Pulsed laser deposition of (110) oriented semiconductive SrFeO3−x thin films

 The semiconductive perovskite-type oxide SrFeO_3-x (x<0.16) (SFO) thin films have been directly fabricated on (001)SrTiO₃ and (001)LaAlO₃ single crystal substrates by pulsed laser deposition(PLD) under high oxygen partial pressure of 100 Pa. The SFO thin films were (110) oriented. The x-ray photoelectron spectroscopy (XPS) analysis showed that the surface of SFO thin film has strong gas absorption capability. The resistance versus temperature has been measured in the temperature range from 77 K to 300 K. The SFO thin film showed typical semiconductive property. Dependence of resistance of SFO thin film on oxygen pressure was measured and result showed that the SFO thin film had better oxygen sensitive property. Received: 14 May 1996/Accepted: 15 August 1996     

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.     

Pulsed laser deposition of ZnO as conductive buffer layer of (001)-LiNbO3 thin films

1 (LO) mode peak at 579 cm^-1, indicating oxygen deficiency in the films. Significant dependence of the electrical property for the films on substrate temperature was shown. The I–V relation of the films exhibited non-ohmic behavior. Whereas the films deposited above 500 °C showed a metal-like property, at a lower substrate temperature semiconducting thin films were achieved. The (001)-oriented LiNbO₃/ZnO heterostructure was successfully prepared on quartz fused and (001) sapphire plates. Received: 6 April 1998/Accepted: 26 May 1998     

Pulsed laser deposition of NiTi shape memory effect thin films

2 O₃(100) substrates. We also produced free-standing NiTi films by deposition on KBr substrates and subsequent substrate removal by immersion in water. The presence of the solid-solid phase transformation responsible for the shape memory effect has been demonstrated through temperature-dependent X-ray diffraction and four-probe resistance versus temperature measurements. On cooling the deposited film, the austenite-martensite transformation was measured at around 195 K; on heating the film the reverse transformation was around 250 K. Evidence of the shape-memory effect for free-standing films was obtained in a bending deformation-shape recovery experiment. Received: 31 July 1996/Accepted: 6 January 1997     

Artificially nanostructured Cu:Al2O3 films produced by pulsed laser deposition

The processes leading to the formation of Cu:Al₂O₃ composite films on Si (001) with a well defined nanostructure by alternate pulsed laser deposition (a-PLD) in vacuum are investigated. Alternately amorphous Al₂O₃ layers and Cu nanocrystals nucleated on the Al₂O₃ surface are formed, according to the PLD sequence. The Al₂O₃ deposited on the Cu nanocrystals fills in the space between them until they are completely buried, and subsequently, a continuous dense layer with a very flat surface (within 1 nm) is developed. The nucleation process of the nanocrystals and their resulting oblate ellipsoidal shape are discussed in terms of the role of the energetic species involved in the PLD process and the metal–oxide interface energy. Received: 4 July 2000 / Accepted: 5 July 2000 / Published online: 13 September 2000     

Pulsed laser deposition and in situ diagnostics of the process applied to shape-memory alloys

NiTi films deposited by pulsed laser ablation on Si/SiO₂ are shown to exhibit structural and functional properties related to the shape-memory effect. Film characterization suggests that relevant temperatures for the solid-to-solid transformation responsible for the shape memory are in substantial agreement with those of the bulk target material, demonstrating a good congruency of the deposition process. Besides the technological interest for this class of thin films, our findings point out the suitability of laser ablation for metal alloy deposition. An investigation based on in situ ion-mass spectroscopy and covariance mapping analysis allows us to determine the main vapor-phase processes leading to the formation of stoichiometric clusters expected to play a relevant role in assisting the growth of NiTi thin films. Received: 6 August 2001 / Accepted: 11 April 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. Fax: +39-50/2214-333, E-mail: fuso@df.unipi.it     

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.     

Effects of growth temperature on Li-N dual-doped p-type ZnO thin films prepared by pulsed laser deposition

Li-N dual-doped p-type ZnO (ZnO:(Li,N)) thin films have been prepared by pulsed laser deposition. The introduction of Li and N was confirmed by secondary ion mass spectrometry measurements. The structural, electrical, and optical properties as a function of growth temperature were investigated in detail. The lowest room-temperature resistivity of 3.99 Ω cm was achieved at the optimal temperature of 450 °C, with a Hall mobility of 0.17 cm²/V s and hole concentration of 9.12 × 10¹⁸ cm⁻³. The ZnO:(Li,N) films exhibited good crystal quality with a complete c-axis orientation, a high transmittance (about 90%) in the visible region, and a predominant UV emission at room temperature. The two-layer-structure p-ZnO:(Li,N)/n-ZnO homojunctions were fabricated on a sapphire substrate. The current-voltage characteristics exhibited the rectifying behavior of a typical p-n junction.     

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     

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     

Study of the ambient optical recording dynamics on sputtered indium oxide thin films

2 O₃) thin films, grown by dc magnetron sputtering, using ultraviolet laser radiation at 325 nm, is investigated. Simultaneous measurements of the recording efficiency and electrical conductivity changes, under ambient conditions, prove that there is a strong relation between the two actions, and measurements of the recording efficiency with respect to the film conductivity history and temperature provide evidence for the presence of two coexisting processes in the recording regime. The reported results provide essential information on the mechanism and nature of holographic recording in this material. Received: 4 November 1997/Accepted: 16 November 1997     

Femtosecond laser ablation of silicon–modification thresholds and morphology

We investigated the initial modification and ablation of crystalline silicon with single and multiple Ti:sapphire laser pulses of 5 to 400 fs duration. In accordance with earlier established models, we found the phenomena amorphization, melting, re-crystallization, nucleated vaporization, and ablation to occur with increasing laser fluence down to the shortest pulse durations. We noticed new morphological features (bubbles) as well as familiar ones (ripples, columns). A nearly constant ablation threshold fluence on the order of 0.2 J/cm² for all pulse durations and multiple-pulse irradiation was observed. For a duration of ≈100 fs, significant incubation can be observed, whereas for 5 fs pulses, the ablation threshold does not depend on the pulse number within the experimental error. For micromachining of silicon, a pulse duration of less than 500 fs is not advantageous. Received: 4 December 2000 / Revised version: 29 March 2001 / Published online: 20 June 2001     

Characterization of a RF/dc-magnetron discharge for the sputter deposition of transparent and highly conductive ITO films

A RF-superimposed dc-magnetron sputter process for coating color filter materials with transparent and conducting ITO films was investigated. In this process, the sputtering cathode is excited simultaneously by dc- and RF-power (at 13.56 MHz). This work summarises the measured properties of the gas discharge. Some basic data of the deposited ITO films are given, also. The dependence of the RF portion of the total sputtering power on the discharge voltage has been monitored for different values of total power and process pressure. The ion energy distribution function of the positively charged ions approaching the substrate surface has been measured using a retarding field plasma analyser probe. It was shown that the mean energy of the ions increases with increasing RF portion of the total power. The electron temperature in the body region of the gas discharge has been derived from measurements of the optical emission of the excited species. Received: 3 November 1998 / Accepted: 8 March 1999 / Published online: 14 July 1999     

Polymer-based multi-layer conductive electrode film for plastic LCD applications

Thin films of polymer-based multi-layer conductive electrode to be used as a substrate for a plastic liquid crystal display (LCD) have been prepared by a DC magnetron roll-to-roll sputtering method. The conductive layer is composed of three layers, ITO/Ag/ITO or ITO/APC/ITO, where APC is Ag-Pd-Cu alloy, on the polymer substrate (Arton?), which has been treated with hard-coat and gas-barrier layers. The properties of the conductive electrode for the plastic LCD were the following: (1) sheet resistance is 6 Ω/square; (2) transparency is 88% at 550 nm; (3) H₂O gas permeation through the plastics is 0.35 g/m² in 24 h; (4) durability against solvents is good for 5% NaOH solution, IPA, methanol, NMP, acetone, etc.; (5) the irreversible shrinkage and the compaction rate are both less than 3 ppm/h after annealing for 100 h at 150 °C. Received: 22 January 2001 / Accepted: 30 January 2001 / Published online: 26 April 2001     

Evolution of the deposition rate during pulsed laser deposition of hydroxyapatite coatings and its relation with target morphology

The evolution of the deposition rate during pulsed laser deposition of hydroxyapatite coatings with a KrF excimer laser was studied. This evolution was related to the changes produced on the target morphology during laser irradiation. Laser fluences in the 1.0–5.2 J/cm² range, typical for the deposition of hydroxyapatite coatings, were investigated. Deposition rates were measured through a quartz-crystal microbalance, and the target surface was observed by scanning electron microscopy. At the lowest fluences, the deposition rate decreases as the number of pulses increases. At the same time, a cone structure is developed on the target surface. At the highest fluences, the deposition rate increases with the number of pulses. In this case, the target surface becomes rough but cones are not formed. In all cases, an enlargement of the effective irradiated area results. This enlargement produces the effect of fluence dilution and also an increase of the emitting area. These opposite effects could account for the different evolutions found for the deposition rate. At low fluences the effect of fluence dilution would predominate over the increase of the emitting area, and at high fluences the second effect would predominate over the first. Received: 28 September 2000 / Accepted: 4 October 2000 / Published online: 10 January 2001     

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     

Optical studies on the deposition of carbon nitride films by laser ablation

2 radicals when the 355 and 1064 nm outputs of a Nd:YAG laser were applied. While for the 532 nm ablation, a relatively higher concentration of excited atomic carbon was obtained. Different Raman and FTIR spectral features were observed from the deposited films with different ablation wavelengths. The 532 nm laser ablation is proposed for the synthesis of high quality carbon nitride films. Received: 16 October 1996 / Accepted: 11 April 1997     

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     

Properties of conductive polymer films deposited by infrared laser ablation

Thin films of the conducting polymer poly(3,4-ethylenedioxy-thiophene):poly(styrenesulfonate) (PEDOT:PSS) were deposited by resonant infrared laser vapor deposition (RIR-LVD). The PEDOT:PSS was frozen in various matrix solutions and deposited using a tunable, mid-infrared free-electron laser (FEL). The films so produced exhibited morphologies and conductivities that were highly dependent on the solvent matrix and laser irradiation wavelength used. When deposited from a native solution (1.3% by weight in water), as in matrix-assisted pulsed laser evaporation (MAPLE), films were rough and electrically insulating. When the matrix included other organic “co-matrices” that were doped into the solution prior to freezing, however, the resulting films were smooth and exhibited good electrical conductivity (0.2 S/cm), but only when irradiated at certain wavelengths. These results highlight the importance of the matrix/solute and matrix/laser interactions in the ablation process.     

Ultrashort-pulse laser ablation of indium phosphide in air

Ablation of indium phosphide wafers in air was performed with low repetition rate ultrashort laser pulses (130 fs, 10 Hz) of 800 nm wavelength. The relationships between the dimensions of the craters and the ablation parameters were analyzed. The ablation threshold fluence depends on the number of pulses applied to the same spot. The single-pulse ablation threshold value was estimated to be φ_th(1)=0.16 J/cm². The dependence of the threshold fluence on the number of laser pulses indicates an incubation effect. Morphological and chemical changes of the ablated regions were characterized by means of scanning electron microscopy and Auger electron spectroscopy. Received: 30 May 2000 / Accepted: 31 May 2000 / Published online: 23 August 2000