Details

Autor(en) / Beteiligte

• Jaffe, Adam
• Lin, Yu
• Mao, Wendy L
• Karunadasa, Hemamala I

Titel

Pressure-Induced Conductivity and Yellow-to-Black Piezochromism in a Layered Cu–Cl Hybrid Perovskite

Ist Teil von

• Journal of the American Chemical Society, 2015-02, Vol.137 (4), p.1673-1678

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2015

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Pressure-induced changes in the electronic structure of two-dimensional Cu-based materials have been a subject of intense study. In particular, the possibility of suppressing the Jahn–Teller distortion of d9 Cu centers with applied pressure has been debated over a number of decades. We studied the structural and electronic changes resulting from the application of pressures up to ca. 60 GPa on a two-dimensional copper(II)–chloride perovskite using diamond anvil cells (DACs), through a combination of in situ powder X-ray diffraction, electronic absorption and vibrational spectroscopy, dc resistivity measurements, and optical observations. Our measurements show that compression of this charge-transfer insulator initially yields a first-order structural phase transition at ca. 4 GPa similar to previous reports on other CuII–Cl perovskites, during which the originally translucent yellow solid turns red. Further compression induces a previously unreported phase transition at ca. 8 GPa and dramatic piezochromism from translucent red-orange to opaque black. Two-probe dc resistivity measurements conducted within the DAC show the first instance of appreciable conductivity in CuII–Cl perovskites. The conductivity increases by 5 orders of magnitude between 7 and 50 GPa, with a maximum measured conductivity of 2.9 × 10–4 S·cm–1 at 51.4 GPa. Electronic absorption spectroscopy and variable-temperature conductivity measurements indicate that the perovskite behaves as a 1.0 eV band-gap semiconductor at 39.7 GPa and has an activation energy for electronic conduction of 0.232(1) eV at 40.2 GPa. Remarkably, all these changes are reversible: the material reverts to a translucent yellow solid upon decompression, and ambient pressure powder X-ray diffraction data taken before and after compression up to 60 GPa show that the original structure is maintained with minimal hysteresis.