO-III (9.77%) to AZO-IV (11.62%), in which the thioethyl group is introduced in the 2-position of the phenothiazine ring. Additionally, unencapsulated PSCs based on AZO-III displayed excellent stabilities (75% of the initial PCEs is retained after 6 months of air exposure for AZO-III to be compared with a 48% decrease of the initial PCE for Spiro-OMeTAD-based devices). The outstanding stability and the extremely low production cost (AZO-III = 9.23 $/g and AZO-IV = 9.03 $/g), together with the environmentally friendly synthesis, purification, and processing, make these materials attractive candidates as HTMs for cost-effective, stable, and eco-friendly PSCs.

Metal-Halide Perovskite Design for Next-Generation Memories: First-Principles Screening and Experimental Verification.

Memory devices have been advanced so much, but still it is highly required to find stable and reliable materials with low‐power consumption. Halide perovskites (HPs) have been recently adopted for memory application since they have advantages of fast switching based on ionic motion in crystal structure. However, HPs also suffer from poor stability, so it is necessary to improve the stability of HPs. In this regard, combined first‐principles screening and experimental verification are performed to design HPs that have high environmental stability and low‐operating voltage for memory devices. First‐principles screening identifies 2D layered AB2X5 structure as the best candidate switching layer for memory devices, because it has lower formation energy and defect formation energy than 3D ABX3 or other layered structures (A3B2X7, A2BX4). To verify results, all‐inorganic 2D layered CsPb2Br5 is synthesized and used in memory devices. The memory devices that use CsPb2Br5 show much better stability and lower operating voltages than devices that use CsPbBr3. These findings are expected to provide new opportunity to design materials for reliable device applications based on calculation, screening, and experimental verification.

The Role of Dimethylammonium in Bandgap Modulation for Stable Halide Perovskites

Halide perovskites with bandgaps of 1.70–1.85 eV are of interest for multijunction photovoltaics. Mixing halides on the X site of the ABX3-structured perovskite system is a common way to reach thes...

Good or evil: what is the role of water in crystallization of organometal halide perovskites?

Perovskite solar cells (PSCs) have the potential to become one of the most cost-efficient photovoltaic devices. However, current fabrication methods of PSCs still require strict environment control and ultrahigh purity chemicals, which could prevent their large-scale commercialization. To tackle this challenge, the role of water is the first to be thoroughly understood in a perovskite formation process. Until now, there is still controversy about whether water is harmful or beneficial for perovskite formation, not to mention exactly what role water plays therein. In this Focus article, we review recent studies on water involved chemical reactions, solvent interaction, intermediates, and crystal growth in the perovskite film formation process, in order to bring out a full picture about what water does in the perovskite formation process. As our current understanding stands, a suitable amount of water could be of help for growing high quality perovskite films due to the resultant formation of intermediates, such as MAPbI3·H2O, which facilitates the conversion from precursors to perovskites. However, too much water would induce the formation of relatively stable components, such as (MA)4PbI6·2H2O, which are left in the product-films as impurities resulting in degraded device performance. Continual efforts should be made to further understand and develop water-involved strategies for consistent PSC fabrication under ambient conditions.

Metal Halide Perovskites for Solar‐to‐Chemical Fuel Conversion

AbstractThis review article presents and discusses the recent progress made in the stabilization, protection, improvement, and design of halide perovskite‐based photocatalysts, photoelectrodes, and devices for solar‐to‐chemical fuel conversion. With the target of water splitting, hydrogen iodide splitting, and CO2 reduction reactions, the strategies established for halide perovskites used in photocatalytic particle‐suspension systems, photoelectrode thin‐film systems, and photovoltaic‐(photo)electrocatalysis tandem systems are organized and introduced. Moreover, recent achievements in discovering new and stable halide perovskite materials, developing protective and functional shells and layers, designing proper reaction solution systems, and tandem device configurations are emphasized and discussed. Perspectives on the future design of halide perovskite materials and devices for solar‐to‐chemical fuel conversion are provided. This review may serve as a guide for researchers interested in utilizing halide perovskite materials for solar‐to‐chemical fuel conversion.

Improving the Stability and Monodispersity of Layered Cesium Lead Iodide Perovskite Thin Films by Tuning Crystallization Dynamics

Assembling halide perovskites into layered structures holds promise for addressing chemical and phase stability challenges; however, several other challenges need to be addressed to create efficient and stable halide perovskite devices. Layered halide perovskites (LHPs) suffer from a broad distribution of layer thicknesses and band gaps within thin films. Reducing polydispersity could substantially improve charge transport within LHP films and the performance of LHP-based solar cells. Herein, we focused on layering α-CsPbI3 ((C4H9NH3)2Csn–1PbnI3n+1) thin films. We found that (C4H9NH3)2Csn–1PbnI3n+1 with nominal layer thicknesses of n = 1, 2, 3, and 4 can be deposited at temperatures as low as 100 °C, substantially below the phase-transition temperature of bulk α-CsPbI3. Furthermore, we demonstrated that incorporating solvents with high complexation strength into the precursor solution promotes the formation of intermediate phases within the thin film, slowing down LHP crystallite nucleation, eventually re...

Graphite-protected CsPbBr3 perovskite photoanodes functionalised with water oxidation catalyst for oxygen evolution in water

Metal-halide perovskites have been widely investigated in the photovoltaic sector due to their promising optoelectronic properties and inexpensive fabrication techniques based on solution processing. Here we report the development of inorganic CsPbBr3-based photoanodes for direct photoelectrochemical oxygen evolution from aqueous electrolytes. We use a commercial thermal graphite sheet and a mesoporous carbon scaffold to encapsulate CsPbBr3 as an inexpensive and efficient protection strategy. We achieve a record stability of 30 h in aqueous electrolyte under constant simulated solar illumination, with currents above 2 mA cm−2 at 1.23 VRHE. We further demonstrate the versatility of our approach by grafting a molecular Ir-based water oxidation catalyst on the electrolyte-facing surface of the sealing graphite sheet, which cathodically shifts the onset potential of the composite photoanode due to accelerated charge transfer. These results suggest an efficient route to develop stable halide perovskite based electrodes for photoelectrochemical solar fuel generation.