Influence of inert gas pressure on deposition rate during pulsed laser deposition

The deposition rates of permalloy and Ag are monitored during pulsed laser deposition in different inert gas atmospheres. Under ultrahigh vacuum conditions, resputtering from the film surface occurs due to the presence of energetic particles in the plasma plume. With increasing gas pressure, a reduction of the particle energy is accompanied with a decrease of resputtering and a rise in the deposition rate for materials with high sputtering yield. In contrast, at higher gas pressures, scattering of ablated material out of the deposition path between target and substrate is observed, leading to a decrease in the deposition rate. While in the case of Xe and Ar these processes strongly overlap, they are best separated in He. A He pressure of about 0.4 mbar should be used to reduce the kinetic energy of the deposited particles, to reach the maximum deposition rate and to avoid implantation of the particles. This is helpful for the preparation of stoichiometric metallic alloy films and multilayers with sharp interfaces. Received: 27 March 2002 / Accepted: 3 April 2002 / Published online: 5 July 2002     

Diamond-like-carbon films produced by magnetically guided pulsed laser deposition

We have compared the quality of carbon films deposited with magnetically guided pulsed laser deposition (MGPLD) and conventional pulsed laser deposition (PLD). In MGPLD, a curved magnetic field is used to guide the plasma but not the neutral species to the substrate to deposit the films while, in conventional PLD, the film is deposited with a mixture of ions, neutral species and clusters. A KrF laser pulse (248 nm) was focused to intensities of 10 GW/cm² on a carbon source target and a magnetic field strength of 0.3 T was used to steer the plasma around a curved arc to the deposition substrate. Electron energy loss spectroscopy was used in order to measure the fraction of sp³ bonding in the films produced. It is shown that the sp³ fraction, and hence the diamond-like character of the films, increased when deposited only with the pure ion component by MGPLD compared with films produced by the conventional PLD technique. The dependence of film quality on the laser intensity is also discussed. Received: 7 December 2000 / Accepted: 20 August 2001 / Published online: 2 October 2001     

Amorphous hydrogenated carbon synthesized by pulsed laser deposition from cyclohexane

It is demonstrated that a liquid hydrocarbon precursor, cyclohexane, is appropriate for laser-induced carbon deposition. Amorphous hydrogenated carbon films (a-C:H) were deposited by KrF excimer laser irradiation of single-crystal silicon surface immersed under cyclohexane. The technique is simple and easy to operate. IR absorption spectra of the deposited films confirmed the presence of carbon in the diamond phase. Raman and XPS studies showed diamond-like character of the deposited films. Moreover, these two studies provided strong evidence that laser fluence played an important role in the formation of DLC bondings and the quality of the deposited films. Received: 15 September 1998 / Accepted: 5 January 1999 / Published online: 5 May 1999     

Microstructures and dielectric properties of compositionally graded (Ba1-xSrx) TiO3 thin films prepared by pulsed laser deposition

Compositionally graded (Ba_1-xSr_x)TiO₃ (BST) (x:0.0∼0.25) thin films were grown on Pt (111)/TiO₂/SiO₂/Si (100) substrates using layer-by-layer pulsed laser deposition in the temperature range 550–650 °C. Both downgraded (Ba/Sr ratio varying from 100/0 at the bottom surface to 75/25 at the top surface) and upgraded (Ba/Sr ratio varying from 75/25 at the bottom surface to 100/0 at the top surface) BST films were prepared. Their microstructures were systematically studied by X-ray diffractometry and scanning electron microscopy. A grain morphology transition from large ‘rosettes’ (>0.30 μm) to small compact grains (70–110 nm) was observed in the downgraded BST films as the deposition temperature was increased from 550 to 650 °C. No such grain morphology transition was detected in the upgraded BST films. Dielectric measurements with metal electrodes revealed an enhanced dielectric behavior in the downgraded films. This enhancement is mainly attributed to the large compressive stress field built up near the interface between the downgraded film and substrate. Furthermore, the BaTiO₃ layer in the downgraded BST films not only serves as a bottom layer but also as an excellent seeding layer for enhancing the crystallization of the subsequent film layers in the downgraded films. Received: 10 December 2001 / Accepted: 12 March 2002 / Published online: 19 July 2002 RID="*" ID="*"Corresponding author. Fax: 86-25/359-5535, E-mail: xhzhu@public1.ptt.js.cn     

Characterization of ablation plumes and carbon nitride films produced by reactive pulsed laser deposition in the presence of a magnetic field

x ) films in a nitrogen atmosphere within the range 5×10^-4–4×10^-1 Torr. In the presence of a magnetic field, the emission intensities of N₂ (second positive system) and CN species in the graphite ablation plumes were altered significantly, depending on the pressure of the N₂ environment. Corresponding to an intense CN emission, a magnetic field-induced enhancement of N incorporation – for example, up to 37% at an N₂ pressure of 300 mTorr – and the formation of sp³ tetrahedral CN bonding were both observed in the films. This suggests that the arrival of CN species at the substrate surface with kinetic energies is important for film deposition. Received: 27 August 1997/Accepted: 8 September 1997     

Inhomogeneity of calcium phosphate coatings deposited by laser ablation at high deposition rate

Calcium phosphate coatings were deposited with a KrF excimer laser onto titanium alloy to study their homogeneity. Deposition was performed at a high deposition rate under a water vapour atmosphere of 45 Pa and at a substrate temperature of 575 °C. Samples were also submitted to annealing under the same conditions of deposition for different times just after deposition. The effects of the annealing were also investigated. The morphology of the coatings was studied by scanning electron microscopy. Their structure and phase distribution was analysed by X-ray diffractometry and infrared and micro-Raman spectroscopies. Besides the non-uniform thickness, the results reveal an inhomogeneity in the spatial distribution of calcium phosphate phases in the coatings. The phase distribution can be almost completely correlated with the deposition rate. High deposition rates (0.5 nm/pulse) occurring in the centre of deposition results in the formation of amorphous calcium phosphate, while lower deposition rates favour the presence of hydroxyapatite and alpha tricalcium phosphate. At intermediate deposition rates, beta tricalcium phosphate is found, probably because the superimposed effect of energetic particles bombardment. The annealing process promotes the crystallisation of the amorphous material. The importance of the deposition rate in the phases obtained is stated after comparing these results with a previous work where homogeneous hydroxyapatite coatings were obtained under the same conditions of laser fluence, temperature and pressure, but at lower deposition rates. Received: 22 November 2001 / Accepted: 12 March 2002 / Published online: 5 July 2002 RID="*" ID="*"Corresponding author. Fax: +34-93/402-1138, E-mail: jmfernandez@fao.ub.es     

Growth of a textured quasicrystalline phase in Ti-Ni-Zr films prepared by pulsed laser deposition

The preparation in thin film form of the known icosahedral phase in Ti-Ni-Zr bulk alloys has been investigated as a function of substrate temperature. Films were deposited by pulsed laser deposition on sapphire substrates at temperatures ranging from room temperature to 350 °C. Morphological and structural modifications have been followed by grazing-incidence and θ–2θ X-ray diffraction, transmission electron diffraction and imaging. Chemical composition has been analyzed by electron probe microanalysis. The in-depth variation of composition has been studied by secondary neutral mass spectroscopy. We show that pulsed laser deposition at 275 °C makes the formation of a 1-μm-thick film of Ti-Ni-Zr quasicrystalline textured nanocrystallites possible. Received: 7 June 2001 / Accepted: 18 February 2002 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +33-3/8357-6300, E-mail: brien@mines.u-nancy.fr     

Thermal stability of amorphous carbon films deposited by pulsed laser ablation

Diamond-like carbon (DLC) films have been grown on Si substrates at ambient temperature by the pulsed-laser ablation technique, using pulses of different durations both in the nano- and picosecond ranges and at various energy fluences. The stability of these films was investigated as a function of thermal anneals performed in UHV conditions up to 1273 K. Their physico-chemical properties have been characterized by different techniques including X-ray photo-emission, Auger electron and electron-energy-loss spectroscopies, Raman scattering, spectroscopic ellipsometry and atomic-force microscopy. The thermal stability of the films has been demonstrated to be related to their initial structural (sp³/sp² ratio) and chemical (contaminant) properties. DLC layers prepared under optimized conditions have been found to show a very good thermal stability up to 900 K. Received: 4 Jule 2000 / Accepted: 6 July 2000 / Published online: 6 September 2000     

Synthesis of carbon nitride films by low-power inductively coupled plasma-activated transport reactions from a solid carbon source

Thin films of carbon nitride were prepared by low-power inductively coupled plasma chemical vapor deposition from a solid carbon source by utilizing transport reactions. The maximum deposition rate achieved was 10 nm/min and depended mainly on the substrate position in the reactor. The nitrogen fraction in the films was not so sensitive to the process parameters and was at about 0.5 for all experiments as measured by Auger electron spectroscopy (AES) and elastic recoil detection (ERD) analysis. The chemical bonding structure studied by Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) showed the presence of triple, double and single bonds between carbon and nitrogen atoms. Received: 12 May 1999 / Accepted: 12 May 1999 / Published online: 24 June 1999     

Optical and waveguiding properties of Nd:KGW films grown by pulsed laser deposition

 Nd: KGd(WO₄)₂ thin films were deposited by KrF laser ablation on MgO, YAP, YAG and Si substrates at temperatures up to 800 °C. Film crystallinity, morphology, stoichiometry (WDX, RBS and PIXE), excitation spectra, fluorescence, refractive index and waveguiding properties were studied in connection with deposition conditions. The best films were crystalline and exhibited losses of approximately 5 dB cm^-1 at a wavelength of 633 nm. Received: 8 January 2001 / Accepted: 7 November 2001 / Published online: 11 February 2002     

Orientation selective growth of MgO films on Si (100) by pulsed laser deposition

Selective growth of single-oriented (110), (100) and (111) MgO films on Si (100) substrates without buffer layers was obtained via a two-step method by pulsed laser deposition. It was found that the orientation of the films was determined at the initial deposition stage by the substrate temperature only. The ambient pressure during deposition, the laser fluence and the etching of the Si substrates have no apparent effect on the orientation of the films, but affect their crystalline quality. Under the present deposition conditions, the surfaces of all three different single-oriented films were very smooth and devoid of any particulates. Received: 23 January 2001 / Accepted: 6 June 2001 / Published online: 2 October 2001     

Optical properties of SrTiO<Subscript>3</Subscript> thin films by pulsed laser deposition

SrTiO₃ thin films were prepared on a fused-quartz substrate by pulsed laser deposition (PLD). Dense and homogeneous films with a thickness of 260 nm were prepared. Optical constants (refractive index n and extinction coefficient k) were determined from the transmittance spectra using the envelope method. The optical band gap energy of the films was found to be 3.58 eV, higher than the 3.22 eV for bulk SrTiO₃, attributable to the film stress exerted by the substrate. The dispersion relation of the refractive index vs. wavelength follows the single electronic oscillator model. The refractive index and the packing density for the PLD-prepared SrTiO₃ thin films are higher than those for the SrTiO₃ films prepared by physical vapor deposition, sol–gel and RF sputtering. Received: 18 March 2002 / Accepted: 7 October 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +86-25/359-5535, E-mail: mszhang@nju.edu.cn     

Dependence of the sp3 bond fraction on the laser wavelength in thin carbon films prepared by pulsed laser deposition

3 bonds in the carbon films prepared by pulsed laser deposition of carbon obtained from graphite was investigated by electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS). The fraction of sp³ bonds increased with a decreasing laser wavelength. Energetic C⁺ ion species were effectively produced by using a short-wavelength laser. The sp³ bond fraction increased with an increasing amount of energetic C⁺ ion species. The fractions of sp³ bonds in the carbon film were 80%, 42%, 26% and 15% at wavelengths of 193, 248, 532 and 1064 nm, respectively. Received: 28 October 1997/Accepted:29 October 1997     

Structural, electrical, and surface characteristics of La0.5Sr0.5CoO3 thin films prepared by pulsed-laser deposition

A parametric study of the growth of La_0.5Sr_0.5CoO₃ (LSCO) thin films on (100) MgO substrates by pulsed-laser deposition (PLD) is reported. Films are grown under a wide range of substrate temperature (450–800 °C), oxygen pressure (0.1–0.9 mbar), and incident laser fluence (0.8–2.6 J/cm²). The optimum ranges of temperature, oxygen pressure, and laser fluence to produce c-axis oriented films with smooth surface morphology and high metallic conductivity are identified. Films deposited at low temperature (500 °C) and post-annealed in situ at higher temperatures (600–800 °C) are also investigated with respect to their structure, surface morphology, and electrical conductivity. Received: 20 November 1998 / Accepted: 6 July 1999 / Published online: 21 October 1999     

The orientation-selective growth of LaNiO3 films on Si(100) by pulsed laser deposition using a MgO buffer

Highly (100)-oriented, (110)-oriented and polycrystalline LaNiO₃ (LNO) films were successfully prepared on Si(100) using an oriented MgO film as a buffer. It was somewhat surprising to find that that the orientation relation between the LNO film and the corresponding MgO buffer was: LNO(100)\MgO(110), LNO(110)\MgO(111) and LNO(polycrystalline)\MgO(100). The crystalline quality of the LNO films was shown to be sensitive to the preparation conditions of the MgO buffer. The film surface was very smooth, without micrometer-sized droplets being observed. All LNO films were of metallic conductivity, with a room-temperature resistivities of approximately 250, 280 and 420 μΩ cm for the (110)-oriented, (100)-oriented and polycrystalline LNO, respectively. Received: 2 April 2001 / Accepted: 23 October 2001 / Published online: 3 June 2002     

Resonant infrared pulsed laser deposition of thin biodegradable polymer films

Thin films of the biodegradable polymer poly(DL-lactide-co-glycolide) (PLGA) were deposited using resonant infrared pulsed laser deposition (RIR-PLD). The output of a free-electron laser was focused onto a solid target of the polymer, and the films were deposited using 2.90 (resonant with O-H stretch) and 3.40 (C-H) μm light at macropulse fluences of 7.8 and 6.7 J/cm², respectively. Under these conditions, a 0.5-μm thick film can be grown in less than 5 min. Film structure was determined from infrared absorbance measurements and gel permeation chromatography (GPC). While the infrared absorbance spectrum of the films is nearly identical with that of the native polymer, the average molecular weight of the films is a little less than half that of the starting material. Potential strategies for defeating this mass change are discussed. Received: 22 August 2001 / Accepted: 23 August 2001 / Published online: 17 October 2001     

SBN thin films growth by RF plasma beam assisted pulsed laser deposition

SBN thin films were grown on MgO and Silicon substrates by PLD and RF-PLD (radiofrequency assisted PLD) starting from single crystal Sr_0.6Ba_0.4Nb₂O₆ and ceramic Sr_0.5Ba_0.5Nb₂O₆ stoichiometric targets. Morphological and structural analyses were performed on the SBN layers by AFM and XRD and optical properties were measured by spectroellipsometry. The films composition was determined by Rutherford Backscattering Spectrometry. The best set of experimental conditions for obtaining crystalline, c-axis preferential texture and with dominant 31° in-plane orientation relative to the MgO (100) axis is identified.     

Growth of completely (110)-oriented Pt film on Si (100) by using MgO as a buffer by pulsed laser deposition

(110)-textured MgO films were grown on Si (100) with etching and without etching by pulsed laser deposition. The deposited MgO films were shown to be droplets-free. The MgO film was used as a buffer layer to further grow Pt film on Si (100). A completely (110)-oriented Pt film was obtained on such a buffer layer and its surface is very smooth with a roughness of about 7.5 nm over 5×5 μm. This can be used as a new oriented Pt electrode on silicon for devices. Received: 23 January 2001 / Accepted: 27 April 2001 / Published online: 27 June 2001     

Deposition and characterization of ITO films produced by laser ablation at 355 nm

Indium tin oxide (ITO) films have been deposited by pulsed laser deposition (PLD) at 355 nm. Even though the absorption of laser light at the wavelength 355 nm is much smaller than that of the standard excimer lasers for PLD at 248 nm and 193 nm, high-quality films can be produced. At high fluence and at high substrate temperatures, the specific resistivity of the films, 2–3×10^-4 Ω cm, is comparable to values obtained with excimer lasers, whereas the resistivities obtained at room temperature are somewhat higher than those of films produced by excimer lasers. The transmission coefficient of visible light, about 0.9, is also comparable to values for films deposited by excimer lasers. The crystalline structure of films produced at 355 nm is similar to that of samples produced by these lasers. Received: 16 January 2001 / Accepted: 24 July 2001 / Published online: 17 October 2001     

Growth of stoichiometric and textured LiNbO3 films on Si by pulsed laser deposition

Laser ablation of single-crystal LiNbO₃ in a gas environment is used to grow films on (100) Si substrates heated to 650 °C. The film composition and crystallinity are studied as a function of the nature (reactive, O₂, or inert, Ar) and pressure of the gas environment applied during deposition and cooling-down processes, the laser energy density and the target–substrate distance. Experimental results show that a gas pressure close to 1 mbar is required to produce stoichiometric films in either O₂ or Ar. The modification of the laser energy density and the target–substrate distance allows us to improve the crystallinity of the films that become textured along the (006) direction. The influence of the experimental parameters on the film properties is discussed in the frame of the formation of a blast wave, that leads to the focusing of the expanding Li species and thus, to the increase of the Li content in the films. Received: 8 February 2001 / Accepted: 9 February 2001 / Published online: 3 May 2001