Different substrate materials effect on structure of ta-C films by Raman spectroscopy for magnetic recording sliders

Raman spectra, using visible (514 nm) and ultraviolet (244 nm) excitation, of tetrahedral amorphous carbon (ta-C) films of thickness of 5 nm have been studied as a function of different substrates materials. These materials are Fe-Co (Fe: 67 at.%, Co: 33 at.%) alloy, Fe-Ni alloy (Fe: 18 at.%, Ni: 82 at.%), Au and Al₂O₃-TiC (Al₂O₃: 64 at.%, TiC: 36 at.%), which are mainly used in magnetic recording sliders. The spectra show that the films deposited on Al₂O₃-TiC contain the highest sp³ content, with a lower sp³ content observed in films deposited to Fe-Co and Fe-Ni alloys. The lowest sp³ content was observed in films on the Au substrate. The results also indicate that the anti-wear performance of ta-C film on different substrates varies as Al₂O₃-TiC (the best) > Fe-Co and Fe-Ni alloy > Au (the worst). Also mechanisms are proposed to explain the effect of substrate material on these thin film properties.     

1H-1,2,3-triazole,a promising precursor for chemical vapor deposition of hydrogenated carbon nitride

Well-crystallized hydrogenated carbon nitride thin films have been prepared by microwave plasma enhanced chemical vapor deposition (MWPECVD). 1H-1,2,3-triazole+N₂ and Si (1 0 0) were used as precursor and substrate, respectively. Substrate temperature during the deposition was recorded to be 850 °C. The synthesized samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photo-electron spectroscopy (XPS) analyses. The plasma compositions were checked by optical emission spectroscopy (OES). XRD observation strongly suggests that the films contain polycrystalline carbon nitride with graphitic structure of (1 0 0), (0 0 2), (2 0 0) and (0 0 4). XPS peak quantification reveals that the atomic ratio of the materials C:N:O:Si is 32:41:18:9. X-ray photo-electron peak deconvolution shows that the most dominant peak of C (1s) and N (1s) narrow scans correspond to sp² hybrid structure of C₃N₄. These observations indicate that 1H-1,2,3-triazole favors the formation of hydrogenated carbon nitride with graphitic phase by CVD method and thus is in good agreement with XRD results. SEM of surface and OES of plasma also support the formation of polycrystalline carbon nitride films from 1H-1,2,3-triazole+N₂ by CVD.     

Growth and microstructural features of laser ablated LiCoO2 thin films

Thin films of LiCoO₂ were prepared by pulsed laser deposition technique and the properties were studied in relation to the deposition parameters. The films deposited from a sintered composite target (LiCoO₂+Li₂O) in an oxygen partial pressure of 100 mTorr and at a substrate temperature of 300 °C exhibited preferred c-axis (0 0 3) orientation perpendicular to the substrate surface. The AFM data demonstrated that the films are composed of uniform distribution of fine grains with an average grain size of 80 nm. The grain size increased with an increase in substrate temperature. The (0 0 3) orientation decreased with increase in (1 0 4) orientation for the films deposited at higher substrate temperatures (>500 °C) indicating that the films’ growth is parallel to the substrate surface. The composition of the experimental films was analyzed using X-ray photoelectron spectroscopy (XPS). The binding energy peaks of Co(2p_3/2) and Co(2p_1/2) are, respectively, observed at 779.3 and 794.4 eV, which can be attributed to the Co³⁺ bonding state of LiCoO₂. The electrochemical measurements were carried out on Li//LiCoO₂ cells with a lithium metal foil as anode and LiCoO₂ film as cathode of 1.5 cm² active area using a Teflon home-made cell hardware. The Li//LiCoO₂ cells were tested in the potential range 2.6-4.2 V. Specific capacity as high as 205 mC/cm² μm was measured for the film grown at 700 °C. The growth of LiCoO₂ films were studied in relation to the deposition parameters for their effective utilization as cathode materials in solid-state microbattery application.     

Effect of N2/CH4 flow ratio on microstructure and composition of hydrogenated carbon nitride films prepared by a dual DC-RF plasma system

Hydrogenated carbon nitride (a-CN:H) films were deposited on n-type (1 0 0) silicon substrates making use of direct current radio frequency plasma enhanced chemical vapor deposition (DC-RF-PECVD), using a gas mixture of CH₄ and N₂ as the source gas in range of N₂/CH₄ flow ratio from 1/3 to 3/1 (sccm). The deposition rate, composition and bonding structure of the a-CN:H films were characterized by means of X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectrometry (FTIR). The mechanical properties of the deposited films were evaluated using nano-indentation test. It was found that the parameter for the DC-RF-PECVD process had significant effects on the growth rate, structure and properties of the deposited films. The deposition rate of the films decreased clearly, while the N/C ratio in the films increased with increasing N₂/CH₄ flow ratio. CN radicals were remarkably formed in the deposited films at different N₂/CH₄ flow ratio, and their contents are related to the nitrogen concentrations in the deposited films. Moreover, the hardness and Young’s modulus of the a-CN:H films sharply increased at first with increasing N₂/CH₄ flow ratio, then dramatically decreased with further increase of the N₂/CH₄ flow ratio, and the a-CN:H film deposited at 1/1 had the maximum hardness and Young’s modulus. In addition, the structural transformation from sp³-like to sp²-like carbon-nitrogen network in the deposited films also was revealed.     

Dependence of chemical composition and bonding of amorphous SiC on deposition temperature and the choice of substrate

Amorphous SiC has superior mechanical, chemical, electrical, and optical properties which are process dependent. In this study, the impact of deposition temperature and substrate choice on the chemical composition and bonding of deposited amorphous SiC is investigated, both 6 in. single-crystalline Si and oxide covered Si wafers were used as substrates. The deposition was performed in a standard low-pressure chemical vapour deposition reactor, methylsilane was used as the single precursor, and deposition temperature was set at 600 and 650 °C. XPS analyses were employed to investigate the chemical composition, Si/C ratio, and chemical bonding of deposited amorphous SiC. The results demonstrate that these properties varied with deposition temperature, and the impact of substrate on them became minor when deposition temperature was raised up from 600 °C to 650 °C. Nearly stoichiometric amorphous SiC with higher impurity concentration was deposited on crystalline Si substrate at 600 °C. Slightly carbon rich amorphous SiC films with much lower impurity concentration were prepared at 650 °C on both kinds of substrates. Tetrahedral Si-C bonds were found to be the dominant bonds in all deposited amorphous SiC. No contribution from Si-H/Si-Si but from sp² and sp³ C-C/C-H bonds was identified.     

Deposition of mechanically hard amorphous carbon nitride films from decomposition of BrCN. Effects of substrate cooling and pulsed rf-bias voltage

Mechanically hard amorphous carbon nitride films were formed by applying a combination of radio frequency (RF) bias voltage to the substrate and the chemical vapor deposition process using the decomposition reaction of BrCN with the microwave discharge flow of Ar. Cooling water was circulated inside the substrate stage. The maximum hardness was (17 ± 1) GPa for the film prepared under the negative RF bias voltage, −V_RF, of 30 V. This hardness was nearly twice that of the film prepared without cooling, suggesting that substrate cooling was effective for suppressing the relaxation of the internal stress of the film due to the temperature rise during the application of the RF bias voltage. Under the continuous operation of the RF bias voltage, films cannot be formed for −V_RF > 40 V because of the sputtering by the bombardment of energetic Ar⁺. Then, the RF bias voltage was applied with a pulsed operation. By using this operation films were prepared in the range of −V_RF = 40-100 V. The hardness, (36 ± 10) GPa, was obtained for the film obtained under the conditions of −V_RF = 100 V, the pulse period of 1000 s, and the pulse-on time of 800 s. The observed hardness scattered largely for the different observation points within this film; a single observation point in that film showed the maximum hardness of 46 GPa. According to the IR spectra of the films, the three-dimensional C-N network structure was developed.     

Characterizations of GaN film growth by ECR plasma chemical vapor deposition

The electron cyclotron resonance plasma-enhanced metalorganic chemical vapor deposition technology (ECR–MOPECVD) is adopted to grow GaN films on (0 0 0 1) α-Al₂O₃ substrate. The gas sources are pure N₂ and trimethylgallium (TMG). Optical emission spectroscopy (OES) and thermodynamic analysis of GaN growth are applied to understand the GaN growth process. The OES of ECR plasma shows that TMG is significantly dissociated in ECR plasma. Reactants N and Ga in the plasma, obtained easily under the self-heating condition, are essential for the GaN growth. They contribute to the realization of GaN film growth at a relatively low temperature. The thermodynamic study shows that the driving force for the GaN growth is high when N₂:TMG>1. Furthermore, higher N₂:TMG flow ratio makes the GaN growth easier. Finally, X-ray diffraction, photoluminescence, and atomic force microscope are applied to investigate crystal quality, morphology, and roughness of the GaN films. The results demonstrate that the ECR–MOPECVD technology is favorable for depositing GaN films at low temperatures.     

Preparation of single-crystalline ZnO films on ZnO-buffered a-plane sapphire by chemical bath deposition

High-quality zinc oxide (ZnO) films were successfully grown on ZnO-buffered a-plane sapphire (Al₂O₃ (1 1 2¯ 0)) substrates by controlling temperature for lateral growth using chemical bath deposition (CBD) at a low temperature of 60 °C. X-ray diffraction analysis and transmission electron microscopy micrographs showed that the ZnO films had a single-crystalline wurtzite structure with c-axis orientation. Rocking curves (ω-scans) of the (0 0 0 2) reflections showed a narrow peak with full width at half maximum value of 0.50° for the ZnO film. A reciprocal space map indicated that the lattice parameters of the ZnO film (a=0.3250 nm and c=0.5207 nm) were very close to those of the wurtzite-type ZnO. The ZnO film on the ZnO-buffered Al₂O₃ (1 1 2¯ 0) substrate exhibited n-type conduction, with a carrier concentration of 1.9×10¹⁹ cm⁻³ and high carrier mobility of 22.6 cm² V⁻¹ s⁻¹.     

Growth and characterization of c-plane AlGaN on γ-LiAlO2

This study demonstrates a pure c-plane AlGaN epilayer grown on a γ-LiAlO₂ (1 0 0) (LAO) substrate with an AlN nucleation layer grown at a relatively low temperature (LT-AlN) by metal-organic chemical vapor deposition (MOCVD). The AlGaN film forms polycrystalline film with m- and c-plane when the nucleation layer grows at a temperature ranging from 660 to 680 °C. However, a pure c-plane AlGaN film with an Al content of approximately 20% can be obtained by increasing the LT-AlN nucleation layer growth temperature to 700 °C. This is because the nuclei density of AlN increases as the growth temperature increases, and a higher nuclei density of AlN deposited on LAO substrate helps prevent the deposition of m-plane AlGaN. Therefore, high-quality and crack-free AlGaN films can be obtained with a (0 0 0 2) ω-rocking curve FWHM of 547 arcsec and surface roughness of 0.79 nm (root-mean-square) using a 700-°C-grown LT-AlN nucleation layer.     

New preparation method of diamond like carbon – the layer-by-layer method

A new method––the layer-by-layer method––is used to prepare diamond like carbon (DLC) films. The layer-by-layer method is a cyclic process for the deposition of DLC by a rf magnetron sputtering using Ar gas and with alternate the atomic hydrogen treatment, which samples are called LL-DLC. A DLC sample without atomic hydrogen treatment and an atomic-hydrogen-treated DLC sample are prepared to compare with LL-DLC. LL-DLC samples are prepared with the substrate temperature from RT to 400 °C. The data of the electrical conductivity including Fermi level E_F, optical energy gap E_O4, X-ray photoelectron spectroscopy, sp³ fraction obtained by Raman spectra, infrared absorption coefficient spectra and atomic force microscope are used to characterize these DLC films. These results are also discussed comparing with amorphous carbon nitride a-CN_X and the layer-by-layer prepared amorphous carbon nitride LLa-CN_X.     

Microstructure and dielectric properties of La2O3 films prepared by ion beam assistant electron-beam evaporation

Ultrathin La₂O₃ gate dielectric films were prepared on Si substrate by ion assistant electron-beam evaporation. The growth processing, interfacial structure and electrical properties were investigated by various techniques. From XRD results, we found that the La₂O₃ films maintained the amorphous state up to a high annealing temperature of 900 °C for 5 min. From XPS results, we also discovered that the La atoms of the La₂O₃ films did not react with silicon substrate to form any La-compound at the interfacial layer. However, a SiO₂ interfacial layer was formed by the diffusion of O atoms of the La₂O₃ films to the silicon substrate. From the atomic force microscopy image, we disclosed that the surface of the amorphous La₂O₃ film was very flat. Moreover, the La₂O₃ film showed a dielectric constant of 15.5 at 1 MHz, and the leakage current density of the La₂O₃ film was 7.56 × 10⁻⁶ A/cm² at a gate bias voltage of 1 V.     

Growth of epitaxial ZnO films on Si (1 1 1) substrates with Cr compound buffer layer by plasma-assisted molecular beam epitaxy

Single crystalline ZnO film was grown on (1 1 1) Si substrate through employing an oxidized CrN buffer layer by plasma-assisted molecular beam epitaxy. Single crystalline characteristics were confirmed from in-situ reflection high energy electron diffraction, X-ray pole figure measurement, and transmission electron diffraction pattern, consistently. Epitaxial relationship between ZnO film and Si substrate is determined to be (0 0 0 1)_ZnO‖(1 1 1)_Si and [1 1 2¯ 0]_ZnO‖[0 1 1]_Si. Full-width at half-maximums (FWHMs) of (0 0 0 2) and (1 0 1¯ 1) X-ray rocking curves (XRCs) were 1.379° and 3.634°, respectively, which were significantly smaller than the FWHMs (4.532° and 32.8°, respectively) of the ZnO film grown directly on Si (1 1 1) substrate without any buffer. Total dislocation density in the top region of film was estimated to be ∼5×10⁹ cm⁻². Most of dislocations have a screw type component, which is different from the general cases of ZnO films with the major threading dislocations with an edge component.     

Epitaxial NiO (1 0 0) and NiO (1 1 1) films grown by atomic layer deposition

Epitaxial NiO (1 1 1) and NiO (1 0 0) films have been grown by atomic layer deposition on both MgO (1 0 0) and α-Al₂O₃ (0 0 l) substrates at temperatures as low as 200 °C by using bis(2,2,6,6-tetramethyl-3,5-heptanedionato)Ni(II) and water as precursors. The films grown on the MgO (1 0 0) substrate show the expected cube on cube growth while the NiO (1 1 1) films grow with a twin rotated 180° on the α-Al₂O₃ (0 0 l) substrate surface. The films had columnar microstructures on both substrate types. The single grains were running throughout the whole film thickness and were significantly smaller in the direction parallel to the surface. Thin NiO (1 1 1) films can be grown with high crystal quality with a FWHM of 0.02–0.05° in the rocking curve measurements.     

Molecular beam epitaxial growth of hexagonal boron nitride on Ni(1 1 1) substrate

We demonstrate hexagonal boron nitride (h-BN) epitaxial growth on Ni(1 1 1) substrate by molecular beam epitaxy (MBE) at 890 °C. Elemental boron evaporated by an electron-beam gun and active nitrogen generated by a radio-frequency (RF) plasma source were used as the group-III and -V sources, respectively. Reflection high-energy electron diffraction revealed a streaky (1×1) pattern, indicative of an atomically flat surface in the ongoing growth. Correspondingly, atomic force microscopy images exhibit atomically smooth surface of the resulting h-BN film. X-ray diffraction characterization confirmed the crystallinity of the epitaxial film to be h-BN, and its X-ray rocking curve has a full-width at half-maximum of 0.61°, which is the narrowest ever reported for h-BN thin film. The epitaxial alignments between the h-BN film and the Ni substrate were determined to be [0 0 0 1]_h−BN∥[1 1 1]_Ni, [1 1 2¯ 0]_h−BN∥[1¯ 1 0]_Ni, and [1 1¯ 0 0]_h−BN∥[1¯ 1¯ 2]_Ni.     

Nanocrystalline TiO2 films studied by optical, XRD and FTIR spectroscopy

We report the deposition of thin titanium dioxide films on Si(1 0 0) and silica glass at low temperatures between 200 and 350 °C by a technique of ultraviolet-assisted injection liquid source chemical vapor deposition (UVILS-CVD) with 222 nm radiation. The composition and optical properties of the films deposited have been studied using a variety of standard characterisation methods. A strong absorption peak around 438 cm⁻¹, corresponding to Ti-O stretching vibration, was observed by Fourier transform infrared spectroscopy for different deposition temperatures. Nanostructured films on Si wafers were observed by atomic force microscopy while X-ray diffraction results showed that crystalline TiO₂ layers could be formed at deposition temperatures as low as 210 °C. The deposition kinetics and influence of the substrate temperature on the film are discussed. The activation energy for this photo-CVD process at temperatures between 200 and 350 °C was found to be 0.435 eV. This is much lower than the value (E_a=5.64 eV) obtained by conventional thermal CVD. The thicknesses of the films grown, from several nanometers to micrometers can be accurately controlled by changing the number of drops introduced by the injection liquid source. Under optimum deposition conditions, refractive index values as high as 2.5 and optical transmittance of between 85% and 90% in the visible region of the spectrum can be obtained.     

Influence of pulsed laser deposition rate on the microstructure and thermoelectric properties of Ca3Co4O9 thin films

The effects of deposition rate on the microstructure and thermoelectric (TE) properties of Ca₃Co₄O₉ thin films fabricated by pulsed laser deposition (PLD) technique were investigated. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM) revealed that a fast deposition rate resulted in not only low crystallinity but also the existence of the Ca_xCoO₂ secondary phase. Formation of Ca_xCoO₂ was inevitable during the thin film growth, and this was discussed from both structural and compositional point of view. With longer deposition interval or with sufficient oxygen at a lower deposition rate, the Ca_xCoO₂ phase was able to transit into the desired Ca₃Co₄O₉ phase during the coalescence process. The quality of the thin films was further analyzed by electrical properties measurements. The Ca₃Co₄O₉ thin film fabricated at a slower deposition rate was found to exhibit a low electrical resistivity of 9.4 mΩ cm and high Seebeck coefficient of 240 μV/K at about 700 °C, indicating a good quality film.     

Structure and growth morphology of Gd2O3-doped CeO2 thin films

Gd₂O₃-doped CeO₂ (Gd_0.1Ce_0.9O_1.95, GDC) thin films were synthesized on (1 0 0) Si single crystal substrates by a reactive radio frequency magnetron sputtering technique. Structures and surface morphologies were characterized by X-ray diffraction (XRD), Atomic Force Microscopy (AFM) and one-dimensional power spectral density (1DPSD) analysis. The XRD patterns indicated that, in the temperature range of 200–700 °C, f.c.c. structured GDC thin films were formed with growth orientations varying with temperature—random growth at 200 °C, (2 2 0) textures at 300–600 °C and (1 1 1) texture at 700 °C. GDC film synthesized at 200 °C had the smoothest surface with roughness of R_rms=0.973 nm. Its 1DPSD plot was characterized with a constant part at the low frequencies and a part at the high frequencies that could be fitted by the f^−2.4 power law decay. Such surface feature and scaling behavior were probably caused by the high deposition rate and random growth in the GDC film at this temperature. At higher temperatures (300–700 °C), however, an intermediate frequency slope (−γ₂≈−2) appeared in the 1DPSD plots between the low frequency constant part and the high frequency part fitted by f⁻⁴ power law decay, which indicated a roughing mechanism dominated by crystallographic orientation growth that caused much rougher surfaces in GDC films (R_rms>4 nm).     

Diamond nanorods from nanocrystalline diamond films

Diamond nanorods (DNRs) have been prepared by hydrogen plasma post-treatment of nanocrystalline diamond films in radio-frequency (RF) plasma-assisted hot-filament chemical vapor deposition. Single-crystal diamond nanorods with diameters of 3–5 nm and with lengths up to 200 nm grow under hydrogen plasma irradiation of nanocrystalline diamond thin film on the Si substrate at high temperatures. The DNRs growth occurs from graphite clusters. The graphite clusters arises from the etching of diamond carbon atoms and from the non-diamond phase present in the parent film. The graphite clusters recrystallized to form nanocrystalline diamonds which further grow for diamond nanorods. The negative applied bias and surface stresses are suggested to support one-dimensional growth. The growth direction of diamond nanorods is perpendicular to the (1 1 1) crystallographic planes of diamond. The studies address the structure and growth mechanism of diamond nanorods.     

Electrical, structural and optical properties of SnO2 thin films prepared by spray pyrolysis

This study investigated the effect of the substrate temperature on the structural, optical, morphological, and electrical properties of undoped SnO₂ films prepared by a spray deposition method. The films were deposited at various substrate temperatures ranging from 300-500 °C in steps of 50 °C and characterized by different optical and structural techniques. X-ray diffraction studies showed that the crystallite size and preferential growth directions of the films were dependent on the substrate temperature. These studies also indicated that the films were amorphous at 300 °C and polycrystalline at the other substrate temperatures used. Infrared and visible spectroscopic studies revealed that a strong vibration band, characteristic of the SnO₂ stretching mode, was present around 630 cm⁻¹ and that the optical transmittance in the visible region varied over the range 75-95% with substrate temperature, respectively. The films deposited at 400 °C exhibited the highest electrical conductivity property.     

An easy sol–gel route for deposition of oriented Ln2Ti2O7 (Ln=La,Nd) films on SrTiO3 substrates

The effect of the orientation of SrTiO₃ (STO) substrates, (1 0 0) or (1 1 0), on the growth of La₂Ti₂O₇ (LTO) and Nd₂Ti₂O₇ (NTO) thin films was investigated. The films were deposited via a sol–gel process coupled to the spin-coating technique. Depending on the substrate orientation, a similar effect was observed on the structural properties for both the LTO and NTO thin films. For (1 1 0)-oriented STO substrate, the films are preferentially (0 0 1) oriented while for (1 0 0)-oriented STO substrates, the orientation is mainly (0 1 2). Those matching appear to be in good agreement with the compatibility between the film/substrate crystal lattices, in relation with the existence of perovskite slabs in Ln₂Ti₂O₇ (Ln=rare earth) compounds. In these latter, a slight disorientation of the (0 1 2) planes with respect to the surface of the substrate was measured. This tilting is even more marked in the case of NTO. The surface morphology was studied by atomic force microscopy.