Amorphous germanium films on nonrefractory glass substrates were annealed by ultrashort near-infrared (1030 nm, 1.4 ps) and mid-infrared (1500 nm, 70 fs) laser pulses. Crystallization of germanium irradiated at a laser energy density (fluence) range from 25 to 400 mJ/cm2 under single-shot and multishot conditions was investigated using Raman spectroscopy. The dependence of the fraction of the crystalline phase on the fluence was obtained for picosecond and femtosecond laser annealing. The regimes of almost complete crystallization of germanium films over the entire thickness were obtained (from the analysis of Raman spectra with excitation of 785 nm laser). The possibility of scanning laser processing is shown, which can be used to create films of micro- and nanocrystalline germanium on flexible substrates.
Silicon–germanium multilayer structures consisting of alternating Si and Ge amorphous nanolayers were annealed by ultrashort laser pulses at near-infrared (1030 nm) and mid-infrared (1500 nm) wavelengths. In this paper, we investigate the effects of the type of substrate (Si or glass), and the number of laser pulses (single-shot and multi-shot regimes) on the crystallization of the layers. Based on structural Raman spectroscopy analysis, several annealing regimes were revealed depending on laser fluence, including partial or complete crystallization of the components and formation of solid Si–Ge alloys. Conditions for selective crystallization of germanium when Si remains amorphous and there is no intermixing between the Si and Ge layers were found. Femtosecond mid-IR laser annealing appeared to be particularly favorable for such selective crystallization. Similar crystallization regimes were observed for both single-shot and multi-shot conditions, although at lower fluences and with a lower selectivity in the latter case. A theoretical analysis was carried out based on the laser energy absorption mechanisms, thermal stresses, and non-thermal effects.
Amorphous germanium films on non-refractory glass substrates were annealed by ultrashort near-infrared (1030 nm, 1.4 ps) and mid-infrared (1500 nm, 70 fs) laser pulses. Crystallization of germanium irradiated at a laser energy density (fluence) range from 25 to 400 mJ/cm2 under single-shot and multi-shot conditions was investigated using Raman spectroscopy. The dependence of the fraction of the crystalline phase on the fluence was obtained for picosecond and femtosecond laser annealings. The regimes of almost complete crystallization of germanium films over the entire thickness are obtained (from the analysis of Raman spectra with excitation of 785 nm laser). The possibility of scanning laser processing is shown, which can be used to create films of micro and nanocrystalline germanium on flexible substrates.
Ultrashort pulsed laser annealing is an efficient technique for crystallizing amorphous semiconductors with the possibility to obtain polycrystalline films at low temperatures, below the melting point, through non-thermal processes. Here, a multilayer structure consisting of alternating amorphous silicon and germanium films was annealed by mid-infrared (1500 nm) ultrashort (70 fs) laser pulses under single-shot and multi-shot irradiation conditions. We investigate selective crystallization of ultrathin (3.5 nm) a-Ge non-hydrogenated films, which are promising for the generation of highly photostable nanodots. Based on Raman spectroscopy analysis, we demonstrate that, in contrast to thicker (above 10 nm) Ge films, explosive stress-induced crystallization is suppressed in such ultrathin systems and proceeds via thermal melting. This is likely due to the islet structure of ultrathin films, which results in the formation of nanopores at the Si-Ge interface and reduces stress confinement during ultrashort laser heating.
This study demonstrates the crystallization of thin-film amorphous hydrogenated germanium (a‐Ge:H) using infrared (1035 nm) ultrashort laser pulses, establishing the processing parameters for future flexible electronics. A 240 nm thick a‐Ge:H film was deposited by PECVD and irradiated with pulses ranging from 220 fs to 10 ps. The crystallization threshold fluence was found to be strongly dependent on pulse duration, decreasing from ~74 mJ/cm² for 10 ps to a minimum of ~46 mJ/cm² for 220 fs pulses. This drastic reduction for femtosecond pulses is attributed to a non-thermal ("cold") melting mechanism initiated by the generation of an ultra-dense electron-hole plasma bypassing the classical thermal pathway dominant at longer durations. Complete crystallization without ablation was achieved with 220 fs pulses at fluences of 151–184 mJ/cm². A key practical outcome is the demonstration that picosecond pulses (2–10 ps) enable effective crystallization at significantly lower peak power densities (~0.07–0.3 PW/m²) compared to the femtosecond regime (~2 PW/m²). The process produces nanocrystalline germanium (~4–5 nm) without inducing surface relief, which is critical for scalability. These results define the physical mechanisms and practical "processing windows" for laser crystallization of germanium, paving the way for its integration into large-area, flexible optoelectronic devices on non-refractory substrates.