Lead-free Halide Research Articles

CO2 photoreduction using encapsulated potassium bismuth iodide (K3Bi2I9) perovskite in porous supports

Lead-free halide perovskites (LFHP) are one of the most promising materials for CO2 photoreduction; however, their stability is an issue that must be solved to scale up the manufacturing. To overcome this limitation, this work proposes the encapsulation of LFHP of K3Bi2I9 in three inorganic supports based on aluminosilicates such as (i) geopolymer, (ii) tobermorite, and other based on (iii) magnesium oxychloride. These supports provide a porous structure and active sites to host the perovskite particles, which favor enhanced light absorption, stability, and their activity for CO2 reduction under visible light. The encapsulated perovskites exhibited activity to photoconvert CO2 into formic acid (HCOOH) with efficiencies up to 2500 μmol h−1 using the K3Bi2I9 host in geopolymer. This support provides stable polysialate-diloxo chains to encapsulate the perovskite, delayed the degradation in aqueous medium, and its activity was demonstrated during 16 h of continuous visible light irradiation. The good stability and efficiency for CO2 reduction was associated to the formation of K3Bi2I9/BiOI heterojunction that prevent the degradation of the structure and enhance the charge transfer between both semiconductors.

Machine learning-enhanced design of lead-free halide perovskite materials using density functional theory

The investigation of emerging non-toxic perovskite materials has been undertaken to advance the fabrication of environmentally sustainable lead-free perovskite solar cells. This study introduces a machine learning methodology aimed at predicting innovative halide perovskite materials that hold promise for use in photovoltaic applications. The seven newly predicted materials are as follows: CsMnCl4, Rb3Mn2Cl9, Rb4MnCl6, Rb3MnCl5, RbMn2Cl7, RbMn4Cl9, and CsIn2Cl7. The predicted compounds are first screened using a machine learning approach, and their validity is subsequently verified through density functional theory calculations. CsMnCl4 is notable among them, displaying a bandgap of 1.37 eV, falling within the Shockley-Queisser limit, making it suitable for photovoltaic applications. Through the integration of machine learning and density functional theory, this study presents a methodology that is more effective and thorough for the discovery and design of materials.

Selecting ns2 electron (Sb3+) and d3 electron (Cr3+) co-doped in lead-free halide double perovskite to achieve blue and near-infrared luminescence

The double-perovskite Cs2NaInCl6 has emerged as a highly favored candidate due to its remarkable stability and eco-friendly properties. However, it is noteworthy that this material does not demonstrate the desired optical performance in the crucial visible and near-infrared (NIR) spectrum, which may limit its potential applications in certain domains. We develop such characteristics in Cs2NaInCl6 by co-doping Sb3+ (s-electron) and Cr3+ (d-electron) ions. Doping with Sb3+ allows for 1S0→3P1 transition absorption, which then emits blue photoluminescence of self-trapped exciton (STE). By co-doping Sb3+ and Cr3+ ions, it causes the transfer of excitation energy from STE to Cr3+, yielding strong NIR emission at 950 nm. Temperature-dependent Photoluminescence (PL), PL excitation, PL decay and Tanabe-Sugano diagram provide insight into photophysical processes. Furthermore, a novel dual-modal optical information encryption based on the integration of blue and NIR luminescence printing patterns using Cs2NaInCl6: Sb3+ and Cs2NaInCl6: Sb3+/Cr3+, respectively, is successfully demonstrated.

Synthesis of low-dimensional metal halide CsAgCl2 for X-ray scintillation applications

Low-dimensional metal halides, which possess efficient luminescent properties, have garnered significant interest in the fields of optoelectronics and radiation detection. This study introduces novel lead-free silver-based metal halide material, CsAgCl2 microcrystals (MCs). These MCs have a one-dimensional atomic chain structure and a unique [AgCl5]4- tetragonal shared triangular configuration. CsAgCl2 MCs exhibit excellent performance as X-ray scintillators due to their bright broadband yellow emission and fast decay time in the microsecond range. The large Stokes shift of 350 nm is produced by self-trapped exciton emission. In X-ray scintillation applications, CsAgCl2 MCs demonstrate a high light yield of 13280 photons/MeV and a wide range of linear scintillation response. It is noteworthy that the CsAgCl2 MCs maintain good stability under both atmospheric conditions and continuous X-ray irradiation. The sample was used in an X-ray imaging screen, which clearly presented the X-ray projection image of a wooden stick. As a result, this research not only contributes to the collection of lead-free metal halide scintillators but also indicates that CsAgCl2 MCs have a wide range of future applications and potential in areas such as medical imaging, scientific research, and diagnostic and detection technologies.

Enhanced temperature sensing in lead-free Cs3Bi2Cl9 perovskite co-doping Yb3+/Er3+ for optical thermometry application

A simple and rapid grinding method for preparing Er3+-doped and Er3+/Yb3+co-doped Cs3Bi2Cl9 upconversion phosphors was developed. We avoid to employ strong acids as reaction solvents, aligning with the principles of green chemistry. By controlling the thermal treatment temperature and adding BiCl3, a reversible phase transformation process between Cs3Bi2Cl9 and Cs3BiCl6 perovskite phosphors was achieved. The Er3+/Yb3+ co-doped Cs3Bi2Cl9 phosphors emit green light under 980 nm excitation, whereas Cs3BiCl6 phosphors emit red light. Their temperature sensing performance was tested through variable-temperature processes. Compared to Er3+-doped Cs3Bi2Cl9 phosphors, the co-doped Er3+/Yb3+ phosphors have a higher relative sensitivity of 1.60 % K−1. Compared to previously reported materials, Cs3Bi2Cl9 phosphors show enhanced sensitivity in temperature sensing. The study demonstrates that lead-free halide perovskites’ unique color-tunability not only underscores the innovativeness of this synthetic strategy but also provides a significant technological foundation for temperature sensing applications. Given their environmental friendliness and facile preparation process, these phosphors possess notable advantages for industrial production and hold promise as potential candidates for next-generation high-performance phosphor materials.

Constructing S-scheme heterojunction Cs3Bi2Br9/BiOBr via in-situ partial conversion to boost photocatalytic N2 fixation

The judicious construction of interfaces with swift charge communication to enhance the utilization efficiency of photogenerated carriers is a viable strategy for boosting the photocatalytic performance of heterojunctions. Herein, an in-situ partial conversion strategy is reported for decorating lead-free halide perovskite Cs3Bi2Br9 nanocrystals onto BiOBr hollow nanotube, resulting in the formation of an S-scheme heterojunction Cs3Bi2Br9/BiOBr. This unique in-situ growth approach imparts a closely contacted interface to the Cs3Bi2Br9/BiOBr heterojunction, facilitating interfacial electron transfer and spatial charge separation compared to a counterpart (Cs3Bi2Br9:BiOBr) fabricated via traditional electrostatic self-assembly. Additionally, the establishment of an S-scheme charge transfer pathway preserves the robust redox capability of photogenerated carriers. Furthermore, the free electron transfer from Cs3Bi2Br9 to BiOBr promotes the activation of the NN bond and diminishes the energy barrier associated with the rate-determining step in the N2 reduction process. Consequently, the Cs3Bi2Br9/BiOBr heterojunction exhibits highly selective photocatalytic N2 reduction to NH3 (nearly 100 %) at a rate of 130 μmol g−1 h−1 under simulated sunlight (100 mW cm−2), surpassing BiOBr, Cs3Bi2Br9, and Cs3Bi2Br9:BiOBr by factors of 6, 4, and 2, respectively.

New semiconducting lead-free halide double perovskite Ag2LiGaF6 for optoelectronic and thermoelectric applications

A comprehensive study of lead-free halide double perovskite using density functional theory (DFT) including structural, electronic, dynamical, mechanical, optical, and thermoelectric properties has been carried out. The tolerance factor and the octahedral factor confirm that the compound belongs to face-centred-cubic structure with Fm-3m space group. The predicted band structure and DOS exhibit that the material is an indirect bandgap semiconductor. Our calculation reveals that material is dynamically stable because of no negative frequency found in phonon-dispersion curve. The material also possesses mechanical stability. The optical spectra of material show good absorbance and low reflectivity in ultraviolet region. The thermoelectric part discusses the Seebeck coefficient, thermal conductivity, electrical conductivity, power factor, and figure of merit (zT) at different chemical potential into temperature range 400–1200 K. The purpose of this investigation is to stimulate researchers to develop this kind of material and assess their potential for the advancement of contemporary thermoelectric and optoelectronic devices.

Exploring photoconduction mechanisms in Lead‐Free Cs3Sb2I9 single crystal thin films

The future commercial advancement of lead-halide perovskites (LHPs) faces obstacles due to the existence of harmful lead and the inadequate stability associated with these materials. To tackle this challenge, we have prepared a Cs3Sb2I9 perovskite single-crystalline thin film (Cs3Sb2I9 device) using a technique based on the restricted evaporation of solvents in space, aiming for effective photodetection. The photodetector in the current study shows a responsivity (R) of around 111 mA/W and a detectivity (D∗) of approximately 3.7 × 1012 Jones. While these performance metrics are comparable to other photodetectors, there is a need for additional optimization to match the capabilities of commercial silicon and germanium-based counterparts. The examination of ultrafast transient absorption provides insights into the essential photophysics inherent in Cs3Sb2I9. The synergy between the deformation potential and the Fröhlich effect plays a crucial role in shaping electronic dynamics. This synergy leads to the self-trapping of charge carriers, resulting in the creation of localized polarons within the Cs3Sb2I9 lattice within just some picoseconds. The restriction of carrier mobility within Cs3Sb2I9 arises from the self-capturing and confinement of small polarons (SPs). Furthermore, it was noted that SPs in a localized state could undergo absorption into an elevated state (photon energy ⁓ 1.60 eV). This process effectively facilitates the charge carriers' mobilization to a more dispersed eigenstate. Our research provides essential comprehension into the light-induced processes of lead-free halide perovskites (LFHPs), offering valuable insights for their prospective use in optoelectronics as promising future semiconducting agents.

Localized Electron Density Engineering for Bright and Stable Near-Infrared Electroluminescence from All-Inorganic Lead-Free Tin Halides

Localized Electron Density Engineering for Bright and Stable Near-Infrared Electroluminescence from All-Inorganic Lead-Free Tin Halides

Excitonic properties and solar harvesting performance of Cs2ZnY2X2 as quasi-2D mixed-halide perovskites

Due to their low toxicity and high-temperature stability, lead-free quasi-2D metal halide perovskites (MHPs) are promising materials for optoelectronic applications. However, understanding their structural and optoelectronic properties, especially excitonic effects (electron-hole pair, e-h), is challenging due to their quantum well topology. We propose an efficient protocol for band gap correction of Cs2ZnX (X = Cl4, Br2Cl2, and I2Cl2) and Cs2PbI2Cl2 (used as a benchmark) quasi-2D MHPs. This protocol is based on a relativistic quasiparticle approach (DFT-1/2) using density functional theory (DFT). We first examined the hybrid contributions of the halide alloys, leading to excitonic characterization using the Bethe–Salpeter equation within the maximally localized Wannier functions tight-binding method. This method provides a cost-effective approach for describing e-h quasiparticle effects. Additionally, we analyzed the crystal structure, thermodynamic stability, and optoelectronic properties of the newly synthesized Zn-based systems, focusing on their structural stability mechanisms. We found a correlation between the allocation of Cs+ cations in the crystal structure and the formation of two distinct stabilization patterns, influenced by the radii of the metal (Zn or Pb) and halide components. The relativistic correction of the band gap energies yielded results within 10 % of the experimental values. Furthermore, incorporating e-h quasiparticle effects for Cs2PbI2Cl2 resulted in an exciton binding energy of 0.160 eV, in excellent agreement with experimental data. This work represents a significant advance in the optoelectronic characterization of Cs2ZnX systems, previously unexplored for their excitonic properties.

Metal Halide Perovskites for Photocatalysis: Performance and Mechanistic Studies.

Metal halide perovskites, both lead-based and lead-free variants, have emerged as highly versatile materials with widespread applications across various fields, including photovoltaics, optoelectronics, and photocatalysis. This review provides a succinct overview of the recent advancements in the utilization of lead and lead-free halide perovskites specifically in photocatalysis. We explore the diverse range of photocatalytic reactions enabled by metal halide perovskites, including organic transformations, carbon dioxide reduction, and pollutant degradation. We highlight key developments, mechanistic insights, and challenges in the field, offering our perspectives on the future research directions and potential applications. By summarizing recent findings from the literature, this review aims to provide a timely resource for researchers interested in harnessing the full potential of metal halide perovskites for sustainable and efficient photocatalytic processes.

Tunable multimode emissions of Yb3+/Er3+-doped rare-earth-based Cs2NaYCl6 double perovskite crystals for versatile applications

Lead-free halide double perovskite materials are gaining recognition because of their excellent optoelectronic performance. However, achieving multimode luminescence with tunable emission colors in single-component double perovskites remains a significant challenge. Understanding the mechanism of trivalent lanthanide-ion doping could provide a valuable solution. Herein, we report the synthesis of rare-earth-based Cs2NaYCl6 double perovskites using a hydrothermal method. Efficient visible to near-infrared down-shifting (DS) photoluminescence and green up-conversion (UC) emissions were realized by incorporating Er3+ ions with abundant energy levels into the hosts. Notably, the DS and UC emission colors could both be adjusted by further introducing Yb3+ ions that acted as sensitizers, and the photoluminescence was significantly enhanced due to the strong absorption at 980 nm. Spectral analysis revealed that the high compatibility of lanthanide ions with the rare-earth-based double perovskites and cross-relaxation processes played a key role in achieving modulated emission and multiple excitation modes. This study aimed to understand the photophysical mechanism of lanthanide-ion-doped double perovskites, as well as to highlight their ability to modulate emissions. Furthermore, this study expands the versatile applications of lanthanide-ion-doped double perovskites in the fields of high-security anti-counterfeiting, tissue imaging, and night-vision systems.

Flexible memristors with low-operation voltage and high bending stability based on Cu2AgBiI6 perovskite

Cu2AgBiI6 films were prepared by a one-step spin coating method, and flexible memristors with an Ag/PMMA/Cu2AgBiI6/ITO structure were constructed. The devices showed a bipolar resistive switching behavior with low switching voltage, which is beneficial for reducing energy consumption. Furthermore, this study found that the device exhibits an endurance of about 900 cycles, a higher ON/OFF ratio of over 103, a long retention time (∼104 s), and high stabilities against mechanical stress. Remarkably, the present flexible memristor displayed extraordinary flexibility and stability, with no significant change for the resistive switching behavior even at various bending angles or after undergoing 900 bending cycles. This study establishes that the lead-free halide perovskite Cu2AgBiI6 can be used for the resistive random-access memory of flexible electronics.

Mechanism of Pressure-Modulated Self-Trapped Exciton Emission in Cs2TeCl6 Double Perovskite.

Pressure-modulated self-trapped exciton (STE) emission mechanism in all-inorganic lead-free metal halide double perovskites characterized by large Stokes-shifted broadband emission, has attracted much attention across various fields such as optics, optoelectronics, and biomedical sciences. Here, by employing the all-inorganic lead-free metal halide double perovskite Cs2TeCl6 as a paradigm, the authors elucidate that the performance of STE emission can be modulated by pressure, attributable to the pressure-induced evolution of the electronic state (ES). Two ES transitions happen at pressures of 1.6 and 5.8GPa, sequentially. The electronic behaviors of Cs2TeCl6 can be jointly modulated by both pressure and ES transitions. When the pressure reaches 1.6GPa, the Huang-Rhys factor S, indicative of the strength of electron-phonon coupling, attains an optimum value of ≈12.0, correlating with the pressure-induced photoluminescence (PL) intensity of Cs2TeCl6 is 4.8-fold that of its PL intensity under ambient pressure. Through analyzing the pressure-dependent STE dynamic behavioral changes, the authors have revealed the microphysical mechanism underlying the pressure-modulated enhancement and quenching of STE emission in Cs2TeCl6.

Supersaturation- and external force-engineered high-quality 2D CsCu2I3 single-crystalline film for heterogeneous integration in photodetectors

Heterogeneous integration of various crystalline materials in electronic and optoelectronic devices have fueled the development of two-dimensional (2D) perovskite single-crystalline (SC) film. However, it is still challenging to synthesize 2D CsCu2I3 SC film due to the uncontrolled nuclei/growth. In the work, the bottleneck for the synthesis of 2D CsCu2I3 SC film can be well tackled by the solution supersaturation and external pressure for the first time, meanwhile, the morphological transformation of CsCu2I3 from dendritic crystal to 2D film are firstly achieved through controlling nucleation driving force. The heterogeneous integration of 2D CsCu2I3 SCs film on various substrates was demonstrated, a self-powered GaN-CsCu2I3 SC film photodetector exhibits high rectification ratio of 1250 (±1 V) with improved responsivity of 460 mA W−1 and EQE of 163 %, which outperforms most reported 2D lead-free halide perovskite film photodetectors. Furthermore, theoretical computational calculation was employed to investigate their crystal structure and electronic distribution, evidencing that 2D CsCu2I3 SC film could facilitate the separation of photo-induced carriers. The study not only shows an in-depth mechanism for perovskite growth, but also advances the development of 2D copper-based perovskite film and hetero-integration, laying the groundwork for future commercial optoelectronics.

NH3 gas sensing and NH3-induced anti-counterfeiting based on nontoxic ternary copper halide

Lead-free ternary copper halides are emerging environmentally friendly materials, which have recently received great attention for their favorable optoelectronic properties. However, few attention was paid to their applications in gas sensing and gas-triggered fluorescence anti-counterfeiting. In this work, we demonstrate an effective Cs3Cu2I5 halide for NH3 sensing and NH3-triggered fluorescence anti-counterfeiting applications. The Cs3Cu2I5-based electrical NH3 sensor exhibits exceptional sensing performance, in which a resistance response of 77.8 % is achieved at 50 ppm NH3 with a rapid response time (9 s). To elucidate the NH3 sensing mechanism, we investigated the NH3-induced optical and structural evolutions including absorption, photoluminescence (PL), and Raman spectra. Our findings suggest that NH3 molecules, acting as electron donors, adsorb on the Cs3Cu2I5 surface, inducing the decomposition of Cs3Cu2I5 into CsCu2I3 and CsI. During this process, the CsCu2I3·NH3 intermediate phase is generated as a shell layer onto the surface of Cs3Cu2I5 grain, leading to an increase in electrical conductivity (or decrease in resistance), and an emission of bright yellow-red fluorescence from CsCu2I3. Inspired by NH3-induced fluorescence emission, we also explored a novel gas-triggered anti-counterfeiting method using Cs3Cu2I5-paper, demonstrating favorable reversibility and convenience, compared to previously reported water-triggered anti-counterfeiting techniques. This work will promote the development of design of Cs3Cu2I5 for gas sensing and gas-triggered fluorescence anti-counterfeiting applications in the future.

Structural, electronic, optical, and thermoelectric features of Rb2XSbX’6 (X= Ag, Cu; X’= Cl, Br): Ab-initio calculations

This study investigates the electronic, optical, and thermoelectric properties of lead-free double halide perovskite materials, Rb2XSbX'6, through first-principles calculations employing Density Functional Theory (DFT) and the Wien2k code, complemented by Boltzmann transport theory. By substituting X with Ag or Cu and X’ with Cl or Br in Rb2XSbX’6, we uncover interesting properties. Rb2AgSbBr6, Rb2AgSbCl6, Rb2CuSbCl6, and Rb2CuSbBr6 exhibit low indirect band gaps of 1.18 eV, 2.17 eV, 1.22 eV, and 0.87 eV, respectively, alongside high absorption in the visible region. The studied compounds sustained a high level of structural and thermodynamic stability, which was confirmed by their high bulk modulus and negative formation energy. Furthermore, extensive values were observed for the figure of merit in the thermoelectric study. Given the strong agreement with previous research, these findings position the investigated materials as promising candidates for visible-light solar cell device applications.

Rational design of efficient boron-doped and nitrogen-deficient g-C3N4/lead-free Cs3Bi2Br9 perovskite nanocrystals Z-scheme heterojunction by optimised surface-active site and interfacial charge transfer

The major limitation for the photodegradation of pollutants by g-C3N4-based and lead-free halide perovskite photocatalysts are the moderate adsorption-photocatalytic ability and interfacial charge transfer rates. Herein, we have synthesized boron doped and nitrogen deficient g-C3N4 (BNCNx/y) and fabricated the BNCNx/y/Cs3Bi2Br9 heterojunctions by anti-solvent method to regulate bandgap and improve photoabsorption. The optimal ratios BNCN0.6/450/Cs3Bi2Br9 (BNCN-CBB-30) exhibited the highest degradation efficiency of 98.62 % for chloroquine phosphate (CQ) within 60 min, which possessed not only high oxidation ability (>82.19 %) for a variety of antibiotics but excellent structural stability and reusability. DFT calculations revealed that BNCNx/y/Cs3Bi2Br9 had the shortest bond distance and greater adsorption energy with CQ. Under visible light irradiation, the rapid electron transfer from Cs3Bi2Br9 to BNCN450/0.6 driven by the built-in electric field enhanced generation of •O2–, 1O2, and •OH. This work provides new insights into the internal structure design of heterojunction photocatalysts.

Solution-Free Melt-Grown CsGeI3 Polycrystals for Lead-Free Perovskite Photovoltaics: Synthesis, Characterization, and Theoretical Insights

Inorganic lead-free metal halide perovskites are being rigorously explored as a substitute for organic lead-based materials for various energy device applications. Germanium as a replacement for lead has been proven to give exemplary results theoretically, and there have been promising results. The current work presents the investigation of CsGeI3 (CGI) polycrystals grown using a solution-free melt-growth technique with low-cost precursors. A soak-ramp profile was designed to synthesize polycrystalline powders, which were evaluated for stability. X-ray diffraction and Raman spectroscopy analysis suggest the formation of CsGeI3 perovskite powders, matching the reported literature. Diffuse reflectance spectroscopy measurements showed the bandgap of the polycrystals to be around 1.6 eV. A prominent photoluminescence peak was obtained at 767 nm. The powders were examined using thermogravimetric analysis to assess the thermal degradation pathways. The as-grown inorganic perovskite polycrystals were relatively stable during storage under ambient conditions. Theoretical studies were also carried out to support the experimental data. Calculations were performed with different approximations, including local density approximation (LDA), generalized gradient approximation (GGA), and Heyd–Scuseria–Ernzerhof (HSE) approximation, out of which the HSE approximation yielded the most accurate results that matched the experimental findings. Moreover, for the CGI device with Ag electrodes simulated using SCAPS-1D software, highest incident photon-to-electron conversion efficiency was observed. The obtained optical and structural properties indicate the suitability of the synthesized CsGeI3 perovskite polycrystals for photovoltaic applications, specifically solar cells and light-emitting diodes.

Geometric and electronic structures of Cs2BB′X6 double perovskites: The importance of exact exchange

A widely adopted computational protocol in contemporary materials research is to first relax materials' geometries using semilocal density functional approximations (DFA), and then determining their electronic band structures using the more expensive hybrid functionals. This procedure often works well, as the popular semilocal DFAs, such as the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation, yield rather good geometries for a wide range of materials. However, here we show that, for some of the lead-free halide double perovskites (HDPs) Cs2BB′X6 (B=Ag+, Na+; B′=In3+, Bi3+; X=Cl−, Br−), the validity of this common practice is questionable. We find that, for these HDPs, the geometrical structures, in particular, the B(B′)−X bond lengths predicted by PBE show large deviations from the experimental values. Additionally, the band gaps of some of these materials (specifically, the In-based HDPs) are sensitive to the B(B′)−X bond lengths. As a consequence, the band gaps obtained using the hybrid functionals (such as the Heyd-Scuseria-Ernzerhof functional) based on the PBE geometries can still be quite off, in particular, for HDPs with B′=In3+. The situation is significantly improved by using hybrid functionals with tuned portion of exact exchange, based on the geometries determined consistently under the same level of theory. The successes and failures of several popular exchange-correlation (XC) functionals are traced back to the so-called delocalization error, and can be quantitatively analyzed and understood via a three-atom linear-chain B−X−B′ molecular model. Finally, our findings provide a practical guide for choosing appropriate XC functionals for describing HDPs and point to a promising path for band structure engineering via doping and alloying. Published by the American Physical Society 2024