(NH4)2AgX3 (X = Br, I): 1D Silver Halides with Broadband White Light Emission and Improved Stability
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ABSTRACT:
SUBMITTER: Creason T
PROVIDER: S-EPMC9888650 | biostudies-literature | 2021 Jun
REPOSITORIES: biostudies-literature
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Project description:We report syntheses, crystal and electronic structures, and characterization of three new hybrid organic-inorganic halides (R)ZnBr3(DMSO), (R)2CdBr4·DMSO, and (R)CdI3(DMSO) (where (R) = C6(CH3)5CH2N(CH3)3, and DMSO = dimethyl sulfoxide). The compounds can be conveniently prepared as single crystals and bulk polycrystalline powders using a DMSO-methanol solvent system. On the basis of the single-crystal X-ray diffraction results carried out at room temperature and 100 K, all compounds have zero-dimensional (0D) crystal structures featuring alternating layers of bulky organic cations and molecular inorganic anions based on a tetrahedral coordination around group 12 metal cations. The presence of discrete molecular building blocks in the 0D structures results in localized charges and tunable room-temperature light emission, including white light for (R)ZnBr3(DMSO), bluish-white light for (R)2CdBr4·DMSO, and green for (R)CdI3(DMSO). The highest photoluminescence quantum yield (PLQY) value of 3.07% was measured for (R)ZnBr3(DMSO), which emits cold white light based on the calculated correlated color temperature (CCT) of 11,044 K. All compounds exhibit fast photoluminescence lifetimes on the timescale of tens of nanoseconds, consistent with the fast luminescence decay observed in π-conjugated organic molecules. Temperature dependence photoluminescence study showed the appearance of additional peaks around 550 nm, resulting from the organic salt emission. Density functional theory calculations show that the incorporation of both the low-gap aromatic molecule R and the relatively electropositive Zn and Cd metals can lead to exciton localization at the aromatic molecular cations, which act as luminescence centers.
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Project description:Recently, the design and fabrication of lead (Pb)-free perovskite or perovskite-like materials have received great interest for the development of perovskite solar cells (PSCs). Manganese (Mn) is a less toxic element, which may be an alternative to Pb. In this work, we explored the role of NH3(CH2)2NH3MnCl4 perovskite as a light absorber layer via SCAPS-1D. A Pb-free PSC device (FTO/TiO2/NH3(CH2)2NH3MnCl4/spiro-OMeTAD/Au) was simulated via SCAPS-1D software. The simulated Pb-free PSCs (FTO/TiO2/NH3(CH2)2NH3MnCl4/spiro-OMeTAD/Au) showed decent power conversion efficiency (PCE) of 20.19%. Further, the impact of the thickness of absorber (NH3(CH2)2NH3MnCl4), electron transport (TiO2), and hole-transport (spiro-OMeTAD) layers were also investigated. Subsequently, various electron transport layers (ETLs) were also introduced to investigate the role of ETL. In further studies, an NH3(CH2)2NH3MnCl4-based PSC device (FTO/TiO2/NH3(CH2)2NH3MnCl4/spiro-OMeTAD/Au) was also developed (humidity = ~30-40%). The fabricated PSCs displayed an open circuit voltage (Voc) of 510 mV with a PCE of 0.12%.
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Project description:2D Ruddlesden-Popper halide perovskites, which incorporate hydrophobic organic interlayers to considerably improve environmental stability and optical properties diversity, have attracted substantial research attention for optoelectronic applications. The burgeoning broad emission arising from exciton self-trapping of 2D perovskites shows a strong dependence on a deformable structure. Here, the pressure-induced broadband emission of layered (001) Pb-Br perovskite with a large Stokes shift in the visible region is observed by finely improving lattice distortion to increase exciton-phonon coupling under hydrostatic pressure. Band gap narrows ≈0.5 eV under modest pressure, mainly due to the large compressibility of the orientational organic layer, confirming that the bulky organic cations notably influence the structure and, in turn, the various properties of materials. Sequential amorphization of the organic and inorganic layer is confirmed by high pressure Raman and X-ray diffraction measurements, suggesting the particularity of layered crystal structures. The mechanism constructed here offers a new route for tuning the optical properties of 2D perovskites.
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Project description:To overcome the drawbacks in three-dimensional (3D) perovskites, such as instability, surface hydration, and ion migration, recently researchers have focused on comparatively stable lower-dimensional perovskite derivatives. All-inorganic zero-dimensional (0D) perovskites (e.g., Cs4PbX6; X = Cl-, Br-, I-) can be evolved as a high performing material due to their larger exciton binding energy and better structural stability. The clear understanding of carrier recombination process in 0D perovskites is very important for better exploitation in light-emitting devices. In this work, we comprehensively studied the light emission process in 0D Cs4PbI6 nanocrystals (NCs) and interestingly we observe intense white light emission at low temperatures. According to our experimental observations, we conclude that the white light emission contains an intrinsic exciton emission at 2.95 eV along with a broadband emission covering from 1.77 eV to 2.6 eV. We also confirm that the broadband emission is related to the carrier recombination of both self-trapped excitons (STE) and defect state trapped excitons. Our investigations reveal the carrier recombination processes in Cs4PbI6 NCs and provide experimental guidelines for the potential application of white light generation.
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Project description:The physical properties of the organic-inorganic hybrid crystals having the formula [NH3(CH2)3NH3]ZnX4 (X = Cl, Br) were investigated. The phase transition temperatures (TC; 268K for Cl and 272K for Br) of the two crystals bearing different halogen atoms in their skeletons were determined through differential scanning calorimetry. The thermodynamic properties of the two crystals were investigated through thermogravimetric analysis. The structural dynamics, particularly the role of the [NH3(CH2)3NH3] cation, were probed through 1H and 13C magic-angle spinning nuclear magnetic resonance spectroscopy as a function of temperature. The 1H and 13C NMR chemical shifts did not show any changes near TC. In addition, the 1H spin-lattice relaxation time (T1ρ) varied with temperature, whereas the 13C T1ρ values remained nearly constant at different temperatures. The T1ρ values of the atoms in [NH3(CH2)3NH3]ZnCl4 were higher than those in [NH3(CH2)3NH3]ZnBr4. The observed differences in the structural dynamics obtained from the chemical shifts and T1ρ values of the two compounds can be attributed to the differences in the bond lengths and halogen atoms. These findings can provide important insights or potential applications of these crystals.
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Project description:Ammonia has recently emerged as a promising hydrogen carrier for renewable energy conversion. Establishing a better understanding and control of ammonia adsorption and desorption is necessary to improve future energy generation. Metal-organic frameworks (MOFs) have shown improved ammonia capacity and stability over conventional adsorbents such as silica and zeolite. However, ammonia desorption requires high temperature over 150 °C, which is not desirable for energy-efficient ammonia reuse and recycling. Here, we loaded silver nanoparticles from 6.6 to 51.4 wt% in MIL-101 (Ag@MIL-101) using an impregnation method to develop an efficient MOF-based hybrid adsorbent for ammonia uptake. The incorporation of metal nanoparticles into MIL-101 has not been widely explored for ammonia uptake, even though such hybrid nanostructures have significantly enhanced catalytic activities and gas sensing capacities. Structural features of Ag@MIL-101 with different Ag wt% were examined using transmission electron microscopy, X-ray powder diffraction, and infrared spectroscopy, demonstrating successful formation of silver nanoparticles in MIL-101. Ag@MIL-101 (6.6 wt%) showed hysteresis in the N2 isotherm and an increase in the fraction of larger pores, indicating that mesopores were generated during the impregnation. Temperature-programmed desorption with ammonia was performed to understand the binding affinity of ammonia molecules on Ag@MIL-101. The binding affinity was the lowest with Ag@MIL-101 (6.6 wt%), including the largest relative fraction in the amount of desorbed ammonia molecules. It was presumed that cooperative interaction between the silver nanoparticle and the MIL-101 framework for ammonia molecules could allow such a decrease in the desorption temperature. Our design strategy with metal nanoparticles incorporated into MOFs would contribute to develop hybrid MOFs that reduce energy consumption when reusing ammonia from storage.
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Project description:Although the perovskite sensing materials have shown high sensitivity and ideal selectivity toward neutral, oxidative, or reductive gases, their structural instability hampers the practical application. To exploit perovskite-based gas-sensing materials with improved stability and decent sensitivity, three adsorption complexes of H2O, NH3, and O2 on the Cs2Pb(SCN)2Br2 surface are built by doping Br- and Cs+ in the parent (CH3NH3)2Pb(SCN)2I2 structure and submitted to quantum dynamics simulations. Changes in the semiconductor material geometric structures during these dynamic processes are analyzed and adsorption ability and charge transfer between Cs2Pb(SCN)2Br2 and the gas molecules are explored so as to further establish a correlation between the geometrical structure variations and the charge transfer. By comparing with the previous CH3NH3PbI3 and (CH3NH3)2Pb(SCN)2I2 adsorption systems, we propose the key factors that enhance the stability of perovskite structures in different atmospheres. The current work is expected to provide clues for developing innovative perovskite sensing materials or for constructing reasonable sensing mechanisms.
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Project description:The title compound, bis-[di-thio-bis-(formamidinium)] hexa-bromido-ruthenium dibromide trihydrate, [(NH2)2CSSC(NH2)2]2[RuBr6]Br2·3H2O, crystallizes in the ortho-rhom-bic system, space group Cmcm, Z = 4. The [RuBr6]2- anionic complex has an octa-hedral structure. The Ru-Br distances fall in the range 2.4779 (4)-2.4890 (4) Å. The S-S and C-S distances are 2.0282 (12) and 1.783 (2) Å, respectively. The H2O mol-ecules, Br- ions, and NH2 groups of the cation are linked by hydrogen bonds. The conformation of the cation is consolidated by intra-molecular O-H⋯Br, O-H⋯O, N-H⋯Br and N-H⋯O hydrogen bonds. The [(NH2)2CSSC(NH2)2]2+ cations form a hydrogen-bonded system involving the Br - ions and the water mol-ecules. Two Br - anions form four hydrogen bonds, each with the NH2 groups of two cations, thus linking the cations into a ring. The rings are connected by water mol-ecules, forming N-H⋯O-H⋯Br hydrogen bonds.
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