Compared with their 3D counterparts, 2D hybrid organic–inorganic halide perovskites (HOIPs) exhibit enhanced chemical stabilities and superior optoelectronic properties, which can be further tuned by the application of external pressure. Here, we report the first high-pressure study on CMA2PbI4 (CMA = cylcohexanemethylammonium), a 2D HOIP with a soft organic spacer cation containing a flexible cyclohexyl ring, using UV–visible absorption, photoluminescence (PL) and vibrational spectroscopy, and synchrotron X-ray microdiffraction, all aided with density functional theory (DFT) calculations. Substantial anisotropic compression behavior is observed, as characterized by unprecedented negative linear compressibility along the b axis. Moreover, the pressure dependence of optoelectronic properties is found to be in strong contrast with those of 2D HOIPs with rigid spacer cations. DFT calculations help to understand the compression mechanisms that lead to pressure-induced bandgap narrowing. These findings highlight the important role of soft spacer cations in the pressure-tuned optoelectronic properties and provide guidance to the design of new 2D HOIPs.

Nonlinear absorption of femtosecond laser pulses provides a unique opportunity to confine energy deposition in any medium to a region that is below the focal diameter of a pulse. Illumination of a polymer film through a transparent high-band-gap material such as glass, followed by nonlinear absorption of 800nm light in polymers, allows us to further restrict absorption to a very thin layer along the propagation direction. We demonstrate this confinement by simulating femtosecond-laser-induced polymer modification by linear, two-photon, and three-photon absorption, and discuss the control over energy absorption in polymers that multiphoton processes offer. Energy deposited in a thin polymer film induces a protruding blister. We present experimental results for blister diameter and height scaling with variation of pulse energy. Using pulse energies of 20-200 nJ and 0.4-NA focusing, we fabricate blisters with diameters of 1-5.5 μm and heights of 75 nm to 2 μm. Using 0.95-NA focusing, we obtain laser-induced blisters with diameters as small as 700 nm, suggesting blister-based laser-induced forward transfer is possible on and below the 1-μm scale. Submicrometer blister formation with use of femtosecond lasers also offers a method of direct, precise laser writing of microstructures on films with single laser pulses. This method is a possible alternative to lithography, laser milling, and laser-based additive machining.

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