Role of vanadium content in ZnO thin films grown by pulsed laser deposition

Vanadium-doped ZnO films (Zn_1−xV_xO, where x = 0.02, 0.03, 0.05 and 0.07), were formed from ceramic targets on c-cut sapphire substrates using pulsed laser deposition at substrate temperature of 600 °C and oxygen pressure of 10 Pa. In order to clarify how the vanadium concentration influences the films’ properties, structural and magnetic investigations were performed. All films crystallised in wurtzite phase and presented a c-axis preferred orientation at low concentrations of vanadium. The results implied that the doping concentration and crystalline microstructure influence strongly the system's magnetic characteristics. Weak ferromagnetism was registered for the film with the lowest doping concentration (2 at.%), which exhibited a ferromagnetic behavior at Curie temperature higher than 300 K. Increasing the vanadium content in the film caused degradation of the magnetic ordering.     

Characterization of polymer thin films obtained by pulsed laser deposition

The development of laser techniques for the deposition of polymer and biomaterial thin films on solid surfaces in a controlled manner has attracted great attention during the last few years. Here we report the deposition of thin polymer films, namely Polyepichlorhydrin by pulsed laser deposition. Polyepichlorhydrin polymer was deposited on flat substrate (i.e. silicon) using an NdYAG laser (266 nm, 5 ns pulse duration and 10 Hz repetition rate).The obtained thin films have been characterized by atomic force microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy and spectroscopic ellipsometry.It was found that for laser fluences up to 1.5 J/cm² the chemical structure of the deposited polyepichlorhydrin polymer thin layers resembles to the native polymer, whilst by increasing the laser fluence above 1.5 J/cm² the polyepichlorohydrin films present deviations from the bulk polymer.Morphological investigations (atomic force microscopy and scanning electron microscopy) reveal continuous polyepichlorhydrin thin films for a relatively narrow range of fluences (1-1.5 J/cm²).The wavelength dependence of the refractive index and extinction coefficient was determined by ellipsometry studies which lead to new insights about the material.The obtained results indicate that pulsed laser deposition method is potentially useful for the fabrication of polymer thin films to be used in applications including electronics, microsensor or bioengineering industries.     

Non-stoichiometry-induced metal-to-insulator transition in nickelate thin films grown by pulsed laser deposition

While controlling the cation contents in perovskite rare-earth nickelate thin films, a metal-to-insulator phase transition is reported. Systematic control of cation stoichiometry has been achieved by manipulating the irradiation of excimer laser in pulsed laser deposition. Two rare-earth nickelate bilayer thin-film heterostructures with the controlled cation stoichiometry (i.e. stoichiometric and Ni-excessive) have been fabricated. It is found that the Ni-excessive nickelate film is structurally less dense than the stoichiometric film, albeit both of them are epitaxial and coherent with respect to the underlying substrate. More interestingly, as a temperature decreases, a metal-to-insulator transition is only observed in the Ni-excessive nickelate films, which can be associated with the enhanced disproportionation of the Ni charge valence. Based on our theoretical results, possible origins (e.g. anti-site defects) of the low-temperature insulating state are discussed with the need of future work for deeper understanding. Our work can be utilized to realize unusual physical phenomena (e.g. metal-to-insulator phase transitions) in complex oxide films by manipulating the chemical stoichiometry in pulsed laser deposition.     

High temperature growth of InN on various substrates by plasma-assisted pulsed laser deposition

InN has attracted much attention due to its optical and electrical properties that make it suitable for the fabrication of infrared optical devices and high-speed electronic devices. In this work we report on the structural properties and morphology of InN thin films grown on different substrates by radiofrequency plasma beam assisted pulsed laser deposition. Sapphire and silicon substrates were considered for the growth of these films. The influence of substrate type and growth parameters on the morphology and structural properties of the resulting InN thin films is discussed. The structural analysis of the samples was performed by means of X-ray diffraction. The morphology of the thin films was investigated through atomic force microscopy. Although growth of InN from a metallic In target using nitrogen radiofrequency plasma assisted pulsed laser deposition was achieved for all the samples, growth conditions were found to play an important role on the crystal quality of the resulting thin films.     

Nanocomposite oxide thin films grown by pulsed energy beam deposition

Highly non-stoichiometric indium tin oxide (ITO) thin films were grown by pulsed energy beam deposition (pulsed laser deposition-PLD and pulsed electron beam deposition-PED) under low oxygen pressure. The analysis of the structure and electrical transport properties showed that ITO films with a large oxygen deficiency (more than 20%) are nanocomposite films with metallic (In, Sn) clusters embedded in a stoichiometric and crystalline oxide matrix. The presence of the metallic clusters induces specific transport properties, i.e. a metallic conductivity via percolation with a superconducting transition at low temperature (about 6 K) and the melting and freezing of the In-Sn clusters in the room temperature to 450 K range evidenced by large changes in resistivity and a hysteresis cycle. By controlling the oxygen deficiency and temperature during the growth, the transport and optical properties of the nanocomposite oxide films could be tuned from metallic-like to insulating and from transparent to absorbing films.     

Study of the structure and electrical properties of the copper nitride thin films deposited by pulsed laser deposition

Copper nitride thin films were prepared on glass and silicon substrates by ablating a copper target at different pressure of nitrogen. The films were characterized in situ by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and ex situ by X-ray diffraction (XRD). The nitrogen content in the samples, x = [N]/[Cu], changed between 0 and 0.33 for a corresponding variation in nitrogen pressure of 9 × 10⁻² to 1.3 × 10⁻¹ Torr. Using this methodology, it is possible to achieve sub-, over- and stoichiometric films by controlling the nitrogen pressure. The XPS results show that is possible to obtain copper nitride with x = 0.33 (Cu₃N) and x = 0.25 (Cu₄N) when the nitrogen pressure is 1.3 × 10⁻¹ and 5 × 10⁻² Torr, respectively. The lattice constants obtained from XRD results for copper nitride with x = 0.25 is of 3.850 Å and with x = 0.33 have values between 3.810 and 3.830 Å. The electrical properties of the films were studied as a function of the lattice constant. These results show that the electrical resistivity increases when the lattice parameter is decreasing. The electrical resistivity of copper nitride with x = 0.25 was smaller than samples with x = 0.33.     

Influence of oxygen partial pressure on the properties of pulsed laser deposited nanocrystalline zirconia thin films

ZrO₂ thin films were deposited at various oxygen partial pressures (2.0 × 10⁻⁵-3.5 × 10⁻¹ mbar) at 973 K on (1 0 0) silicon and quartz substrates by pulsed laser deposition. The influence of oxygen partial pressure on structure, surface morphology and optical properties of the films were investigated. X-ray diffraction results indicated that the films are polycrystalline containing both monoclinic and tetragonal phases. The films prepared in the oxygen partial pressures range 2.0 × 10⁻⁵-3.5 × 10⁻¹ mbar contain nanocrystals of sizes in the range 54-31 nm for tetragonal phase. The peak intensity of the tetragonal phase decreases with the increase of oxygen partial pressures. Surface morphology of the films examined by AFM shows the formation of nanostructures. The RMS surface roughness of the film prepared at 2.0 × 10⁻⁵ mbar is 1.3 nm while it is 3.2 nm at 3.5 × 10⁻¹ mbar. The optical properties of the films were investigated using UV-visible spectroscopy technique in the wavelength range of 200-800 nm. The refractive index is found to decrease from 2.26 to 1.87 as the oxygen partial pressure increases from 2.0 × 10⁻⁵ to 3.5 × 10⁻¹ mbar. The optical studies show two different absorption edges corresponding to monoclinic and tetragonal phases.     

Cobalt and tantalum additions for enhanced electrochromic performances of nickel-based oxide thin films grown by pulsed laser deposition

Aiming at improving the durability of anodic electrochromic nickel oxide thin films, Ni-M-O (M = Co, Ta) thin films were grown by pulsed laser deposition (PLD), using optimized conditions, namely room temperature and 10⁻¹ mbar oxygen pressure. For low Co and Ta contents (<5%), both additions lead to a loss of the [1 1 1] preferred orientation of the NiO rock-salt structure followed by a film amorphization with increasing Ta amount. Among the two series of metal additions (M ≤ 20%), the Ni-Co-O (5% Co) and Ni-Ta-O (10% Ta) thin films show the highest electrochemical performances especially in respect of improved durability. If the enhanced properties are associated with a limited dissolution of the oxidized phase for the Ni-Ta-O system, the opposite trend is observed for the Ni-Co-O system as compared to pure NiO.     

Oxygen incorporation in ZnTe thin films grown by plasma-assisted pulsed laser deposition

We studied oxygen incorporation into ZnTe thin films with nitrogen and oxygen plasma during a plasma-assisted pulsed laser deposition (PA-PLD). It was shown that ZnTe:O layer formed with oxygen plasma exhibits an enhancement of optical transparency in visible spectral region due to the formation of amorphous TeO_x. Especially, the ZnTe:NO deposited by PA-PLD under nitrogen and oxygen partial pressures with N₂:O₂ of 10:3 sccm showed p-type semiconducting characteristics and the formation of intermediate band at about 0.5–0.8 eV below the ZnTe band edge. These results for oxygen incorporation in ZnTe thin film such as the enhancement of optical transparency in visible spectral region and the intermediate band formation will be useful for optoelectronic devices or intermediate band solar cells.     

Properties of Dy-doped ZnO nanocrystalline thin films prepared by pulsed laser deposition

Highly transparent conductive Dy₂O₃ doped zinc oxide (ZnO)_1-x(Dy₂O₃)_x nanocrystalline thin films with x from 0.5% to 5% have been deposited on glass substrate by pulsed laser deposition technique. The structural, electrical and optical properties of Dy₂O₃ doped thin films were investigated as a function of the x value. The experimental results show that the Dy concentration in Dy-doped ZnO thin films has a strong influence on the material properties especially electrical properties. The resistivity decreased to a minimum value of 5.02 × 10⁻⁴ Ω cm with x increasing from 0.5% to 1.0%, then significantly increased with the further increasing of x value. On the contrary, the optical direct band gap of the (ZnO)_1-x(Dy₂O₃)_x films first increased, then decreased with x increasing. The average transmission of Dy₂O₃ doped zinc oxide films in the visible range is above 90%.     

Pulsed laser deposition and its current research status in preparing hydroxyapatite thin films

Pulsed laser deposition (PLD) is a conceptually and experimentally simple yet highly versatile tool for thin films and multi-layer film research. The mechanisms, advantages and disadvantages of pulsed laser deposition were reviewed. The process and some methods to resolve the drawbacks of PLD were discussed. Pulsed laser deposition of hydroxyapatite thin films was reviewed. Simple adjustment of PLD parameters can deposit hydroxyapatite in situ in crystalline form, amorphous films or HA with other calcium phosphate phases. Compared with plasma sprayed HA coatings the pulsed laser deposition HA thin films have higher coating/substrate adhesion and have minor undesirable phases under optimal conditions. Finally, we suggested some new researches should be done.     

Electrical characterisation of phosphorus-doped ZnO thin films grown by pulsed laser deposition

Phosphorus-doped ZnO films were grown by pulsed laser deposition using a ZnO:P₂O₅-doped target as the phosphorus source with the aim of producing p-type ZnO material. ZnO:P layers (with phosphorus concentrations of between 0.01 to 1 wt%) were grown on a pure ZnO buffer layer. The electrical properties of the films were characterised from temperature dependent Hall-effect measurements. The samples typically showed weak n-type conduction in the dark, with a resistivity of 70 Ω cm, a Hall mobility of μ_n0.5 cm² V ⁻¹ s⁻¹ and a carrier concentration of n3×10¹⁷ cm⁻³ at room temperature. After exposure to an incandescent light source, the samples underwent a change in conduction from n- to p-type, with an increase in mobility and decrease in concentration for temperatures below 300 K.     

Effects of deposition temperature on the structural and morphological properties of thin ZnO films fabricated by pulsed laser deposition

ZnO thin films were grown on Si(1 0 0) substrates using pulsed laser deposition in O₂ gas ambient (10 Pa) and at different substrate temperatures (25, 150, 300 and 400 °C). The influence of the substrate temperature on the structural and morphological properties of the films was investigated using XRD, AFM and SEM. At substrate temperature of T=150 °C, a good quality ZnO film was fabricated that exhibits an average grain size of 15.1 nm with an average RMS roughness of 3.4 nm. The refractive index and the thickness of the thin films determined by the ellipsometry data are also presented and discussed.     

Optical and electrical properties of aluminum-doped ZnO thin films grown by pulsed laser deposition

Transparent aluminum-doped zinc oxide (AZO) thin films were deposited on quartz glass substrates by pulsed laser deposition (PLD) from ablating Zn-Al metallic targets. The structural, electrical and optical properties of these films were characterized as a function of Al concentration (0-8 wt.%) in the target. Films were deposited at a low substrate temperature of 150 °C under 11 Pa of oxygen pressure. It was observed that 2 wt.% of Al in the target (or 1.37 wt.% of Al doped in the AZO film) is the optimum concentration to achieve the minimum film resistivity and strong ultraviolet emission. The presence of Al in the ZnO film changes the carrier concentration and the intrinsic defects.     

ZnO nanostructured thin films grown by pulsed laser deposition in mixed O2 / Ar background gas

We report on the properties of ZnO nanostructured thin films grown on either bare or gold patterned a-plane sapphire substrates. The pulsed laser deposition technique was used to deposit all the films at a temperature of 700 C in a mixture of oxygen and argon under a total pressure of 35 Pa. SEM surface characterizations typically showed pyramidal nanostructures with hexagonal symmetry and a coverage density strongly dependent on the O₂ partial pressure. For the patterned samples, wall-like structures of nanoneedles were observed. For all samples, x-ray diffraction results confirmed the high crystalline quality of the nanostructures, with the rocking curve widths of the (0002) reflection as low as 0.09. Similarly, photoluminescence results at room temperature testified to the high optical quality of the material.     

Characteristics of ZrC/ZrN and ZrC/TiN multilayers grown by pulsed laser deposition

ZrC/ZrN and ZrC/TiN multilayers were grown on (1 0 0) Si substrates at 300 °C by the pulsed laser deposition (PLD) technique using a KrF excimer laser. X-ray diffraction investigations showed that films were crystalline, the strain and grain size depending on the nature and pressure of the gas used during deposition. The elemental composition, analyzed by Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS), showed that films contained a low level of oxygen contamination. Simulations of the X-ray reflectivity (XRR) curves acquired from films indicated a smooth surface morphology, with roughness below 1 nm (rms) and densities very close to bulk values.Nanoindentation results showed that the ZrC/ZrN and ZrC/TiN multilayer samples exhibited hardness values between 30 and 33 GPa, slightly higher than the values of 28-30 GPa measured for pure ZrC, TiN and ZrN 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.     

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.     

Bioactive glass and hydroxyapatite thin films obtained by pulsed laser deposition

Bioactive glass (BG), calcium hydroxyapatite (HA), and ZrO₂ doped HA thin films were grown by pulsed laser deposition on Ti substrates. An UV KrF^* (λ = 248 nm, τ ≥ 7 ns) excimer laser was used for the multi-pulse irradiation of the targets. The substrates were kept at room temperature or heated during the film deposition at values within the (400-550 °C) range. The depositions were performed in oxygen and water vapor atmospheres, at pressure values in the range (5-40 Pa). The HA coatings were heat post-treated for 6 h in a flux of hot water vapors at the same temperature as applied during deposition. The surface morphology, chemical composition, and crystalline quality of the obtained thin films were studied by scanning electron microscopy, atomic force microscopy, and X-ray diffractometry. The films were seeded for in vitro tests with Hek293 (human embryonic kidney) cells that revealed a good adherence on the deposited layers. Biocompatibility tests showed that cell growth was better on HA than on BG thin films.