Chemical and structural analysis of low-temperature excimer-laser annealing in indium-tin oxide sol-gel films

We investigated the influence of excimer-laser annealing (ELA) on the electrical, chemical, and structural properties of indium–tin oxide (ITO) films prepared by a solution process. The ITO film was prepared by the sol-gel method and annealed by excimer-laser pulses with an energy density up to 240?mJ/cm². Hall measurements showed that the ELA substantially enhanced the electrical properties of the ITO films, including their resistivity, carrier density, and mobility, as increasing the laser energy density. In-depth x-ray photoelectron spectroscopy analysis of the chemical states in the film surface showed that the ELA reduced carbon species and promoted both an oxidation and crystallization. These changes were consistent with results of x-ray diffraction and transmission electron microscopy measurements, where expansions in the microcrystal growth were observed for higher laser energy density. We comprehensively understand that the chemical rearrangement and concomitant crystallization are the main factors for achieving the electrical properties during the ELA. These results suggest the potential of the ELA-treated sol-gel films for providing high-quality ITO films at low temperatures toward the flexible device applications.     

Field emission measured from nanostructured germanium and silicon thin films

We have prepared nanostructured thin films of germanium and silicon. The films were grown by an ion beam sputtering technique followed by a rapid annealing step using an electron beam annealer. The annealing temperature is a comparatively low 500 °C, resulting in well defined nano-islands on the film surface. Electron field emission has been measured from the surfaces under high vacuum. The threshold electric field value for significant current flow was measured as 2.5 V μm⁻¹ for a silicon thin film which is comparable to other silicon technologies. A value of 0.5 V μm⁻¹ for a germanium thin film represents an order of magnitude improvement for related germanium nanostructured systems.     

Influence of the laser wavelength on the epitaxial growth and electrical properties of La0.8Sr0.2MnO3 films grown by excimer laser-assisted MOD

Epitaxial La_1−xSr_xMnO₃ (LSMO) films were prepared by excimer laser-assisted metal organic deposition (ELAMOD) at a low temperature using ArF, KrF, and XeCl excimer lasers. Cross-section transmission electron microscopy (XTEM) observations confirmed the epitaxial growth and homogeneity of the LSMO film on a SrTiO₃ (STO) substrate, which was prepared using ArF, KrF, and XeCl excimer lasers. It was found that uniform epitaxial films could be grown at 500 °C by laser irradiation. When an XeCl laser was used, an epitaxial film was formed on the STO substrate at a fluence range from 80 to 140 mJ/cm² of the laser fluence for the epitaxial growth of LSMO film on STO substrate was changed. When the LaAlO₃ (LAO) substrate was used, an epitaxial film was only obtained by ArF laser irradiation, and no epitaxial film was obtained using the KrF and XeCl lasers. When the back of the amorphous LSMO film on an LAO substrate was irradiated using a KrF laser, no epitaxial film formed. Based on the effect of the wavelength and substrate material on the epitaxial growth, formation of the epitaxial film would be found to be photo thermal reaction and photochemical reaction. The maximum temperature coefficient of resistance (TCR) of the epitaxial La_0.8Sr_0.2MnO₃ film on an STO substrate grown using an XeCl laser is 4.0%/K at 275 K. XeCl lasers that deliver stabilized pulse energies can be used to prepare LSMO films with good a TCR.     

Crystal growth of phosphor perovskite titanate thin films under excimer laser irradiation

Ca_0.997Pr_0.002TiO₃ (CPTO) thin films that show strong red luminescence were successfully prepared by means of an excimer laser assisted metal organic deposition (ELAMOD) process with a KrF laser at a fluence of 100 mJ/cm², a pulse duration of 26 ns, and a repetition rate of 20 Hz at 100°C in air. The CPTO films grew on the silica, borosilicate, and indium-tin-oxide (ITO) glasses. The crystallinity of the CPTO films depended on the substrates; the films were well grown on the borosilicate and ITO glasses compared to the silica glass. To elucidate the key factors for the crystallization of the CPTO films in this process, we carried out numerical simulations for the temperature variation at the laser irradiation, using a heat diffusion equation, and compared the experimental data with thermal simulations. According to the results, we have shown that a large optical absorbance of the film and a small thermal conductivity of the substrate provide effective annealing time and temperature for the crystallization of the CPTO films, and polycrystalline intermediate layer which has a large optical absorption such as the ITO also plays a key role for the nucleation of the CPTO crystals in the ELAMOD process.     

Epitaxial growth of lattice mismatched SrF2 films on (100) GaAs

For the first time insulating epitaxial SrF₂ films on (100) GaAs substrates have been grown by thermal deposition followed by in situ annealing process. Structural properties of SrF₂ films examined by X-ray diffraction, scanning electron microscopy and transmission electron microscopy indicate a very good crystalline quality. It is observed from the X-ray analysis that SrF₂ layers thinner than 100 nm suffer two dimensional compressive stress due to the lattice misfit while those thicker than 100 nm suffer two dimensional tensile stress due to the difference in the thermal expansion coefficients.NCL Communication No. 5077     

Influence of Different Substrates on Laser Induced Damage Thresholds at 1064nm of Ta2O5 Films

Ta2O5 films are prepared on Si, BK7, fused silica, antireflection （AR） and high reflector （HR） substrates by electron beam evaporation method, respectively. Both the optical property and laser induced damage thresholds （LIDTs） at 1064 nm of Ta2O5 films on different substrates are investigated before and after annealing at 673 K for 12 h. It is shown that annealing increases the refractive index and decreases the extinction index, and improves the O/Ta ratio of the Ta2O5 films from 2.42 to 2.50. Moreover, the results show that the LIDTs of the Ta2O5 films are mainly correlated with three parameters： substrate property, substoichiometry defect in the films and impurity defect at the interface between the substrate and the films. Details of the laser induced damage models in different cases are discussed.     

Growth and structure of Bi0.5(Na0.7K0.2Li0.1)0.5TiO3 thin films prepared by pulsed laser deposition technique

Bi_0.5(Na_0.7K_0.2Li_0.1)_0.5TiO₃ (BNKLT) thin films were prepared on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition (PLD) technique. The films prepared were examined by using X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The effects of the processing parameters, such as oxygen pressure, substrate temperature and laser power, on the crystal structure, surface morphology, roughness and deposition rates of the thin films were investigated. It was found that the substrate temperature of 600 °C and oxygen pressure of 30 Pa are the optimized technical parameters for the growth of textured film, and all the thin films prepared have granular structure, homogeneous grain size and smooth surfaces.     

Synthesis and characterization of GaN nanowires

In this work, GaN nanowires were fabricated on Si substrates coated with NiCl₂ thin films using chemical vapor deposition (CVD) method by evaporating Ga₂O₃ powder at 1100 °C in ammonia gas flow. X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscope (HRTEM) and photoluminescence (PL) spectrum are used to characterize the samples. The results demonstrate that the nanowires are single-crystal GaN with hexagonal wurtzite structure. The growth mechanism of GaN nanowires is also discussed.     

Fabrication and characterization of Au/SiO2 nanocomposite films

Au/SiO₂ nanocomposite films were prepared by radio frequency sputtering technique and annealing. The above nanocomposite films were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and atomic force microscopy (AFM). The surface of the nanocomposite films was uniform with the particle diameter of 100-300 nm. The size of Au crystallites increased on increasing annealing time. The luminescent behavior of the nanocomposite films was characterized by photoluminescence (PL) with different excitation wavelengths. Two emission peaks at around 525 nm and 560 nm were observed with the excitation wavelength at 325 nm. An intensive emission peak at around 325 nm was observed with the excitation wavelength at 250 nm, which is related to the defective structure of the amorphous SiO₂ layer because of oxygen deficiency, and could be applied to many fields, such as ultraviolet laser and ultraviolet detector.     

Fs-Laser structuring of ridge waveguides

Thin films made by PLD from Er:ZBLAN and Nd:Gd₃Ga₅O₁₂ are micro machined to form optical wave guiding structures using Ti:sapphire and Yb:glass fiber laser radiation. For the manufacturing of the ridge waveguides grooves are structured by ablation using femtosecond laser radiation. The fluence, the scanning velocity, the repetition rate, and the orientation of the polarization with respect to the scanning direction are varied. The resulting structures are characterized using optical microscopy and scanning electron microscopy. Damping and absorption coefficients of the waveguides are determined by observing the light scattered from the waveguides due to droplets in the thin films and the surface roughness of the structured edges. To discriminate between damping due to droplets and the structured edges, damping measurements in the non-structured films and the structured waveguides are performed. Ridge waveguides with non-resonant damping losses smaller than 3 dB/cm are achieved. Due to the high repetition rate of the Yb:glass fiber laser, the manufacturing time for one waveguide has been decreased by a factor of more than 100 compared to earlier results achieved with the Ti:sapphire laser.     

Dynamical resolidification behavior of silicon thin films during frontside and backside excimer laser annealing

Excimer laser annealing (ELA) is frequently employed to fabricate low-temperature polycrystalline silicon films on glass substrate. The grain size and crystallinity of polycrystalline silicon films are significantly affected by the resolidification behavior during ELA. A real-time in situ time-resolved optical measurement system is developed to record the rapid phase transformation process during ELA. The average solidification velocity of liquid-Si is calculated from these optical spectra using MATLAB and Excel softwares. Field emission scanning electron microscopy images reveal maximum grain size of poly-Si films with a diameter of 1 μm, which is obtained in the complete melting regime of both frontside ELA and backside ELA. Recrystallization mechanisms of complete melting of Si thin films in frontside ELA and backside ELA are demonstrated. Resolidification scenarios of partial melting, near-complete melting and complete melting in frontside ELA and backside ELA are proposed.     

Fast solid-phase crystallization of amorphous silicon films on glass using low-temperature multi-step rapid thermal annealing

Effects of multi-step rapid thermal annealing of plasma-deposited amorphous silicon films on Corning 7059 glass are investigated. A three-step rapid thermal annealing for 10 s/step at 730° C after film deposition reduces the activation energy of electrical conductivity for silicon films from 0.64 to 0.51 eV and causes (111) grain growth with a size of 1500 Å, which is determined using scanning electron microscopy, Raman spectroscopy and X-ray diffractometry.     

A novel optical diagnostic technique for analyzing the recrystallization characteristics of polycrystalline silicon thin films following frontside and backside excimer laser irradiation

Excimer laser annealing (ELA) is a widely used technique for producing polycrystalline silicon (poly-Si) thin films. An optical inspection system with simple optical arrangements for rapid measurement of recrystallization results of poly-Si thin films is developed in this study. The recrystallization results after both frontside ELA and backside ELA can be easily visible from the profile of peak power density distribution using the optical inspection system developed with an optimized moving velocity of 0.312 mm/s of the specimen. The method of backside ELA is suggested for batch production of low-temperature polycrystalline silicon thin-film transistors due to higher laser beam utilization efficiency and lower surface roughness of poly-Si films.     

Enhanced electrical and optical properties of room temperature deposited Aluminium doped Zinc Oxide (AZO) thin films by excimer laser annealing

High quality transparent conductive oxides (TCOs) often require a high thermal budget fabrication process. In this study, Excimer Laser Annealing (ELA) at a wavelength of 248 nm has been explored as a processing mechanism to facilitate low thermal budget fabrication of high quality aluminium doped zinc oxide (AZO) thin films. 180 nm thick AZO films were prepared by radio frequency magnetron sputtering at room temperature on fused silica substrates. The effects of the applied RF power and the sputtering pressure on the outcome of ELA at different laser energy densities and number of pulses have been investigated. AZO films deposited with no intentional heating at 180 W, and at 2 mTorr of 0.2% oxygen in argon were selected as the optimum as-deposited films in this work, with a resistivity of 1×10⁻³ Ω.cm, and an average visible transmission of 85%. ELA was found to result in noticeably reduced resistivity of 5×10⁻⁴ Ω.cm, and enhancing the average visible transmission to 90% when AZO is processed with 5 pulses at 125 mJ/cm². Therefore, the combination of RF magnetron sputtering and ELA, both low thermal budget and scalable techniques, can provide a viable fabrication route of high quality AZO films for use as transparent electrodes.     

Pulsed-laser crystallization and epitaxial growth of metal-organic films of Ca-doped LaMnO3 on STO and LSAT substrates

Ca-doped LaMnO₃ (LCMO) thin films have been successfully prepared on SrTiO₃ (STO) and [(LaAlO₃)_0.3-(SrAlTaO₆)_0.7] (LSAT) substrates using the excimer laser assisted metal-organic deposition (ELAMOD) process. The crystallization and the epitaxial growth of the amorphous metal-organic LCMO thin films have been achieved using a KrF excimer laser irradiation while the substrates were kept at constant temperature of 500 °C. Epitaxial films were obtained using laser fluence in the interval of 50-120 mJ/cm². The microstructure of the LCMO films was studied using cross-section transmission electron microscopy. High quality of LCMO films having smooth surfaces and sharp interfaces were obtained on both the STO and the LSAT substrates. The effect of the laser fluence on the temperature coefficient of resistance (TCR) was investigated. The largest values of TCR of the LCMO grown on the LSAT and the STO substrates of 8.3% K⁻¹ and 7.46% K⁻¹ were obtained at different laser fluence of 80 mJ/cm² and 70 mJ/cm², respectively.     

Laser deposition of amorphous diamond films from liquid aromatic hydrocarbons

6 H₅CH₃, C₆H₆, and C₆H₅CH(CH₃)₂) to pulsed visible laser radiation of a copper vapor laser (λ=510.6 nm). The X-ray Auger electron spectroscopy (XAES), reflection high energy electron diffraction (RHEED), and Raman analysis are employed to characterize the deposited films. The sp³ fraction in deposited films amounts to 60–70% and depends on the precursor. The average film thickness on a glass substrate is about 100 nm. The films show excellent adherence, are transparent in the visible and have microhardness of 50–70 GPa, as measured by nanoindentor. Received: 28 September 1998 / Accepted: 13 January 1999     

Correlation between optical properties and Si nanocrystal formation of Si-rich Si oxide films prepared by plasma-enhanced chemical vapor deposition

We have investigated the phase separation and silicon nanocrystal (Si NC) formation in correlation with the optical properties of Si suboxide (SiO_x, 0 < x < 2) films by thermal annealing in high vacuum. The SiO_x films were deposited by plasma-enhanced chemical vapor deposition at different nitrous oxide/silane (N₂O/SiH₄) flow ratios. The as-deposited films show increased Si concentration with decreasing N₂O/SiH₄ flow ratio, while the deposition rate and surface roughness have strong correlations with the flow ratio in the N₂O/SiH₄ reaction. After thermal annealing at temperatures above 1000 °C, Fourier transform infrared spectroscopy, Raman spectroscopy, and transmission electron microscopy manifest the progressive phase separation and continuous growth of crystalline-Si (c-Si) NCs in the SiO_x films with increasing annealing temperature. We observe a transition from multiple-peak to single peak of the strong red-range photoluminescence (PL) with increasing Si concentration and annealing temperature. The appearance of the single peak in the PL is closely related to the c-Si NC formation. The PL also redshifts from ∼1.9 to 1.4 eV with increasing Si concentration and annealing temperature (i.e., increasing NC size). The good agreements of the PL evolution with NC formation and the PL peak energy with NC size distribution support the quantum confinement model.     

Characterization of a thin CeO2-ZrO2-Y2O3 films electrochemical deposited on stainless steel

In this paper, we report for the first time formation of a thin CeO₂-ZrO₂-Y₂O₃ films electrodeposited on a stainless steel substrate. The samples have been characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The XRD and XPS data indicate formation of a solid solution and additional existence of Ce³⁺ states near the surface. After annealing, SEM examination has shown a microstructure formed by dispersed spherical agglomerates having a size between 20 and 60 nm.     

Observation of ferromagnetism at room temperature for Cr ions implanted ZnO thin films

Single crystalline ZnO films were grown on c-plane GaN/sapphire (0 0 0 1) substrates by molecular beam epitaxy. Cr⁺ ions were implanted into the ZnO films with three different doses, i.e., 1 × 10¹⁴, 5 × 10¹⁵, and 3 × 10¹⁶ cm⁻². The implantation energy was 150 keV. Thermal treatment was carried out at 800 °C for 30 s in a rapid thermal annealing oven in flowing nitrogen. X-ray diffraction (XRD), atomic force microscopy, Raman measurements, transmission electron microscopy and superconducting quantum interference device were used to characterize the ZnO films. The results showed that thermal annealing relaxed the stress in the Cr⁺ ions implanted samples and the implantation-induced damage was partly recovered by means of the proper annealing treatment. Transmission electron microscopy measurements indicated that the first five monolayers of ZnO rotated an angle off the [0 0 0 1]-axis of the GaN in the interfacial layer. The magnetic-field dependence of magnetization of annealed ZnO:Cr showed ferromagnetic behavior at room temperature.     

Influence of Annealing Temperature on Structure, Optical Loss and Laser-Induced Damage Threshold of TiO2 Thin Films

TiO2 thin films are prepared on fused silica with conventional electron beam evaporation deposition. After annealed at different temperatures for 4h, the spectra and XRD patterns of the TiO2 thin film are obtained. Weak absorption of coatings is measured by the surface thermal lensing technique, and laser-induced damage threshold （LIDT） is determined. It is found that with the increasing annealing temperature, the transmittance of TiO2 films decreases. Especially when coatings are annealed at high temperature over 1173K, the optical loss is very serious. Weak absorption detection indicates that the absorption of coatings decreases firstly and then increases, and the absorption and defects play major roles in the LIDT of TiO2 thin films.