Growth of stoichiometric TiO2 thin films on Au(100) substrates by molecular beam epitaxy

The present study reports on the growth of thin TiO₂ films onto Au(100) single crystals by Ti evaporation in a reactive O₂ atmosphere at two different substrate temperatures: room temperature (RT) and 300 °C. The growth of the oxide films was monitored by means of X-ray photoemission spectroscopy, while the valence and conduction band electronic structure was investigated by UV and inverse photoemission spectroscopy, respectively.The TiO₂ film grows epitaxially on the Au(100) substrate at 300 °C exhibiting the rutile (100) surface. The evolution of the Ti 2p lineshape with the oxide coverage shows the presence of reduced oxide species (characterized by Ti^3 + ions) at the Au(100) interface. A crystalline and stoichiometric TiO₂ oxide is produced at high substrate temperature, while growth at RT gives a measurable concentration of defects. Post growth annealing in ultra-high vacuum of the RT grown film increases this concentration, while subsequent annealing in O₂ atmosphere restores the sample to the as-grown conditions.     

Effect of film thickness and the presence of surface fluorine on the structure of a thin barrier film deposited from tetrakis-(dimethylamino)-titanium onto a Si(100)-2 × 1 substrate

The structure of a thin film deposited using tetrakis-(dimethylamino)-titanium (Ti(N(CH₃)₂)₄) as a precursor onto a Si(100)-2 × 1 substrate at ultra-high-vacuum conditions was investigated as a function of film thickness for the films of 20 and 145 nm in the presence of surface copper and fluorine produced by in situ dosing of a common copper deposition precursor, (hexafluoroacetylacetonate)Cu(vinyltrimethylsilane), (hfac)Cu(VTMS), and a hydrogenated form of the hfac ligand, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, hfacH. A combination of surface, depth-profiling, and microscopy analytical techniques suggests that the structure of the titanium carbonitride film depends profoundly on its thickness. While the composition of the film was relatively constant throughout its whole thickness, the nanometer-scale structure changed from amorphous at the top of a 145-nm-thick film, to having a significant amount of small (∼ 5 nm) crystallites closer to the TiCN/Si interface. These studies also confirmed the absence of microfractures in the film prepared by this approach. The ex situ depth profiling investigation suggested that if (hfac)Cu(VTMS) is deposited on a TiCN-precovered silicon substrate and briefly annealed to 800 K, the film acts as a diffusion barrier for copper, while surface fluorine penetrates the film rather easily, resulting in fluorine that is distributed uniformly throughout the film.     

Physico-chemical and electrochemical characterization of Ti/RhOx–IrO2 electrodes using sol–gel technology

Sol–gel technology has been successfully used for the incorporation of RhO_x–IrO₂ on a Ti substrate. RhO_x–IrO₂ was prepared from chloride precursors of Rh and Ir, for surface studies. These metal oxides were then immobilised on solid Ti substrates via dip withdrawal coating methods to form thin films. The Ti/RhO_x–IrO₂ thin films were extensively characterized in terms of surface characterization and chemical composition and used in the oxidation of phenol. Thermo-gravimetric analysis (TGA) determined the calcination temperature at 700 °C where no further structural changes occurred due to mass loss. The rhodium oxide showed two-phase formations, RhO₂ and Rh₂O₃, which were attributed to high calcinated temperatures compare to one phase IrO₂ which was stable at lower temperatures. The scanning electron microscopy (SEM) showed that the morphology of the film was found to be rough with a grain-like appearance in the 150-nm range. The phase composition of these metal oxides was determined by X-ray diffraction (XRD) technique and found to have crystalline structures. The results obtained from Rutherford backscattering spectrometry (RBS) revealed information regarding the chemical composition of the metal oxides and confirmed the diffusion of Rh and Ir into the Ti substrate. Electrochemical characterization of the Ti/RhO_x–IrO₂ electrode, via cyclic voltammetry (CV), showed distinctive redox peaks: anodic and cathodic peaks associated with the oxidation and reduction of the ferricyanide–ferrocyanide couple was seen at 250 and 100 mV respectively; the peak observed at 1000 mV was associated with oxygen evolution and a broad reductive wave at −600 mV can be ascribed to the Ti/RuO_x–IrO₂ reduction, which proved that the Ti/RhO_x–IrO₂ electrode were electroactive and exhibit fast electrochemistry.     

Synthesis of type-II textured tungsten disulfide thin films with bismuth interfacial layer as a texture promoter

Highly textured tungsten disulfide (WS₂) thin films have been obtained by sulfurization of tungsten trioxide. The properties of WS₂ thin films prepared with bismuth interfacial layer as texture promoter has been studied. The WS₂ thin films were found to have predominant type-II orientation. The stacking of 2H-WS₂ crystallites observed with scanning electron microscopy was not reported hitherto. The films can be pictured as an assembly of WS₂ hexagonal crystallites. The energy dispersive X-ray analysis and X-ray photoelectron spectroscopy (XPS) studies confirm that the films are stoichiometric. The XPS analysis described the local environment of the tungsten atoms and the formal oxidation states of the tungsten and sulfur atoms were + 4 and − 2. Together with the high degree of crystallinity and excellent texture of the film, a relatively smooth morphology, on submicron scale, is revealed through atomic force microscopy study. The conditions for the desired textured growth with the van der Waals planes parallel to the substrate surface are reported.     

Wear behaviour and rolling contact fatigue life of Ti/TiN/DLC multilayer films fabricated on bearing steel by PIIID

In order to improve the friction and wear behaviours and rolling contact fatigue (RCF) life of bearing steel materials, Ti/TiN/DLC (diamond-like carbon) multilayer hard films were fabricated onto AISI52100 bearing steel surface by plasma immersion ion implantation and deposition (PIIID) technique. The micro-Raman spectroscopy analysis confirms that the surface film layer possess the characteristic of diamond-like carbon, and it is composed of a mixture of amorphous and crystalline phases, with a variable ratio of sp²/sp³ carbon bonds. Atomic force microscope (AFM) reveals that the multilayer films have extremely smooth area, excellent adhesion, high uniformity and efficiency of space filling over large areas. The nanohardness (H) and elastic modulus (E) measurement indicates that the H and E of DLC multilayer films is about 32 GPa and 410 GPa, increases by 190.9% and 86.4%. The friction and wear behaviours and RCF life of DLC multilayer films specimen have also been investigated by ball-on-disc and three-ball-rod fatigue testers. Results show that the friction coefficient against AISI52100 steel ball decreases from 0.92 to 0.25, the longest wear life increases nearly by 22 times. In addition, wear tracks of the PIIID samples as well as wear tracks of the sliding steel ball were analyzed with the help of optical microscopy and scanning electron microscopy (SEM). The L₁₀, L₅₀, L_a and mean RCF life L of treated bearing samples, in 90% confidence level, increases by 10.1, 4.2, 3.5 and 3.4 times, respectively. Compared with the bearing steel substrate, the RCF life scatter extent of Ti/TiN/DLC multilayer films sample is improved obviously.     

Influence of secondary phases during annealing on re-crystallization of CuInSe2 electrodeposited films

Electrodeposited CuInSe₂ thin films are of potential importance, as light absorber material, in the next generation of photovoltaic cells as long as we can optimize their annealing process to obtain dense and highly crystalline films. The intent of this study was to gain a basic understanding of the key experimental parameters governing the structural-textural-composition evolution of thin films as function of the annealing temperature via X-ray diffraction, scanning/transmission electron microscopy and thermal analysis measurements. The crystallization of the electrodeposited CuInSe₂ films, with the presence of Se and orthorhombic Cu_2 − xSe (o-Cu_2 − xSe) phases, occurs over two distinct temperature ranges, between 220 °C and 250 °C and beyond 520 °C. Such domains of temperature are consistent with the melting of elemental Se and the binary CuSe phase, respectively. The CuSe phase forming during annealing results from the reaction between the two secondary species o-Cu_2 − xSe and Se (o-Cu_2 − xSe + Se → 2 CuSe) but can be decomposed into the cubic β-Cu_2 − xSe phase by slowing down the heating rate. Formation of liquid CuSe beyond 520°C seems to govern both the grain size of the films and the porosity of the substrate-CuInSe₂ film interface. A simple model explaining the competitive interplay between the film crystallinity and the interface porosity is proposed, aiming at an improved protocol based on temperature range, which will enable to enhance the film crystalline nature while limiting the interface porosity.     

In-situ energy-dispersive X-ray diffraction of metal sulfide assisted crystallization of strongly (001) textured photoactive tungsten disulfide thin films

Highly (001) textured tungsten disulphide (WS₂) thin films were grown by rapid metal (Ni, Pd) sulfide assisted crystallization of amorphous reactively sputtered sulfur-rich tungsten sulfide (WS_3 + x) and by metal sulfide assisted sulfurization of tungsten metal films. The rapid crystallization was monitored by real-time in-situ energy dispersive X-ray diffraction (EDXRD). Provided that a thin nickel or palladium film was deposited prior to the deposition of WS_3 + x or W, the films crystallized very fast (about 20 nm/s) at temperatures above the metal sulfide eutectic temperature. After crystallization, isolated MeS_x crystallites are located on the surface of the WS₂ layer, which was proved by scanning electron microscopy. The metal sulfide assisted crystallized WS₂ layers exhibit a pronounced (001) orientation with large crystallites up to 2 µm. The in-situ EDXRD analysis revealed distinct differences of the two crystallization routes from tungsten and from amorphous, sulfur-rich WS_3 + x precursors, respectively. The crystallized WS₂ films showed photoactivity. Combined with the high absorption coefficient of 10⁵ cm^− 1 and a indirect band gap of 1.8 eV these properties make such films suitable for absorber layers in thin film solar cells.     

Structure and magnetic properties of Fe epitaxial thin films prepared by UHV rf magnetron sputtering on GaAs single-crystal substrates

Fe thin films were prepared on GaAs single-crystal substrates of (100)_B3, (110)_B3, and (111)_B3 orientations by ultra high vacuum rf magnetron sputtering. The effects of substrate orientation and substrate temperature on the film growth, the structure, and the magnetic properties were investigated. On GaAs(100)_B3 substrates, Fe(100)_bcc single-crystal films are obtained at 300 °C, whereas Fe films consisting of bcc(100) and bcc(221) crystals epitaxially grow at room temperature (RT). Fe(110)_bcc and Fe(111)_bcc single-crystal films are respectively obtained on GaAs(110)_B3 and GaAs(111)_B3 substrates at RT-300 °C. The in-plane lattice spacings of these Fe epitaxial films are 0-9% larger than the out-of-plane lattice spacings due to accommodation of lattice mismatch between the films and the substrates. The film strain is decreased by employing an elevated substrate temperature of 300 °C. The in-plane magnetization properties are reflecting the magnetocrystalline anisotropy of bulk bcc-Fe crystal.     

Investigation of the microstructure, mechanical properties and tribological behaviors of Ti-containing diamond-like carbon films fabricated by a hybrid ion beam method

Diamond-like carbon (DLC) films with various titanium contents were investigated using a hybrid ion beam system comprising an anode-layer linear ion beam source and a DC magnetron sputtering unit. The film composition and microstructure were characterized carefully by X-ray photoelectron spectroscopy, transmission electron microscopy and Raman spectroscopy, revealing that the doped Ti atoms had high solubility in the DLC films. The maximum solubility was found to lie between about 7 and 13 at.%. When the Ti content was lower than this solubility, the doped Ti atoms dissolved in the DLC matrix and the films exhibited the typical features of the amorphous DLC structure and displayed low compressive stresses, friction coefficients and wear rates. However, as the doped content exceeded the solubility, Ti atoms bonded with C atoms, resulting in the formation of carbide nano-particles embedded in the DLC matrix. Although the emergence of the carbide nano-particles promoted graphitizing due to a catalysis effect, the film hardness was enhanced to a great extent. On the other hand, the hard carbides particles caused abrasive wear behavior, inducing a high friction coefficient and wear rate.     

X-ray absorption spectroscopy study of thermally annealed Cu–Al–O thin films

Cu–Al–O thin films are deposited on (0001) sapphire substrates by radio-frequency sputtering using an Al–Cu mosaic target. The Cu/Al atomic ratio of as-deposited Cu–Al–O films is measured to be 1.1. After deposition, the Cu–Al–O films are annealed at 600, 800, and 1000 °C, respectively, for 1 h in a N₂ atmosphere. The film crystal structure, electronic structure, valence band, and electrical properties are studied. The as-deposited films are amorphous and films annealed at 600 °C contain the crystallized CuO phase; the structure becomes crystallized CuAlO₂ after annealing at 800 °C and 1000 °C. The 800 °C annealed film grows along the (00l) plane. The crystallization decreases with the growth of the (012) and (018) planes for films annealed at 1000 °C. The resistivity values of the 800 °C and 1000 °C annealed films were measured as 1.07 Ω-cm and 864.01 Ω-cm, respectively. The lower resistivity of the 800 °C annealed film is attributed to preferred (00l) growth orientation and a reduction of the energy band gap.     

Effects of ambient oxygen pressures and substrate temperatures in pulsed laser deposited Zn0.85Li0.15O thin films

Li doped zinc oxide Zn_1−xLi_xO (x = 0.15) thin films were grown by using the pulsed laser deposition method. The depositions were done onto Pt(111)/Ti/SiO₂/Si(100) substrate set at temperatures ranging from 300 °C to 700 °C, with varying the ambient O₂ pressure range of 3-20 mTorr. The effects of substrate temperatures and ambient O₂ pressures on the surface morphology and structural properties of the Zn_0.85Li_0.15O thin films were investigated by using the scanning probe microscopy and X-ray diffraction spectra, respectively. Also the chemical structures of the films were investigated by observing the X-ray photoelectron spectra of the core and shallower levels. We observed the deep blue PL emissions centered at about 390 nm (3.20 eV) from the Zn_0.85Li_0.15O thin films. It was investigated with respect to the ambient O₂ pressures during the deposition. It is considered that the deep blue PL emission in the Zn_0.85Li_0.15O thin film may be related to the incorporation of oxygen vacancies.     

CdTe thin film solar cells: Interrelation of nucleation, structure, and performance

The performance of CdTe solar cells as prototype of thin film solar cells strongly depends on film morphology. The needs for high solar cell performance using thin film materials will be addressed covering nucleation and growth control of thin film materials. In order to understand the basic growth mechanisms and their impact on cell performance, we have systematically investigated the growth of CdTe thin films by Close Spaced Sublimation (CSS) using the integrated ultra-high vacuum system DAISY-SOL. CdTe thin films were deposited on TCO/CdS substrates (transparent conductive oxide) held at 270 °C to 560 °C. The properties of the films were determined before and after CdCl₂ treatment using X-ray diffraction and electron microscopy. In addition, solar cells were prepared to find correlations between material properties and cell efficiency. At low sample temperature the films tend to form compact layers with preferred (111) orientation which is lost at elevated temperatures above 450 °C. For CdS layers without (0001) texture there is in addition a low temperature regime (350 °C) with (111) texture loss. After activation treatment the (111) texture is lost for all deposited layers leading to strong recrystallisation of the grains. But the texture still depends on the previous growth history. The loss of (111) texture is evidently needed for higher performance. A clear correlation between cell efficiency and the texture of the CdTe film is observed.     

Enhancement on effective piezoelectric coefficient of Bi3.25Eu0.75Ti3O12 ferroelectric thin films under moderate annealing temperature

Bi_3.25Eu_0.75Ti₃O₁₂ (BET) thin films were deposited on Pt/Ti/SiO₂/Si(111) substrates by a metal-organic decomposition method. The effects of annealing temperatures 600-800 °C on microstructure, ferroelectric, dielectric and piezoelectric properties of BET thin films were studied in detail. The spontaneous polarization (87.4 × 10^− 6 C/cm² under 300 kV/cm), remnant polarization (65.7 × 10^− 6 C/cm² under 300 kV/cm), the dielectric constant (992.9 at 100 kHz) and the effective piezoelectric coefficient d₃₃ (67.3 pm/V under 260 kV/cm) of BET thin film annealed at 700 °C are better than those of the others. The mechanisms concerning the dependence of the enhancement d₃₃ are discussed according to the phenomenological equation, and the improved piezoelectric performance could make the BET thin film a promising candidate for piezoelectric thin film devices.     

Preparation of LaNiO3 thin films with very low room-temperature electrical resistivity by room temperature sputtering and high oxygen-pressure processing

LaNiO₃ (LNO) thin films were deposited by radio frequency magnetron sputtering on n-type Si (100) wafers at room temperature (RT). The as-sputtered LNO thin films were amorphous and had very high RT electrical resistivity even after post-annealing at 800 °C. The amorphous as-sputtered LNO films could be transformed to polycrystalline LNO films in rhombohedral phase by heating at 400 °C in an O₂ atmosphere at pressure ranging from 1.5 to 8.0 MPa. Very low RT resistivity of LNO films were obtained by this high oxygen-pressure processing. The lowest value was as low as 1.09 × 10^− 4 Ω cm by processing at oxygen pressure of 8 MPa. Such preparation of LNO thin films is compatible with the Si-based readout integrated circuits. Highly (100)-oriented perovskite structure of Pb(Zr_0.52Ti_0.48)O₃ thin films was formed on this rhombohedral phase LNO, and good ferroelectricity could also be obtained on these HOPP-processed rhombohedral phase LNO films.     

Structural and electrical characteristics of chemical solution derived (Bi3.2La0.4Nd0.4)Ti3O12 thin films

(Bi_3.2La_0.4Nd_0.4)Ti₃O₁₂ (BLNT) thin films were prepared on Pt/Ti/SiO₂/Si substrates by using chemical solution deposition technique, and the effects of annealing temperatures in the range of 550-750 °C on structure and electrical properties of the thin films were investigated. X-ray diffraction analysis shows that the thin films have a bismuth-layered perovskite structure with preferred (117) orientation. The surface morphology observation by field-emission scanning electron microscopy confirms that films are dense and smooth with uniformly distributed grains. The grain size of the thin films increases with increasing annealing temperature; meanwhile, the structural distortion of the thin films also increases. It was demonstrated that the thin films show good electrical properties. The dielectric constant and dielectric loss are 191 and 0.028, respectively, at 10 kHz for the thin film annealed at 600 °C, and the 2Pr value of the thin film annealed at 700 °C is 20.5 μC/cm² at an electric field of 500 kV/cm.     

The tribological behavior of W–S–C films in pin-on-disk testing at elevated temperature

W–S–C films were deposited by magnetron sputtering in an Ar atmosphere with a Ti interlayer. A carbon target with several pellets of WS₂ incrusted in the zone of the preferential erosion was used. The number of pellets was changed to modify the carbon content in the films, which varied from 29 up to 70 at%. Doping W–S films with carbon led to a substantial increase of the hardness in the range 4–10 GPa; the maximum of hardness was obtained for coatings with the carbon content of 40 at%. X-ray diffraction (XRD) patterns showed that there was a loss of crystallinity with the increase of the carbon content in the film.The coatings were tested by pin-on-disk from room temperature (RT) up to 400 °C. At RT, the friction coefficient was in the range 0.2–0.30. At temperatures higher than 100 °C, the friction is below 0.05 for all compositions. The tribological behavior of the coatings with increasing temperatures depended on the films carbon content. For low-carbon content up to 40%, the wear rate was almost independent of the temperature up to 300 °C, while it increased dramatically in the case of the coatings with high-carbon content. In general, the limiting temperature for W–S–C coatings is 400 °C.     

Electrodeposition of SmS optical thin films on ITO glass substrate

SmS optical thin films were deposited on the surface of ITO glass with an electrodeposition method using aqueous solution containing SmCl₃·6H₂O and Na₂S₂O₃·5H₂O. The phase composition was analyzed by X-ray diffraction (XRD) and microstructure of the film was characterized by atomic force microscope (AFM). It is showed that SmS thin film could be obtained in the solution with n(Sm)/n(S) = 1:4, pH = 4.0 and annealing in Ar atmosphere at 200 °C for 0.5 h. The as-prepared thin films on the ITO glass exhibit a dense microstructure. The band gap of the thin film has been found to be 3.6 eV.     

Fabrication of low-resistivity and gold-colored TiN films by halide chemical vapor deposition with a low [NH3]/[TiCl4] flow ratio

This work describes the preparation of titanium nitride (TiN) films on Si (111) substrates by atmospheric pressure halide chemical vapor deposition (AP-HCVD). Various TiN films were obtained by exploiting TiCl₄ + NH₃ gas chemistry with flow ratios [NH₃]/[TiCl₄] from 0.2 to 1.4, and deposition temperatures (T_d) from 600 to 900 °C. When T_d = 800 °C gold-colored films with electrical resistivities of under 100 μΩ cm were formed at almost all of the investigated [NH₃]/[TiCl₄] flow ratios. In particular, a lowest resistivity of about 23.7 μΩ cm, which is quite close to that of bulk TiN, was achieved using an [NH₃]/[TiCl₄] flow ratio of 0.3. Atomic force microscopy indicated that the root mean square surface roughness of that film was only about 5.1 nm. Under the same [NH₃]/[TiCl₄] flow ratio as above, X-ray diffraction analyses revealed the presence of a cubic TiN phase with a preferred orientation of (200) for T_d ≤ 800 °C, while additional (111) and (220) orientations emerged when the film was deposited at 900 °C. In conclusion, a low resistivity (< 100 μΩ cm) TiN film can be formed by AP-HCVD with very low [NH₃]/[TiCl₄] flow ratios 0.3-1.4.     

Low temperature annealing effects on the structure and optical properties of ZnO films grown by pulsed laser deposition

ZnO thin films were deposited on glass substrates at room temperature (RT) ∼500 °C by pulsed laser deposition (PLD) technique and then were annealed at 150-450 °C in air. The effects of annealing temperature on the microstructure and optical properties of the thin films deposited at each substrate temperature were investigated by XRD, SEM, transmittance spectra, and photoluminescence (PL). The results showed that the c-axis orientation of ZnO thin films was not destroyed by annealing treatments; the grain size increased and stress relaxed for the films deposited at 200-500 °C, and thin films densified for the films deposited at RT with increasing annealing temperature. The transmittance spectra indicated that E_g of thin films showed a decreased trend with annealing temperature. From the PL measurements, there was a general trend, that is UV emission enhanced with lower annealing temperature and disappeared at higher annealing temperature for the films deposited at 200-500 °C; no UV emission was observed for the films deposited at RT regardless of annealing treatment. Improvement of grain size and stoichiometric ratio with annealing temperature can be attributed to the enhancement of UV emission, but the adsorbed oxygen species on the surface and grain boundary of films are thought to contribute the annihilation of UV emission. It seems that annealing at lower temperature in air is an effective method to improve the UV emission for thin films deposited on glass substrate at substrate temperature above RT.     

Microstructure-Property relationships in thin film ITO

Polycrystalline tin-doped indium oxide (ITO) thin films were prepared by pulsed laser deposition (PLD) with an ITO (In₂O₃-10 wt.% SnO₂) target and deposited on borosilicate glass substrates. By changing independently the deposition temperature and the oxygen pressure, a variety of microstructures were deposited. These different microstructures were mainly investigated not only by transmission electron microscopy (TEM) with cross-section and plan-view electron micrographs, but also by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction. Composition changes in ITO thin films grown under different deposition conditions were characterized by energy dispersive X-ray spectroscopy (EDX). The optical and electrical properties were studied respectively by UV-visible spectrophotometry and a four-point probe. The best compromise in terms of high transmittance (T) in the visible range and low resistivity (ρ) was obtained for films deposited between 0.66 and 2 Pa oxygen pressure (P_O2) at 200 °C substrate temperature (T_s). The influence of P_O2 and T_s on the microstructure and ITO film properties is discussed.