Hybrid Charge-Transfer Semiconductors: (C7H7)SbI4, (C7H7)BiI4, and Their Halide Congeners

Oswald, Iain W. H.; Moseley, Ian P.; Ahn, Hyochul; Neilson, James R.

doi:10.1021/acs.inorgchem.9b00170

Cited by 41 publications

(43 citation statements)

References 54 publications

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“…The remaining factor influencing the band gap width is the interaction between the cation and anion. Unlike the case of (C 7 H 7 )BiI 4 , in which the cation-to-anion charge transfer takes place [51], the shrinkage of the band gap in the title compound can be attributed to the contribution of hydrogen bonds. Firstly, strong (N)H•••I hydrogen bonds slightly push iodine 5p orbitals to higher energy rendering smaller width of the ban gap; secondly, hydrogen bonds are capable of promoting mobility of charge carriers, ensuring 3D conductivity in solids composed of 0D Bi/I anions [34,39,52,53].…”

Section: D-h•••a D(h•••a) å D(d•••a) å Angle (D-h•••a)mentioning

confidence: 79%

Assembling Polyiodides and Iodobismuthates Using a Template Effect of a Cyclic Diammonium Cation and Formation of a Low-Gap Hybrid Iodobismuthate with High Thermal Stability

et al. 2020

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Exploiting a template effect of 1,4-diazacycloheptane (also known as homopiperazine, Hpipe), four new hybrid iodides, (HpipeH2)2Bi2I10·2H2O, (HpipeH2)I(I3), (HpipeH2)3I6·H2O, and (HpipeH2)3(H3O)I7, were prepared and their crystal structures were solved using single crystal X-ray diffraction data. All four solid-state crystal structures feature the HpipeH22+ cation alternating with Bi2I104–, I3–, or I– anions and solvent water or H3O+ cation. HpipeH22+ assembles anionic and neutral building blocks into polymer structures by forming four strong (N)H···I and (N)H···O hydrogen bonds per cation, with the H···I distances ranging from 2.44 to 2.93 Å and H···O distances of 1.88–1.89 Å. These hydrogen bonds strongly affect the properties of compounds; in particular, in the case of (HpipeH2)2Bi2I10·2H2O, they ensure narrowing of the band gap down to 1.8 eV and provide high thermal stability up to 240 °C, remarkable for a hydrated molecular solid.

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Section: D-h•••a D(h•••a) å D(d•••a) å Angle (D-h•••a)mentioning

confidence: 79%

Assembling Polyiodides and Iodobismuthates Using a Template Effect of a Cyclic Diammonium Cation and Formation of a Low-Gap Hybrid Iodobismuthate with High Thermal Stability

et al. 2020

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“…[ 7 ] The second method is the exploration of perovskite‐like phosphors with chemical formulas of AB III X 4 , A 2 B′X 4 (B′ = Cu 2+ , Sn 2+ , Mn 2+ , Fe 2+ , and Zn 2+ ) and A 3 B III 2 X 9 . [ 8 ] The third way is to replace half of the B‐site ions with B IV (B IV = Sn 4+ , Pd 4+ , Ti 4+ , Te 4+ , Se 4+ , and A+RE 3+ (RE is rare‐earth element)) and meanwhile remove the remaining half, thus forming double perovskites derivatives A 2 B IV X 6 with good chemical stability , such as Cs 2 PdX 6 and Cs 2 SnCl 6 . [ 9 ] However, the luminescence of almost all the phosphors wrought above originates from self‐trapped excitons (STEs) emission, which is not easy to control, and the luminescence efficiency still needs to be improved for practical applications.…”

Section: Introductionmentioning

confidence: 99%

Aliovalent Doping and Surface Grafting Enable Efficient and Stable Lead‐Free Blue‐Emitting Perovskite Derivative

Xiong

Yuan

Jin

et al. 2020

Advanced Optical Materials

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properties, low cost, facile preparation and high defect tolerance. [1] Remarkable progress has been made, especially in terms of widespread applications spanning from solar cells, photodetectors, photocatalysts, and solid-state lasers to light-emitting diodes (LEDs). [2] In more recent years, owing to the exceptional luminescence properties, such as high brightness, color tunability, and intense absorption coefficient, lead halide perovskites have found promising potential applications as color converter for next-generation solid-state lightings and backlight displays. [3] Unfortunately, the intrinsic nature of poor stability and toxicity of lead halide perovskites are some serious issues to be tackled if the materials are to be used on a large scale. The chemical instability will severely restrict the lifespan of devices, and the accumulation of lead will cause serious environmental problems and fatal threat to human health. [4] Extensive efforts have been devoted to overcome the thorny challenges on the way to practical applications. To completely eliminate the potential danger of lead leakage, the simplest and practicable way is to replace it in the B site of ABX 3 with nontoxic isovalent metal ions. [5] As reasonable candidates, Ge 2+ and Sn 2+ ions are the first to come to mind for the substitution of Pb 2+ due to the same electronic configuration of ns 2 np 0 Lead halide perovskites have emerged as superstar semiconductors owing to their superior optoelectronic properties. However, the issues of chemical and thermodynamic instability and toxicity are yet to be resolved. Here, the non-and Bi 3+-doped all-inorganic lead-free perovskite derivatives are reported. Most remarkable is the successful extending of excitation of Cs 2 ZrCl 6 to match with the commercial near ultraviolet light-emitting diode chips via deliberate Bi 3+ aliovalent doping. The blue emission, contrary to self-trapped exciton (STE) emissions amply reported previously, originates from Bi 3+ ionoluminescence with a high photoluminescence quantum efficiency of 50%. The competition for harvesting electrons between STEs and Bi 3+ is studied in detail by steady-and transient-state fluorescence spectroscopy in combination with theoretical calculations. Surface grafting endows Cs 2 ZrCl 6 :Bi 3+ with a robust water-resistant core-shell-like structure and abiding emission. Surprisingly, the emission intensity even increases to 115.94% of the initial level after immersing in water for 2 h. The as-obtained phosphor enables the fabrication of a white light-emitting diode (w-LED), achieving CCT = 4179 K and Ra = 81.9. This work not only promotes the step toward development of leadfree, stable, and high-efficiency perovskite derivatives for the next-generation warm w-LEDs, but also reveals the structure-PL relationship.

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“…More experimental and theoretical details are available in Supporting Information. 39,50 As illustrated in Scheme S1, the hydrogen-bond-free cations Me4ppi…”

Section: Experimental Methodsmentioning

confidence: 99%

Double Free: A Promising Route toward Moisture-Stable Hypotoxic Hybrid Perovskites

Zhao

2022

CCS Chem

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The moisture instability and toxicity of lead have hindered the development of lead organometal halide perovskites (Pb-OHPs). Similar to Pb-OHPs, OHPs based on Pb-free elements, including VA-group metals Bi and Sb (denoted as M), exhibit optoelectronic properties due to their isoelectronic configuration and close chemistry of the lone-pair ns 2 state. However, M-OHPs are mostly based on hydrophilic protonated organic countercations and possess low structural dimensionalities, which affect the moisture stability and disrupt continuous carrier transport, respectively. Herein, we demonstrate a "double-free" strategy to realize the rational synthesis of moisture-stable hypotoxic hybrid perovskites. A hydrogen-bond-free alkylated countercation was assembled with Pb-free OHP bearing an extended structure in one molecule. As a proof of concept, two double-free M-OHPs are synthesized, which show greatly improved moisture and photostability than their corresponding hydrogen bond OHPs and the extensively studied MA 3 M 2 X 9 (MA = CH 3 NH 3 + ).The photoconduction behaviors of both double-free OHPs display short rise and decay recovery time and exhibit excellent photocurrent reproducibility. Importantly, (1-methyl-4-phenylpyridin-1-ium)BiI 4 (Me4ppi-BiI 4 ) displays a comparable switching on/off ratio with MA 3 Bi 2 I 9 , and can endure 75% relative humidity for at least 243 days. The photophysical property measurements and theoretical calculation show that the remarkable photoconversion performance results from the relatively low exciton binding energy and greatly improved carrier mobility and concentration.

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Hybrid Charge-Transfer Semiconductors: (C₇H₇)SbI₄, (C₇H₇)BiI₄, and Their Halide Congeners

Cited by 41 publications

References 54 publications

Assembling Polyiodides and Iodobismuthates Using a Template Effect of a Cyclic Diammonium Cation and Formation of a Low-Gap Hybrid Iodobismuthate with High Thermal Stability

Assembling Polyiodides and Iodobismuthates Using a Template Effect of a Cyclic Diammonium Cation and Formation of a Low-Gap Hybrid Iodobismuthate with High Thermal Stability

Aliovalent Doping and Surface Grafting Enable Efficient and Stable Lead‐Free Blue‐Emitting Perovskite Derivative

Double Free: A Promising Route toward Moisture-Stable Hypotoxic Hybrid Perovskites

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