The energy density crystallization threshold of amorphous GeSb films has been studied for the first time as a function of the laser pulse duration in the range from 170 fs to 8 ns. The results obtained provide evidence of the existence of enhanced crystallization upon irradiation with pulses shorter than 800 fs, which is most likely related to electronic excitation effects. The study of the interaction of ultrashort laser pulses with solids has raised some important questions concerning the nature of the transformations occurring at the material surface in the presence of very strong levels of electronic excitation. The existence of electronic excitation induced phase transitions has been already demonstrated in several materials (Si [1], GaAs [2‐ 4], graphite [5]). In the case of crystalline semiconductors, excitation with pulses shorter than the longitudinal optical phonon emission time [6] may lead to a structural instability of the lattice, leading to the formation of a metastable transient phase with (semi)metallic character. It is not clear, however, whether the presence of such transient strong electronic excitation and/or transient phases may influence the final state or structure induced since, once the energy of the excited carriers has been transferred to the lattice, the structural transformation path is thermal in nature. Different nonthermal mechanisms which could lead to enhanced crystallization and to crystal damage recovery upon pulsed laser irradiation were proposed during the early 1980s [7,8]. More recently, both photonic effects and electron-hole plasma induced network softening have been invoked to explain structural changes induced in amorphous Si and Ge upon ns and ps laser pulse irradiation [9 ‐ 11]. High Sb-content GeSb amorphous and crystalline thin films have been shown to both crystallize and amorphize upon irradiation with subnanosecond laser pulses. Both processes show optical contrast [12] making this material a potential candidate for applications in ultrashort laser pulse driven phase change optical recording [13,14]. These characteristics also make this material interesting for the study of possible high electronic excitation induced and enhanced crystallization processes. The aim of this work is to elucidate whether the high electronic excitation, induced by irradiation with subnanosecond laser pulses, can induce or enhance the crystallization process of the amorphous phase. Such an enhancement process should lead to appreciable changes in the minimum energy density required for crystallization as the laser pulse duration changes, according to the differences in the excited carrier populations induced. We have performed what we believe to be the first experiment to determine the minimum energy density required for crystallization of an amorphous phase upon irradiation with laser pulses whose durations extend over 3 orders of magnitude, covering the range 170 fs to 8 ns. The samples used in the experiment were 50 nm thick, Ge 0.07Sb 0.93 films grown at room temperature in a multitarget magnetron dc sputtering system from Ge and Sb (99.999% purity) targets onto glass, carbon-coated mica, and Si(100) substrates. In order to improve the sensitivity of the material and to enhance the crystallization rate upon pulsed laser irradiation, two different kinds of samples were grown: (a) fully amorphous layers with the composition Ge 0.07Sb 0.93 and (2) bilayered films formed by an amorphous surface layer of similar composition and an underlayer slightly richer in Sb and therefore polycrystalline. Since the bilayered films showed smaller transformation times and improved sensitivity upon pulsed laser irradiation with 10 ps laser pulses at 583 nm, they were chosen for the present work. The samples on mica and Si were used, respectively, to prepare planar and cross-section transmission electron microscopy (TEM) specimens in order to characterize film structure and composition. The latter was determined by energy dispersive x-ray spectroscopy on planar TEM specimens. An ultrashort CPA laser pulse source (described in Ref. [15]) was used to irradiate the samples on glass. The experimental configuration is shown in Fig. 1. A commercial fs Ti:Al 2O 3 oscillator providing 150 fs duration pulses at a repetition rate of 82 MHz at 830 nm was used to seed an Ar 1 ion pumped Cr-LiSAF solid state regenerative amplifier. Before seeding the amplifier, the oscillator pulses were stretched to approximately 300 ps with a diffraction grating pulse stretcher. After amplification the pulses were recompressed with a grating pair compressor. The typical output of the laser system consisted of a 10 kHz repetition rate pulse train with energies per pulse in the order of 5 mJ. A second Pockels cell, synchronized to the one in the regenerative amplifier, was used
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