Effect of nitrogen pressure on structure and optical properties of pulsed laser deposited BCN thin films

Amorphous boron carbon nitride (BCN) thin films were deposited on Si (100) and quartz substrates by laser ablation of a boron carbide (B₄C) target in nitrogen atmosphere. The effects of the nitrogen pre ssure (p_N2) on the film deposition rate, composition, structure and optical properties were investigated. The film deposition rate was measured by a surface profiler, which increased from 3.4 to 6.25 nm/min at elevated p_N2. Structure and composition of the films were investigated by X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared (FTIR) spectroscopy. FTIR and XPS analyses indicated that the as-deposited BCN films contained B-C, N-C and B-N chemical bonds, implying the formation of ternary BCN compounds. The nitrogen content in the films increased gradually and then saturated up to ∼ 26 at.% at 10 Pa p_N2. The optical band gap (E_g) increased from 3.78 to 3.92 eV with increasing p_N2 from 2 to 15 Pa. The evolution of E_g is in accordance with the change of film compositions and bonding states.     

Characterization of calcium titanate thin films deposited on titanium with reactive sputtering and pulsed laser depositions

In the present study, characteristics of calcium titanate thin films deposited on titanium by reactive sputtering and pulsed laser deposition techniques were investigated. In both techniques, a calcium titanate target was used as a deposition source, and the titanium substrate was heated at 873 K during the deposition. The oxygen flow for the reactive sputtering was in the range of 1 to 10 sccm, and the oxygen pressure for the pulsed laser deposition was in the range of 0.13 to 13 Pa. The deposited films were crystallized into perovskite-type calcium titanate; furthermore, a titanium-dioxide layer formed in the interface between the film and substrate. In the film deposited by reactive sputtering with low oxygen flow, titanium-to-calcium ratio ([Ti]/[Ca]) is lower than that of stoichiometric calcium titanate due to the formation of calcium hydroxide. The ratio increases with an increase of oxygen flow, and the ratio of the film deposited with a 10-sccm oxygen flow was almost in accordance with that of stoichiometric calcium titanate. On the other hand, in the pulsed laser deposition, [Ti]/[Ca] ratios of the deposited film were almost in accordance with that of stoichiometric calcium titanate at the oxygen pressure under the present experimental condition. In both deposition techniques, the thickness of the titanium-oxide layer increased with an increase of the amount of oxygen gases. The results indicate that the pulsed laser deposition has an advantage for the preparation of the stoichiometric calcium titanate film without formation of a thick titanium-oxide layer.     

High-repetition rate pulsed laser deposition of ZrC thin films

ZrC thin films were grown on (100) Si substrates by the pulsed laser deposition (PLD) technique using a high-repetition rate excimer laser working at 40 Hz. The substrate temperature during depositions was set at 300 °C and the cooling rate was 5 °C/min. X-ray diffraction investigations showed that the films were crystalline. Films deposited under residual vacuum or 2 × 10^− 3 Pa of CH₄ atmosphere exhibited a (200)-axis texture, while those deposited under 2 × 10^− 2 Pa of CH₄ atmosphere were found to be equiaxed. The surface elemental composition of as-deposited films, analyzed by Auger electron spectroscopy (AES), showed the usual high oxygen contamination of carbides. Once the topmost − 3-5 nm region was removed, the oxygen concentration rapidly decreased, being around 3-4% only in bulk. Scanning electron microscopy (SEM) investigations showed a smooth, featureless surface morphology, corroborating the roughness values below 1 nm (rms) obtained from simulations of the X-ray reflectivity (XRR) curves. From the same simulations we also estimated films mass density values of around 6.32-6.57 g/cm³ and thicknesses that correspond to a deposition rate of around 8.25 nm/min. Nanoindentation results showed a hardness of 27.6 GPa and a reduced modulus of 228 GPa for the best quality ZrC films deposited under an atmosphere of 2 × 10^− 3 Pa CH₄.     

Influence of europium oxide doping on the structural and optical properties of pulsed laser ablated barium tungstate thin films

Nanostructured Eu₂O₃ doped Barium tungstate (BaWO₄) crystallites are successfully synthesized using pulsed laser deposition (PLD) technique. The influence of different Eu₂O₃ doping concentrations (1,2,3 & 5 wt.%) on the structural, surface morphological and optical properties are systematically studied using XRD, micro-Raman, SEM, AFM, UV-vis and photoluminescence spectroscopy. All the films are polycrystalline with tetragonal scheelite structure. The vibrational analysis of the atoms in BaWO₄ is studied by micro-Raman spectra using factor group analysis. The surface morphological analysis by SEM and AFM reveals the presence of fine nanoparticles with distinct grain boundaries in all the films. The band gap energy variation in the Eu₂O₃ doped BaWO₄ films is in accordance with the variation of the sizes of nano particles in the films. The films with higher Eu³⁺ doping concentrations (≥2 wt.%) show a PL emission peak centered around 614 nm when excited at 394 nm which can be attributed to the ⁵D₀ → ⁷F₂ (0-2) transition of Eu³⁺ ion.     

Tribological properties of pulsed laser deposited Mo-S-Te composite films at moderate high temperatures

Tribological investigations of Mo-S-Te composite films were conducted on films grown at room temperature by pulsed laser deposition. The chemistry and microstructure of the films were characterized by X-ray diffraction, scanning electron microscopy, X-ray energy dispersive spectroscopy, and micro Raman spectroscopy. The films showed a granular morphology and a preferred basal plane growth of 2H-MoS₂ parallel to the substrate after annealing at high temperatures. The friction coefficients of the films were 0.05 at 300 °C and 0.10 at 450 °C for more than 10,000 cycles in air. Smeared hexagonal MoS₂ lubricant films were observed inside wear tracks while the tribochemical formation of wear debris occurred both inside and outside the wear tracks. The Te additives for increasing the film durability were proposed to slow oxidation of the lubricants at elevated temperatures by thermally-induced tellurium migration to the surface and the subsequent formation of the Te diffusion barrier. This mechanism could be significantly effective in high-temperature tribotests because of the increased tellurium mobility at high temperatures.     

Oriented nanocrystals in SrLaMnTiO6 perovskite thin films grown by pulsed laser deposition

We have fabricated SrLaMnTiO₆ thin films by PLD on different substrates (SrTiO₃, LaAlO₃ and Si). Their texture, width, homogeneity and morphology have been evaluated from XRD, SEM and complex impedance spectroscopy. The thickness ranged between 500 and 8800 nm depending on the synthesis conditions. The epitaxial growing could be interpreted in terms of two contributions of microstructural origin: a matrix part and some surface formations (hemi-spheres), with different texture and size distributions. The films were nanostructured and contained vertically aligned nanopores (VANPs) with a pore average size of 30-60 nm, which are very interesting for eventual SOFC anode applications. Magnetization results indicate an improved response respect to nano-sized powder samples.     

Properties of multilayer gallium and aluminum doped ZnO(GZO/AZO) transparent thin films deposited by pulsed laser deposition process

Multilayer gallium and aluminum doped ZnO (GZO/AZO) films were fabricated by alternative deposition of Ga-doped zinc oxide(GZO) and Al-doped zinc oxide(AZO) thin film by using pulsed laser deposition(PLD) process. The electrical and optical properties of these GZO/AZO thin films were investigated and compared with those of GZO and AZO thin films. The GZO/AZO (1:1) thin film deposited at 400 °C shows the electrical resistivity of 4.18×10-4 Ω·cm, an electron concentration of 7.5×1020 /cm3, and carrier mobility of 25.4 cm2/(V·s). The optical transmittances of GZO/AZO thin films are over 85%. The optical band gap energy of GZO/AZO thin films linearly decreases with increasing the Al ratio.     

Microstructure and grain growth kinetics of nanocrystalline SnO2 thin films prepared by pulsed laser deposition

The isothermal grain growth of SnO₂ thin films prepared by pulsed laser deposition techniques was investigated at Si (100) substrate temperatures between 300 and 450 °C with 50 °C intervals for different annealing times. X-ray diffraction patterns proved that the average grain sizes are in the range of 2.4–27.8 nm. The grain growth data were analyzed using two different models. The first model, assuming normal grain growth as that in conventional polycrystalline materials, yields large grain growth exponent (n) and extremely low activation energy (Q). Although it can describe the evolution of grain sizes, it fails to give satisfactory physical interpretation of n and Q, both beyond the theoretical predictions. The second model is based on the structural relaxation of the interface component in nanocrystalline materials. In this case, the ordering of distorted interfaces by structural relaxation proceeds with grain growth. This structure relaxation model not only describes the evolutions of grain growth well, but also makes reasonable attribution of the low activation energy to the short-range rearrangement of atoms in the interface region as well.     

Fabrication, microstructure and tribological behavior of pulsed laser deposited a-CNx/TiN multilayer films

a-CN_x/TiN multilayer films were deposited onto high-speed steel substrates by pulsed laser ablation of graphite and Ti target alternately in nitrogen gas. The composition, morphology and microstructure of the films were characterized by energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy. The tribological properties of the films in humid air were investigated using a ball-on-disk tribometer. The multilayer films consist of crystalline TiN, metallic Ti and amorphous CN_x (a-CN_x). With an increase in thickness ratio of CN_x to bilayer, the hardness of multilayer film decreases, friction coefficient decreases from 0.26 to 0.135, and wear rate increases. The film with thickness ratio of CN_x to bilayer of 0.47 exhibits a maximum hardness of 30 GPa and excellent wear rate of 2.5 × 10^− 7 mm³ N^− 1 m^− 1. The formation of tribo-layer was observed at contact area of Si₃N₄ ball. The film undergoes the combined wear mechanism of abrasion wear and adhesion wear.     

A novel method to synthesis magnetic thin film of iron oxide

A novel method is used to deposit iron oxide thin film. Frozen iron acetate is used as a target for pulsed laser deposition of iron oxide thin film. KrF excimer laser having wavelength of 248 nm with pulsed duration of 20 ns is used to deposit the film. Structural characterizations were performed using X-ray diffraction and atomic/magnetic force microscopy. The X-ray diffraction patterns confirmed the polycrystalline nature of α-Fe₂O₃. Temperature dependence magnetic measurements in zero field cooled showed the presence of blocking temperature at ∼60 K. The magnetic measurements revealed the existence of superparamagnetic behavior above blocking temperature and freezing of magnetic moments arising from uncompensated surface spins below blocking temperature.     

Yttria-stabilized zirconia thin films deposited by pulsed-laser deposition and magnetron sputtering

Yttria-stabilized zirconia (YSZ, ZrO₂:Y₂O₃) was deposited on (100) silicon by two physical vapor deposition techniques: pulsed laser deposition (PLD) and reactive magnetron sputtering (RMS). PLD thin films were grown on silicon substrates at 500 °C from the ablation of a 8YSZ ceramic target by a KrF excimer laser. RMS thin films were obtained by direct current magnetron sputtering of a Zr/Y metallic target in an oxygen/argon atmosphere. The deposition rate of the PLD technique using an UV excimer laser delivering pulses at a repetition rate of 40 Hz was found two orders of magnitude lower than the RMS method one. Both techniques led to the growth of crystalline films with a (111) preferential orientation. PLD films were dense and featureless whereas RMS ones exhibited well defined but compact columnar structure. Growth of a YSZ film of about 1 μm covering a rough and porous commercial anode support (NiO-YSZ cermet) was successfully carried out with both methods.     

Influence of nitrogen background pressure on structure of niobium nitride films grown by pulsed laser deposition

Depositions of niobium nitride thin films on Nb using pulsed laser deposition (PLD) with different nitrogen background pressures (10.7 to 66.7 Pa) have been performed. The effect of nitrogen pressure on NbN formation in this process was examined. The deposited films were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), atomic force microscope (AFM), and energy dispersive X-ray (EDX) analysis. Hexagonal β-Nb₂N and cubic δ-NbN phases resulted when growth was performed in low nitrogen background pressures. With an increase in nitrogen pressure, NbN films grew in single hexagonal β-Nb₂N phase. The formation of the hexagonal texture during the film growth was studied. The c/a ratio of the hexagonal β-Nb₂N unit cell parameter increases with increasing nitrogen pressure. Furthermore, the N:Nb ratio has a strong influence on the lattice parameter of the δ-NbN, where the highest value was achieved for this ratio was 1.19. It was found that increasing nitrogen background pressure leads to change in the phase structure of the NbN film. With increasing nitrogen pressure, the film structure changes from hexagonal to a mixed phase and then back to a hexagonal phase.     

Thickness modulation effect of CeO_2 layer for YBCO films grown by pulsed laser deposition

CeO_2 film plays an essential role in nucleation and growth of YBa_2 Cu_3 O_7-x(YBCO) films. In this work,the dependence of superconducting properties of YBCO on CeO_2 films with different thicknesses was investigated,in order to achieve fabrication of high-performance YBCO coated conductors in industrial scale. The crystalline structure and morphology of CeO2 films with thickness ranging from 21 to 563 nm were systematically characterized by means of X-ray diffraction(XRD), atomic force microscope(AFM) and reflection high-energy electron diffraction(RHEED). Additional focus was addressed on evolution of the surface quality of CeO_2 films with thickness increasing. The results show that at the optimal thickness of 221 nm, CeO_2 film exhibits sharp in-plane and out-of-plane texture with full width of half maximum(FWHM) values of 5.9° and 1.8°, respectively, and smooth surface with a mean root-mean-square(RMS) roughness value as low as 0.6 nm. Combing RHEED and transmission electron microscope(TEM) cross-sectional analysis, it is found that nucleation and growth of CeO_2 films at early stage remain in island growth mode with rougher surface,while further increasing the thickness beyond the optimal thickness leads to weak surface quality, consequently resulting in degradation of superconductor layers deposited subsequently. Eventually, a critical current density(J_c) as high as 4.6×10~6 A·cm^-2(77 K, self-field) is achieved on a YBCO film on a thickness-modulated CeO_2/MgO/Y_2 O_3/Al_2 O_3/C276 architecture, demonstrating the advantages of CeO_2 films as buffer layer in high-throughput manufacture of coated conductors.     

Film growth phenomena in high-energetic room temperature pulsed laser deposition on polymer surfaces

Coating of plastics by inorganic metal-based films requires profound knowledge about the phenomena occurring in connecting materials of very high and very low (visco-)elastic properties. Buckling and delamination are unwanted, stress-release induced effects leading to severe failure. To overcome the problem of delamination, higher energetic deposition conditions for strengthening the polymer surface by ion implantation are seen as a chance, but bear the risk of high film stresses and, thus, an increase of buckling.To understand these phenomena in pulsed laser deposition (PLD) the current work focuses on topographical, morphological and chemical investigations of polymers coated with thin interface films between 5 and 100 nm thickness. Applying this approach in the room temperature PLD (RT-PLD) enables the understanding of ion implantation during interface growth.The results reveal a strong chemical binding between implanted atoms and polymer chains as well as a hardening of the soft polymer surface, which increases the load capacity. Only very low changes of the surface topography after coating by wrinkling phenomena reveal scarce influence of the ion bombardment and high adhesion of the films.     

Effect of annealing and O2 pressure on structural and optical properties of pulsed laser deposited TiO2 thin films

In this paper, effect of annealing and O₂ pressure on the structural and optical properties of pulsed laser deposited thin films of TiO₂ is reported. XRD, FTIR spectra and SEM images confirm that at high annealing temperatures, the rutile phase and crystalline quality of thin films increases. Higher pressure of O₂ during deposition improves the rutile phase and favors the rod like growth of TiO₂ thin film. The red shift in photoluminescence (PL) spectra of TiO₂ thin films with annealing temperature is reported. Contact angle measurement data for the thin films reveals the hydrophobic nature of the films. The very low reflectivity (～10%) reported in this paper may be promising for anti-reflection coating applications of pulsed laser deposited TiO₂ thin films.     

脉冲激光沉积及硒化法制备Cu(In,Ga)Se2薄膜研究

采用脉冲激光沉积和硒化后热处理的方法在石英衬底上制备Cu(In,Ga)Se2（简写为CIGS）薄膜,研究脉冲激光沉积（PLD）技术在制备CIGS薄膜太阳能电池材料上的应用,分析了不同预制层沉积顺序及厚度对CIGS薄膜组织结构、表面形貌、成分以及光学性能的影响。实验结果表明：(1)利用PLD技术及后硒化处理的工艺,制得的CIGS太阳能电池吸收层具有纯相和高结晶度等特性;(2)CuGa/In金属预制层的叠层顺序和叠层数、硒化退火温度对薄膜的结晶质量、晶粒尺寸、成分都具有重要的影响,其中叠层顺序影响最为明显;(3)样品均表现出对可见光区具有透射率低和吸收系数高的光学特性。本工作为制备性能优良的CIGS太阳能电池吸收层,提供了一个新颖的工艺手段。     

Pulsed laser deposition of anatase and rutile TiO2 thin films

The investigation deals with the preparation of both anatase and rutile thin films from a sintered rutile target of TiO₂ by pulsed laser ablation technique. Microstructural characterization of the sintered target was carried out using X-ray diffraction and AC impedance spectroscopy. Thin films of titania were deposited on (111) Si substrates at 673 K in the laser energy range 200-600 mJ/pulse at two different conditions: (i) deposition at 3.5 × 10^− 5 mbar of oxygen, and (ii) deposition at an oxygen partial pressure of 0.1 mbar. The influence of laser energy and oxygen addition on the film growth has been studied. X-ray diffraction analysis of the films indicated that the films are single phasic and nano crystalline. Titania films deposited in the energy range 200-600 mJ/pulse at a base pressure of 5 × 10^− 5 mbar are rutile with particle sizes in the range 5-10 nm, whereas the films formed at the oxygen partial pressure 0.1 mbar are anatase with particle sizes in the range 10-24 nm. In addition, at higher energies, a significant amount of particulates of titania are found on the surface of the films. The change in the microstructural features of the films as a function of laser energy and oxygen addition is discussed in relation with the interaction of the ablated species with the background gas.     

Reactive pulsed laser deposition and characterization of niobium nitride thin films

We present a systematic study to explore the effect of important process variables on the composition and structure of niobium nitride thin films synthesized by Reactive Pulsed Laser Deposition (RPLD) technique through ablation of high purity niobium target in the presence of low pressure nitrogen gas. Secondary Ion Mass Spectrometry has been used in a unique way to study and fix gas pressure, substrate temperature and laser fluence, in order to obtain optimized conditions for one variable in single experimental run. The x-ray diffraction and electron microscopic characterization have been complemented by proton elastic backscattering spectroscopy and x-ray photoelectron spectroscopy to understand the incorporation of oxygen and associated non-stoichiometry in the metal to nitrogen ratio. The present study demonstrates that RPLD can be used for obtaining thin film architectures using non-equilibrium processing. Finally the optimized NbN thin films were characterized for their hardness using nano-indentation technique and found to be ~ 30 GPa at the deposition pressure of 8 Pa.     

Interface growth morphologies in pulsed laser deposited, room temperature grown multilayer hard coatings

The mechanical behaviour - hardness, elasticity, and adhesion - of multilayer coatings is strongly influenced by the type of the formed interfaces between the different layers. In industrially applied tribological coatings the interface region is predominantly not a perfect sudden change of the chemical composition of the adjacent crystal planes, but a transition zone of a thickness, which is strongly dependent on the energetic conditions during deposition. Multilayer coatings grown by high-energetic deposition techniques always struggle with high atomic mixing of both adjacent coating materials due to high energetic ion implantation.One of these high-energetic deposition techniques is the Pulsed Laser Deposition (PLD), characterized by pulsed and within one pulse alternating high- and low-energetic particle fractions, hitting successively the substrate surface. Such deposition conditions were shown to be highly advantageous for low temperature deposition by the densification of the growth structures due to activated diffusion and re-sputtering, but increases the difficulty in depositing multilayer structures.The current paper addresses these specific growth conditions based on Ti/TiN and Cr/CrN multilayer coatings. High resolution transmission electron microscopy results show that the atomic mixing at the interface is not highly critical for the deposition of multilayer coatings and that extremely dense growth structures are forming even in the interface regions.     

Low temperature processed highly conducting, transparent, and wide bandgap Gd doped CdO thin films for transparent electronics

Gadolinium (Gd) doped cadmium oxide (CdO) thin films are grown at low temperature (100 °C) using pulsed laser deposition technique. The effect of oxygen partial pressures on structural, optical, and electrical properties is studied. X-ray diffraction studies reveal that these films are polycrystalline in nature with preferred orientation along (1 1 1) direction. Atomic force microscopy studies show that these films are very smooth with maximum root mean square roughness of 0.77 nm. These films are highly transparent and transparency of the films increases with increase in oxygen partial pressure. We observe an increase in optical bandgap of CdO films by Gd doping. The maximum optical band gap of 3.4 eV is observed for films grown at 1 × 10⁻⁵ mbar. The electrical resistivity of the films first decreases and then increases with increase in oxygen partial pressure. The lowest electrical resistivity of 2.71 × 10⁻⁵ Ω cm and highest mobility of 258 cm²/Vs is observed. These low temperature processed highly conducting, transparent, and wide bandgap semiconducting films could be used for flexible optoelectronic applications.