Synthesis and characterization of hard ternary AlMgB composite films prepared by sputter deposition

Hard and superlight thin films laminated with boron carbide have been proposed as candidates for strategic use such as armor materials in military and space applications. Aluminum magnesium boride (AlMgB) films are excellent candidates for these purposes. We prepared AlMgB films by sputter deposition using multiple unbalanced planar magnetrons equipped with two boron and one AlMg targets. The film morphology changed and the film's root mean square (rms) roughness varied from 1.0 to 18 nm as the power density of the AlMg target increased from 0.2 to 1.0 W/cm² while the power density of each boron target was maintained at 2 W/cm². Chemical analyses show dominating Al, Mg, B and trace elements of oxygen, carbon and argon. The film composition also varies with altering the power density supplied to the AlMg target. The film with an atomic ratio of Al:Mg:B = 1.38:0.64:1 exhibits the highest hardness (~ 30 GPa). This value surpasses the hardness of hydrogenated diamond-like carbon films (24-28 GPa) prepared by plasma enhanced chemical vapor deposition.     

A study of growth and surface performance analysis of nanographites grown using microwave plasma jet chemical vapor deposition system

Nanographites were grown using a microwave plasma jet chemical vapor deposition (MPJCVD) system. The E-H tuner of the MPJCVD was controlled by a personal computer. Monitoring of plasma jet was done through an optical emission spectroscopy and a charge coupled detector camera. High frequency structure simulator software was used to calculate electrical fields around specimens at different positions of the E-H tuner of the MPJCVD. Nanographites, composed of sp² hybrid orbital, were grown at a microwave power of 800?W. The carbon bonds, both C–C and C=C bonds, of as-grown nanographites were measured to have characteristic peaks at 1309 and 1595?cm^?1 using Raman spectroscopy. The mean size of the nanostructured graphite was nearly 50?nm under scanning electron microscopy observation. The measurement of contact angle on such graphite films was made by laying drops of deionized (DI) water, 0.03 and 0.09?M sodium chloride (NaCl) and was found to be 153°, 147°, and 136°, respectively. An electro-wetting test was also performed on the graphite films by adding electrical voltage through the CA measurement. It was found that contact angles of electro-wetting test for graphite films become 110° and 37° for DI water and NaCl solution, respectively.     

Field emission from diamond and diamond-like carbon films

Field emission from diamond and diamond-like carbon thin films deposited on silicon substrates has been studied. The diamond films were synthesized using hot filament chemical vapor deposition technique. The diamond-like carbon films were deposited using the radio frequency chemical vapor deposition method. Field emission studies were carried out using a sphere-to-plane electrode configuration. The results of field emission were analyzed using the Fowler-Nordheim model. It was found that the diamond nucleation density affected the field emission properties. The films were characterized using standard scanning electron microscopy, Raman spectroscopy, and electron spin resonance techniques. Raman spectra of both diamond and diamond-like films exhibit spectral features characteristic of these structures. Raman spectrum for diamond films exhibit a well-defined peak at 1333cm^?1. Asymmetric broad peak formed in diamond-like carbon films consists of D-band and G-band around 1550 cm^?1 showing the existence of both diamond (sp³ phase) and graphite (sp² phase) in diamond-like carbon films.     

Formation of a diamond-like carbon film by magnetron sputtering of a graphite target under radiation flux from a black-body model

A method of depositing a film (under a radiation flux from a high-temperature black-body model) by magnetron sputtering of a graphite target has been implemented. The elemental composition and structure of deposited films have been analyzed by X-ray photoelectron spectroscopy and characteristic electron-energy-loss spectroscopy. The investigations have shown that chemically pure diamond-like films can be formed at a radiation-flux density no less than 1.5 × 10^?4 W/m² in the spectral range of 170–255 nm.     

Effect of process parameters on the growth and properties of impurity-doped zinc oxide transparent conducting thin films by RF magnetron sputtering

Zinc oxide transparent conducting thin films co-doped with aluminum and ruthenium were grown on polyethylene terephthalate substrates at room temperature using RF magnetron sputtering. The crystal growth and physical properties of the films were investigated with respect to the variation of discharge power density from 1.5 to 6.1 W/cm² and sputtering pressure from 0.13 to 2.0 Pa. X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) showed that the films grown with 3.6 W/cm² power density and sputtering pressure of 0.4 Pa had the best crystallinity and larger pyramid-like grains. The optimized electrical resistivity had a lowest measured value of about 9 × 10⁻⁴ Ω cm. The low carrier mobilities of the films (3-8.9 cm² V⁻¹ s⁻¹) have been discussed in terms of what is believed to be the dominant effect of ionized impurity scattering, but in addition chemisorption of oxygen on the film surface and effect of grain boundaries are also thought to be significant. The transmittances of the films in the visible range are greater than 80%, while the optical band gaps are in the order of 3.337-3.382 eV.     

A study on the electrical and optical characteristics of IGZO films

The electrical and optical properties of InGaZnO (IGZO) thin films were studied in the research. It was found that all the films deposited at room temperature exhibit amorphous structures. A better film quality was obtained at a lower pressure with sputtering ambiance. The RF power toward the IZO target was constant at 125 W; the RF power toward the Ga₂O₃ target varied from 0 to 70 W. A best IGZO film with corresponding resistivity, carrier concentration, and mobility is 7.94 × 10^?4 Ω-cm, 1.68 × 10²⁰ cm^?3, and 47 cm²/V-s, respectively. Due to the doping of gallium in the IGZO film, it led to a lower resistivity than that of the IZO film. A blue shift effect of the film was also observed in the doping of gallium to the IGZO film. The H₂ plasma effects toward the IGZO were also observed.     

Synthesis of isotopically-labeled graphite films by cold-wall chemical vapor deposition and electronic properties of graphene obtained from such films

We report the synthesis of isotopically-labeled graphite films on nickel substrates by using cold-wall chemical vapor deposition (CVD). During the synthesis, carbon from ¹²C- and ¹³C-methane was deposited on, and dissolved in, a nickel foil at high temperature, and a uniform graphite film was segregated from the nickel surface by cooling the sample to room temperature. Scanning and transmission electron microscopy, micro-Raman spectroscopy, and X-ray diffraction prove the presence of a graphite film. Monolayer graphene films obtained from such isotopically-labeled graphite films by mechanical methods have electron mobility values greater than 5000 cm²·V⁻¹·s⁻¹ at low temperatures. Furthermore, such films exhibit the half-integer quantum Hall effect over a wide temperature range from 2 K to 200 K, implying that the graphite grown by this cold-wall CVD approach has a quality as high as highly oriented pyrolytic graphite (HOPG). The results from transport measurements indicate that ¹³C-labeling does not significantly affect the electrical transport properties of graphene.     

Structural and optical properties of amorphous oxygenated iron boron nitride thin films produced by reactive co-sputtering

Amorphous oxygenated iron boron nitride (a-FeBN:O) thin films were prepared by reactive radio-frequency (RF) sputtering, from hexagonal boron nitride chips placed on iron target, under a total pressure of a gas mixture of argon and oxygen maintained at 1 Pa. The films were deposited onto silicon and glass substrates, at room temperature. The power of the generator RF was varied from 150 to 350 W. The chemical and structural analyses were investigated using X-ray photoelectron spectroscopy (XPS), energy dispersive of X-ray and X-ray reflectometry (XRR). The optical properties of the films were obtained from the optical transmittance and reflectance measurements in the ultraviolet-visible-near infrared wavelengths range. XPS reveals the presence of boron, nitrogen, iron and oxygen atoms and also the formation of different chemical bonds such as Fe-O, B-N, B-O and the ternary BNO phase. This latter phase is predominant in the deposited films as observed in the B 1s and N 1s core level spectra. As the RF power increases, the contribution of N-B bonds in the as-deposited films decreases. The XRR results show that the mass density of a-FeBN:O thin films increases from 2.6 to 4.12 g/cm³ with increasing the RF power from 150 to 350 W. This behavior is more important for films deposited at RF power higher than 150 W, and has been associated with the enhancement of iron atoms in the film structure. The optical band gap decreases from 3.74 to 3.12 eV with increasing the RF power from 150 to 350 W.     

Influence of argon neutral beam energy on the structural properties of amorphous carbon thin films grown by neutral particle beam assisted sputtering

The effects of argon neutral beam (NB) energy on amorphous carbon (a-C) films were investigated, the a-C films were deposited by a neutral particle beam assisted sputtering (NBAS) system. The energy of the neutral particle beam can be directly controlled by a reflector bias voltage as a unique operating parameter of the system. The results from the analysis by Raman spectra, Fourier transform infrared (FT-IR), UV-visible spectroscopy and electrical conductivity indicate the properties of the amorphous carbon films can be manipulated by simply adjusting the NB energy (or reflector bias voltage) without changing any other process parameters. By increasing the reflector bias voltage, the amount of cross-linked sp² clusters as well as the sp³ bonding in the a-C film coating from the NBAS system can be increased effectively and the composition of carbon thin films can be changed from a nano-crystalline graphite phase to an amorphous carbon phase. In addition, the deposition rate increases with reflector bias voltage due to additional sputtering at the carbon reflector without any variation of physical and electrical properties of the a-C film.     

Enhanced field emission from ZnO nanoneedles on chemical vapour deposited diamond films

ZnO nanoneedles were coated on hot filament chemical vapour deposited diamond thin films to enhance the field emission properties of ZnO nanoneedles. The virgin diamond films and ZnO nanoneedles on diamond films were characterized using scanning electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. The field emission studies reveal that the ZnO nanoneedles coated on diamond film exhibit better emission characteristics, with minimum threshold field (required to draw a current density ~ 1 μA/cm²) as compared to ZnO needles on silicon and virgin diamond films. The better emission characteristic of ZnO nanoneedles on diamond film is attributed to the high field-enhancement factor resulting due to the combined effect of the ZnO nanoneedles and diamond film.     

Structural, morphological, and mechanical properties of amorphous carbon and carbon nitride thin films deposited by reactive and ion beam assisted laser ablation

Amorphous carbon nitride thin films have been prepared on Si (100) wafers by nitrogen ion beam assisted Nd:YAG laser ablation techniques. Amorphous carbon and carbon nitride films have also been prepared by the conventional laser ablation techniques for comparison. Raman spectroscopy and spectroscopic ellipsometry have been performed for the films to analyze structural properties, atomic force microscopy to observe surface morphologies, and scratch, acoustic emission, and Vicker hardness test to examine mechanical properties. The amorphous carbon nitride films deposited by the ion beam assisted laser ablation techniques had generally better mechanical properties compared to the amorphous carbon films and amorphous carbon nitride films deposited in N₂ atmosphere. The amorphous carbon nitride films deposited at optimum ion beam current of 10 mA and laser power density of 1.7 × 10⁹ W/cm² showed excellent mechanical properties: root mean square surface roughness of 0.33 nm, friction coefficient of 0.02–0.08, the first crack and critical load of 11.5 and 19.3 N respectively, and Vicker hardness of 2300 [Hv]. It is considered that the films have high potential for protective coatings for microelectronic devices such as magnetic data storage media and heads.     

Deposition of amorphous carbon-silver composites

Composites of amorphous carbon films and silver were deposited by co-sputtering, where the target (10 cm diameter) was of pure graphite with small inclusion of pure silver (less than 1 cm²). The films were deposited under different powers, from 40 to 250 W, and different target-substrate distances. The substrate was earthed and rotated in order to obtain a uniform distribution of the silver content. The addition of the Ag piece into the target increased the deposition rate of the carbon films, which could be related to the higher sputter yield of the silver, but there seems to be also a contribution from a larger emission of secondary electrons from the Ag that enhances the plasma and therefore the sputtering process becomes more efficient.Scanning electron micrographs acquired using backscattered electrons showed that the silver was segregated from the carbon matrix, forming nanoparticles or larger clusters as the power was increased. The X-ray diffraction pattern showed that the silver was crystalline and the carbon matrix remained amorphous, although for certain conditions a peak attributed to fullerene-like structures was obtained. Finally, we used Raman spectroscopy to understand the bonding characteristics of the carbon-silver composites, finding that there are variations in the D/G ratio, which can be correlated to the observed structure and X-ray diffraction results.     

Growth of CZTS thin films by sulfurization of sputtered single-layered Cu–Zn–Sn metallic precursors from an alloy target

Cu₂ZnSnS₄ (CZTS) thin films were prepared by sulfurizing single-layered metallic Cu–Zn–Sn precursors which were deposited by DC magnetron sputtering using a Cu–Zn–Sn ternary alloy target. The composition, microstructure and properties of the CZTS thin films prepared under different sputtering pressure and DC power were investigated. The results showed that the sputtering rate of Cu atom increases as the sputtering pressure and DC power increased. The microstructure of CZTS thin films can be optimized by sputtering pressure and DC power. The CZTS thin film prepared under 1 Pa and 30 W showed a pure Kesterite phase and a dense micro-structure. The direct optical band gap of this CZTS thin film was calculated as 1.49 eV with a high optical absorption coefficient over 10⁴ cm^?1. The Hall measurement showed the film is a p-type semiconductor with a resistivity of 1.06 Ω cm, a carrier concentration of 7.904 × 10¹⁷ cm^?3 and a mobility of 7.47 cm² Vs^?1.     

Microstructure and hardness of electroplated gold prepared by D.C., pulse and asymmetric A.C. plating

Initially procedures for preparing insulating carbon films of exceptional hardness by ion beam deposition and ion impact growth in hydrocarbon plasmas are reviewed; for completeness reference is also made to thermally cracked carbon films grown on diamond. We described experiments on the coating of germanium targets on a water-cooled electrode in a butane r.f. plasma (13.56 MHz) with the electrode capacitively coupled to the supply to provide a negative bias to enhance ion impact. Films prepared at a low power input-to-pressure ratio of 1–2 W cm^-2Torr^-1 were polymers with some oxygen contamination as shown by their infrared absorption bands. Raising the ratio to 40 W cm^-2 Torr^-1 produced carbon films without absorption in the measured region λ = 2–20 μm. The films were amorphous with a refractive index of 1.9–2.0 and a resistivity of 10¹² Ω cm. At higher power-to-pressure ratios or target temperatures the film resistivity fell with loss of the infrared transparency. A critical ratio exists at which energetic ion impact is sufficient to rupture all CH bonded species reaching the target and to damage any structure ordering which may otherwise arise. At high ratios the target cooling is considered to be insufficient to prevent the film temperature rising and resulting in a transition from a metastable to a graphitic form. In conclusion the properties of vacuum-deposited carbon and the nature of some reported defects in diamond are considered in relation to the characteristics of ion impact films.     

Hydrogen-free diamond-like carbon films prepared by microwave electron cyclotron resonance plasma-enhanced direct current magnetron sputtering

Hydrogen-free diamond-like carbon (DLC) films were prepared by means of microwave electron cyclotron resonance plasma enhanced direct current magnetron sputtering. To study the influence of enhanced plasma on film fabrication and properties, the structures as well as mechanical and electrical properties of these films were studied as a function of applied microwave power. Results showed that higher microwave power could induce higher plasma density and electron temperature. The hardness increased from 3.5 GPa to 13 GPa with a variation of microwave power from 0 W to 1000 W. The resistivity showed a drastic increase from 4.5 × 10⁴ Ωcm at 0 W to 1.3 × 10¹⁰ Ωcm at 1000 W. The variation of the intensity ratio I(D)/I(G) and the position of the G-peak of the DLC films with respect to changes in microwave power were also investigated by Raman spectroscopy.     

Plasma etching of virtually stress-free stacked silicon nitride films

Stacked silicon nitride films for use in manufacturing of surface micromachined membranes were deposited using custom made plasma-enhanced chemical vapor deposition instrument with silane (SiH₄) and ammonia (NH₃) gas mixture as deposition precursor. Deposition conditions were adjusted by varying substrate temperature and SiH₄ to NH₃ flow ratio and temperature to obtain the required stress related and electrical properties of the membranes. Transmission Fourier transformed infrared spectroscopy and scanning electron microscopy were used to investigate the chemical composition and morphology of the stacked film components. An increase in the SiH₄ to NH₃ flow ratio and a decrease in temperature resulted in a silicon-rich silicon nitride film, as well as an increased silicon oxide concentration. To avoid underetch and sidewall defects, the plasma power density during the plasma etching was changed from 0.5 W/cm² during the etching of both top and bottom layers in a stacked film, to 1.0 W/cm² during the etching of the middle both silicon and silicon oxide rich film. This resulted in an improved overall stacked film sidewall quality and reduced the unwanted underetch.     

Effect of oxygen plasma treatment on bonding states for columnar structured a-CNx thin films prepared by reactive sputtering

Amorphous carbon nitride (a-CN) thin films were deposited on silicon single crystal substrates by rf-reactive sputtering method using a graphite target and nitrogen gas. The substrate temperature was varied from room temperature (RT) to 853 K. After deposition, the effect of oxygen plasma treatment on bonding structures of the film surface has been studied by using an oxygen discharge at 16 Pa and rf power of 85 W. The chemical bonding states and film composition were analyzed by X-ray photoelectron spectroscopy (XPS), while film thickness was obtained from scanning electron microscopy (SEM) and ellipsometer. XPS study revealed that the films have NO₂ and NO₃ bonding structures when the films are deposited at temperatures higher than 673 K. After exposure to oxygen plasma, carbon in the film surface was etched selectively and this phenomenon was observed in all films. In contrast, the surface concentration of nitrogen was ket at constant values before and after oxygen plasma treatment. The NO₃ bonding state had dramatically increased after oxygen plasma treatment for films deposited at higher deposition temperatures. The film surfaces have been observed to change the function from hydrophobic to hydrophilic after oxygen plasma treatment.     

Nanocrystalline graphite films nucleation by the radio frequency bias pretreatment

New method for nucleation of different nanocrystalline carbon films upon monocrystalline Si substrate was proposed. The process is based on a combination of microwave and radio frequency plasma assisted chemical vapor deposition methods. Potential of the method for nucleation was demonstrated by deposition of nanocrystalline diamond film in pure microwave plasma in one process, immediately after "seeding" procedure. The method was also used for growth of nanocrystalline graphite (NCG) films, which are currently under intensive investigation due to their exceptional electronic properties, particularly fine electron emission characteristics. Deposited NCG films have demonstrated remarkable electron field emission properties having current density of up to 10 A/cm2. The films have also possessed good adhesion to silicon substrate. Carbon films and nucleation layer were characterized by scanning electron microscopy, transmission electron microscopy and Raman spectroscopy.     

Deposition and characterization of TiBCN films by cathodic arc plasma evaporation

TiBCN thin films were deposited on Si(100) substrate by reactive cathodic arc evaporation from a graphite/boron-containing composite target and Ti target in an N₂ atmosphere. Characteristics and microstructures of the films were investigated, deposited under different target currents. Raman spectroscopy and high resolution X-ray photoelectron spectroscopy (HRXPS) were employed to investigate the spectrum and bonding states of films. The film microstructures were evaluated by using an atomic force microscope (AFM), a field emission scanning electron microscopy (FEGSEM), a glancing angle X-ray diffractometry (GAXRD) and a high-resolution transmission electron microscopy (HRTEM). Results demonstrated that the TiBCN films were synthesized successfully and adhered well to the silicon substrate. The Raman spectra showed that wavenumbers ranging from 900 to 1800 cm^− 1 consisted of D and G bands, similar to that of cathodic arc plasma deposited DLC. Raman spectra proved that the intensity of D and G bands decreased by increasing Ti target currents. HRTEM results established that TiBCN films revealed an amorphous structure while the Ti target current was low. As the Ti target current increased, the TiBCN films revealed a nanocomposite structure, an amorphous matrix consisting of nano scale Ti(C,N) and TiB crystalline, which were comparable to GAXRD, Raman and HRXPS results. The HRXPS spectra of B1s, C1s, N1s and Ti2p in the TiBCN films reveal much broader peaks; this indicated that there is more than one category of bonding state surrounding each of Ti, B, C and N atoms. Morphology, characteristics and film concentration as a function of deposition parameters were also investigated in this study.     

Solid-phase interaction in the hydroxyapatite/titanium heterostructures upon high-temperature annealing in air and argon

Samples of 100- and 500-nm-thick hydroxyapatite films on titanium were investigated using scanning electron microscopy, electron probe X-ray microanalysis, and X-ray powder diffraction. The films were prepared by high-frequency magnetron sputtering of a target in an argon atmosphere (1 × 10^?1 Pa) at a magnetron power density of 40–70 W/cm². These conditions provided growth of films at a rate as high as 0.7 nm/s. It was demonstrated that the hydroxyapatite film annealed in argon is characterized by deep pores that have diameters ranging from 0.3 to 8.0 µm and are uniformly distributed throughout the film surface. The electron probe X-ray microanalysis confirmed the presence of all elements (Ti, O, Ca, P) under investigation, except for hydrogen, in the samples of the films. For biologically compatible hydroxyapatite, the optimum ratio Ca : P ? 1.5–1.7 was achieved in the hydroxyapatite/titanium system with a 500-nm-thick hydroxyapatite layer upon annealing in argon at a temperature of 1050°C for 30 min. It was established that the hydroxyapatite/titanium system contains intermediate phases, including calcium titanate CaTiO₃, which proved the interaction of hydroxyapatite with titanium.