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Title: Lead free CH{sub 3}NH{sub 3}SnI{sub 3} perovskite thin-film with p-type semiconducting nature and metal-like conductivity

Abstract

Lead free CH{sub 3}NH{sub 3}SnI{sub 3} perovskite thin film was prepared by low temperature solution processing and characterized using current sensing atomic force microscopy (CS-AFM). Analysis of electrical, optical, and optoelectrical properties reveals unique p-type semiconducting nature and metal like conductivity of this material. CH{sub 3}NH{sub 3}SnI{sub 3} film also showed a strong absorption in visible and near infrared spectrum with absorption onset of 1.3 eV. X-ray Diffraction analysis and scanning electron microscopy (SEM) confirmed a structure of this compound and uniform film formation. The morphology, film uniformity, light harvesting and electrical properties strongly depend on preparation method and precursor solution. CH{sub 3}NH{sub 3}SnI{sub 3} films prepared based on dimethylformamide (DMF) showed higher crystallinity and light harvesting capability compared to the film based on combination of dimethyl sulfoxide (DMSO) with gamma-butyrolactone (GBL). Local photocurrent mapping analysis showed that CH{sub 3}NH{sub 3}SnI{sub 3} can be used as an active layer and have a potential to fabricate lead free photovoltaic devices.

Authors:
; ; ; ;  [1]
  1. South Dakota State University, Brookings, South Dakota (United States)
Publication Date:
OSTI Identifier:
22611412
Resource Type:
Journal Article
Resource Relation:
Journal Name: AIP Advances; Journal Volume: 6; Journal Issue: 8; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ABSORPTION; ATOMIC FORCE MICROSCOPY; DMSO; ELECTRIC CONDUCTIVITY; ELECTRICAL PROPERTIES; INFRARED SPECTRA; IODINE COMPOUNDS; LAYERS; NEAR INFRARED RADIATION; OPTICAL PROPERTIES; ORGANIC SEMICONDUCTORS; PEROVSKITE; PHOTOCURRENTS; PHOTOVOLTAIC EFFECT; P-TYPE CONDUCTORS; SCANNING ELECTRON MICROSCOPY; THIN FILMS; TIN COMPOUNDS; X-RAY DIFFRACTION

Citation Formats

Iefanova, Anastasiia, Adhikari, Nirmal, Dubey, Ashish, Khatiwada, Devendra, and Qiao, Qiquan, E-mail: qiquan.qiao@sdstate.edu. Lead free CH{sub 3}NH{sub 3}SnI{sub 3} perovskite thin-film with p-type semiconducting nature and metal-like conductivity. United States: N. p., 2016. Web. doi:10.1063/1.4961463.
Iefanova, Anastasiia, Adhikari, Nirmal, Dubey, Ashish, Khatiwada, Devendra, & Qiao, Qiquan, E-mail: qiquan.qiao@sdstate.edu. Lead free CH{sub 3}NH{sub 3}SnI{sub 3} perovskite thin-film with p-type semiconducting nature and metal-like conductivity. United States. doi:10.1063/1.4961463.
Iefanova, Anastasiia, Adhikari, Nirmal, Dubey, Ashish, Khatiwada, Devendra, and Qiao, Qiquan, E-mail: qiquan.qiao@sdstate.edu. 2016. "Lead free CH{sub 3}NH{sub 3}SnI{sub 3} perovskite thin-film with p-type semiconducting nature and metal-like conductivity". United States. doi:10.1063/1.4961463.
@article{osti_22611412,
title = {Lead free CH{sub 3}NH{sub 3}SnI{sub 3} perovskite thin-film with p-type semiconducting nature and metal-like conductivity},
author = {Iefanova, Anastasiia and Adhikari, Nirmal and Dubey, Ashish and Khatiwada, Devendra and Qiao, Qiquan, E-mail: qiquan.qiao@sdstate.edu},
abstractNote = {Lead free CH{sub 3}NH{sub 3}SnI{sub 3} perovskite thin film was prepared by low temperature solution processing and characterized using current sensing atomic force microscopy (CS-AFM). Analysis of electrical, optical, and optoelectrical properties reveals unique p-type semiconducting nature and metal like conductivity of this material. CH{sub 3}NH{sub 3}SnI{sub 3} film also showed a strong absorption in visible and near infrared spectrum with absorption onset of 1.3 eV. X-ray Diffraction analysis and scanning electron microscopy (SEM) confirmed a structure of this compound and uniform film formation. The morphology, film uniformity, light harvesting and electrical properties strongly depend on preparation method and precursor solution. CH{sub 3}NH{sub 3}SnI{sub 3} films prepared based on dimethylformamide (DMF) showed higher crystallinity and light harvesting capability compared to the film based on combination of dimethyl sulfoxide (DMSO) with gamma-butyrolactone (GBL). Local photocurrent mapping analysis showed that CH{sub 3}NH{sub 3}SnI{sub 3} can be used as an active layer and have a potential to fabricate lead free photovoltaic devices.},
doi = {10.1063/1.4961463},
journal = {AIP Advances},
number = 8,
volume = 6,
place = {United States},
year = 2016,
month = 8
}
  • Strong spin-orbit coupled 5d transition metal based ABO{sub 3} oxides, especially iridates, allow tuning parameters in the phase diagram and may demonstrate important functionalities, for example, by means of strain effects and symmetry-breaking, because of the interplay between the Coulomb interactions and strong spin-orbit coupling. Here, we have epitaxially stabilized high quality thin films of perovskite (Pv) CaIrO{sub 3}. Film on the best lattice-matched substrate shows semi-metal-like characteristics. Intriguingly, imposing tensile or compressive strain on the film by altering the underlying lattice-mismatched substrates still maintains semi-metallicity with minute modification of the effective correlation as tensile (compressive) strain results in tinymore » increases (decreases) of the electronic bandwidth. In addition, magnetoresistance remains positive with a quadratic field dependence. This persistent semi-metal-like nature of Pv-CaIrO{sub 3} thin films with minute changes in the effective correlation by strain may provide new wisdom into strong spin-orbit coupled 5d based oxide physics.« less
  • In this study, computational, thin-film deposition and characterization approaches have been used to examine the ternary halide semiconductor Cs 3Sb 2I 9. Cs 3Sb 2I 9 has two known structural modifications, the 0-D dimer form (space group P6 3/mmc, No. 194) and the 2-D layered form (Pmore » $$\bar{3}$$ m1, No. 164), which can be prepared via solution and solid state or gas phase reactions, respectively. Our computational investigations suggest that the layered form, which is a one-third Sb-deficient derivative of the ubiquitous perovskite structure, is a potential candidate for high-band-gap photovoltaic (PV) applications. In this work, we describe details of a two-step deposition approach that enables the preparation of large grain (>1 µm) and continuous thin films of the lead-free layered perovskite derivative Cs 3Sb 2I 9. Depending on the deposition conditions, films that are c-axis oriented or randomly oriented can be obtained. The fabricated thin films show enhanced stability under ambient air, compared to methylammonium lead (II) iodide perovskite films stored under similar conditions, and an optical band gap value of 2.05 eV. Photoelectron spectroscopy study yields an ionization energy of 5.6 eV, with the valence band maximum approximately 0.85 eV below the Fermi level, indicating near-intrinsic, weakly p-type character. Density Functional Theory (DFT) analysis points to a nearly direct band gap for this material (less than 0.02 eV difference between the direct and indirect band gaps) and a similar high-level of absorption compared to CH 3NH 3PbI 3. The photoluminescence peak intensity of Cs 3Sb 2I 9 is substantially suppressed compared to that of CH 3NH 3PbI 3, likely reflecting the presence of deep level defects that result in non-radiative recombination in the film, with computational results pointing to I i, IS b, and V I as being likely candidates. A key further finding from this study is that, despite a distinctly layered structure, the electronic transport anisotropy is less pronounced due to the high ionicity of the I atoms and the strong anti-bonding interactions between the Sb s lone pair states and I p states, which leads to a moderately dispersive valence band.« less
  • In this study, computational, thin-film deposition and characterization approaches have been used to examine the ternary halide semiconductor Cs 3Sb 2I 9. Cs 3Sb 2I 9 has two known structural modifications, the 0-D dimer form (space group P6 3/mmc, No. 194) and the 2-D layered form (Pmore » $$\bar{3}$$ m1, No. 164), which can be prepared via solution and solid state or gas phase reactions, respectively. Our computational investigations suggest that the layered form, which is a one-third Sb-deficient derivative of the ubiquitous perovskite structure, is a potential candidate for high-band-gap photovoltaic (PV) applications. In this work, we describe details of a two-step deposition approach that enables the preparation of large grain (>1 µm) and continuous thin films of the lead-free layered perovskite derivative Cs 3Sb 2I 9. Depending on the deposition conditions, films that are c-axis oriented or randomly oriented can be obtained. The fabricated thin films show enhanced stability under ambient air, compared to methylammonium lead (II) iodide perovskite films stored under similar conditions, and an optical band gap value of 2.05 eV. Photoelectron spectroscopy study yields an ionization energy of 5.6 eV, with the valence band maximum approximately 0.85 eV below the Fermi level, indicating near-intrinsic, weakly p-type character. Density Functional Theory (DFT) analysis points to a nearly direct band gap for this material (less than 0.02 eV difference between the direct and indirect band gaps) and a similar high-level of absorption compared to CH 3NH 3PbI 3. The photoluminescence peak intensity of Cs 3Sb 2I 9 is substantially suppressed compared to that of CH 3NH 3PbI 3, likely reflecting the presence of deep level defects that result in non-radiative recombination in the film, with computational results pointing to I i, IS b, and V I as being likely candidates. A key further finding from this study is that, despite a distinctly layered structure, the electronic transport anisotropy is less pronounced due to the high ionicity of the I atoms and the strong anti-bonding interactions between the Sb s lone pair states and I p states, which leads to a moderately dispersive valence band.« less
  • High-quality metal halide perovskite single crystals have low defect densities and excellent photophysical properties, yet thin films are the most sought after material geometry for optoelectronic devices. Perovskite single-crystal thin films (SCTFs) would be highly desirable for high-performance devices, but their growth remains challenging, particularly for inorganic metal halide perovskites. Herein, we report the facile vapor-phase epitaxial growth of cesium lead bromide perovskite (CsPbBr 3) continuous SCTFs with controllable micrometer thickness, as well as nanoplate arrays, on traditional oxide perovskite SrTiO 3(100) substrates. Heteroepitaxial single-crystal growth is enabled by the serendipitous incommensurate lattice match between these two perovskites, and overcomingmore » the limitation of island-forming Volmer–Weber crystal growth is critical for growing large-area continuous thin films. Time-resolved photoluminescence, transient reflection spectroscopy, and electrical transport measurements show that the CsPbBr 3 epitaxial thin film has a slow charge carrier recombination rate, low surface recombination velocity (10 4 cm s –1), and low defect density of 10 12 cm –3, which are comparable to those of CsPbBr 3 single crystals. This work suggests a general approach using oxide perovskites as substrates for heteroepitaxial growth of halide perovskites. Furthermore, the high-quality halide perovskite SCTFs epitaxially integrated with multifunctional oxide perovskites could open up opportunities for a variety of high-performance optoelectronics devices.« less
    Cited by 2
  • High-quality metal halide perovskite single crystals have low defect densities and excellent photophysical properties, yet thin films are the most sought after material geometry for optoelectronic devices. Perovskite single-crystal thin films (SCTFs) would be highly desirable for high-performance devices, but their growth remains challenging, particularly for inorganic metal halide perovskites. Herein, we report the facile vapor-phase epitaxial growth of cesium lead bromide perovskite (CsPbBr 3) continuous SCTFs with controllable micrometer thickness, as well as nanoplate arrays, on traditional oxide perovskite SrTiO 3(100) substrates. Heteroepitaxial single-crystal growth is enabled by the serendipitous incommensurate lattice match between these two perovskites, and overcomingmore » the limitation of island-forming Volmer–Weber crystal growth is critical for growing large-area continuous thin films. Time-resolved photoluminescence, transient reflection spectroscopy, and electrical transport measurements show that the CsPbBr 3 epitaxial thin film has a slow charge carrier recombination rate, low surface recombination velocity (10 4 cm s –1), and low defect density of 10 12 cm –3, which are comparable to those of CsPbBr 3 single crystals. This work suggests a general approach using oxide perovskites as substrates for heteroepitaxial growth of halide perovskites. Furthermore, the high-quality halide perovskite SCTFs epitaxially integrated with multifunctional oxide perovskites could open up opportunities for a variety of high-performance optoelectronics devices.« less