Inducing ferroelastic domains in single-crystal 
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 perovskite nanowires using atomic force microscopy

Marçal, Lucas L.A.B.; Benter, Sandra; Irish, Austin; Dzhigaev, Dmitry; Oksenberg, Eitan; Rothman, Amnon; Sanders, Ella; Hammarberg, Susanna; Zhang, Zhaojun; Sala, Simone; Björling, Alexander; Unger, Eva; Mikkelsen, Anders; Joselevich, Ernesto; Timm, Rainer; Wallentin, Jesper

doi:10.1103/physrevmaterials.5.l063001

Cited by 8 publications

(8 citation statements)

References 50 publications

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“…It is notable in figure 3(a) that both α and β maps present vertical striped domains along the nanowire axis, with sizes in the order of a few hundreds of nanometers. This is a signature of the ferroelastic nature of this material, which has been previously described by our group and others [26,39,40]. Subsequent domains in the β show stepped tilts of about 0.20°.…”

Section: Resultssupporting

confidence: 79%

Structural and chemical properties of anion exchanged CsPb(Br_(1−x)Cl_x)₃ heterostructured perovskite nanowires imaged by nanofocused x-rays

Marçal,

Lamers,

Hammarberg

et al. 2024

Nanotechnology

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Over the last years metal halide perovskites have demonstrated remarkable potential for integration in light emitting devices. Heterostructures allow for tunable bandgap depending on the local anion composition, crucial for optoelectronic devices, but local structural effects of anion exchange in single crystals is not fully understood. Here, we investigate how the anion exchange of CsPbBr3 nanowires fully and locally exposed to HCl vapor affects the local crystal structure, using nanofocused x-rays. We study the nanoscale composition and crystal structure as function of HCl exposure time and demonstrate the correlation of anion exchange with changes in the lattice parameter. The local composition was measured by x-ray fluorescence and x-ray diffraction, with general agreement of both methods but with much less variation using latter. The heterostructured nanowires exhibit unintentional gradients in composition, both axially and radially. Ferroelastic domains are observed for all HCl exposure times, and the magnitude of the lattice tilt decreases for higher Cl concentrations.

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Section: Resultssupporting

confidence: 79%

Structural and chemical properties of anion exchanged CsPb(Br_(1−x)Cl_x)₃ heterostructured perovskite nanowires imaged by nanofocused x-rays

Marçal,

Lamers,

Hammarberg

et al. 2024

Nanotechnology

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“…This latter process can be understood as an immunity response to the loss of symmetry when, upon minimizing the Gibbs free energy, the system relaxes into a thermodynamically stable state by forming ferroelastic, near-orthogonal domains. These formations have been widely studied at the nano-, micro-, and mesoscales. − In perovskites, crystal twinning is associated with lowering of the lattice symmetry by tilting and contortion of octahedra, which causes spontaneous intrinsic stress. The introduction of such structural distortions will significantly affect the local electronic structure and hence transition probabilities.…”

Section: Introductionmentioning

confidence: 99%

Light-Controlled Multiphase Structuring of Perovskite Crystal Enabled by Thermoplasmonic Metasurface

et al. 2023

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Halide perovskites belong to an important family of semiconducting materials with electronic properties that enable a myriad of applications, especially in photovoltaics and optoelectronics. Their optical properties, including photoluminescence quantum yield, are affected and notably enhanced at crystal imperfections where the symmetry is broken and the density of states increases. These lattice distortions can be introduced through structural phase transitions, allowing charge gradients to appear near the interfaces between phase structures. In this work, we demonstrate controlled multiphase structuring in a single perovskite crystal. The concept uses cesium lead bromine (CsPbBr 3 ) placed on a thermoplasmonic TiN/Si metasurface and enables single-, double-, and triple-phase structures to form on demand above room temperature. This approach promises application horizons of dynamically controlled heterostructures with distinctive electronic and enhanced optical properties.

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“…X-ray diffraction (XRD) is the method of choice to study both heterostructures and ferroelasticity due to its high reciprocal space resolution, but it has previously been plagued by poor real space resolution. However, with the brilliance of the fourth-generation synchrotrons, together with modern X-ray focusing capabilities reaching below 100 nm, variations of strain and lattice tilts can be imaged in nanostructures. − Scanning nano-XRD is a technique to probe lattice spacings, strain, and lattice tilts in samples on the nanoscale with high resolution and superior strain sensitivity, − and it has been used to image MHP nanowires to probe ferroelastic domains and phase transitions. − With simultaneous scanning X-ray fluorescence (XRF) measurements, variations in a crystal can be correlated to compositional analysis.…”

Section: Introductionmentioning

confidence: 99%

“… 17 − 19 Scanning nano-XRD is a technique to probe lattice spacings, strain, and lattice tilts in samples on the nanoscale with high resolution and superior strain sensitivity, 20 − 24 and it has been used to image MHP nanowires to probe ferroelastic domains and phase transitions. 25 − 27 With simultaneous scanning X-ray fluorescence (XRF) measurements, variations in a crystal can be correlated to compositional analysis.…”

Section: Introductionmentioning

confidence: 99%

Nanoscale X-ray Imaging of Composition and Ferroelastic Domains in Heterostructured Perovskite Nanowires: Implications for Optoelectronic Devices

Hammarberg,

Marçal,

Lamers

et al. 2023

ACS Appl. Nano Mater.

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Metal halide perovskites (MHPs) have garnered significant interest as promising candidates for nanoscale optoelectronic applications due to their excellent optical properties. Axially heterostructured CsPbBr 3 − CsPb(Br (1−x) Cl x ) 3 nanowires can be produced by localized anion exchange of pregrown CsPbBr 3 nanowires. However, characterizing such heterostructures with sufficient strain and real space resolution is challenging. Here, we use nanofocused scanning X-ray diffraction (XRD) and X-ray fluorescence (XRF) with a 60 nm beam to investigate a heterostructured MHP nanowire as well as a reference CsPbBr 3 nanowire. The nano-XRD approach gives spatially resolved maps of composition, lattice spacing, and lattice tilt. Both the reference and exchanged nanowire show signs of diverse types of ferroelastic domains, as revealed by the tilt maps. The chlorinated segment shows an average Cl composition of x = 66 and x = 70% as measured by XRD and XRF, respectively. The XRD measurements give a much more consistent result than the XRF ones. These findings are consistent with photoluminescence measurements, showing x = 73%. The nominally unexchanged segment also has a small concentration of Cl, as observed with all three methods, which we attribute to diffusion after processing. These results highlight the need to prevent such unwanted processes in order to fabricate optoelectronic devices based on MHP heterostructures.

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Inducing ferroelastic domains in single-crystal CsPbBr3 perovskite nanowires using atomic force microscopy

Cited by 8 publications

References 50 publications

Structural and chemical properties of anion exchanged CsPb(Br_(1−x)Cl_x)₃ heterostructured perovskite nanowires imaged by nanofocused x-rays

Structural and chemical properties of anion exchanged CsPb(Br_(1−x)Cl_x)₃ heterostructured perovskite nanowires imaged by nanofocused x-rays

Light-Controlled Multiphase Structuring of Perovskite Crystal Enabled by Thermoplasmonic Metasurface

Nanoscale X-ray Imaging of Composition and Ferroelastic Domains in Heterostructured Perovskite Nanowires: Implications for Optoelectronic Devices

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Inducing ferroelastic domains in single-crystal CsPbBr3 perovskite nanowires using atomic force microscopy

Cited by 8 publications

References 50 publications

Structural and chemical properties of anion exchanged CsPb(Br(1−x)Cl x )3 heterostructured perovskite nanowires imaged by nanofocused x-rays

Structural and chemical properties of anion exchanged CsPb(Br(1−x)Cl x )3 heterostructured perovskite nanowires imaged by nanofocused x-rays

Light-Controlled Multiphase Structuring of Perovskite Crystal Enabled by Thermoplasmonic Metasurface

Nanoscale X-ray Imaging of Composition and Ferroelastic Domains in Heterostructured Perovskite Nanowires: Implications for Optoelectronic Devices

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Product

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Structural and chemical properties of anion exchanged CsPb(Br_(1−x)Cl_x)₃ heterostructured perovskite nanowires imaged by nanofocused x-rays

Structural and chemical properties of anion exchanged CsPb(Br_(1−x)Cl_x)₃ heterostructured perovskite nanowires imaged by nanofocused x-rays