Research Progress on Perovskite Structural Distortion and Performance Regulation

doi:10.16553/j.cnki.issn1000-985x.2025.0088

Abstract

Abstract: Metal halide perovskite materials have demonstrated significant application potential in fields such as solar cells， light-emitting diodes， and photodetectors due to their excellent optoelectronic properties and tunable crystal structures. Structural distortion， as a crucial means of regulating the performance of perovskite materials， can significantly influence their electronic structure， carrier dynamics， and optoelectronic properties， providing an important pathway for designing novel functional materials. In recent years， research on the regulation of lattice distortion in perovskite single crystals has made remarkable progress. By altering substrate properties， introducing organic cations， modulating halide composition， or applying external stress， researchers can effectively adjust the lattice symmetry and electronic band structure of perovskite single crystals， thereby optimizing their optoelectronic performance. In particular， the regulatory effects of lattice distortion on carrier dynamics， exciton behavior， and defect state density offer new avenues for developing high-performance perovskite devices. This paper first elaborates on the characterization methods and mechanistic principles of structural distortions in perovskite materials， then thoroughly analyzes the key influencing factors that induce structural distortions under experimental conditions. Furthermore， it provides an in-depth discussion on the structure-property relationship between lattice distortions and optoelectronic performance， offering both theoretical foundations and practical guidance for structural distortion control and performance optimization of perovskite optoelectronic materials.

Key words: perovskite; metal halide; structural distortion; strain engineering; grazing incidence X-ray diffraction

CLC Number:

O469

JIN Tong, NIU Guangda. Research Progress on Perovskite Structural Distortion and Performance Regulation[J]. Journal of Synthetic Crystals, 2025, 54(7): 1160-1174.

Figures/Tables 11

Fig.1 （a） The plot of estimated X-ray penetration depth versus incident angles in FAPbI3［19］；（b） diffraction geometries of the depth-dependent strain distribution measurement. The relation between instrument reference （Z） frame and diffraction vector （α and β are the incident and exit angles of X-rays， defined as the angle between the incident/diffracted X-rays and the sample surface）；（c） schematic illustration of the residual strain distribution measurement. The corresponding XRD patterns and lattice structure strain information can be obtained by fixing the test crystal plane and adjusting the instrument tilt angle ψ， where N0 is the sample normal direction and Nk is the diffraction vector［11］

Fig.2 （a） Schematic diagram of surface strain state；（b） GIXRD patterns at different tilt angles at the depth of 50 nm for the tensile-strained film；（c） residual strain distribution in the depth of 50， 200， 500 nm for the tensile-strained film；（d） GIXRD patterns at different tilt angles at the depth of 50 nm for the strain-free film；（e） residual strain distribution in the depth of 50， 200， 500 nm for the strain-free film；（f） GIXRD patterns at different tilt angles at the depth of 50 nm for the compressive strained film；（g） residual strain distribution in the depth of 50， 200， 500 nm for the compressive strained film［11］

Fig.3 Schematic diagram of strain. （a） Out-of-plane XRD patterns of the MAPbI3 annealed film （AF）， scraped powder （SP）， single-crystal powder （SCP）， and non-annealed film （NAF）；（b） in-plane and out-of-plane XRD patterns of AF and out-of-plane XRD pattern of SCP；（c） schematic diagram of the out-of-plane structure；（d） schematic diagram of the in-plane structure［10］

Fig.4 （a） The crystal under growing is free of cracks；（b） solution-grown CsPbBr3 single crystals with cracks，（c） paralleled domains indicate the formation of twin boundaries in CsPbBr3；（d） a photograph of several as-grown FA x Cs1-x PbBr3 single crystals from different precursor solutions with Cs/（Cs?+?FA） ratios varying from 0% to 100%［20］

Fig.5 Schematic diagram and XRD patterns of the strain formation process. （a） Without substrate， the perovskite forming at 100 °C contracts vertically and laterally during cooling；（b） with the substrate adhesion， the annealed perovskite film only contracts vertically， in situ out-of-plane XRD of scraped powder （c） and annealed film （d） at different temperatures［10］

Fig.6 Epitaxial α-FAPbI3 thin films and structural characterizations. （a） Optical images of the as-grown epitaxial α-FAPbI3 thin films；（b） a cross-sectional scanning electron microscope （SEM） image of the epitaxial thin film with controlled uniform thickness；（c） high-resolution XRD ω-2θ scan of the （001） peaks of the epitaxial samples on different substrates showing the increasing tetragonality with increasing lattice mismatch；（d） reciprocal space mapping with （104） asymmetric reflection of the α-FAPbI3， for different lattice mismatches with the substrate［9］

Fig.7 （a） Cross-sectional TEM image of device；（b） PL depth profile of confocal fluorescence microscope， the inset represents TOF-SIMS depth profiles of the （FAPbI3）0.85（MAPbBr3）0.15 perovskite film with tensile strain［11］

Fig.8 （a） Residual strain distribution in the depth of 100， 300， 500 nm for PEA2PbBr4 single crystal （measured （points） and Gauss fitted （line） diffraction strain data as a function of sin2φ）；（b） the plot of lattice constant versus penetration depth；（c） the results of the layer-decomposed density of state calculation for PEA2PbI4 with and without （PEA+-I-） defect and schematics of the model structures vertically aligned with the layers；（d） N 1s XPS of the surface and interior of two-dimensional perovskites PEA2PbI4［28］

Fig.9 Strain-induced electronic structure analysis. （a） Calculated band structures under biaxial tensile， zero， and compressive strains from first-principle DFT-based approaches， the band structure alignment is made by using the vacuum energy level as reference；（b） the evolution of band-edge energies under gradually increasing tensile strains in perovskite films （left panel）， and the schematic of the band alignment between tensile strain/strain-free film and hole transport layer in solar cell；（c） UV-Vis absorption spectra and PL spectra under tensile strain， strainfree， and compressive strain conditions［11］

Fig.10 The energy transfer process between the surface and inside excitons of two-dimensional perovskite. （a） Time-resolved PL kinetics collected in the emission channels of 500~590 nm；（b） normalized PL spectra with the different time delays of 2D-perovskites；（c） normalized PL decay curves monitored at 520 and 559 nm wavelength， respectively；（d） schematic illustration of the energy level and exciton funneling process of the self-wavelength shifting in two-dimensional perovskites［28］

Fig.11 （a） Effective masses of the carriers at different strains， and electronic bandstructures under three strain levels （3%， 0% and -3%）；（b） hole mobilities by Hall effect measurements showing that α-FAPbI3 with strain of -1.2% has the highest hole mobility；（c） transient photocurrent curves of the epitaxial α-FAPbI3 under different strains；（d） plots of calculated carrier mobilities as a function of the strain magnitudes［9］

References 32

[1]	CHUNG I， LEE B， HE J Q， et al. All-solid-state dye-sensitized solar cells with high efficiency［J］. Nature， 2012， 485（7399）： 486-489.
[2]	KOVALENKO M V， PROTESESCU L， BODNARCHUK M I. Properties and potential optoelectronic applications of lead halide perovskite nanocrystals［J］. Science， 2017， 358（6364）： 745-750.
[3]	JENA A K， KULKARNI A， MIYASAKA T. Halide perovskite photovoltaics： background， status， and future prospects［J］. Chemical Reviews， 2019， 119（5）： 3036-3103.
[4]	FENG J， QIAN X F， HUANG C W， et al. Strain-engineered artificial atom as a broad-spectrum solar energy funnel［J］. Nature Photonics， 2012， 6（12）： 866-872.
[5]	KURDI M， BERTIN H， MARTINCIC E， et al. Control of direct band gap emission of bulk germanium by mechanical tensile strain［J］. Applied Physics Letters， 2010， 96（4）： 041909.
[6]	AHN G H， AMANI M， RASOOL H， et al. Strain-engineered growth of two-dimensional materials［J］. Nature Communications， 2017， 8（1）： 608.
[7]	HUBBARD S M， CRESS C D， BAILEY C G， et al. Effect of strain compensation on quantum dot enhanced GaAs solar cells［J］. Applied Physics Letters， 2008， 92（12）： 123512.
[8]	OSHIMA R， TAKATA A， OKADA Y. Strain-compensated InAs/GaNAs quantum dots for use in high-efficiency solar cells［J］. Applied Physics Letters， 2008， 93（8）： 083111.
[9]	CHEN Y M， LEI Y S， LI Y H， et al. Strain engineering and epitaxial stabilization of halide perovskites［J］. Nature， 2020， 577（7789）： 209-215.
[10]	ZHAO J J， DENG Y H， WEI H T， et al. Strained hybrid perovskite thin films and their impact on the intrinsic stability of perovskite solar cells［J］. Science Advances， 2017， 3（11）： 5616.
[11]	ZHU C， NIU X X， FU Y H， et al. Strain engineering in perovskite solar cells and its impacts on carrier dynamics［J］. Nature Communications， 2019， 10（1）： 815.
[12]	LEBLEBICI S Y， LEPPERT L， LI Y B， et al. Facet-dependent photovoltaic efficiency variations in single grains of hybrid halide perovskite［J］. Nature Energy， 2016， 1： 16093.
[13]	BUSH K A， ROLSTON N， GOLD-PARKER A， et al. Controlling thin-film stress and wrinkling during perovskite film formation［J］. ACS Energy Letters， 2018， 3（6）： 1225-1232.
[14]	VAILIONIS A， BOSCHKER H， SIEMONS W， et al. Misfit strain accommodation in epitaxial ABO₃ perovskites： lattice rotations and lattice modulations［J］. Physical Review B， 2011， 83（6）： 064101.
[15]	CHEN Z， PRUD’HOMME N， WANG B， et al. Residual stress gradient analysis with GIXRD on ZrO₂ thin films deposited by MOCVD［J］. Surface and Coatings Technology， 2011， 206（2/3）： 405-410.
[16]	PENG J， JI V， SEILER W， et al. Residual stress gradient analysis by the GIXRD method on CVD tantalum thin films［J］. Surface and Coatings Technology， 2006， 200（8）： 2738-2743.
[17]	BENEDIKTOVITCH A， ULYANENKOVA T， KECKES J， et al. Stress gradient analysis by noncomplanar X-ray diffraction and corresponding refraction correction［J］. Advanced Materials Research， 2014， 996： 162-168.
[18]	STEFENELLI M， TODT J， RIEDL A， et al. X-ray analysis of residual stress gradients in TiN coatings by a Laplace space approach and cross-sectional nanodiffraction： a critical comparison［J］. Journal of Applied Crystallography， 2013， 46（5）： 1378-1385.
[19]	QIN M C， XUE H B， ZHANG H K， et al. Precise control of perovskite crystallization kinetics via sequential A-site doping［J］. Advanced Materials， 2020， 32（42）： 2004630.
[20]	ZHAO L， ZHOU Y， SHI Z F， et al. High-yield growth of FACsPbBr₃ single crystals with low defect density from mixed solvents for gamma-ray spectroscopy［J］. Nature Photonics， 2023， 17（4）： 315-323.
[21]	LIU G， KONG L P， GONG J， et al. Pressure-induced bandgap optimization in lead-based perovskites with prolonged carrier lifetime and ambient retainability［J］. Advanced Functional Materials， 2017， 27（3）： 1604208.
[22]	CHEN B， LI T， DONG Q F， et al. Large electrostrictive response in lead halide perovskites［J］. Nature Materials， 2018， 17（11）： 1020-1026.
[23]	WANG Y P， GAO L， YANG Y B， et al. Nontrivial strength of van der Waals epitaxial interaction in soft perovskites［J］. Physical Review Materials， 2018， 2（7）： 076002.
[24]	YU J X， LIU G X， CHEN C M， et al. Perovskite CsPbBr₃ crystals： growth and applications［J］. Journal of Materials Chemistry C， 2020， 8（19）： 6326-6341.
[25]	FENG Y X， PAN L， WEI H T， et al. Low defects density CsPbBr₃ single crystals grown by an additive assisted method for gamma-ray detection［J］. Journal of Materials Chemistry C， 2020， 8（33）： 11360-11368.
[26]	HE Y H， MATEI L， JUNG H J， et al. High spectral resolution of gamma-rays at room temperature by perovskite CsPbBr₃ single crystals［J］. Nature Communications， 2018， 9（1）： 1609.
[27]	JACOBSSON T J， SCHWAN L J， OTTOSSON M， et al. Determination of thermal expansion coefficients and locating the temperature-induced phase transition in methylammonium lead perovskites using X-ray diffraction［J］. Inorganic Chemistry， 2015， 54（22）： 10678-10685.
[28]	JIN T， LIU Z， LUO J J， et al. Self-wavelength shifting in two-dimensional perovskite for sensitive and fast gamma-ray detection［J］. Nature Communications， 2023， 14（1）： 2808.
[29]	MELONI S， PALERMO G， ASHARI-ASTANI N， et al. Valence and conduction band tuning in halide perovskites for solar cell applications［J］. Journal of Materials Chemistry A， 2016， 4（41）： 15997-16002.
[30]	YIN W J， YANG J H， KANG J， et al. Halide perovskite materials for solar cells： a theoretical review［J］. Journal of Materials Chemistry A， 2015， 3（17）： 8926-8942.
[31]	PANUGANTI S， BESTEIRO L V， VASILEIADOU E S， et al. Distance dependence of Förster resonance energy transfer rates in 2D perovskite quantum wells via control of organic spacer length［J］. Journal of the American Chemical Society， 2021， 143（11）： 4244-4252.
[32]	GIORGI G， FUJISAWA J I， SEGAWA H， et al. Small photocarrier effective masses featuring ambipolar transport in methylammonium lead iodide perovskite： a density functional analysis［J］. The Journal of Physical Chemistry Letters， 2013， 4（24）： 4213-4216.