Extending lead-free hybrid photovoltaic materials to new structures: thiazolium, aminothiazolium and imidazolium iodobismuthates

Li, Tianyue; Wang, Qifei; Nichol, Gary S.; Morrison, Carole A.; Han, Hongwei; Hu, Yue; Robertson, Neil

doi:10.1039/c8dt00864g

Cited by 34 publications

(35 citation statements)

References 57 publications

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“…The bandgap energies (E g ) were determined from the onset of UV-vis absorption spectra, where absorption edges of Tauc plot (n = 2) correspond to the direct transition ( Fig. 1d) [29].…”

Section: Resultsmentioning

confidence: 99%

Comparative Study of Charge Carrier Dynamics in Bismuth-based Dimer and Double Perovskites

Nishikubo

Saeki

2019

J. Photopol. Sci. Technol.

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From the environmental and economical aspects, the development of less-toxic lead-free perovskite is an imperative challenge for next generation photovoltaics. Although bismuthbased dimer perovskite (A 3 B 2 X 9) and double perovskite (A 2 BB'X 6) (A = cation, B = Bi, B' = Ag, X = halogen) have been considered as the plausible candidates, their power conversion efficiencies (PCE) are still low (~2.2%). In this work, we comparatively evaluated the photoconductivity and charge carrier transfer to electron/hole transport layer (ETL/HTL) in A 3 B 2 X 9 and A 2 BB'X 6 by time-resolved microwave conductivity (TRMC). In contrast to A 3 B 2 X 9 , A 2 BB'X 6 showed much higher photoconductivity and charge transfer efficiency to ETL/HTL. This result is consistent with the PCEs of our photovoltaic devices, in which the double perovskite of Cs 2 AgBiBr 6 exhibited greatly improved fill factor and one order larger photocurrent density than dimer perovskites (Cs 3 Bi 2 I 9 , MA 3 Bi 2 I 9 , and FA 3 Bi 2 I 9 ; MA = methlyammonium cation, FA = formamidinium cation). Our results provide an insight into the key role of photoactive layer and charge transfer process.

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“…The bandgap energies (E g ) were determined from the onset of UV-vis absorption spectra, where absorption edges of Tauc plot (n = 2) correspond to the direct transition ( Fig. 1d) [29].…”

Section: Resultsmentioning

confidence: 99%

Comparative Study of Charge Carrier Dynamics in Bismuth-based Dimer and Double Perovskites

Nishikubo

Saeki

2019

J. Photopol. Sci. Technol.

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“…At the same time, the majority of these compounds have rather wide band gaps exceeding 2 eV, which makes them poor light harvesters. However, recent literature provides several examples of hybrid iodobismuthates with low band gaps, ranging from 1.59 to 1.80 eV [ 32 , 33 , 34 , 35 , 36 ]. These compounds contain various organic cations and, more importantly, have different dimensionality of the anionic substructure, ranging from isolated anions to vertex-sharing BiI 5 chains to edge-sharing BiI 4 – chains.…”

Section: Introductionmentioning

confidence: 99%

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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“…22,35 This predicament is mainly caused by their low structural and electronic dimensionalities, which disrupts continuous carrier transport. [36][37][38] To make progress, extended M 3+ halide networks have been obtained in terms of 1D chain-like structures, including (MI 4 ) -22,39 and (MI 5 ) 2-. 24,[40][41] However, the organic countercations employed therein are hydrophilic protonated amine-type cations or heteroaromatic cations with strong hydrophilic groups (typically -NH 3 + , =NH 2 + or NH + ), which could form strong N-H•••O hydrogen bond with external water molecules, thereby greatly reducing the moisture stability of OHPs.…”

Section: Introductionmentioning

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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Extending lead-free hybrid photovoltaic materials to new structures: thiazolium, aminothiazolium and imidazolium iodobismuthates

Cited by 34 publications

References 57 publications

Comparative Study of Charge Carrier Dynamics in Bismuth-based Dimer and Double Perovskites

Comparative Study of Charge Carrier Dynamics in Bismuth-based Dimer and Double Perovskites

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

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

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