All-inorganic Halide Perovskite Research Articles

A Prediction of All-Inorganic Lead-Free Halide Perovskites for Photovoltaic Application: Rb3Mo2Br9 and Rb3Mo2Cl9.

Lead-based organic-inorganic hybrid perovskites show promise as photovoltaic materials due to their high energy conversion efficiencies. However, concerns regarding lead toxicity and the poor environmental and operational stability of the organic cationic group have limited their widespread application. To address these challenges, the design of all-inorganic lead-free halide perovskites offers potential solutions for photovoltaic applications. Here, two layered perovskite derivatives, Rb3Mo2Cl9 and Rb3Mo2Br9, are explored, and their electronic, structural, and photovoltaic properties are analyzed using advanced theoretical calculations. Rb3Mo2Br9 exhibits a suitable direct bandgap of 1.60eV, making it a promising candidate for use as a light absorber in low-cost, high-efficiency solar cells. On the other hand, Rb3Mo2Cl9 demonstrates a wide direct bandgap exceeding 1.70eV, positioning it as a viable option for use as a top cell in tandem photovoltaic systems alongside silicon. Both materials display ideal optical properties in the visible light region and hold promise as excellent inorganic lead-free perovskite alternatives.

3D/2D lead-free halide perovskite CsSnBr3/MoX (X = Se2, SSe, S2) heterostructures for high-efficiency solar cell: Interface engineering strategies and transition of band alignments

The rapid progress in the fabrication of van der Waals (vdW) heterostructures based on perovskite has significantly advanced the fields of optoelectronics and solar cells by integrating the exceptional properties of different materials. Overall, perovskite-based vdW heterostructures display unique functional characteristics due to their varied type-I, type-II, and type-III energy band configurations. However, it is a challenge to achieve flexible regulation of band edge alignment in heterostructures for different applications. Using first-principles density functional theory, we systematically study the electronic and optical properties of vdW heterostructures system consisting of three-dimensional lead-free all-inorganic halide perovskite materials CsSnBr3 and MoX (X = Se2, SSe, S2). The research results show that in the CsSnBr3/MoX vdW heterostructures, type I, II, and III transitions of band arrangements are achieved through interface engineering strategy to adapt to different applications. Meanwhile, by calculating the light absorption efficiency of the constructed 3D/2D vdW heterostructures, it was found that the interface effect enhances the optical absorption range and intensity of the perovskite-based heterostructures. The theoretically estimated power conversion efficiency (PCE) of the heterostructure thin-film solar cell reaches 21.4 %. The results of our research indicate that the controllable band alignment of CsSnBr3/MoX heterostructures has significant potential for future applications in optoelectronics.

Effects of Ferroelastic Domain Walls on the Macroscopic Transport and Photoluminescent Properties of Bulk CsPbBr3 Single Crystals.

The all-inorganic halide perovskite CsPbBr3 has emerged as an excellent class of semiconductive and optoelectronic materials, in which its excellent properties are strongly related to the dynamics of its microstructures, i.e., ferroelastic domain walls. Here, the influence of ferroelastic domain walls on the macroscopic charge transport and photoluminescent properties in bulk single-crystal CsPbBr3 is experimentally and intrinsically studied across wide temperature intervals. The larger area of the same domain orientation, along with denser and thinner domain walls in a bulk CsPbBr3 single crystal, is formed through the Pnma↔P4/mbm↔Pm3̅m phase transitions. Remarkable motion of the domain walls near the P4/mbm↔Pm3̅m transition point is observed using in situ polarized optical microscopy. We initially observed a sharp decrease in resistivity after inducing larger areas with long-range order and denser, thinner domain walls in the temperature range from 273 to 343 K upon heating. In addition, the ferroelastic domain walls modulate exciton-phonon interactions and enhance radiative recombination in the CsPbBr3 single crystal, which correlates with the decrease in resistivity. These results will motivate strategies to design high-performance semiconductive and optoelectronic materials or devices by inducing specific ferroelastic domain walls in metal halide perovskites.

Tb3+-doped a zero-dimensional all-inorganic metal halide perovskite scintillator Cs2ScCl5·H2O for X-ray imaging

All-inorganic zero-dimensional (0D) metal halide perovskite materials have been widely studied in solid-state lighting due to their unique optical properties. However, there are few researchs on their potential applications in X-ray imaging. Herein, we synthesized an all-inorganic 0D metal halide perovskite scintillator, Cs2ScCl5·H2O:Tb3+, was prepared by using a hydrothermal method. Upon 240 nm excitation, the emission spectrum of Cs2ScCl5·H2O:Tb3+ is primarily composed of characteristic emissions from Tb3+, with the strongest emission peak at 548 nm. Additionally, under X-ray excitation, it exhibits blue light showing an intense emission band centered at 425 nm due to self-trapped (STE) emission, and a rather weaker green emission caused by energy transfer from STE emission to Tb3+ ions. Based on this, a flexible film prepared by using the as-obtained scintillator Cs2ScCl5·H2O:Tb3+ demonstrates real-time X-ray imaging with a resolution of 9.5 lp mm−1. These results suggest the potential application prospect of Cs2ScCl5·H2O:Tb3+ in X-ray detection and imaging.

Switchable Bulk Photovoltaic Effect in Intrinsically Ferroelectric 3D All-Inorganic CsPbBr3 Perovskite Nanocrystals.

Ferroelectric all-inorganic halide perovskite nanocrystals with both spontaneous polarization and visible light absorption are promising candidates for designing ferroelectric photovoltaic applications. It remains a challenge to realize ferroelectric photovoltaic devices with all-inorganic halide perovskites that can be operated in the absence of an external electric field. Here we report that a popular all-inorganic halide perovskite nanocrystal, CsPbBr3, exhibits a ferroelectricity-driven photovoltaic effect under visible light in the absence of an external electric field. Pristine CsPbBr3 nanocrystals exhibit intrinsic ferroelectric key properties with a notable saturated polarization of ∼0.15 μC/cm2 and a high Curie temperature of 462 K, driven by the stereochemical activity of the Pb(II) lone pair. Furthermore, application of an external electric field allows the photovoltaic effect to be enhanced and the spontaneous polarization to be switched with the direction of the electric field. CsPbBr3 nanocrystals exhibit a robust fatigue performance and a prolonged photoresponse under continuous illumination in the absence of an external electric field. These findings establish all-inorganic halide perovskite nanocrystals as potential candidates for designing photoferroelectric devices by coupling optical functionalities and ferroelectric responses.

Electronic and optical properties of all-inorganic TiX3 transition metal halide nanowires

Transition metal halides are promising for use in photovoltaics and optoelectronics. This research systematically investigated the composition-dependent electronic and optical properties of all-inorganic TiX3 (X = Cl/Br/I) transition metal halide nanowires using first-principles density functional theory (DFT) and time-dependent DFT calculations. The findings emphasize the significant impact of the specific halide type on the electronic and optical characteristics of TiX3 nanowires. Particularly, the type of halide significantly influences the electronic states near the Fermi level and the infrared photoabsorption properties. An important discovery is the exceptional photoabsorption strength observed in the TiCl3 nanowire, reaching an impressive value of 26000 cm−1. The study also offers insights into exciton generation, aided by Transition Contribution Maps. Apart from its theoretical implications, we expect that the insights gained from this research will contribute to the advancement of active optical devices utilizing all-inorganic halide perovskites.

Ultralow Thermal Conductivity in Vacancy-Ordered Halide Perovskite Cs3Bi2Br9 with Strong Anharmonicity and Wave-Like Tunneling of Low-Energy Phonons.

Halide perovskites are of great interest due to their exceptional optical and optoelectronic properties. However, thermal conductivity of many halide perovskites remains unexplored. In this study, an ultralow lattice thermal conductivity κL (0.24W m-1 K-1 at 300 K) is reported and its weak temperature dependence (≈T-0.27) in an all-inorganic vacancy-ordered halide perovskite, Cs3Bi2Br9. The intrinsically ultralow κL can be attributed to the soft low-lying phonon modes with strong anharmonicity, which have been revealed by combining experimental heat capacity and Raman spectroscopy measurements, and first-principles calculations. It is shown that the highly anharmonic phonons originate from the Bi 6s2 lone pair expression with antibonding states of Bi 6s and Br 4p orbitals driven by the dynamic BiBr6 octahedral distortion. Theoretical calculations reveal that these low-energy phonons are mostly contributed by large Br motions induced dynamic distortion of BiBr6 octahedra and large Cs rattling motions, verified by the synchrotron X-ray pair distribution function analysis. In addition, the weak temperature dependence of κL can be traced to the wave-like tunneling of phonons, induced by the low-lying phonon modes. This work reveals the strong anharmonicity and wave-like tunneling of low-energy phonons for designing efficient vacancy-ordered halide perovskites with intrinsically low κL.

Nanoscale Insights into the Thermal Phase Behavior of All-Inorganic Halide Perovskites by In Situ 4D STEM

Nanoscale Insights into the Thermal Phase Behavior of All-Inorganic Halide Perovskites by In Situ 4D STEM

High-performance transistors based on monolayer all-inorganic two-dimensional halide perovskite Cs2PbI2Cl2 and its optoelectronic application

The two-dimensional (2D) Ruddlesden−Popper phase all-inorganic halide perovskite Cs2PbI2Cl2 has attracted tremendous attention because of its high carrier mobility, strong light-absorbing ability, and excellent environmental stability, possessing enormous potential for use as a high-performance optoelectronic device. Here, we present two transistor devices based on monolayer (ML) Cs2PbI2Cl2 and reveal their performance and current transport mechanisms through ab initio quantum transport calculations. The n-type 10 nm metal-oxide-semiconductor field-effect transistor shows a high on-state current Ion of 3160 μA/μm, and excellent performance regarding subthreshold swing, intrinsic delay time (τ), and power consumption, which completely match the International Roadmap for Device and Systems (2021 version) targets for high-performance devices and low-power devices in 2028. Moreover, phototransistors based on monolayer Cs2PbI2Cl2 also display a strong response to UV light, with a light-to-dark current ratio reaching a maximum of 104. Meanwhile, a high specific detectivity of 2.45 × 1011 Jones is obtained. The results of our study suggest that ML Cs2PbI2Cl2 is a promising candidate for high-performance transistors.

Growth and photoelectrical properties of CsPbBr3-xIx (0 ≤ x < 1) single crystals

The all-inorganic halide perovskite CsPbBr3 possesses excellent optoelectronic characteristics and has a high opportunity for application in a variety of photoelectric devices. CsPbBr3 is known for its relatively low ionic migration and higher resistivity compared to other perovskite compositions. In addition, the performance in X-ray detectors can be further improved by the addition of I- dopants. The addition of I- dopants has been shown to be an effective way to improve these properties. The vertical Bridgman method was used to grown I--doped CsPbBr3 crystals. The crystal structure, optical characteristics, electrical characteristics, and X-ray detection capabilities of CsPbBr3-xIx (0 ≤ x < 1) single crystals were all systematically investigated. The results indicate that I--doping can adjust the band gap, increase the resistivity and carrier mobility, and reduce the trap density and dark current, providing the possible application of halide perovskite in various optoelectronic devices.

On-Wire Design of Axial Periodic Halide Perovskite Superlattices for High-Performance Photodetection.

Precise synthesis of all-inorganic lead halide perovskite nanowire heterostructures and superlattices with designable modulation of chemical compositions is essential for tailoring their optoelectronic properties. Nevertheless, controllable synthesis of perovskite nanostructure heterostructures remains challenging and underexplored to date. Here, we report a rational strategy for wafer-scale synthesis of one-dimensional periodic CsPbCl3/CsPbI3 superlattices. We show that the highly parallel array of halide perovskite nanowires can be prepared roughly as horizontally guided growth on an M-plane sapphire. A periodic patterning of the sapphire substrate enables position-selective ion exchange to obtain highly periodic CsPbCl3/CsPbI3 nanowire superlattices. This patterning is further confirmed by micro-photoluminescence investigations, which show that two separate band-edge emission peaks appear at the interface of a CsPbCl3/CsPbI3 heterojunction. Additionally, compared with the pure CsPbCl3 nanowires, photodetectors fabricated using these periodic heterostructure nanowires exhibit superior photoelectric performance, namely, high ION/IOFF ratio (104), higher responsivity (49 A/W), and higher detectivity (1.51 × 1013 Jones). Moreover, a spatially resolved visible image sensor based on periodic nanowire superlattices is demonstrated with good imaging capability, suggesting promising application prospects in future photoelectronic imaging systems. All these results based on the periodic CsPbCl3/CsPbI3 nanowire superlattices provides an attractive material platform for integrated perovskite devices and circuits.

Enhanced ambient-stability and charge transport property of the CsPbBr3@Polyaniline

Although all-inorganic lead halide perovskites (CsPbX3 (X = Cl, Br, I)) have received widespread attention due to excellent optoelectronic properties, their low carrier mobility and poor stability have limited their application in photodetection. In this study, to alleviate these problems, CsPbBr3@Polyaniline composite is fabricated by passivating CsPbBr3 quantum dots (QDs) into a CSA-doped polyaniline conducting polymer. Notably, polyaniline is employed as a protective layer to block the structure damage of CsPbBr3 QDs against water, light and heat. The contact between polyaniline and CsPbBr3 QDs forms a type II heterojunction for charge transfer, which greatly reduces the recombination rate of charge carriers compared to pristine CsPbBr3 QDs. Benefiting from the high stability and enhanced charge mobility, CsPbBr3@Polyaniline-based photodetector achieves improved photocurrent signal and optical response time. The results demonstrate that the surface passivation could resolve the crucial stability problem and simultaneously facilitate the superior performance of perovskite optoelectronic devices.

Size Dependence of Ultrafast Electron Transfer from Didodecyl Dimethylammonium Bromide-Modified CsPbBr3 Nanocrystals to Electron Acceptors.

Charge transfer efficiencies in all-inorganic lead halide perovskite nanocrystals (NCs) are crucial for applications in photovoltaics and photocatalysis. Herein, CsPbBr3 NCs with different sizes are synthesized by varying the ligand contents of didodecyl dimethylammonium bromide at room temperature. Adding benzoquinone (BQ) molecules leads to a decrease in the PL intensities and PL decay times in NCs. The electron transfer (ET) efficiency (ηET) increases with NC size in complexes of CsPbBr3 NCs and BQ molecules (NC-BQ complexes), when the same concentration of BQ is maintained, as investigated by transient photobleaching and photoluminescence spectroscopies. Controlling the same number of attached BQ acceptor molecules per NC induces the same ηET in NC-BQ complexes even though with different NC sizes. Our findings provide new insights into ultrafast charge transfer behaviors in perovskite NCs, which is important for designing efficient light energy conversion devices.

Synthesis and performance optimization of CsPbBr3/CdS core/shell lead halide perovskite nanocrystals by an ion exchange method

All-inorganic lead halide perovskite nanocrystals (NCs) have excellent optoelectronic properties and promising applications. Improving the stability of inorganic halide NCs and optimizing their photoluminescence quantum yields (PLQY) has become an urgent task. Constructing core-shell structures is an effective method to improve the environmental stability and PLQY, however, realizing core-shell structured perovskite NCs with good dispersion and multiple perovskites encapsulated within the shell material remains challenging. In this work, CdS shells were grown on the surface of CsPbBr3 NCs by ion-exchange method utilizing perovskite NCs with their ionic properties, and the effectiveness of the surface shell protection is reflected in its enhancement of long-term storage stability, storage stability in water, and thermal stability of NCs. In addition, the PLQY and exciton binding energies of CsPbBr3/CdS NCs are increased. Finally, the NCs were packaged into green emitting LED devices and performed high stability. The results will facilitate the further commercialization of all-inorganic lead halide perovskite materials for optoelectronic devices.

Full-color, time-valve controllable and Janus-type long-persistent luminescence from all-inorganic halide perovskites

Long persistent luminescence (LPL) has gained considerable attention for the applications in decoration, emergency signage, information encryption and biomedicine. However, recently developed LPL materials – encompassing inorganics, organics and inorganic-organic hybrids – often display monochromatic afterglow with limited functionality. Furthermore, triplet exciton-based phosphors are prone to thermal quenching, significantly restricting their high emission efficiency. Here, we show a straightforward wet-chemistry approach for fabricating multimode LPL materials by introducing both anion (Br−) and cation (Sn2+) doping into hexagonal CsCdCl3 all-inorganic perovskites. This process involves establishing new trapping centers from [CdCl6-nBrn]4− and/or [Sn2-nCdnCl9]5− linker units, disrupting the local symmetry in the host framework. These halide perovskites demonstrate afterglow duration time ( > 2,000 s), nearly full-color coverage, high photoluminescence quantum yield ( ~ 84.47%), and the anti-thermal quenching temperature up to 377 K. Particularly, CsCdCl3:x%Br display temperature-dependent LPL and time-valve controllable time-dependent luminescence, while CsCdCl3:x%Sn exhibit forward and reverse excitation-dependent Janus-type luminescence. Combining both experimental and computational studies, this finding not only introduces a local-symmetry breaking strategy for simultaneously enhancing afterglow lifetime and efficiency, but also provides new insights into the multimode LPL materials with dynamic tunability for applications in luminescence, photonics, high-security anti-counterfeiting and information storage.

CsPbBrxCl3-x Solid Solutions: Understanding the Relationship between Lattice Expansion and Optical Properties.

All-inorganic halide perovskite semiconductors have received extensive attention due to their excellent photoelectronic conversion efficiency. Prior studies have reported on compounds CsPbBr3 and CsPbCl3. However, the transition phases between them have not been systematically studied. Here, a series of large-size single crystals of CsPbBrxCl3-x (x = 0-3) were successfully grown by the Bridgman method, which proves that the Br and Cl atoms can be miscible in any proportion in the solid solution system, and the change of lattice parameters conforms to Vegard's law. Also, the bandgap and light emission were studied. It is found that the band gap (2.90-2.29 eV) and photoluminescence characteristics (from blue light to green light) can be effectively tuned by adjusting the content of the Br atom. These results provide valuable guidance for the development and optimization of photoelectronic semiconductors that can meet different practical demands.

Air-Processed All-Inorganic Halide Perovskites Integrated Photorechargeable Supercapacitors.

Due to their easy integration for self-powered operation, integrated energy harvesting and storage could be the game changer in smart, flexible, and portable electronic devices. Three-electrode integration is the most promising approach among all possible configurations because it is less complex and compatible with most techniques. Although the photoconversion efficiency has increased above 20% due to the integration of high-performance perovskite solar cells, the electrochemical storage efficiency (efficacy of the integration) is much below 80% due to a significant potential drop and impedance mismatch. In this context, we introduced perovskite-based solid-state thin film supercapacitors integrated with stable, air-processed perovskite solar cells for an uninterrupted power supply. Our measurement shows that the best performance can be achieved by optimizing several parameters, including series-connected solar cells, light intensity, and photovoltaic active area. The critical challenge with these integrated systems is to maintain a uniform charging current of the supercapacitors throughout the charging cycle while minimizing self-discharging. We achieved an electrochemical storage efficiency of ∼87% at an overpotential of 0.8 V. The overpotential can be as low as 2 mV. We fabricated fully solution-processed series-connected solar cells to integrate with stacked supercapacitors to improve the operating voltage beyond 2.1 V. The photocharging and dark discharging of these integrated devices have been tested over 200 cycles, and a negligible drop in efficiency has been observed. Our detailed energy conversion and storage analysis in these systems unveils the mechanism and losses due to three-terminal integration.

Doping Up the Light: A Review of A/B-Site Doping in Metal Halide Perovskite Nanocrystals for Next-Generation LEDs.

All-inorganic metal halide perovskite nanocrystals (PeNCs) show great potential for the next generation of perovskite light-emitting diodes (PeLEDs). However, trap-assisted recombination negatively impacts the optoelectronic properties of PeNCs and prevents their widespread adoption for commercial exploitation. To mitigate trap-assisted recombination and further enhance the external quantum efficiency of PeLEDs, A/B-site doping has been widely investigated to tune the bandgap of PeNCs. The bandgap of PeNCs is adjustable within a small range (no more than 0.1 eV) by A-site cation doping, resulting in changes in the bond length of Pb-X and the angle of [PbX6]4. Nevertheless, B-site doping of PeNCs has a more significant impact on the bandgap level through modification of surface defect states. In this perspective, we delve into the synthesis of PeNCs with A/B-site doping and their impacts on the structural and optoelectronic properties, as well as their impacts on the performance of subsequent PeLEDs. Furthermore, we explore the A-site and B-site doping mechanisms and the impact of device architecture on doped PeNCs to maximize the performance and stability of PeLEDs. This work presents a comprehensive overview of the studies on A-site and B-site doping in PeNCs and approaches to unlock their full potential in the next generation of LEDs.

Enhanced Efficiency and Stability of Sky Blue Perovskite Light-Emitting Diodes via Introducing Lead Acetate.

All-inorganic metal halide perovskite is promising for highly efficient and thermally stable perovskite light-emitting diodes (PeLEDs). However, there is still great room for improvement in the film quality, including low coverage and high trap density, which play a vital role in achieving high-efficiency PeLEDs. In this work, lead acetate (Pb(Ac)2) was introduced into the perovskite precursor solution as an additive. Experimental results show that perovskite films deposited from a one-step anti-solvent free solution process with increased surface coverage and reduced trap density were obtained, leading to enhanced photoluminescence (PL) intensity. More than that, the valence band maximum (VBM) of perovskite films was reduced, bringing about a better energy level matching the work function of the hole-injection layer (HIL) poly (3,4-ethylenedioxythiophene)-poly (styrene sulfonate) (PEDOT: PSS), which is facilitated for the hole injection, leading to a decrease in the turn-on voltage (Vth) of PeLEDs from 3.4 V for the control device to 2.6 V. Finally, the external quantum efficiency (EQE) of the sky blue PeLEDs (at 484 nm) increased from 0.09% to 0.66%. The principles of Pb(Ac)2 were thoroughly investigated by using X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). This work provides a simple and effective strategy for improving the morphology of perovskite and therefore the performance of PeLEDs.

Theoretical study on photoelectric properties of ferroelectric photovoltaic perovskite CsGeBr3 based on first-principle calculations

Ferroelectric photovoltaic materials have attracted great attention because of their unique photoelectric conversion mechanism, high photo-generated voltage, and adjustable polarization intensity. Traditional ferroelectric oxide perovskites such as BaTiO3, BiFeO3, and Pb(ZrTi)O3 have attracted much attention but they are not suitable as light absorbing layers in solar cells, due to the large optical bandgap, low light absorption rate, and small photogenerated current. Therefore, it is necessary to seek prominent materials with both ferroelectric and suitable band gaps. Recently, the evidence of ferroelectricity in the typical three-dimensional all-inorganic halide perovskites CsGeX3, with band gaps of 1.6 eV to 2.3 eV has been confirmed. However, the spontaneous polarization of ferroelectric perovskite CsGeX3 is ∼10 to 20 μc cm−2 which is weaker than that of ABO3 (∼26 to 75 μc cm−2). Strain engineering has a significant influence on the properties of semiconductor materials by controlling the lattice scaling and the internal atomic spacing. Hence, in this work, strain engineering is introduced to adjust the ferroelectric polarization and the photoelectric properties of ferroelectric perovskite CsGeBr3. The calculated results show that when the applied compressive strain increases from 0% to −4%, the spontaneous polarization of ferroelectric perovskite CsGeBr3 increases from 14.23 μc cm−2 to 51.61 μc cm−2, and the band gap reduces from 2.3631 eV to 1.5310 eV. The effective mass of electrons and holes gradually reduces, exciton binding energies decrease from 48 meV to 5 meV, and the optical absorption coefficient is strongly enhanced from 3 × 105 cm−1 to 5 × 105 cm−1 in the visible range. Besides, the power conversion efficiency(PCE) of CsGeBr3 is significantly increased from 16.95% to 26.77%. Therefore, the results indicate that the application of compressive strain can increase the ferroelectric polarization and enhance the original photovoltaic performance of ferroelectric perovskite CsGeBr3. Our theoretical calculations can provide useful insights and beneficial guidance into experimental studies of ferroelectric perovskites in photoelectric applications.