Searching for promising new perovskite-based photovoltaic absorbers: the importance of electronic dimensionality

Xiao, Zewen; Meng, Weiwei; Wang, Jianbo; Mitzi, David B.; Yan, Yanfa

doi:10.1039/c6mh00519e

Cited by 642 publications

(709 citation statements)

References 107 publications

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“…[55] The electronic dimensionality is defined by the connectivity of the electronic orbitals that comprise the conduction band bottom and the valence band top. [55] The electronic dimensionality is defined by the connectivity of the electronic orbitals that comprise the conduction band bottom and the valence band top.…”

Section: High Electronic Dimensionalitymentioning

confidence: 99%

“…[158] Giustino et al [160] counted the elements of the periodic table which belong to known halide elpasolites. [55] Second, for B(III) cations, the transition metal cations with multiple oxidation states and/or partially occupied d or f orbitals are not desirable for designing photovoltaic absorbers, because they may introduce deep defect states and too localized band edges. Although a straightforward multiplication of these numbers yields 9520 combinations (without considering the phase stabi lity), most of them, however, can be ruled out for photovoltaic applications by simply screening the B(I), B(III), and X ions based on their impacts on the optoelectronic properties including bandgap and carrier transport.…”

Section: A 2 B(i)b(ii)x 6 Halide Double Perovskitesmentioning

confidence: 99%

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From Lead Halide Perovskites to Lead‐Free Metal Halide Perovskites and Perovskite Derivatives

2019

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serious challenges due to the inclusion of toxic Pb and instability against moisture, heat, and irradiation. In recent years, significant efforts have been paid to develop Pb-free halide perovskite and perovskite derivative absorber materials. However, so far, solar cells based on these materials show significantly inferior performances as compared to their Pb halide perovskite counterparts. Herein, we provide reviews on the fundamental understandings of the photovoltaic properties from Pb halide perovskites to Pb-free metal halide perovskites and perovskite derivatives as well as the experimental results reported in the literature. The results suggest that replacing Pb by nontoxic elements may degrade the superior photovoltaic properties seen in Pb halide perovskites, explaining the fact that all reported solar cells based on Pb-free perovskites or perovskite derivatives show performances significantly lower than Pb halide perovskite solar cells. Overview: Approaches and Consequences of Pb ReplacementWe first provide an overview of the approaches and consequences of Pb replacement reported in the literature, as shown in Figure 1. In general, there are two categories for Pb replacement: using either homovalent elements such as Sn and Ge or heterovalent elements such as Bi and Sb. The heterovalent replacement category can be divided into two subcategories based on the ways to maintain the charge neutrality: ion-splitting and ordered vacancy. The ion-splitting subcategory can be further divided into mixed anion compounds with the formula of AB(Ch,X) 3 , where Ch represents a chalcogen element, and X represents a halogen element, and mixed cation compounds with a formula of A 2 B(I)B(III)X 6 , which are commonly called double perovskites. The ordered vacancy subcategory can also be divided into the B(III) compounds with a formula of A 3 ◻B(III)X 9 and the B(IV) compounds with a formula of A 2 ◻ B(IV)X 6 (the sign of ◻ indicates vacancy). Figure 1 also summarizes the photovoltaic properties and the stabilities of each group of materials, which provides a clear overview of the consequences of Pb replacement. While the homovalent replacement by Sn or Ge leads to instability, the heterovalent Pb replacement leads to degraded electronic properties mainly due to the reduction on electronic dimensionality. As a result, all the reported Pb-free perovskite and perovskite derivative solar Despite the exciting progress on power conversion efficiencies, the commercialization of the emerging lead (Pb) halide perovskite solar cell technology still faces significant challenges, one of which is the inclusion of toxic Pb. Searching for Pb-free perovskite solar cell absorbers is currently an attractive research direction. The approaches used for and the consequences of Pb replacement are reviewed herein. Reviews on the theoretical understanding of the electronic, optical, and defect properties of Pb and Pb-free halide perovskites and perovskite derivatives are provided, as well as the experimental results available in the literature....

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Section: High Electronic Dimensionalitymentioning

confidence: 99%

Section: A 2 B(i)b(ii)x 6 Halide Double Perovskitesmentioning

confidence: 99%

From Lead Halide Perovskites to Lead‐Free Metal Halide Perovskites and Perovskite Derivatives

2019

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“…[5,8] However, doping also tends to cause nonradiation recombination loss. [14] Through density functional theory (DFT) calculation, in 1D CsCu 2 I 3 SC, [Cu 2 I 3 ] − octahedra contributes most electronic states, and Cs + only forms a 1D electronic structure with isolated [Cu 2 I 3 ] − in 2D direction. [12,13] The "one dimension" we noted here is localized dimension of electron.…”

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confidence: 99%

All‐Inorganic CsCu₂I₃ Single Crystal with High‐PLQY (≈15.7%) Intrinsic White‐Light Emission via Strongly Localized 1D Excitonic Recombination

et al. 2019

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In order to achieve a high quantum efficiency, doping crystals with appropriate elements such as sodium cations (ref. [8]) to reduce electronic dimension is a useful method. [5,8] However, doping also tends to cause nonradiation recombination loss. [13] Therefore, a reliable and promising way is to synthesize high-quality inorganic metal halide single crystal (SC) with natural lowdimensional structure to realize stable and high quantum efficiency white-light illumination application.In this work, we successfully synthesized 1D CsCu 2 I 3 SC by replacing toxic Pb with eco-friendly and abundant Cu, and organic molecules with large-radius Cs. [12,13] The "one dimension" we noted here is localized dimension of electron. [14] Through density functional theory (DFT) calculation, in 1D CsCu 2 I 3 SC, [Cu 2 I 3 ] − octahedra contributes most electronic states, and Cs + only forms a 1D electronic structure with isolated [Cu 2 I 3 ] − in 2D direction. Therefore, CsCu 2 I 3 SC obtains a high photoluminescence quantum yield (PLQY ≈15.7%) of the IWE at room temperature. [2] We also calculated that the crystal has a high radiation recombination rate which is owning to the 1D localized electronic structure, and this rate is the key to its high PLQY. [15,16] Under a strong injection and atmospheric environment, the PL intensity of all-inorganic CsCu 2 I 3 SC only decays about 5% after 750 min ( Figure S5, Supporting Information). This excellent stability demonstrates that the all-inorganic CsCu 2 I 3 SC possesses a great prospect in high-efficiency lighting applications.High-quality CsCu 2 I 3 SCs were synthesized by antisolvent infiltration method. [17,18] Cesium iodide and cuprous (I) iodide in certain ratio were dissolved in dimethyl formamide (DMF)dimethyl sulfoxide (DMSO) (4:1) to obtain a saturated solution. Then, methanol (antisolvent) was slowly dropped into the saturated solution to form a white precipitate (the white precipitate quickly dissolved again) until it no longer dissolved. The solution was filtered and then placed in a beaker with methanol atmosphere to grow crystals. Several days later, centimeter-scale high-quality CsCu 2 I 3 SCs were obtained (refer to the Supporting information and the Experimental Section for more details). Figure 1a shows an optical image of a rod-shaped CsCu 2 I 3 SCs excited by ultraviolet light. The SC has a size of about 10 mm × 1.5 mm, being colorless and transparent at room temperature but having strong white-light emission under ultraviolet light. Crystal structure of the CsCu 2 I 3 SC was obtained through single-crystal X-ray diffraction (SCXRD) test (Figure 1b,c), which belongs to orthorhombic system. The 1D Energy-saving white lighting from the efficient intrinsic emission of semiconductors is considered as a next-generation lighting source. Currently, white-light emission can be composited with a blue light-emitting diode and yellow phosphor. However, this solution has an inevitable light loss, which makes the improvement of the energy utilization efficiency more difficult. T...

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“…32,33 One possible reason for this is that the iodobismuthates are built from discrete Bi/I binuclear anions with low structural and electronic dimensionality, which leads to limited charge carrier transport. 34 Attempts to increase the dimensionality have been made by investigating A 2 MBiX 6 (M = Ag, K, Na, etc.) bismuth-based double perovskite materials.…”

Section: Introductionmentioning

confidence: 99%

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

Wang

Nichol

et al. 2018

Dalton Trans.

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We report on the synthesis, crystal structures, optoelectronic properties and solar cell device studies of three novel organic-inorganic iodobismuthates - ]) as the light absorber in a hole-conductor-free, fully printable solar cell, with relatively good reproducibility. We also note the observation of a capacitance effect for the first time in a photovoltaic device with bismuth-based solar absorber, which may be related to the mesoporous carbon counter-electrode.

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Searching for promising new perovskite-based photovoltaic absorbers: the importance of electronic dimensionality

Abstract: The concept of electronic dimensionality,i.e., the connectivity of the atomic orbitals that comprise the lower conduction band and upper valence band, is introduced to better account for the device performance of the perovskite-based solar cells.

Cited by 642 publications

References 107 publications

From Lead Halide Perovskites to Lead‐Free Metal Halide Perovskites and Perovskite Derivatives

From Lead Halide Perovskites to Lead‐Free Metal Halide Perovskites and Perovskite Derivatives

All‐Inorganic CsCu₂I₃ Single Crystal with High‐PLQY (≈15.7%) Intrinsic White‐Light Emission via Strongly Localized 1D Excitonic Recombination

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

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Searching for promising new perovskite-based photovoltaic absorbers: the importance of electronic dimensionality

Abstract: The concept of electronic dimensionality,i.e., the connectivity of the atomic orbitals that comprise the lower conduction band and upper valence band, is introduced to better account for the device performance of the perovskite-based solar cells.

Cited by 642 publications

References 107 publications

From Lead Halide Perovskites to Lead‐Free Metal Halide Perovskites and Perovskite Derivatives

From Lead Halide Perovskites to Lead‐Free Metal Halide Perovskites and Perovskite Derivatives

All‐Inorganic CsCu2I3 Single Crystal with High‐PLQY (≈15.7%) Intrinsic White‐Light Emission via Strongly Localized 1D Excitonic Recombination

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

Contact Info

Product

Resources

About

All‐Inorganic CsCu₂I₃ Single Crystal with High‐PLQY (≈15.7%) Intrinsic White‐Light Emission via Strongly Localized 1D Excitonic Recombination