Reactive pulsed laser deposition of zinc oxide thin films

Zinc oxide thin films have been obtained by reactive pulsed laser ablation of a Zn target in O₂ atmosphere (gas pressure 2 Pa) using a doubled frequency Nd:YAG laser (532 nm) which was also assisted by a 13.56 MHz radiofrequency (rf) plasma. The gaseous species have been deposited on Si(100) substrates positioned in on-axis configuration and heated from RT up to 500 °C. The obtained thin films have been compared to those produced in the same conditions by ablation of a ZnO target. The deposited thin films have been characterized by scanning electron microscopy, X-ray diffraction, Raman and infrared spectroscopy techniques. The influence of the rf plasma on the morphological and structural characteristics of these thin films is also briefly discussed. PACS 81.15.Fg; 68.55.Jk; 78.30.j     

Titanium oxide nanostructured films by reactive pulsed laser deposition

Nanostructured titanium oxide thin films have been grown by nanosecond UV pulsed laser deposition (PLD) performed in a reactive background atmosphere. We exploited laser ablation of a Ti target at different pressures of pure oxygen and Ar:O₂ mixtures to show that film growth can be tuned at the nanoscale from compact and dense to columnar and to porous, leading to different morphology, density and structure (oxidized fraction and degree of crystallinity). We observed that the position of the substrate relative to the time integrated visible plume front is fundamental in the determination of film structure and morphology. Film growth and film properties can be related to a non-dimensional parameter L which is the ratio between the target-to-substrate distance and the visible plume length. In particular, surface morphology and degree of structural order are strictly related to L irrespective of the oxygen content, while the latter mainly affects the oxidized fraction in the film.     

Effects of oxygen pressures on pulsed laser deposition of ZnO films

Zinc oxide (ZnO) thin films on Si (1 1 1) substrates were deposited by pulsed laser ablation of ZnO target at different oxygen pressures. A pulsed Nd:YAG laser with wavelength of 1064 nm was used as laser source. The deposited thin films have been characterized by X-ray diffraction (XRD), Atomic force microscopy (AFM), and Raman spectroscopy. XRD measurements indicate that the ZnO thin films deposited at the oxygen pressure of 1.3 Pa have the best crystalline quality. AFM results show that the surface roughness of ZnO film increases with the increase of oxygen pressure. The Raman results indicate that oxygen ambient plays an important role in removing defects due to excess zinc.     

Growth regimes in pulsed laser deposition of aluminum oxide films

Alumina is technologically exploited in several forms, ranging from compact hard films as protective coatings to open microstructures of high specific area as supports for catalysts. Currently, various production processes are used to deposit the different forms. PLD has the potential of obtaining not only the different forms, but also a continuous modulation of properties, by tuning of the process parameters. This work investigates the relationship between the process parameters and the resulting film morphology, structure and properties for PLD performed with an alumina target in a background oxygen atmosphere. Three distinct growth regimes are found, leading, respectively, to compact homogeneous films, columnar structures and open microstructures. These structures are quantitatively characterized, and the ranges of the process parameters corresponding to the three regimes are identified. An empirical scaling law is proposed, which can be exploited as a guide for the design of growth processes aimed at obtaining specific film properties.     

The effect of substrate material on pulsed laser deposition of HgCdTe films

This paper describes some recent results of the HgCdTe thin film grown directly on different substrates (sapphire, GaAs and Si) by pulsed laser deposition (PLD). The influences of the substrate material on the properties of HgCdTe thin films were investigated by X-ray diffraction (XRD), selected area electron diffraction (SAED), atomic force microscopy (AFM) and energy dispersive X-ray spectroscopy (EDS). It was found that the quality of the HgCdTe film has a strong relation to the structure and properties of the substrate. The experiment results indicate that the HgCdTe epitaxial thin films grown directly on the sapphire substrates have a high quality, and the composition of the films is close to that of the target. While the quality of the HgCdTe films deposited on the Si and GaAs substrates are not very good.     

p-Type zinc oxide films grown by infrared-light-assisted pulsed laser deposition

In this paper, ZnO films were grown on sapphire (0001) substrates by infrared-light-assisted pulsed-laser deposition (IRA-PLD). In addition, a nitrogen-plasma-assisted (PA-N) system was utilized for effectively doping the acceptor by radio frequency induction coupled plasma (RF-ICP). The effect of IRA-PLD and PA-N systems was investigated by studying the difference in substrate temperature with and without plasma assistance. We found that ZnO films exhibit no exciton emission with PA-N at a high temperature and that an increase in the substrate temperature yields ZnO films with a (002) and c-axis preferred orientation in a nitrogen (N₂) gas atmosphere. ZnO films are changed from n-type to p-type at a substrate temperature of 673 K by IRA-PLD with an N₂ background atmosphere.     

Synthesis of p-type zinc oxide films by plasma-assisted pulsed laser deposition

Heavily acceptor doped zinc oxide (ZnO) films were deposited on quartz substrates by plasma-assisted pulsed laser deposition (PA-PLD) using a non-sintered target heavily doped with phosphorus or copper and radio frequency induction-coupled nitrogen or oxygen plasma (RF-ICP). The p-type ZnO layer was achieved by a nitrogen acceptor dopant using the technique of plasma-assisted nitrogen (PA-N) pulsed laser deposition. Photoluminescence spectra showed a peak from phosphorus- or copper-bound excitons at about 380 nm and a broad, green defect-related band occurring at about 550 nm. Transmission spectra showed a blue shift of the near-band-edge wavelength and a worsening of transmission by heavily copper-doped zinc oxide.     

CEMS study on diluted magneto titanium oxide films prepared by pulsed laser deposition

6% ⁵⁷Fe doped titanium oxide films, prepared by pulsed laser deposition (PLD) on sapphire substrate at 650°C under various vacuum conditions, were characterized mainly by conversion electron Mössbauer spectrometry (CEMS). Two magnetic sextets with hyperfine fields 33 and 29 T, and one doublet were observed in the CEMS spectra of TiO₂ films prepared under PO₂ = 10^?6 and 10^?8 torr, which showed ferromagnetism at room temperature, whereas only the doublet of paramagnetic Fe³⁺ species was observed for the film prepared under PO₂ = 10^?1 torr.     

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.     

Correlation between target–substrate distance and oxygen pressure in pulsed laser deposition of complex oxide thin films

A physico-chemical model is developed to describe a typical pulsed laser deposition (PLD) process. The interaction of atoms in the plume, ejected from the target, with those of the background gas (e.g. oxygen) is specifically considered. The model gives a physical definition of the ‘plume range’, which depends on the particular PLD system, and calculates the range. One prediction is that when the target-to-substrate distance (D) is optimised with respect to the oxygen pressure (P), the plasma dynamics plays an important role in growing high-quality complex oxide thin films. Our model predicts a scaling law PD³=const from thermodynamic data and the experimental volumetric erosion rate of the metallic elements ejected from the target. The volumetric erosion rate was experimentally determined by atomic force microscopy, measuring the dimensions of the crater formed in the target after a number of shots. The model was applied to the growth of three ternary oxides, CdTeO₃, AlVO₄ and PbFe₁₂O₁₉ thin films, and the scaling laws predicted by our model using 420, 400 and 700 °C as substrate temperatures, respectively, were PD³=(3.3086,5.9827,30.3)×10³ mTorr cm³, respectively, for the CdTeO₃, AlVO₄ and PbFe₁₂O₁₉ thin films. In order to grow the thin films, we used an energy density of laser beam of 2 J/cm², and fixed D=4.0, 4.0 and 3.0 cm from our scaling law; the values of P were 51.7, 130.0 and 751.8 mTorr, respectively. X-ray diffraction shows that the films are polycrystalline and the observed peaks in the samples were similar with respect at its JCPDF patterns respectively. PACS 81.05.Dz; 81.15.Fg; 52.40.Hf; 52.25.Fi; 81.15.A; 81.65.Mq     

Nanostructured tungsten oxide thin films by the reactive pulsed laser deposition technique

Preparation of nanostructured tungsten oxide thin films using the reactive pulsed laser ablation technique is reported. The structural, morphological, optical and electrical properties of deposited films are systematically studied by changing the ambient oxygen pressure (pO₂). Structural dependence of tungsten oxide films on ambient oxygen pressure is discussed using grazing incidence X-ray diffraction (GIXRD) and micro-Raman spectra. The section analysis using atomic force microscopy exposed the smooth surface features of the deposited films. The blue shift in optical bandgap with an increase in ambient oxygen pressure is expounded in terms of electronic band structure of tungsten oxide. The influence of oxygen pressure on optical constants like extinction coefficient, band edge sharpness, refractive index and optical bandgap is also conveyed. The temperature variation of electrical resistance for films deposited at 0.12 mbar furnishes evidence for its semiconducting nature. PACS 68.55-a; 72.80.Ga; 81.15.Fg; 81.07.Bc; 78.68.+m; 78.20.Ci     

XRD study on the effect of the deposition condition on pulsed laser deposition of ZnO films

Using a pulsed laser deposition (PLD) process on a ZnO target in an oxygen atmosphere, thin films of this material have been deposited on Si(111) substrates. An Nd: YAG pulsed laser with a wavelength of 1064 nm was used as the laser source. The influences of the deposition temperature, laser energy, annealing temperature and focus lens position on the crystallinity of ZnO films were analyzed by X-ray diffraction. The results show that the ZnO thin films obtained at the deposition temperature of 400°C and the laser energy of 250 mJ have the best crystalline quality in our experimental conditions. The ZnO thin films fabricated at substrate temperature 400°C were annealed at the temperatures from 400°C to 800°C in an atmosphere of N₂. The results show that crystalline quality has been improved by annealing, the optimum temperature being 600°C. The position of the focusing lens has a strong influence on pulsed laser deposition of the ZnO thin films and the optimum position is 59.5 cm from the target surface for optics with a focal length of 70 cm.      

Morphology and photoluminescence properties of zinc oxide films grown by pulsed laser deposition

Zinc oxide films with different morphologies have been grown by pulsed laser deposition, varying substrate temperature and oxygen pressure. At low oxygen pressure and low substrate temperature continuous films with different roughness have been obtained, while at high substrate temperature a film with sparse hexagonal pyramids has been observed. Increasing the oxygen pressure the film became rougher and at 100 Pa a rod-array has been deposited. The columns of this rod-array grew along the wurtzite c-axis perpendicularly to the substrate surface as proved by X-ray diffraction measurements. Near to the sample borders the columns were slightly tilted towards the center of the sample. The possible growth mechanisms giving rise to the different morphologies have been discussed. Low-temperature photoluminescence measurements allowed to get information about the film quality, showing the variations of the excitonic peak and two defect bands (green and violet-blue) with the different deposition parameters.     

Homogeneous films by inverse pulsed laser deposition

Recently, we proposed an alternative arrangement to traditional on- or off-axis PLD geometries, termed inverse PLD (IPLD) that is capable of producing films of improved surface morphology. Two configurations of this new target-substrate arrangement were developed, namely static and co-rotating IPLD. In the static IPLD configuration, the substrate is stationary with respect to the ablated spot; while in the co-rotating IPLD configuration the substrate is fixed to the target surface and rotates simultaneously with the target, hence offering an appealingly simple approach to homogenize film properties.Here we report the growth of CN_x and Ti films, simultaneously deposited in the co-rotating and static IPLD arrangements. The homogeneity of the co-rotating films is described by a thickness inhomogeneity index, which allows for the comparison of films of different lateral dimension. A semi-analytical, semi-numerical model is proposed to derive the radial variation of the growth rate of co-rotating IPLD films from the lateral growth rate distributions measured along the symmetry axes of static IPLD films. The laterally averaged growth rate, LAGR is used to describe how the ambient pressure affects growth in the 0.5-50 Pa domain. As an example, the absolute error between the measured and calculated radial growth rate variation, obtained at 5 Pa, was less than 3%, while the LAGR of CN_x layers grown by co-rotating IPLD was predicted with 20% accuracy.     

Effect of temperature on pulsed laser deposition of HgCdTe films

HgCdTe thin films have been deposited on Si(1 1 1) substrates at different substrate temperatures by pulsed laser deposition (PLD). An Nd:YAG pulsed laser with a wavelength of 1064 nm was used as laser source. The influences of the substrate temperature on the crystalline quality, surface morphology and composition of HgCdTe thin films were characterized by X-ray diffraction (XRD), selected area electron diffraction (SAED), atomic force microscopy (AFM) and energy dispersive X-ray spectroscopy (EDS). The results show that in our experimental conditions, the HgCdTe thin films deposited at 200 °C have the best quality. When the substrate temperature is over 250 °C, the HgCdTe film becomes thermodynamically unstable and the quality of the film is degraded.     

Effect of temperature on pulsed laser deposition of ZnO films

ZnO thin films have been deposited on Si(1 1 1) substrates at different substrate temperature by pulsed laser deposition (PLD) of ZnO target in oxygen atmosphere. An Nd:YAG pulsed laser with a wavelength of 1064 nm was used as laser source. The influences of the deposition temperature on the thickness, crystallinity, surface morphology and optical properties of ZnO films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), selected area electron diffraction (SAED), photoluminescence (PL) spectrum and infrared spectrum. The results show that in our experimental conditions, the ZnO thin films deposited at 400 °C have the best surface morphology and crystalline quality. And the PL spectrum with the strongest ultraviolet (UV) peak and blue peak is observed in this condition.     

Pulsed laser deposition of oxide thin films

The pulsed laser deposition (PLD) process was studied in detail during oxide thin film growth by constructing a sophisticated PLD chamber combined with an energy-stable excimer laser. It was revealed that the transmitting laser energy at the entrance view port decreased exponentially with deposition runs, roughly by A e^−0.02x%, where A is the original transmission and x is the run number, and transmission loss could become considerable (up to 90%) in 100 deposition runs. In addition, area of the focused spot on the target was found a function of charging high voltage, which is a parameter of excimer laser operation, even through a slit forming rectangular sharp-edge beam profile. Laser energy density is one of the most important parameter governing grown film properties, and therefore accurate laser energy and spot area calibration is vital for reproducible film growth. In course of this study, the importance of spot area as well as the energy density is discussed in the view of deposition rate.     

The effect of relative plasma plume delay on the properties of complex oxide films grown by multi-laser, multi-target combinatorial pulsed laser deposition

We report the effects of relative time delay of plasma plumes on thin garnet crystal films fabricated by dual-beam, combinatorial pulsed laser deposition. Relative plume delay was found to affect both the lattice constant and elemental composition of mixed Gd₃Ga₅O₁₂ (GGG) and Gd₃Sc₂Ga₃O₁₂ (GSGG) films. Further analysis of the plasmas was undertaken using a Langmuir probe, which revealed that for relative plume delays shorter than 200 μs, the second plume travels through a partial vacuum created by the first plume, leading to higher energy ion bombardment of the growing film. The resulting in-plane stresses are consistent with the transition to a higher value of lattice constant normal to the film plane that was observed around this delay value. At delays shorter than 10 μs, plume propagation was found to overlap, leading to scattering of lighter ions from the plume and a change in stoichiometry of the resultant films.     

Zinc oxide nanostructures grown by pulsed laser deposition

We report the use of PLD to grow different ZnO nanostructures. Very different film morphologies have been observed using different laser wavelengths to ablate the target. The influence of substrate temperature and oxygen background pressure on the film morphology has been investigated too. Smooth and rough films, hexagonal pyramids and columns have been obtained by using a KrF excimer laser (248 nm) for the target ablation, while hexagonal hierarchical structures and pencils have been obtained by using ArF (193 nm). Photoluminescence and X-ray diffraction measurements revealed the good quality of the samples, in particular of those deposited using the ArF laser beam.