Zero-dimensional Perovskite Research Articles

Efficient zero-dimensional near-infrared perovskite synthesis using an ultrasound-assisted strategy and its application in information encryption

Efficient zero-dimensional near-infrared perovskite synthesis using an ultrasound-assisted strategy and its application in information encryption

Zero-Dimensional Lead-Free Perovskite Single Crystals for the Sensitive Detection of Visible Light and X-Rays.

The excellent performance and facile fabrication process of perovskite semiconductor materials make them highly promising candidates in the field of optoelectronic devices. Whether for visible light or X-rays, detectors with low detection limits can better identify weak light signals, significantly reducing the intensity of the received light source during device operation. In particular, for X-ray detectors, reducing X-ray dosage can greatly enhance the safety of X-ray imaging technology. This work develops detectors with low detection limit based on zero-dimensional (0D) MA3Bi2I9 single crystals. The anisotropy of MA3Bi2I9 and its influence on the detector's performance were investigated in detail. Detectors perpendicular to the (001) crystal plane have better weak light detection capability and require significantly less light intensity compared to devices parallel to the (001) crystal plane. X-ray detector with a limit of detection (LoD) of 0.68 nGyair s-1 and sensitivity of 5072 μC Gyair -1 cm-2 was obtained. The present study offers comprehensive insights into the operational mechanism of layered perovskites, which can provide valuable guidelines for future designs and fabrications of highly sensitive photo and X-ray detectors.

(Invited) Low-Dimensional Hybrid Perovskite Materials: Discoveries and Properties

As an emerging class of light-responsive semiconductors, hybrid perovskites seamlessly marry the characteristics of organic and inorganic materials, offering a new fertile playground to explore light-matter interaction and advance optoelectronic technologies. In comparison to three-dimensional perovskites, low-dimensional counterparts have been less investigated, but they offer a vast chemical and functional space to navigate. Here, I will discuss our recent effort to use high-throughput calculations to generate large datasets containing structural and property information for 2D hybrid perovskite materials, which is further used to train and validate machine learning models to establish accurate structure-property relationships. The result helps shed light on the impact of various conjugated organic spacers on the electronic structures of 2D Dion-Jacobson perovskites. In addition, I will talk about the exceptional physical properties of a series of zero-dimensional copper-halide perovskites demonstrating efficient self-trapped exciton and single-mode lasing.

The origin of broadband blue emission in zero-dimensional organic lead iodine perovskites: A first-principles study.

Broadband blue emission in zero-dimensional perovskites has received considerable attention, which is very important for the realization of stable blue-light emitters; however, the underlying formation mechanism remains unclear. Based on first-principles calculations, we have systematically studied the self-trapped excitons (STEs) behavior and luminescence properties in 0D-(DMA)4PbI6 perovskite. Our calculations show that there is a significant difference between the intrinsic STE luminescence mechanism (∼2.51eV) and experimental observations (∼2.70eV). In contrast, we found that the iodine vacancy (VI) is energetically accessible and exhibits a shallow charge transition level at ∼2.69eV (0/+1) above the valence band maximum, which provides the initial local well for the STEs formation. Moreover, the low electronic dimension synergistic Jahn-Teller distortion facilitates the formation of extrinsic excitons self-trapping. Further excited state electronic structure analysis and configuration coordinate diagram calculations confirmed that the broadband blue emission in 0D-(DMA)4PbI6 is the origin of VI-induced extrinsic STEs instead of intrinsic STEs. Therefore, our simulation results rationalize the experimental phenomena and provide important insights into the formation mechanism of STEs in low-dimensional perovskite systems.

Improving photoluminescence properties of lead-free Cs4SnBr6 zero-dimensional perovskite via Mn2+/Sb3+ Co-doping

Zero-dimensional tin-based halide perovskites have emerged as promising materials for optoelectronic applications owing to their outstanding optical properties. However, improving their PL efficiency and stability remains a significant challenge. Here, we demonstrate a novel codoping strategy by introducing Mn2+/Sb3+ ions to enhance both the PL intensity and thermal stability of Cs4SnBr6 perovskites. Our experiments reveal that Mn2+/Sb3+ incorporation increases light emission from self-trapped excitons (STEs) in Cs4SnBr6, achieving a PL quantum yield of approximately 67.7 %. Additionally, the doped samples show remarkable thermal stability. Detailed analyses, including X-ray diffraction, energy-dispersive spectroscopy, time-resolved PL, and temperature-dependent PL, suggest that the improved emission is driven by Mn2+/Sb3+-induced distortion of the [SnBr6]4- octahedra, which strengthens electron-phonon coupling and increases STE binding energy.

Perovskite Light-Emitting Diodes with Quantum Wires and Nanorods.

Perovskite materials, celebrated for their exceptional optoelectronic properties, have seen extensive application in the field of light-emitting diodes (LEDs), where research is as abundant as the proverbial "carloads of books." In this review, the research of perovskite materials is delved into from a dimensional perspective, with a focus on the exemplary performance of low-dimensional perovskite materials in LEDs. This discussion predominantly revolves around perovskite quantum wires and perovskite nanorods. Perovskite quantum wires are versatile in their growth, compatible with both solution-based and vapor-phase growth, and can be deposited over large areas-even on spherical substrates-to achieve commendable electroluminescence (EL). Perovskite nanorods, on the other hand, boast a suite of superior characteristics, such as polarization properties and tunability of the transition dipole moment, endowing them with the great potential to enhance light extraction efficiency. Furthermore, zero-dimensional (0D) perovskite materials like nanocrystals (NCs) are also the subject of widespread research and application. This review reflects on and synthesizes the unique qualities of the aforementioned materials while exploring their vital roles in the development of high-efficiency perovskite LEDs (PeLEDs).

From nonemission to nearly unity quantum yield: Breaking parity-forbidden transitions in rubidium indium chloride through 5s2 lone pair Sb-doping

Halide perovskites doped with ns2 metal ions have stimulated widespread research owing to their efficient and stable self-trapped emissions. Here we observe the strictly forbidden transition 3P0→1S0 is broken and afford nearly unity triplet orange self-trapped excitons (O-STEs) emission, through 5 s2 lone pair Sb cation doping in host Rb2InCl5·H2O single crystal. In particular, additional triplet blue self-trapped excitons (B-STEs) emission centered at 475 nm, stemming from partially allowed 3P1→1S0, is also observed. Spectroscopic characterization along with literature analysis demonstrates that the behavior of forbidden transition breaking originates from the mixing of 3P0 and 3P1 states. First-principles density-functional theory (DFT) calculations as well confirm the involvement of atomic orbitals in bandgap construction, as evidence of 5s5p-5 s2 transition, affording the STEs emission. Combining the efficient, stable broad emission Rb2In96.39 %Cl5·H2O: 3.61 % Sb3+ crystal with Cs3Cu2Cl5 and Cs3Cu2I5 phosphors, a lead-free white light-emitting diode with a high color rendering index of 93.4 has been achieved. Furthermore, the unique sensitive and steep temperature dependence photoluminescence (PL) lifetimes may prompt this type of self-trapped zero-dimensional (0D) perovskites to great potential in the field of thermometry application.

Chiral Zero-Dimensional Transition Metal Halide Hybrid Perovskite with Ehanced Circular Dichroism and Magnetism

Chiral Zero-Dimensional Transition Metal Halide Hybrid Perovskite with Ehanced Circular Dichroism and Magnetism

Influence of Ce3+ Doping on Photoluminescence Properties and Stability of Cs4SnBr6 Zero-Dimensional Perovskite

Zero-dimensional tin-based halide perovskites have garnered considerable interest owing to their remarkable optical properties, including broad-band emission, high photoluminescence (PL) efficiency, and low self-absorption. Nevertheless, enhancing the PL efficiency and stability of these materials remains a pressing challenge. In this study, the enhancement of PL and stability in Cs4SnBr6 zero-dimensional perovskite was investigated through Ce3+ doping. Our experimental results demonstrate that the incorporation of Ce3+ can significantly boost the light emission intensity from self-trapped excitons (STEs) in Cs4SnBr6, achieving over a 150% increase compared to the undoped sample, with a PL quantum yield of approximately 64.7%. Moreover, the thermal stability of the corresponding doped sample is markedly enhanced. Through comprehensive analyses, including X-ray diffraction, energy-dispersive spectroscopy, time-resolved PL, and temperature-dependent PL measurements, we elucidate that the enhanced light emission is attributed to the distortion of the [SnBr6]4− octahedral structure induced by Ce3+ doping, which strengthens electron–phonon coupling and elevates the binding energy of STEs.

Lead-Free Bismuth-Based Perovskite X-ray Detector with High Sensitivity and Low Detection Limit.

Bismuth-based halide perovskites have shown great potential for direct X-ray detection, attributable to their nontoxicity and advantages in detection sensitivity and spatial resolution. However, the practical application of such materials still faces the critical challenge of combining both high sensitivity and low detection limits. Here, we report a new type of zero-dimensional (0D) perovskite (HIS)BiI5 (1, where HIS2+ = histamine) with high sensitivity and a low detection limit. Structurally, the strong N-H···I hydrogen bonds between HIS2+ cations and inorganic frameworks enhance the rigidity of the structure and diminish the intermolecular distance between adjacent inorganic [Bi2I10]4- dimers. By virtue of such structural merits, single crystal 1 exhibits excellent physical properties perpendicular to both the (001) and (010) faces. Perpendicular to the (010) face, 1 exhibited a high electrical resistivity (2.31 × 1011 Ω cm) and a large carrier mobility-lifetime product (μτ) (2.81 × 10-4 cm2 V-1) under X-ray illumination. Benefiting from these superior physical properties, it demonstrates an excellent X-ray detection capability with a sensitivity of approximately 103 μC Gyair-1 cm-2 and a detection limit of 36 nGyair s-1 in both directions perpendicular to the (001) and (010) crystal faces. These results provide a promising candidate material for the development of new, lead-free, high-performance X-ray detectors.

A zero-dimensional perovskite with high-efficiency luminescence and transient response for advanced information encryption

Due to the increasingly complex network attacks and advancements in computational technology, finding new and efficient encryption techniques is an urging task. As a promising material, the application of perovskite luminescent materials in information encryption is limited to pre-planned specific scenarios or applications, lacking the ability to respond to temporary demands. In this work, we have designed a novel cadmium-based zero-dimensional perovskite, TEA2CdCl4, which presents blue luminescence centered at 413 nm originating from organic cations. Upon Sb3+ doping, it not only exhibits intense red emission at 623 nm with a high photoluminescence quantum efficiency up to 100 %, but also brings outstanding resistance to thermal quenching. Especially, an ultrafast response speed could be achieved during decryption process which has been verified by first-principles calculations. Based on the advantages, a large-area optical anti-counterfeiting paper for temporary information encryption transmission is designed, which not only verifies the potential for secure information transmission and protection, but also introduces a new concept for the application of organic–inorganic hybrid perovskites in the field of information encryption.

Antimony doping towards fast digital encryption and decryption and high-efficiency WLED in zero-dimensional hybrid indium chlorides

Lead-free metal halides with thermally induced reversible fluorescence transitions are promising smart optoelectronic materials. However, it is challenging to obtain such materials with reversible and fast fluorescent thermochromism at relatively low temperatures. Herein, two series of new zero-dimensional (0-D) hybrid perovskite indium chlorides doped with Sb3+ are synthesized and characterized, namely (TAEA)InCl6·Cl·4H2O: xSb3+ (1: xSb3+) and (TETA)InCl6·Cl·H2O: xSb3+ (2: xSb3+) (TAEA = quadruply protonated tris(aminoethyl)amine; TETA = quadruply protonated triethylenetetramine; x = 0 − 15 %). Compound 1: 0.5 %Sb3+ displays green broadband emission with photoluminescence quantum yield (PLQY) of 44.4 %, while compound 2: 1 %Sb3+ produces yellow emission with PLQY of 73.46 %. A reversible transition between green and orange light emission for 1: 0.5 %Sb3+ can be triggered by thermal stimulation; such photoluminescence (PL) color switching happens with a fast response time of 20 s and a low transition temperature of 333 K. In addition, the materials combining compounds 2: 1 %Sb3+ and 1: 0.5 %Sb3+ can achieve complex digital encryption and decryption upon heating. Furthermore, due to its excellent luminous efficiency, the 2: 1 %Sb3+ is employed as yellow phosphor for white light-emitting diode (WLED). The WLED shows a CRI of 90.5 and a CCT of 5415 K, superior to most WLEDs based on hybrid metal halides. Finally, the impact of forming the self-trapped excitons state and complex PL mechanism of compound 1: 0.5 %Sb3+ are investigated through DFT calculations and femtosecond transient absorption techniques. This work provides new insights into the design of hybrid metal halides with multiple optical properties, paving the way to obtaining materials for multiple optical applications.

Considerable Piezochromism in All-Inorganic Zero-Dimensional Perovskite Nanocrystals via Pressure-Modulated Self-Trapped Exciton Emission.

Piezochromic materials refer to a class of matters that alter their photoluminescence (PL) colors in response to the external stimuli, which exhibit promising smart applications in anti-counterfeiting, optoelectronic memory and pressure-sensing. However, so far, most reported piezochromic materials have been confined to organic materials or hybrid materials containing organic moieties with limited piezochromic range of less than 100 nm in visible region. Here, we achieved an intriguing piezochromism in all-inorganic zero-dimensional (0D) Cs3Cu2Cl5 nanocrystals (NCs) with a considerable piezochromic range of 232 nm because of their unique inorganic rigid structure. The PL energy shifted from the lowest-energy red fluorescence (1.85 eV) to the highest-energy blue fluorescence (2.83 eV), covering almost the entire visible wavelength range. Pressure-modulated self-trapped exciton emission between different energy levels of self-trapped states within Cs3Cu2Cl5 NCs was the main reason for this piezochromism property. Note that the quenched emission, which is over five times more intense than that in the initial state, is retained under ambient conditions upon decompression. This work provides a promising pressure indicating material, particularly used in pressure stability monitoring for equipment working at extreme environments.

Unveiling Sb3+ Doping and Tricolor Luminescence from Intrinsic Self-Trapped Excitons in Cs2ZnCl4 Crystals.

Zero-dimensional (0D) lead-free halide perovskites have lately received significant interest owing to their captivating broadband emissions. An in-depth understanding of the luminescence mechanism of self-trapped excitons (STEs) and realization of effective regulation of luminescence properties have become a major challenge in the research of lead-free metal halides. Herein, we have synthesized the Cs2ZnCl4 and Sb3+-doped Cs2ZnCl4 crystals and conducted a comprehensive investigation into their distinct electronic structures and optical characteristics. The findings from both experimental and theoretical investigations indicate that the tricolor luminescence in Cs2ZnCl4 and blue emission in Sb3+-doped Cs2ZnCl4 stem from intrinsic STEs, and the near-infrared emission originates from extrinsic STEs associated with the Sb3+ ion in Sb3+-doped Cs2ZnCl4. Sb3+ doping increases the quantum yield of Cs2ZnCl4 to a large extent. In addition, intersystem crossing, exciton self-trapping, and lattice relaxation are the main reasons for the large Stokes shift. The present study is expected to provide a novel perspective for researchers in comprehending the luminescent mechanism of STEs and advancing the utilization of 0D lead-free metal halides in optoelectronic applications.

High Q-Factor Single-Mode Lasing in Inorganic Perovskite Microcavities with Microfocusing Field Confinement.

The realization of high-Q single-mode lasing on the microscale is significant for the advancement of on-chip integrated light sources. It remains a challenging trade-off between Q-factor enhancement and light-field localization to raise the lasing emission rate. Here, we fabricated a zero-dimensional perovskite microcavity integrated with a nondamage pressed microlens to three-dimensionally tailor the intracavity light field and demonstrated linearly and nonlinearly (two-photon) pumped lasing by this microfocusing configuration. Notably, the microlensing microcavity experimentally achieves a high Q-factor (16700), high polarization (99.6%), and high Purcell factor (11.40) single-mode lasing under high-repetition pulse pumping. Three-dimensional light-field confinement formed by the microlens and plate microcavity simultaneously reduces the mode volume (∼3.66 μm3) and suppresses diffraction and transverse walk-off loss, which induces discretization on energy-momentum dispersions and spatial electromagnetic-field distributions. The Q factor and Purcell factor of our lasing come out on top among most of the reported perovskite microcavities, paving a promising avenue toward further studying electrically driven on-chip microlasers.

A lead-free zero-dimensional hybrid antimony halide perovskite X-ray scintillator with exceptional emission efficiency and excellent stability as a highly sensitive fluorescent probe

A zero-dimensional perovskite [FPPP]2SbCl7 with 99.26% PLQY is an efficient X-ray scintillator (46 927 photons per MeV) with a low detection limit and a PL probe for nitrobenzene.

Self-powered humidity sensors based on zero-dimensional perovskite-like structures with fast response and high stability.

With the rapid development of technology, the development of self-powered sensors has garnered significant attention. The importance of monitoring humidity has grown significantly in various technological contexts, from environmental monitoring to biomedical applications. In this work, we have fabricated a low-cost and self-powered humidity sensor using zero-dimensional perovskite-like structures. Switching tests at different relative humidity levels have shown that the zero-dimensional perovskites have visible coloration at high humidities and discoloration upon reducing the humidity. The humidity sensor was fabricated by spin coating the zero-dimensional perovskites on a patterned fluorine doped tin oxide (FTO) substrate and the sensor not only shows high response values of around 500 mV and few micro amperes of short circuit current densities, but also shows good cycling performance and stability. Also high selectivity to humidity is observed in comparison to different gases and volatile organic compounds. The high selectivity to humidity arises due to the fact that the exclusion of MAI from the MA4PbI6 strucuture does not happen with all the other analytes which has been confirmed from the XRD studies. In addition, due to the low temperature fabrication they can be deposited on flexible substrates and the sensor displayed excellent resistance to bending and durability. Furthermore, the study explored the humidity monitoring capabilities of this sensor, revealing an outstanding response performance to human respiration. This observation suggests that the sensor holds significant potential for practical applications in the monitoring of human health and environmental conditions. This work paves the way for developing organic-inorganic hybrid perovskite materials for self-powered sensing applications.

Construction of a zero-dimensional halide perovskite in micron scale towards a deeper understanding of phase transformation mechanism and fluorescence applications.

Zero-dimensional (0D) halide perovskites have garnered significant interest due to their novel properties in optoelectronic and energy applications. However, the mechanisms underlying their phase transformations and fluorescence properties remain poorly understood. In this study, we have synthesized a micron-scale 0D perovskite observable under confocal laser scanning microscopy (CLSM). This approach enables us to trace the phase transformation process from 0D to three-dimensional (3D) structures, offering a deeper understanding of the underlying mechanisms. Remarkably, we discovered that this in situ transformation is highly sensitive to water, allowing for label-free fluorescent analysis of trace amounts of water in organic solvents through the phase transformation process. Additionally, we have designed a reusable paper strip for humidity analysis leveraging this sensitivity as an application of the micron scale material. Our findings not only elucidate the physicochemical properties of perovskites but also expand the potential of halide perovskite materials in analytical chemistry.

Solution-grown millimeter-scale Mn-doped CsPbBr3/Cs4PbBr6 crystals with enhanced photoluminescence and stability for light-emitting applications.

Metal halide perovskites are particularly emerging for optoelectronic applications in light-emitting diodes, photodetectors, and solar cells due to their flourishing photophysical properties. However, the poor stability of three-dimensional (3D) lead halide perovskite nanocrystals (NCs) significantly hampers their optoelectronics and photovoltaics applications. Embedding 3D perovskites into zero-dimensional (0D) perovskite crystals and doping ions of appropriate elements into host lattices provide effective approaches to improve the stability and optical-electronic performance. In this study, millimeter-scale Mn-doped and undoped CsPbBr3/Cs4PbBr6 perovskite crystals were successfully fabricated by a one-step slow cooling method. We systematically investigated the effects of Mn2+ ion doping on the PL performance and stability of CsPbBr3/Cs4PbBr6 crystals. Compared with undoped crystals, the existence of Mn2+ ions not only blue-shifted the PL peak but also improved the luminescence performance and stability of the prepared millimeter-sized crystals. Moreover, doping Mn2+ ions can increase the proportion of radiative recombination at low temperature, which may be because Mn2+ ions can effectively accelerate the decay of a dark exciton by the magnetic mixing of bright and dark excitons. In addition, green LED devices with high efficiency packaged as-grown crystals are explored, which promises further application in display backlights.

Evolution of fractal patterns in lead-free zero-dimensional perovskite Cs2InBr5(H2O)

The fractal patterns were obtained in lead-free zero-dimensional perovskite Cs2InBr5(H2O).