CsPbI3 Perovskite Research Articles

Dipolar Chemical Bridge Induced CsPbI3 Perovskite Solar Cells with 21.86 % Efficiency.

CsPbI3 perovskite receives tremendous attention for photovoltaic applications due to its ideal band gap and good thermal stability. However, CsPbI3 perovskite solar cells (PSCs) significantly suffer from photovoltage deficits because of serious interfacial energy losses within the PSCs, which to a large extent affects the photovoltaic performance of PSCs. Herein, a dipolar chemical bridge (DCB) is constructed between the perovskite and TiO2 layers to lower interfacial energy losses and thus improve the charge extraction of PSCs. The results reveal that the DCB could form a beneficial interfacial dipole between the perovskite and TiO2 layers, which could optimize the interfacial energetics of perovskite/TiO2 layers and thus improve the energy level alignment within the PSCs. Meanwhile, the constructed DCB could also simultaneously passivate the surface defects of perovskite and TiO2 layers, greatly lowering interfacial recombination. Consequently, the photovoltage deficit of CsPbI3 PSCs is largely reduced, leading to a record efficiency of 21.86 % being realized. Meanwhile, the operation stability of PSCs is also largely improved due to the high-quality perovskite films with released interfacial tensile strain being obtained after forming the DCB within the PSCs.

Dipolar Chemical Bridge Induced CsPbI3 Perovskite Solar Cells with 21.86 % Efficiency

AbstractCsPbI3 perovskite receives tremendous attention for photovoltaic applications due to its ideal band gap and good thermal stability. However, CsPbI3 perovskite solar cells (PSCs) significantly suffer from photovoltage deficits because of serious interfacial energy losses within the PSCs, which to a large extent affects the photovoltaic performance of PSCs. Herein, a dipolar chemical bridge (DCB) is constructed between the perovskite and TiO2 layers to lower interfacial energy losses and thus improve the charge extraction of PSCs. The results reveal that the DCB could form a beneficial interfacial dipole between the perovskite and TiO2 layers, which could optimize the interfacial energetics of perovskite/TiO2 layers and thus improve the energy level alignment within the PSCs. Meanwhile, the constructed DCB could also simultaneously passivate the surface defects of perovskite and TiO2 layers, greatly lowering interfacial recombination. Consequently, the photovoltage deficit of CsPbI3 PSCs is largely reduced, leading to a record efficiency of 21.86 % being realized. Meanwhile, the operation stability of PSCs is also largely improved due to the high‐quality perovskite films with released interfacial tensile strain being obtained after forming the DCB within the PSCs.

Kinetic Process with Anti-Frenkel Disorder in a CsPbI3 Perovskite.

Halide perovskites are rich in ionic diffusion phenomena due to their low activation energy. The soft lead iodide lattice can, in theory, endow the system with more complex defect collaborative motions. In this work, we systematically investigated the hopping mechanics of iodide interstitials with respect to various defect behaviors, such as anti-Frenkel disorder creation and annihilation. We found that the existence of iodide vacancies and interstitials can effectively lower the creation barrier of additional anti-Frenkel disorder in the halide perovskite. The free energy barriers for generating additional Frenkel defect pairs vary from 0.25 to 0.43 eV, in the proximity of those of the original iodide defects at 300 K. This finding suggests that the spontaneous creation of a specific level of anti-Frenkel disorder facilitates long-range annihilation and defect hopping processes.

Fabricating Solid‐Solution‐Type Perovskite/Fluoride Nanocomposites Through Sublattice Interlocking for High‐Performance Photovoltaics

AbstractAll‐inorganic α‐phase CsPbI3 perovskite with a suitable bandgap and superb optoelectronic properties is transforming the landscape of perovskite photovoltaics, but its long‐term lability associated with “soft” ionic lattice still imposes a great challenge for practical applications. Herein, a unique solid‐solution fluorination strategy is proposed to deliver an “ideal” perovskite matrix of α‐phase CsPbI3 abundant with F ions through interlocking the soft lattice of CsPbI3 with cubic‐phase CsF·3/2HF. Such a sublattice interlocking can not only stabilize the soft lattice of α‐phase CsPbI3 perovskite nanocrystals but also passivate their notorious surface defects, thereby producing a “rigid” solid‐solution‐type perovskite/fluoride CsPbI3/CsF (termed as CsPbI3:F) nanocomposite with excellent long‐term stability and a near‐unity photoluminescence efficiency. Of particular note is that these CsPbI3:F nanocomposites can work well as effective grain boundary anchors to significantly improve the photovoltaic performance of perovskite solar cells because of their F‐rich perovskite lattice, achieving a T80 stability of 1500 h under continuous maximum power point tracking and AM 1.5G illumination without the need for encapsulation. This work paves a new way to deliver perovskite materials with desirable properties for photovoltaics.

Direct linearly polarized electroluminescence from perovskite nanoplatelet superlattices

Polarized light is critical for a wide range of applications, but is usually generated by filtering unpolarized light, which leads to substantial energy losses and requires additional optics. Here we demonstrate the direct emission of linearly polarized light from light-emitting diodes made of CsPbI3 perovskite nanoplatelet superlattices. The use of solvents with different vapour pressures enables the self-assembly of the nanoplatelets with fine control over their orientation (either face-up or edge-up) and therefore their transition dipole moment. As a result of the highly uniform alignment of the nanoplatelets, as well as their strong quantum and dielectric confinement, large exciton fine-structure splitting is achieved at the film level, leading to pure red light-emitting diodes with linearly polarized electroluminescence exhibiting a high degree of polarization of 74.4% without any photonic structures. This work demonstrates the potential of perovskite nanoplatelets as a promising source of linearly polarized light, opening up the development of next-generation three-dimensional displays and optical communications from a highly versatile, solution-processable system.

A theoretical study of all-inorganic perovskite solar cells: Computational modeling of the CsPbI[formula omitted]/RbGeI[formula omitted] bilayer absorber structure

All-inorganic perovskite solar cells (AI-PSCs) have garnered significant attention in the perovskite community due to their stability and efficient photogeneration and absorption capabilities. Despite the toxicity associated with all-inorganic CsPbI3 perovskites containing lead (Pb), its presence remains crucial for achieving excellent photovoltaic properties. However, the imperative shift towards AI-PSCs using less toxic materials with suitable photovoltaic properties is imperative. The incorporation of a double perovskite absorber layer allows for broadening the absorption spectrum of PSCs and enhancing cell stability. In this study, we propose a novel AI-PSC structure with CsPbI3 as the top absorber with a wide bandgap of 1.69 eV and a lead-free RbGeI3 perovskite as the bottom absorber layer with a low bandgap of 1.31 eV. Utilizing numerical simulations with the SCAPS-1D simulator, we analyze the photovoltaic parameters of AI-PSCs with single and double absorber layers. Our investigations reveal that a double absorber layer structure, comprising CsPbI3 and RbGeI3 materials, outperforms a single-junction PSC based on CsPbI3. By optimizing critical device parameters, we achieved an impressive efficiency of 31.91% in an AI-PSC device with a CsPbI3(0.6 μm)/RbGeI3(2 μm) bilayer configuration. This study positions lead-free RbGeI3 perovskite as a promising partner for CsPbI3, offering a potential pathway for the development of highly efficient AI-PSCs.

Pure-red electroluminescence of quantum-confined CsPbI3 perovskite nanocrystals obtained by the gradient purification method

Pure-red emission light-emitting diodes (LEDs) are highly desirable for display and lighting applications. Here, we present a synergistic approach to fabricate pure-red emission LEDs based on quantum-confined CsPbI3 nanocrystals (NCs). By introducing ZnI2 acting as a co-precursor and passivating agent into the synthesis, and applying a gradient post-synthesis purification method allowing us to obtain size-selected fractions with precisely adjusted emission colors, we obtained uniform and small (about 6 nm), quantum-confined CsPbI3 NCs exhibiting high stability in ambient conditions and a superior photoluminescence quantum yield of up to 88%. These NCs exhibited the tendency to undergo oriented attachment, resulting in self-assembled superstructures with a pure-red emission at 629 nm. Importantly, partial recrystallization into fused superstructures led to removal of the insulating ligand barriers between NCs. LEDs based on the CsPbI3 NCs showed pure-red electroluminescence at 633 nm, with an external quantum efficiency of 14.7% and a luminance of over 1000 cd/m2. Our study reveals the mechanism behind the oriented attachment and assembly of small, quantum-confined CsPbI3 NCs, and contributes to the development of pure-red electroluminescent LEDs.

Synchronous surface reconstruction and grain boundary healing toward efficient and stable inverted CsPbI3 perovskite solar cells

Cesium lead iodide (CsPbI3) perovskite has gained considerable attentions due to its unique photoelectric properties. However, numerous defects are inevitably existed on the surface and grain boundaries (GBs) of CsPbI3 resulting from the rapid crystallization and growth progress. Herein, different from the traditional ammonium salt treatment mechanism, we propose a facile strategy to synchronously achieve surface reconstruction and grain boundary healing by using 1,3-propylene diamine (PDA) post-treatment on CsPbI3 film. It is discovered that the PDA with suitable concentration can preferentially invade the defect sites of surface and GBs of CsPbI3 film, thereby break the soft perovskite structure in the shallow surface. With further low temperature annealing treatment, the broken CsPbI3 surface would undergo rapid secondary crystal growth to acquire smoother and blurred morphology with reduced GBs and pinholes, primarily derived from the strong interaction between the highly active amino groups of liquid PDA and Pb of perovskite. Meanwhile, the residual PDA molecules mainly anchor at the surface and GBs, and thus connect neighboring perovskite grains, coordinate uncoordinated sites to effectively passivate defects, and also resist the external invasions. Consequently, the inverted PDA-based CsPbI3 device yields a champion PCE of 20.02% with significantly improved long-term storage stability and operational stability.

Unveiling the Potential of Ambient Air Annealing for Highly Efficient Inorganic CsPbI3 Perovskite Solar Cells.

Here, we report a detailed surface analysis of dry- and ambient air-annealed CsPbI3 films and their subsequent modified interfaces in perovskite solar cells. We revealed that annealing in ambient air does not adversely affect the optoelectronic properties of the semiconducting film; instead, ambient air-annealed samples undergo a surface modification, causing an enhancement of band bending, as determined by hard X-ray photoelectron spectroscopy measurements. We observe interface charge carrier dynamics changes, improving the charge carrier extraction in CsPbI3 perovskite solar cells. Optical spectroscopic measurements show that trap state density is decreased due to ambient air annealing. As a result, air-annealed CsPbI3-based n-i-p structure devices achieved a 19.8% power conversion efficiency with a 1.23 V open circuit voltage.

Dimethylamine oxalate manipulating CsPbI3 perovskite film crystallization process for high efficiency carbon electrode based perovskite solar cells

Crystallization process determines the quality of perovskite films and the performances of resultant perovskite solar cells (PSCs). Dimethylamine oxalate has been proven as a multifunctional modulator, and is explored as an efficient additive in manipulating the crystallization process of CsPbI3 perovskite films. On one hand, oxalate serves as the precipitator that facilitates the nucleation process of intermediate. The larger size of intermediate is conductive to the larger size and smaller grain boundaries of resultant perovskite. On the other hand, in subsequent annealing process, the phase conversion and growth process of transient perovskite can be decelerated due to the strong interactions of oxalate with both dimethylamine cation (DMA+) and Pb2+. Due to the optimized crystallization kinetics, the morphology and quality of CsPbI3 perovskite films are comprehensively improved with lower defect concentrations, and charge recombination loss is effectively suppressed. Benefiting from the optimized crystal quality of perovskite films, the carbon electrode-based CsPbI3 PSCs exhibit a champion efficiency of 18.48%. This represents one of the highest levels among all hole transport layer-free inorganic perovskite solar cells.

Controlling Nucleation and Crystallization of CsPbI3 Perovskites for Efficient Inverted Solar Cells.

The unfavorable morphology and high crystallization temperature (Tc) of inorganic perovskites pose a significant challenge to their widespread application in photovoltaics. In this study, an effective approach is proposed to enhance the morphology of cesium lead triiodide (CsPbI3) while lowering its Tc. By introducing dimethylammonium acetate into the perovskite precursor solution, a rapid nucleation stage is facilitated, and significantly enhances the crystal growth of the intermediate phase at low annealing temperatures, followed by a slow crystal growth stage at higher annealing temperatures. This results in a uniform and dense morphology in CsPbI3 perovskite films with enhanced crystallinity, simultaneously reducing the Tc from 200 to 150°C. Applying this approach in positive-intrinsic-negative (p-i-n) inverted cells yields a high power conversion efficiency of 19.23%. Importantly, these cells exhibit significantly enhanced stability, even under stress at 85°C.

Proton-Prompted Ligand Exchange to Achieve High-Efficiency CsPbI3 Quantum Dot Light-Emitting Diodes

HighlightsA new proton-promoted in situ ligand exchange strategy based on CsPbI3 quantum dots.The ligand exchange strategy maintains the quantum confinement effect of quantum dots and significantly improves the stability and photophysical properties of CsPbI3 quantum dots.The performance of light-emitting diodes based on CsPbI3 quantum dots is significantly improved, the external quantum efficiency is increased from 18.63% to 24.45%, and the half-operational lifetime is increased by 70 times.

Design of highly selective and stable CsPbI3 perovskite catalyst for photocatalytic reduction of CO2 to C1 products

Finding efficient photocatalytic carbon dioxide reduction catalysts is one of the core issues in addressing global climate change. Herein, the pristine CsPbI3 perovskite and doped CsPbI3 perovskite were evaluated in carbon dioxide reduction reaction (CO2RR) to C1 products by using density functional theory. Free energy testing and electronic structure analysis methods have shown that doped CsPbI3 exhibits more effective catalytic performance, higher selectivity, and stability than undoped CsPbI3. Additionally, it is discovered that CsPbI3 (100) and (110) crystal surfaces have varied product selectivity. The photo-catalytic effectiveness is increased by the narrower band gap of Bi and Sn doped CsPbI3, which broadens the absorption spectrum of visible light and makes electron transport easier. The calculation results indicate that Bi doped CsPbI3 (100) and CsPbI3 (110) crystal faces exhibit good selectivity towards CH4, with free energy barriers as low as 0.55 eV and 0.58 eV, respectively. Sn doped CsPbI3 (100) and CsPbI3 (110) crystal planes exhibit good selectivity for HCOOH and CH3OH, respectively. The results indicate that the Bi and Sn doped CsPbI3 perovskite catalyst can further improve the CO2 photocatalytic activity and high selectivity for C1 products, making it a suitable substrate material for high-performance CO2RR.

First-principles calculations for heterostructure studies Involving CsPbI3 perovskite and IV-VI semiconductors

The PbX(X = S, Se, Te)/CsPbI3 heterostructure, formed by lead chalcogenides and halide perovskite CsPbI3, holds promise for optoelectronic devices. Utilizing first-principles calculations with VASP software, this study investigates its structural, electronic, and optical properties. With confirmed appropriate lattice mismatch rates (4.6%, 2.4%, 3.8%) and similar octahedral frameworks, constructing the PbX/CsPbI3 heterostructure is feasible. Calculations of electronic properties reveal mechanisms to improve optical performance. The type-I band alignment at the PbX/CsPbI3 interface(−5.27 eV < PbX < −3.73 eV, −5.34 eV < CsPbI3 < −3.57 eV) reduces electron and hole recombination losses, enhancing energy transfer efficiency. This arrangement facilitates electron and hole transfer from CsPbI3 to PbX, supported by charge density differences. Among the three heterostructures, PbSe/CsPbI3 demonstrates superior charge transfer capabilities, with more pronounced electron clouds. The PbX/CsPbI3 heterostructure extends CsPbI3’s light absorption into the near-infrared via PbX influence. Spectral comparison reveals PbTe/CsPbI3 > PbSe/CsPbI3 > PbS/CsPbI3, with PbSe/CsPbI3 excelling in stability, charge density transfer, and optical properties. Furthermore, under the premise of ensuring stability, different optical absorption characteristics can be achieved by adjusting the composition of Se atoms in PbSe/CsPbI3. This work provides a theoretical basis for the physical mechanisms behind enhancing the performance of PbX/CsPbI3 heterostructures as visible-to-near-infrared optoelectronic materials. It offers a promising avenue for the design of high-performance visible-to-near-infrared optoelectronic materials.

All inorganic CsPbI3 perovskite solar cells with reduced mobile ion concentration and film stress

All inorganic CsPbI3 perovskite solar cells with reduced mobile ion concentration and film stress

Layer-dependent spin texture and origins of Rashba splitting quenching in the 2D CsPbI3 perovskite.

The spin-orbit coupling in inorganic perovskite materials containing heavy elements causes interesting electronic characteristics such as Rashba and Dresselhaus effects. Several studies have reported significant band splitting in the presence of asymmetry, while the impacts of the external field strength, surface termination on the electronic structure still need to be resolved. In the current study, a systematic relation between the external parameters and the band splitting in CsPbI3 slabs is clarified through first-principles calculations. Here, we examine the band splitting and spin patterns of CsPbI3 slabs exposed to an external electric field ranging from zero to hundreds of kV cm-1. Our results indicate apparent non-linear behavior of the Rashba coefficient along with a turning point for the band splitting for a definite external field. Here, the origin of this quench in the band splitting is explained in terms of spatial localization of the wave functions and clear change in their center of charge going from low to high electric fields. The findings not only explain the origin of quenching band splitting but also reveal the external field's significance in the spin texture and recombination rate of 2D perovskites. The current research outcome paves the way for atomic scale engineering of perovskite materials for a wide range of applications.

Efficient open-air synthesis of Mg2+-doped CsPbI3 nanocrystals for high-performance red LEDs.

Inorganic CsPbI3 perovskite nanocrystals (NCs) exhibit remarkable optoelectronic properties for illumination. However, their poor stability has hindered the development of light-emitting diodes (LEDs) based on these materials. In this study, we propose a facile method to synthesize Mg2+-doped CsPbI3 NCs with enhanced stability and high photoluminescence (PL) intensity under ambient air conditions. Theoretical calculations confirm that doped NCs possess stronger formation energy compared to undoped NCs. The undoped CsPbI3 NCs emit red light at approximately 653 nm. We optimize the doping ratio to 1/30, which significantly enhances the photoluminescence of single-particle CsPbI3 NCs. Subsequently, we fabricate a red LED by combining the CsPbI3 NCs with a blue chip. The resulting LED, based on the doped CsPbI3 NCs, exhibits excellent performance with a high luminance of 4902.22 cd m-2 and stable color coordinates of (0.7, 0.27). This work not only presents a simple process for synthesizing perovskite NCs but also provides a design strategy for developing novel red LEDs for various applications.

Temperature dependence of the electron and hole Landé g-factors in CsPbI3 nanocrystals embedded in a glass matrix.

The coherent spin dynamics of electrons and holes in CsPbI3 perovskite nanocrystals in a glass matrix are studied by the time-resolved Faraday ellipticity technique in magnetic fields up to 430 mT across a temperature range from 6 K to 120 K. The Landé g-factors and spin dephasing times are evaluated from the observed Larmor precession of electron and hole spins. The nanocrystal size in the three studied samples varies from about 8 to 16 nm, resulting in exciton transition varying from 1.69 to 1.78 eV at a temperature of 6 K, allowing us to study the corresponding energy dependence of the g-factors. The electron g-factor decreases with increasing confinement energy in the NCs as a result of NC size reduction, and also with increasing temperature. The hole g-factor shows the opposite trend. Model analysis shows that the variation of g-factors with NC size arises from the transition energy dependence of the g-factors, which becomes strongly renormalized by temperature.

Surface engineering based on ionic liquids for efficient and stable CsPbI3 perovskite solar cells

TBAPF6 ionic liquid is employed to treat CsPbI3 perovskite films, and thereby low-dimensional [TBA]PbI3 forms on the surface and the surface defects are passivated, which contribute to longer moisture stability and higher PCE.

Cl alloying improves thermal stability and increases luminescence in iodine-rich inorganic perovskites.

The inorganic perovskite CsPbI3 shows promising photophysical properties for a range of potential optoelectronic applications but is metastable at room temperature. To address this, Br can be alloyed into the X-site to create compositions such as CsPbI2Br that are stable at room temperature but have bandgaps >1.9 eV - severely limiting solar applications. Herein, in an effort to achieve phase stable films with bandgaps <1.85 eV, we investigate alloying chlorine into iodine-rich triple-halide CsPb(I0.8Br0.2-x Cl x )3 with 0 < x < 0.1. We show that partial substitution of iodine with bromine and chlorine provides a path to maintain broadband terrestrial absorption while improving upon the perovskite phase stability due to chlorine's smaller size and larger ionization potential than bromine. At moderate Cl loading up to ≈5%, X-ray diffraction reveals an increasingly smaller orthorhombic unit cell, suggesting chlorine incorporation into the lattice. Most notably, this Cl incorporation is accompanied by a significant enhancement over Cl-free controls in the duration of black-phase stability of up to 7× at elevated temperatures. Additionally, we observe up to 5× increased steady state photoluminescence intensity (PL), along with a small blue-shift. In contrast, at high loading (≈10%), Cl accumulates in a second phase that is visible at grain boundaries via synchrotron fluorescence microscopy and negatively impacts the perovskite phase stability. Thus, replacing small fractions of bromine for chlorine in the iodine-rich inorganic perovskite lattice results in distinct improvement thermal stability and optoelectronic quality while minimally impacting the bandgap.