Low-temperature synthesis of AlN films through electron cyclotron resonance plasma-aided reactive pulsed laser deposition

Combination of pulsed laser ablation with electron cyclotron resonance microwave discharge was demonstrated for a novel method for low-temperature thin film growth. Aluminum nitride thin films were synthesized on silicon substrates at temperatures below 80 °C by means of reactive pulsed laser deposition in nitrogen plasma generated from the electron cyclotron resonance discharge. The synthesized films show a very smooth surface and were found to have a stoichiometric AlN composition. X-ray photoelectron spectroscopy analysis evidenced the formation of aluminum nitride compound. Fourier transform infrared spectroscopy revealed the characteristic phonon modes of AlN. The AlN films were observed to be highly transparent in the visible and near-IR regions and have a sharp absorption edge near 190 nm. The band gap of the synthesized AlN films was determined to be 5.7 eV. The mechanisms responsible for the low-temperature film synthesis are also discussed in the paper. The nitrogen plasma facilitates the nitride formation and enhances the film growth. Received: 17 March 2000 / Accepted: 28 March 2000 / Published online: 23 May 2001     

Influence of substrate temperature and ion-beam energy on the syntheses of aluminium nitride thin films by nitrogen-ion-assisted pulsed-laser deposition

Aluminium nitride (AlN) thin films have been grown on Si(100), Si(111) and Sapphire Al₂O₃(001) substrates by pulsed KrF excimer laser (wavelength 248 nm, duration 30 ns) ablation of an AlN target with the assistance of nitrogen-ion-beam bombardment. The influence of process parameters such as substrate temperature and ion-beam energy has been investigated in order to obtain high-quality AlN films. The AlN films deposited by pulsed-laser deposition (PLD) have been characterized by X-ray diffraction (XRD) to determine the crystalline quality, grain size and growth orientation with respect to the substrate. The XRD spectra of AlN films on Si(100), Si(111) and Sapphire substrates yield full-width-half-maximum (FWHM) values of approximately 1.6. The bonding characteristics in the films have been evaluated by Raman spectroscopy. The chemical composition of the films has been characterized by X-ray photoelectron spectroscopy (XPS). The surface morphology of the films has been measured by atomic force microscopy (AFM). At a substrate temperature of at least 600 °C, polycrystalline AlN films with orientations of AlN(100) and AlN(101) have been synthesized. PACS 68.55.-a; 81.15.Fg; 77.84.Bw     

A comparative study of gadolinium gallium garnet growth by femtosecond and nanosecond pulsed laser deposition

The growth of epitaxial Nd:Gd₃Ga₅O₁₂ (GGG) on Y₃Al₅O₁₂ (YAG) by femtosecond pulsed laser deposition is reported. We have used a Ti:sapphire laser at a wavelength of 800 nm and pulse length of 130 fs, operating at a repetition rate of 1 kHz. The film properties have been studied systematically as a function of the deposition parameters of laser fluence, spot-size, oxygen pressure, target-substrate distance and temperature. Scanning electron microscopy, atomic force microscopy and X-ray diffractometry were used to characterise the surface structure and crystallinity of the films. X-ray diffraction analysis shows that epitaxial growth has occurred. A comparison between the ion velocities produced by nanosecond and femtosecond laser ablation of the GGG target material has been investigated by the Langmuir probe technique. The results indicate a large difference in the plasma characteristics between femtosecond and nanosecond ablation, with ion velocities up to eight times faster observed in the femtosecond case.     

Effect of deposition temperature on the microstructure and surface morphology of c-axis oriented AlN films deposited on sapphire substrate by RF reactive magnetron sputtering

In this paper, c-axis oriented AlN films were prepared on sapphire substrate by RF reactive magnetron sputtering at various deposition temperatures (30–700 °C). The influences of deposition temperature on the chemical composition, crystalline structure and surface morphology of the AlN films were systematically investigated. The as-deposited films were characterized by X-ray photoelectron spectroscopy (XPS), two-dimensional X-ray diffraction (2D-XRD) and atomic force microscopy (AFM). The experimental results show that it can be successfully grown for high-purity and near-stoichiometric (Al/N = 1.12:1) AlN films except for the segregation of a few oxygen impurities exist in the form of Al–O bonding. The chemical composition of as-deposited films is almost independent of substrate temperature in the range of 30–700 °C. However, the crystalline structure and surface morphology of the deposited AlN films are strongly influenced by the deposition temperature. The optimum deposition temperature is 300 °C, giving a good compromise between crystalline structure and surface morphology to grow AlN films.     

Pressure-controlled preparation of nanocrystalline complex oxides using pulsed-laser ablation at room temperature

Nanocrystalline thin films of complex oxides such as BaTiO₃ and LaFeO₃ were prepared by pulsed laser ablation without substrate heating. Targets under various Ar pressures were irradiated using an ArF excimer laser. The off-axis configuration of targets and substrates was used to synthesize the films. The crystallinity and chemical composition of the deposited films were strongly dependent on the processing Ar gas pressure. In case of BaTiO₃, the film deposited at 10 Pa was a single phase of BaTiO₃ with a crystallite size around 7.2 nm. With increasing Ar pressure to 200 Pa, XRD peaks of BaTiO₃ as well as BaCO₃ were observed. The by-products could be due to reaction with carbon dioxide in air after taking the sample out of the chamber. For LaFeO₃, the films deposited under 50 to 200 Pa had a single phase with a crystallite size below 10 nm. When the Ar pressure exceeded 100 Pa, the crystallite size tended to decrease for both BaTiO₃ and LaFeO₃, which could be due to formation of aggregated nanoparticles. Below 10 Pa, oxygen deficiency was observed. Over 50 Pa, the atomic concentration of all the constituent elements was almost constant, especially the [Ba]/[Ti] and [La]/[Fe] ratios, which were nearly unity. Received: 19 June 2002 / Accepted: 24 June 2002 / Published online: 22 November 2002 RID="*" ID="*"Corresponding author. Fax: +81-298/61-6355, E-mail: yoon-jw@aist.go.jp     

Chemical analysis of a-CNx thin films synthesized by nanosecond and femtosecond pulsed laser deposition

An ArF excimer laser (22 ns, 193 nm) and a hybrid dye/excimer laser system (500 fs, 248 nm) are used to deposit amorphous carbon nitride films at room temperature by ablation of a graphite target in nitrogen atmosphere. The chemical composition and structure of the films is characterized by X-ray photoelectron spectroscopy. In the nanosecond case, the nitrogen content increases with reactive gas pressure up to 45 atomic %, while in the subpicosecond case it remains below 7 at. %. When processed with nanosecond pulses, the films' nitrogen content steeply increases with fluence up to a maximum. The target-to-substrate distance has only minor influence on the amount of nitrogen incorporated into the films. The dependence of the carbon-carbon and carbon-nitrogen bond configurations on the processing parameters is also given.     

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     

Formation of CNx thin films by reactive pulsed laser deposition assisted by electron cyclotron resonance microwave discharge

Amorphous carbon nitride thin films were synthesized by pulsed laser deposition combined with electron cyclotron resonance (ECR) microwave discharge in nitrogen gas. The ECR discharge supplies active nitrogen species in the deposition environment and to the growing film surface, enhancing the film growth in complex processes accompanied by chemical reaction. The synthesized films were characterized by Rutherford backscattering spectroscopy (RBS), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR), and Raman spectroscopy. The films were determined to consist purely of carbon and nitrogen with a nitrogen concentration of 42%, and have a thickness of 550 nm over which carbon and nitrogen are well distributed. Structural characterizations based on XPS, FTIR and Raman analysis showed that these films appear to contain several bonding configurations between carbon and nitrogen with a small amount of C≡N bonds compared with other bonding states. Received: 31 August 2000 / Accepted: 12 December 2000 / Published online: 23 May 2001     

Mechanical and physicochemical properties of AlN thin films obtained by pulsed laser deposition

AlN thin films have been deposited on Si(100) substrates by a pulsed laser deposition method. The deposition parameters (pressure, temperature, purity of target) play an important role in the mechanical and physicochemical properties. The films have been characterized using X-ray diffraction, atomic force microscopy, Brillouin light scattering, Fourier transform infrared spectroscopy and wettability testing. With a high purity target of AlN and a temperature deposition of 750 C, the measured Rayleigh wave velocity is close to the one previously determined for AlN films grown at high temperature by metal–organic chemical vapour deposition. Growth of nanocrystalline AlN at low temperature and of AlN film with good crystallinity for samples deposited at higher temperature is confirmed by infrared spectroscopy, as it was by atomic force microscopy, in agreement with X-ray diffraction results. A high hydrophobicity has been measured with zero polar contribution for the surface energy. These results confirm that films made by pulsed laser deposition of pure AlN at relatively low temperature have good prospects for microelectromechanical systems applications.     

Femtosecond pulsed-laser deposition of BaTiO<Subscript>3</Subscript>

The elemental composition and the surface morphology of thin films grown by laser ablation of barium titanate with femtosecond pulses at 620 nm laser wavelength have been systematically studied according to the experimental pulsed-laser deposition parameters : laser energy density, oxygen pressure, substrate temperature, target–substrate distance and substrate position (in- and off-axis geometry). Firstly, even at high temperature (700 °C), the deposits consist of coalesced particles up to 1-μm in size, mixed in a poorly crystallised tetragonal BaTiO₃ thin film. The particles formed in femtosecond pulsed-laser deposition induce a high surface roughness, which is observed whatever the experimental growth conditions and does not correspond to the droplets often observed during laser ablation in the nanosecond regime. As shown by plasma expansion dynamics, these particles propagate toward the substrate in the plasma plume with a low velocity, and are assumed to be produced by gas-phase reactions. Moreover, the cationic concentration evaluated through the Ba/Ti ratio strongly depends on the oxygen pressure in the ablation chamber and the angular position of the substrate along the normal to the target at laser impact. Indeed, the films appear to be enriched in the heavy element (Ba) when the substrate is located at high angular deviation. This fact is correlated to an increase in the lighter species (i.e. Ti) in the central part of the plasma plume. Received: 30 April 2002 / Accepted: 26 August 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +33-1/4354-2878, E-mail: millon@gps.jussieu.fr RID="**" ID="**"Also at: LSMCL, Université de Metz, 57078 Metz Cedex 3, France     

Texturing effects in molybdenum and aluminum nitride films correlated to energetic bombardment during sputter deposition

Molybdenum films sputter-deposited at low pressure show a (110) to (211) texture turnover with increasing film thickness, which is accompanied by a transition from a fiber texture to a mosaic-like texture. The degree of (002) texturing of sputtered aluminum nitride (AlN) films strongly depends on nitrogen pressure in Ar/N₂ or in a pure N₂ atmosphere. For the understanding of these phenomena, the power density at the substrate during sputter deposition was measured by a calorimetric method and normalized to the flux of deposited atoms. For the deposition of Mo films and various other elemental films, the results of the calorimetric measurements are well described by a model. This model takes into account the contributions of plasma irradiation, the heat of condensation and the kinetic energy of sputtered atoms and reflected Ar neutrals. The latter two were calculated by TRIM.SP Monte Carlo simulations. An empirical rule is established showing that the total energy input during sputter deposition is proportional to the ratio of target atomic mass to sputtering yield. For the special case of a circular planar magnetron the radial dependence of the Mo and Ar fluxes and related momentum components at the substrate were calculated. It is concluded that mainly the lateral inhomogeneous radial momentum component of the Mo atoms is the cause of the in-plane texturing. For AlN films, maximum (002) texturing appears at about 250 eV per atom energy input. Received: 23 June 2000 / Accepted: 12 December 2000 / Published online: 3 April 2001     

Pulsed laser deposition of semiconducting crystalline double-doped barium titanate thin films on nickel substrates

We synthesized by pulsed laser deposition (Ba,Sr,Y)TiO₃ and (Ba,Pb,Y)TiO₃ thin films on mechanically polished nickel substrates.The synthesized thin films were analyzed for: crystalline structure by X-ray diffractometry, morphology and surface topography by atomic force microscopy, optical and scanning electron microscopy, and elemental composition by energy dispersive X-ray spectroscopy and electrical properties by electrical measurements.We have shown that film properties were determined by the dopants, target composition, and deposition parameters (oxygen pressure, substrate temperature and incident laser fluence). All films exhibited a semiconducting behavior, as proved by the decrease of electrical resistance with heating temperature.     

Structural and morphological characterization of TiO2 nanostructured films grown by nanosecond pulsed laser deposition

TiO₂ has attracted a lot of attention due to its photocatalytic properties and its potential applications in environmental purification and self cleaning coatings, as well as for its high optical transmittance in the visible-IR spectral range, high chemical stability and mechanical resistance. In this paper, we report on the growth of TiO₂ nanocrystalline films on Si (1 0 0) substrates by pulsed laser deposition (PLD). Rutile sintered targets were irradiated by KrF excimer laser (λ = 248 nm, pulse duration ∼30 ns) in a controlled oxygen environment and at constant substrate temperature of 650 °C. The structural and morphological properties of the films have been studied for different deposition parameters, such as oxygen partial pressure (0.05-5 Pa) and laser fluence (2- 4 J/cm²). X-ray diffraction (XRD) shows the formation of both rutile and anatase phases; however, it is observed that the anatase phase is suppressed at the highest laser fluences. X-ray photoelectron spectroscopy (XPS) measurements were performed to determine the stoichiometry of the grown films. The surface morphology of the deposits, studied by scanning electron (SEM) and atomic force (AFM) microscopies, has revealed nanostructured films. The dimensions and density of the nanoparticles observed at the surface depend on the partial pressure of oxygen during growth. The smallest particles of about 40 nm diameter were obtained for the highest pressures of inlet gas.     

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.     

Growth of Bi2Sr2Cu1Ox films by laser ablation

The formation and the properties of thin BiSrCuO films grown on MgO single crystal substrates by the pulsed laser ablation of a Bi₂Sr₂Cu₁O₆ target have been studied. The precise influence of the oxygen pressure and substrate temperature on the atomic composition, nature and structure of the grown phases, crystalline quality and superconductivity of the films has been analyzed. In the 600–750°C temperature range and 0.05–0.5 mbar oxygen pressure range, highly textured films of the 2201 phase (Bi₂Sr₂Cu₁O₆ phase) were formed despite large composition deviations (Bi enrichment and Sr depletion) with respect to the ideal composition. A high crystalline quality was evidenced for films grown at low and intermediate pressure and high temperature. χ_min values in the films deduced from channeling experiments were similar to the case of single crystal material. Despite this high crystalline quality, incomplete or very low T_c superconducting transitions were observed in the resistivity measurements.     

Synthesis of nanocrystalline material by sputtering and laser ablation at low temperatures

Physical vapor deposition techniques such as sputtering and laser ablation – which are very commonly used in thin film technology – appear to hold much promise for the synthesis of nanocrystalline thin films as well as loosely aggregated nanoparticles. We present a systematic study of the process parameters that facilitate the growth of nanocrystalline metals and oxides. The systems studied include TiO₂, ZnO, γ-Al₂O₃, Cu₂O, Ag and Cu. The mean particle size and crystallographic orientation are influenced mainly by the sputtering power, the substrate temperature and the nature, pressure and flow rate of the sputtering gas. In general, nanocrystalline thin films were formed at or close to 300 K, while loosely adhering nanoparticles were deposited at lower temperatures. Received: 31 October 2000 / Accepted: 9 January 2001 / Published online: 26 April 2001     

Yttrium nitride thin films grown by reactive laser ablation

Yttrium nitride thin films were grown on silicon substrates by laser ablating an yttrium target in molecular nitrogen environments. The composition and chemical state were determined with Auger electron, X-Ray photoelectron, and energy loss spectroscopies. The reaction between yttrium and nitrogen is very effective using this method. Ellipsometry measurements indicate that the films are metallic. We attribute this behavior to a small oxygen contamination. Each oxygen atom introduces two additional electrons to the unit cell, resulting in a complex semiconductor-ionic-metallic system. These results are corroborated by first principles total energy calculations of clean and oxygen doped YN.     

Al<Subscript>2</Subscript>O<Subscript>3</Subscript> plasma production during pulsed laser deposition

A Nd:YAG laser operating in second harmonic (532 nm), 3 ns pulse duration, 150 mJ pulse energy, and 10 Hz repetition rate, is employed to irradiate Al₂O₃ target placed in high vacuum. The produced plasma is investigated by an ion collector used in time-of-flight configuration and by a mass quadrupole spectrometer, in order to determine the equivalent plasma temperature and the atomic and molecular composition. Pulsed laser deposition technique has been used to produce thin films on different substrates placed close to the target. Different surface analyses, such as energy dispersive X-ray fluorescence (EDXRF), X-ray photoelectron spectroscopy (XPS) and surface profilometry are employed to characterize the produced films. Measurements of ablation yield, plasma equivalent temperature, acceleration voltage and characterization of grown thin films are presented and discussed.     

Oxygen-segregation-controlled epitaxy of Y2O3 films on Nb(110)

We demonstrate a very simple and reliable method of manufacturing clean, single-crystalline Y₂O₃ films on Nb(110) substrates in situ. The method exploits the oxygen bulk contamination of Nb as a source of clean oxygen. For substrate temperatures above 800 K oxygen segregation to the Nb surface is so efficient, that yttrium becomes oxidized during deposition without any background oxygen pressure required in the ultrahigh vacuum system. The crystallinity and stoichiometry of these films can be tuned by the deposition temperature. For Y deposition at 1300 K the formation of well-ordered (111)-oriented Y₂O₃ films is achieved. Received: 19 April 2000 / Accepted: 20 April 2000 / Published online: 23 August 2000     

Characteristic properties of Y2SiO5:Ce thin films grown with PLD

Three different gases (nitrogen (N₂), oxygen (O₂) and argon (Ar)) were used as background gases during the growth of pulsed laser deposition (PLD) Y₂SiO₅:Ce thin films. A Krypton fluoride laser (KrF), 248 nm was used for the PLD of the films on silicon (Si) (1 0 0) substrates. The effect of the background gases on the surface morphology, crystal growth and luminescent properties were investigated. All the experimental parameters, the gas pressure (455 mT), the substrate temperature (600 °C), the pulse frequency (8 Hz), the number of pulses (4000) and the laser fluence (1.6±0.2) J/cm² were kept constant. The only parameter that was changed during the deposition was the ambient gas species. The surface morphology and average particle sizes were monitored with scanning electron microscopy (SEM) and atomic force microscopy (AFM). X-ray diffraction (XRD) and Auger electron spectroscopy (AES) were used to determine the crystal structure and composition, respectively. Cathodo- (CL) and photoluminescence (PL) were used to measure the luminescent intensities for the different phosphor thin films. The nature of the particles, ablated on the substrate, is related to the collisions between the ejected particles and the ambient gas particles. The CL and PL intensities also depend on the particle sizes. A 144 h (coulomb dose of 1.4×10⁴ C cm⁻²) electron degradation study on the thin films ablated in the Ar gas environment resulted in a decrease in the main CL intensity peak at 440 nm and to the development of a new very broad luminescent peak spectra ranging from 400 to 850 nm due to the growth of a SiO₂ layer on the surface.