Property improvement of pulsed laser deposited boron carbide films by pulse shortening

Growth characteristics and surface morphology of boron carbide films fabricated by ablating a B₄C target in high vacuum with a traditional KrF excimer laser and a high brightness hybrid dye/excimer laser system emitting at the same wavelength while delivering 700 fs pulses are compared. The ultrashort pulse processing is highly effective. Energy densities between 0.25 and 2 J cm⁻² result in apparent growth rates ranging from 0.017 to 0.085 nm/pulse. Ablation with nanosecond pulses of one order of magnitude higher energy densities yields smaller growth rates, the figures increase from 0.002 to 0.016 nm/pulse within the 2-14.3 J cm⁻² fluence window. 2D thickness maps derived from variable angle spectroscopic ellipsometry reveal that, when ablating with sub-ps pulses, the spot size rather than the energy density determines both the deposition rate and the angular distribution of film material. Pulse shortening leads to significant improvement in surface morphology, as well. While droplets with number densities ranging from 1 × 10⁴ to 7 × 10⁴ mm⁻² deteriorate the surface of the films deposited by the KrF excimer laser, sub-ps pulses produce practically droplet-free films. The absence of droplets has also a beneficial effect on the stoichiometry and homogeneity of the films fabricated by ultrashort pulses.     

Characterization of pulsed laser deposited chalcogenide thin layers

In this work we report on pulsed laser deposition (PLD) of chalcogenide thin films from the systems (AsSe)_100−xAgI_x and (AsSe)_100−xAg_x for sensing applications. A KrF* excimer laser (λ = 248 nm; τ_FWHM = 25 ns) was used to ablate the targets that had been prepared from the synthesised chalcogenide materials. The films were deposited in either vacuum (4 × 10⁻⁴ Pa) or argon (5 Pa) on silicon and glass substrates kept at room temperature. The basic properties of the films, including their morphology, topography, structure, and composition were characterised by complementary techniques. Investigations by X-ray diffraction (XRD) confirmed the amorphous nature of the films, as no strong diffraction reflections were found. The film composition was studied by energy dispersive X-ray (EDX) spectroscopy. The morphology of the films investigated by scanning electron microscopy (SEM), revealed a particulate-covered homogeneous surface, typical of PLD. Topographical analyses by atomic force microscopy (AFM) showed that the particulate size was slightly larger in Ar than in vacuum. The uniform surface areas were rather smooth, with root mean square (rms) roughness increasing up to several nanometers with the AgI or Ag doping. Based upon the results from the comprehensive investigation of the basic properties of the chalcogenide films prepared by PLD and their dependence on the process parameters, samples with appropriate sorption properties can be selected for possible applications in cantilever gas sensors.     

Nonlinear optical absorption studies of an organo-metallic complex by Z-scan technique

An organo-metallic complex, [(CH₃)₄N][Ni(dmit)₂] (dmit²⁻ = (1,3-dithiole-2-thione-4,5-dithiolate), abbreviated as MeNi, is synthesized. The nonlinear optical absorption properties of MeNi dissolved in acetone have been studied using the open-aperture Z-scan technique with 40 ps pulse width at 1064 nm and 1 ns, 15 ns pulse width at 1053 nm, respectively. Strong saturable absorption has been found when the sample solution is irradiated by 40 ps and 1 ns laser pulses. While irradiated with 15 ns laser pulse, a stronger reverse saturable absorption has been found. The nonlinear optical absorption coefficients are −1.03 × 10⁻¹¹ m/W, −1.85 × 10⁻¹¹ m/W and 3.84 × 10⁻¹⁰ m/W, respectively. The mechanism responsible for the difference between the results is analyzed. All the results suggest that this material may be a promising candidate for the application to laser pulse compression in the near-infrared waveband.     

Morphological and optical properties of silicon thin films by PLD

Silicon thin films have been prepared on sapphire substrates by pulsed laser deposition (PLD) technique. The films were deposited in vacuum from a silicon target at a base pressure of 10⁻⁶ mbar in the temperature range from 400 to 800 °C. A Q-switched Nd:YAG laser (1064 nm, 5 ns duration, 10 Hz) at a constant energy density of 2 J × cm⁻² has been used. The influence of the substrate temperature on the structural, morphological and optical properties of the Si thin films was investigated.Spectral ellipsometry and atomic force microscopy (AFM) were used to study the thickness and the surface roughness of the deposited films. Surface roughness values measured by AFM and ellipsometry show the same tendency of increasing roughness with increased deposition temperature.     

Structural characterization of AlN films synthesized by pulsed laser deposition

We obtained AlN thin films by pulsed laser deposition (PLD) from a polycrystalline AlN target using a pulsed KrF* excimer laser source (248 nm, 25 ns, intensity of ∼4 × 10⁸ W/cm², repetition rate 3 Hz, 10 J/cm² laser fluence). The target-Si substrate distance was 5 cm. Films were grown either in vacuum (10⁻⁴ Pa residual pressure) or in nitrogen at a dynamic pressure of 0.1 and 10 Pa, using a total of 20,000 subsequent pulses. The films structure was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and spectral ellipsometry (SE). Our TEM and XRD studies showed a strong dependence of the film structure on the nitrogen content in the ambient gas. The films deposited in vacuum exhibited a high quality polycrystalline structure with a hexagonal phase. The crystallite growth proceeds along the c-axis, perpendicular to the substrate surface, resulting in a columnar and strongly textured structure. The films grown at low nitrogen pressure (0.1 Pa) were amorphous as seen by TEM and XRD, but SE data analysis revealed ∼1.7 vol.% crystallites embedded in the amorphous AlN matrix. Increasing the nitrogen pressure to 10 Pa promotes the formation of cubic (≤10 nm) crystallites as seen by TEM but their density was still low to be detected by XRD. SE data analysis confirmed the results obtained from the TEM and XRD observations.     

Pulsed laser deposition of polyhydroxybutyrate biodegradable polymer thin films using ArF excimer laser

We demonstrated the pulsed laser deposition (PLD) of high quality films of a biodegradable polymer, the polyhydroxybutyrate (PHB). Thin films of PHB were deposited on KBr substrates and fused silica plates using an ArF (λ = 193 nm, FWHM = 30 ns) excimer laser with fluences between 0.05 and 1.5 J cm⁻². FTIR spectroscopic measurements proved that at the appropriate fluence (0.05, 0.09 and 0.12 J cm⁻²), the films exhibited similar functional groups with no significant laser-produced modifications present. Optical microscopic images showed that the layers were contiguous with embedded micrometer-sized grains. Ellipsometric results determined the wavelength dependence (λ ∼ 245-1000 nm) of the refractive index and absorption coefficient which were new information about the material and were not published in the scientific literature. We believe that our deposited PHB thin films would have more possible applications. For example to our supposal the thin layers would be applicable in laser induced forward transfer (LIFT) of biological materials using them as absorbing thin films.     

Chemical composition of ZrC thin films grown by pulsed laser deposition

ZrC films were grown on (1 0 0) Si substrates by the pulsed laser deposition (PLD) technique using a KrF excimer laser working at 40 Hz. The nominal substrate temperature during depositions was set at 300 °C and the cooling rate was 5 °C/min. X-ray diffraction investigations showed that films deposited under residual vacuum or under 2 × 10⁻³ Pa of CH₄ atmosphere were crystalline, exhibiting a (2 0 0)-axis texture, while those deposited under 2 × 10⁻² Pa of CH₄ atmosphere were found to be equiaxed and with smaller grain size. The surface elemental composition of as-deposited films, analyzed by Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS), showed the usual high oxygen contamination of carbides. Once the topmost 2-4 nm region was removed, the oxygen concentration rapidly decreased, down to around 3-8% only in bulk. Simulations of the X-ray reflectivity (XRR) curves indicated a smooth surface morphology, with roughness values below 1 nm (rms) and films density values of around 6.30-6.45 g/cm³, very close to the bulk density. The growth rate, estimated from thickness measurements by XRR was around 8.25 nm/min. Nanoindentation results showed for the best quality ZrC films a hardness of 27.6 GPa and a reduced modulus of 228 GPa.     

Comparing study of subpicosecond and nanosecond wet etching of fused silica

The effectiveness of the laser induced backside wet etching (LIBWE) of fused silica produced by subpicosecond (600 fs) and nanosecond (30 ns) KrF excimer laser pulses (248 nm) was studied. Fused silica plates were the transparent targets, and naphthalene-methyl-methacrylate (c = 0.85, 1.71 M) and pyrene-acetone (c = 0.4 M) solutions were used as liquid absorbents. We did not observe etching using 600 fs laser pulses, in contrast with the experiments at 30 ns, where etched holes were found. The threshold fluences of the LIBWE at nanosecond pulses were found to be in the range of 360-450 mJ cm⁻² depending on the liquid absorbers and their concentrations. On the basis of the earlier results the LIBWE procedure can be explain by the thermal heating of the quartz target and the high-pressure bubble formation in the liquid. According to the theories, these bubbles hit and damage the fused silica surface. The pressure on the irradiated quartz can be derived from the snapshots of the originating and expanding bubbles recorded by fast photographic setup. We found that the bubble pressure at 460 mJ cm⁻² fluence value was independent of the pulse duration (600 fs and 30 ns) using pyrene-acetone solution, while using naphthalene-methyl-methacrylate solutions this pressure was 4, 5 times higher at 30 ns pulses than it was at 600 fs pulses. According to the earlier studies, this result refers to that the pressure should be sufficiently high to remove a thin layer from the quartz surface using pyrene-acetone solution. These facts show that the thermal and chemical phenomena in addition to the mechanical effects also play important role in the LIBWE procedure.     

Preparation of transparent conductive TiO2:Nb thin films by pulsed laser deposition

This study investigated the optical and electrical properties of Nb-doped TiO₂ thin films prepared by pulsed laser deposition (PLD). The PLD conditions were optimized to fabricate Nb-doped TiO₂ thin films with an improved electrical conductivity and crystalline structure. XRD analyses revealed that the deposition at room temperature in 0.92 Pa O₂ was suitable to produce anatase-type TiO₂. A Nb-doped TiO₂ thin film attained a resistivity as low as 6.7 × 10⁻⁴ Ω cm after annealing at 350 °C in vacuum (<10⁻⁵ Pa), thereby maintaining the transmittance as high as 60% in the UV-vis region.     

Fabrication and vacuum annealing of transparent conductive Ga-doped Zn0.9Mg0.1O thin films prepared by pulsed laser deposition technique

In this study, highly transparent conductive Ga-doped Zn_0.9Mg_0.1O (ZMO:Ga) thin films have been deposited on glass substrates by pulsed laser deposition (PLD) technique. The effects of substrate temperature and post-deposition vacuum annealing on structural, electrical and optical properties of ZMO:Ga thin films were investigated. The properties of the films have been characterized through Hall effect, double beam spectrophotometer and X-ray diffraction. The experimental results show that the electrical resistivity of film deposited at 200 °C is 8.12 × 10⁻⁴ Ω cm, and can be further decreased to 4.74 × 10⁻⁴ Ω cm with post-deposition annealing at 400 °C for 2 h under 3 × 10⁻³ Pa. In the meantime, its band gap energy can be increased to 3.90 eV from 3.83 eV. The annealing process leads to improvement of (0 0 2) orientation, wider band gap, increased carrier concentration and blue-shift of absorption edge in the transmission spectra of ZMO:Ga thin films.     

Influence of oxygen partial pressure on optoelectrical properties of aluminum-doped CdO thin films

Highly conducting and transparent aluminum-doped CdO thin films were deposited on quartz by ablating the sintered target of CdO containing 2 wt% of aluminum with a KrF excimer laser (λ = 248 nm and pulsed duration of 20 ns). The effect of oxygen partial pressure on structural, electrical, and optical properties was studied. It is observed that the (2 0 0) plane is highly preferred for the films grown under high oxygen pressure. The conductivity, carrier concentration and mobility of the films decrease with increase in the oxygen pressure after attaining maximum. Low resistivity (2.27 × 10⁻⁵ Ω cm), and high mobility (79 cm² V⁻¹ s⁻¹) is observed for the film grown under oxygen pressure of 1.0 × 10⁻³ mbar. The optical band gap is found varying between 2.68 and 2.90 eV for various oxygen pressure.     

Femtosecond pulsed laser deposition of diamond-like carbon films: The effect of double laser pulses

The bonding structure of carbon films prepared by pulsed laser deposition is determined by the plasma properties especially the change of the kinetic energy. Using double laser pulses the ablation process and the characteristics of the generated plasma can be controlled by the setting of the delay between the pulses. In our experiments, amorphous carbon films have been deposited in vacuum onto Si substrates by double pulses from a Ti:sapphire laser (180 fs, λ = 800 nm, at 1 kHz) and a KrF laser system (500 fs, λ = 248 nm, at 5 Hz). The intensities have been varied in the range of 3.4 × 10¹² to 2 × 10¹³ W/cm². The morphology and the main properties of the thin layers were investigated as a function of the time delay between the two ablating pulses (0-116.8 ps) and as a function of the irradiated area on the target surface. Atomic force microscopy, spectroscopic ellipsometry and Raman-spectroscopy were used to characterize the films. It was demonstrated that the change of the delay and the spot size results in the modification of the thickness distribution of the layers, and the carbon sp²/sp³ bonding ratio.     

Opto-electrical properties of Ti-doped In2O3 thin films grown by pulsed laser deposition

By ablating titanium containing In₂O₃ target with a KrF excimer laser, highly conducting and transparent films on quartz were obtained to investigate the effects of growth temperature and oxygen pressure on the structural, optical and electrical properties of these films. We find that the transparency of the films depends more on the growth temperature and less on the oxygen pressure. Electrical properties, however, are found to be sensitive to both the growth temperature and oxygen pressure. We report in this paper that a growth temperature of 500 °C and an oxygen pressure of 7.5 × 10⁻⁷ bar lead to titanium-doped indium oxide films which have high mobility (up to 199 cm² V⁻¹ s⁻¹), low resistivity (9.8 × 10⁻⁵ Ω cm), and relatively high transmittance (∼88%).     

Preparation of ZnMgO:Ga thin films on flexible substrates by pulsed laser deposition

Transparent conducting ZnMgO:Ga films were deposited on flexible PET substrates by pulsed laser deposition (PLD). Effects of deposition pressure and time on the structural, electrical and optical properties of ZnMgO:Ga films were investigated. The films showed a low resistivity about 7.68 × 10⁻⁴ Ω cm when deposited at the pressure of 0.03 Pa for 40 min. All the films exhibited a high transmittance over 80% in the visible and near-ultraviolet region. The band gap of as-grown films was about 3.50 eV.     

Femtosecond Z-scan measurement of third-order optical nonlinearities in anatase TiO2 thin films

Anatase phase TiO₂ films have been grown on fused silica substrate by pulsed laser deposition technique at substrate temperature of 750 °C under the oxygen pressure of 5 Pa. From the transmission spectra, the optical band gap and linear refractive index of the TiO₂ films were determined. The third-order optical nonlinearities of the films were measured by Z-scan method using a femtosecond laser (50 fs) at the wavelength of 800 nm. The real and imaginary parts of third-order nonlinear susceptibility χ⁽³⁾ were determined to be −7.1 × 10⁻¹¹esu and −4.42 × 10⁻¹²esu, respectively. The figure of merit, T, defined by T=βλ/n₂, was calculated to be 0.8, which meets the requirement of all-optical switching devices. The results show that the anatase TiO₂ films have great potential applications for nonlinear optical devices.     

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.     

Structure and properties of transparent conductive doped ZnO films by pulsed laser deposition

High quality transparent conductive ZnO thin films were deposited on quartz glass substrates using pulsed laser deposition (PLD). We varied the growth conditions such as the substrate temperature and oxygen pressure. X-ray diffraction (XRD), X-ray photoelectron spectrometer (XPS), and atomic force microscopy (AFM) measurements were done on the samples. All films show n-type conduction, the best transparent conductive oxide (TCO) performance (Al-doped ZnO = 1.33 × 10⁻⁴ Ω cm, Ga-doped ZnO = 8.12 × 10⁻⁵ Ω cm) was obtained on the ZnO film prepared at pO₂ = 5 mTorr and T_s = 300 °C.     

Ultrafast motion of liquids C2H4Cl2 and C2H4Br2 studied with a femtosecond laser

Transient optical Kerr effect of liquids C₂H₄Cl₂ and C₂H₄Br₂ is investigated, for the first time to our knowledge, with a femtosecond (fs) probe laser delayed with respect to a coherent fs pump laser. Coherent coupling and electronic Kerr signals are observed around zero delay when pump and probe overlap. Persisting after the pump-probe overlap are Kerr signals arising from the torsional and other intramolecular vibrations of the trans and gauche conformations; Kerr signals arising from the intermolecular motion are also observed. Vibrational quantum interference is only observed in liquid C₂H₄Br₂ and the related beats data are fitted with the torsional vibrations, 91 cm⁻¹ (gauche) and 132 cm⁻¹ (trans), and the CCBr angle-bending vibrations, 231 cm⁻¹ (gauche) and 190 cm⁻¹ (trans), with dephasing times, 0.45 ps, 0.45 ps, 2 ps, and 1.5 ps, respectively. These vibrational frequencies agree with those obtained in the frequency-domain. That no vibrational mode is observed for C₂H₄Cl₂ might be attributed to ineffective Raman-pumping. Kerr signals observed after the pump-probe overlap are Fourier transformed to give the spectra of the intermolecular motion and the vibrational spectrum, which agrees with the one observed in the infrared absorption and/or Raman scattering heretofore.     

Atomic force microscopic characterization of films grown by inverse pulsed laser deposition

Carbon nitride films have been deposited by KrF excimer laser ablation of a rotating graphite target in 5 Pa nitrogen ambient in an inverse pulsed laser deposition configuration, where the backward motion of the ablated species is utilised for film growth on substrates lying in the target plane. Topometric AFM scans of the films, exhibiting elliptical thickness distribution, have been recorded along the axes of symmetry of the deposition area. High resolution AFM scans revealed the existence of disk-like, or somewhat elongated rice-like features of 5-10 nm average thickness and ∼100 nm largest dimension, densely packed over the whole, approximately 14 × 10 cm² deposition area. The RMS roughness of the film decreased from 9 nm near to the laser spot down to 2 nm in the outer regions. Even the highest RMS value obtained for IPLD films was less than half of the typical, 25 nm roughness measured on simultaneously deposited PLD films.