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.
Blister formation occurs when a laser pulse interacts with the underside of a polymer film on a glass substrate and is fundamental in Laser-Induced Forward Transfer (LIFT). We present a novel method of controlling blister formation using a thin metal film situated between two thin polymer films. This enables a wide range of laser pulse energies by limiting the laser penetration in the film, which allows us to exploit nonlinear interactions without transmitting high intensities that may destroy a transfer material. We study blisters using a helium ion microscope, which images their interiors, and find that laser energy deposition is primarily in the metal layer and the top polymer layer remains intact. Blister expansion is driven by laser-induced spallation of the gold film. Our work shows that this technique could be a viable platform for contaminant-free LIFT using nonlinear absorption beyond the diffraction limit.
We report a decreased surface wettability when polymer films on a glass substrate are treated by ultrafast laser pulses in a back-illumination geometry. We propose that back illumination through the substrate confines chemical changes beneath the surface of polymer films, leaving the surface blistered but chemically intact.To confirm this hypothesis, we measure the phase contrast of the polymer when imaged with a focused ion beam. We observe a void at the polymer-quartz interface that results from the expansion of an ultrafast laser-induced plasma. A modified polymer layer surrounds the void, but otherwise the film seems unmodified. We also use x-ray photoelectron spectroscopy to confirm that there is no chemical change to the surface. When patterned with partially overlapping blisters, our polymer surface shows increased hydrophobicity. The increased hydrophobicity of back-illuminated surfaces can only result from the morphological change. This contrasts with the combined chemical and morphological changes of the polymer surface caused by a front-illumination geometry.
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