Correlation between density and structure. in boron nitride thin films by X-ray diffraction

* _ion=100 eV. Above E^* _ion the average density (deduced from X-ray reflectivity) shows a strong increase, indicating the sudden appearance of the cubic boron nitride phase consistent with the sp³ concentration deduced from IR absorption spectroscopy. The in-plane X-ray diffraction shows that this cubic phase consists of small nanocrystals of 70 Å linear size. Received: 26 November 1996/Accepted: 27 January 1997     

Structural and electrical properties of tantalum nitride thin films fabricated by using reactive radio-frequency magnetron sputtering

TaN thin film is an attractive interlayer as well as a diffusion barrier layer in [FeN/TaN]_n multilayers for the application as potential write-head materials in high-density magnetic recording. We synthesized two series of TaN films on glass and Si substrates by using reactive radio-frequency sputtering under 5-mtorr Ar/N₂ processing pressure with varied N₂ partial pressure, and carried out systematic characterization analyses of the films. We observed clear changes of phases in the films from metallic bcc Ta to a mixture of bcc Ta(N) and hexagonal Ta₂N, then sequentially to fcc TaN and a mixture of TaN with N-rich phases when the N₂ partial pressure increased from 0.0% to 30%. The changes were associated with changes in the grain shapes as well as in the preferred crystalline orientation of the films from bcc Ta [100] to [110], then to random and finally to fcc TaN [111], correspondingly. They were also associated with a change in film resistivity from metallic to semiconductor-like behavior in the range of 77–295 K. The films showed a typical polycrystalline textured structure with small, crystallized domains and irregular grain shapes. Clear preferred (111) stacks parallel to the substrate surface with embedded amorphous regions were observed in the film. TaN film with [111]-preferred orientation and a resistivity of 6.0 mΩ cm was obtained at 25% N₂ partial pressure, which may be suitable for the interlayer in [FeN/TaN]_n multilayers. Received: 6 December 1999 / Accepted: 24 July 2000 / Published online: 9 November 2000     

Synthesis of phosphorus‐carbide thin films by magnetron sputtering

Phosphorus‐carbide, CP_x (0.025 ≤ x ≤ 0.1), thin films have been synthesized by magnetron sputtering from pressed graphite–phosphorus targets. The films were characterized by X‐ray photoelectron spectroscopy, transmission electron microscopy and diffraction, and nanoindentation. CP_0.1 ex‐hibits C–P bonding in an amorphous structure with elements of curved graphene planes, yielding a material with unique short range order. These features are consistent with what has been predicted by our results of theoretically modeled synthetic growth of CP_x . The films are mechanically resilient with hardness up to 24 GPa and elastic recovery up to 72%. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Properties of NiO thin films deposited by chemical spray pyrolysis using different precursor solutions

NiO thin films have been deposited by chemical spray pyrolysis using a perfume atomizer to grow the aerosol. The influence of the precursor, nickel chloride hexahydrate (NiCl₂·6H₂O), nickel nitrate hexahydrate (Ni(NO₃)₂·6H₂O), nickel hydroxide hexahydrate (Ni(OH)₂·6H₂O), nickel sulfate tetrahydrate (NiSO₄·4H₂O), on the thin films properties has been studied. In the experimental conditions used (substrate temperature 350 °C, precursor concentration 0.2-0.3 M, etc.), pure NiO thin films crystallized in the cubic phase can be achieved only with NiCl₂ and Ni(NO₃)₂ precursors. These films have been post-annealed at 425 °C for 3 h either in room atmosphere or under vacuum. If all the films are p-type, it is shown that the NiO films conductivity and optical transmittance depend on annealing process. The properties of the NiO thin films annealed under room atmosphere are not significantly modified, which is attributed to the fact that the temperature and the environment of this annealing is not very different from the experimental conditions during spray deposition. The annealing under vacuum is more efficient. This annealing being proceeded in a vacuum no better than 10⁻² Pa, it is supposed that the modifications of the NiO thin film properties, mainly the conductivity and optical transmission, are related to some interaction between residual oxygen and the films.     

Seebeck and magnetoresistive effects of Ga-doped ZnO thin films prepared by RF magnetron sputtering

In this paper, Ga-doped ZnO (GZO) films were deposited on glass substrates at different substrate temperatures by RF magnetron sputtering. The effect of substrate temperature on the structural, surface morphological properties, Seebeck and magnetoresistive effects of GZO films was investigated. It is found that the GZO films are polycrystalline and preferentially in the [0 0 2] orientation, and the film deposited at 300 °C has an optimal crystal quality. Seebeck and magnetoresistive effects are apparently observed in GZO films. The thermoelectromotive forces are negative. Decreasing substrate temperature and annealing in N₂ flow can decrease carrier concentration. The absolute value of the Seebeck coefficient increases with decreasing carrier concentration. The maximal absolute value of Seebeck coefficient is 101.54 μV/K for the annealed samples deposited at the substrate temperature of 200 °C. The transverse magnetoresistance of GZO films is related to both the magnetic field intensity and the Hall mobility. The magnetoresistance increases almost linearly with magnetic field intensity, and the films deposited at higher substrate temperature have a stronger magnetoresistance under the same magnetic field, due to the larger Hall mobility.     

Influence of direct current plasma magnetron sputtering parameters on the material characteristics of polycrystalline copper films

Physical vapor processes using glow plasma discharge are widely employed in microelectronic industry. In particular magnetron sputtering is a major technique employed for the coating of thin films. This paper addresses the influence of direct current (DC) plasma magnetron sputtering parameters on the material characteristics of polycrystalline copper (Cu) thin films coated on silicon substrates. The influence of the sputtering parameters including DC plasma power and argon working gas pressure on the electrical and structural properties of the thin Cu films was investigated by means of surface profilometer, four-point probe and atomic force microscopy.     

Investigation of microstructure evolution in Pt-doped TiO2 thin films deposited by rf magnetron sputtering

Pt-doped titanium dioxide or titania (TiO₂) films were grown by rf magnetron sputtering and then annealed in the conventional thermal annealing (CTA) process. Raman spectroscopy was used to characterize the structure of the films deposited. The effect of sputtering parameters was studied in focus of the nucleation sites energies (influenced by the substrate temperature) and substrate bombardment energies (influenced by the sputtering pressure or rf power). The X-ray diffractions technique was used to investigate the structural variation after the films were annealed at different temperatures. It was found that 0.75% Pt-doped TiO₂ film exhibits better thermal stability and smaller grain sizes than 0.35% Pt-doped TiO₂ film, suggesting that the suppression of crystallization can be expected with a proper increase of Pt doping level. And the obtained optical transparency higher than 80% even after annealing has demonstrated the films’ prospect for future developments.     

Deposition of Ag nanostructures on TiO2 thin films by RF magnetron sputtering

Ag nanostructures on TiO₂ films were deposited by RF magnetron sputtering under variable deposition parameters, such as DC potential, RF-power and total pressure. The concentration, shape, and distribution of the deposited nanostructures and continuous Ag films on thin films of TiO₂ can be tailored by careful variation of the deposition parameters. Controllable clusterlike, islandlike and film Ag structures on TiO₂ film were obtained, respectively. DC potential was found as an appropriate parameter to tailor the change of Ag nanostructure and the overall Ag amount. The compositions, nanostructures and morphologies of nanocomposite films appreciably influence the optical response.     

Synthesis of silicon carbide films by combined implantation with sputtering techniques

Silicon carbide (SiC) films were synthesized by combined metal vapor vacuum arc (MEVVA) ion implantation with ion beam assisted deposition (IBAD) techniques. Carbon ions with 40 keV energy were implanted into Si(1 0 0) substrates at ion fluence of 5 × 10¹⁶ ions/cm². Then silicon and carbon atoms were co-sputtered on the Si(1 0 0) substrate surface, at the same time the samples underwent assistant Ar-ion irradiation at 20 keV energy. A group of samples with substrate temperatures ranging from 400 to 600 °C were used to analyze the effect of temperature on formation of the SiC film. Influence of the assistant Ar-ion irradiation was also investigated. The structure, morphology and mechanical properties of the deposited films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and nanoindentation, respectively. The bond configurations were obtained from IR absorption and Raman spectroscopy. The experimental results indicate that microcrystalline SiC films were synthesized at 600 °C. The substrate temperature and assistant Ar-ion irradiation played a key role in the process. The assistant Ar-ion irradiation also helps increasing the nanohardness and bulk modulus of the SiC films. The best values of nanohardness and bulk modulus were 24.1 and 282.6 GPa, respectively.     

Study of hydrogenated amorphous silicon nitride films prepared by RF magnetron sputtering

Hydrogenated amorphous silicon nitride films have been deposited by the rf magnetron sputtering method with non-stoichiometric and stoichiometric compositions using a poly-Si target and a mixture of Ar, H₂ and N₂ as the sputtering gas. Data on optical and infrared absorption, electrical conductivity, breakdown voltage, capacitance measurements and thermal evolution of hydrogen have been presented as a function of nitrogen concentration in the films, especially in the stoichiometric region of composition. Attempts have been made to identify the roles of hydrogen and nitrogen in determining the electrical and optical properties and thermal stability exhibited by the films. Properties relevant for device application of the material have been shown to be comparable to those obtained by glow discharge or electron cyclotron resonance plasma chemical vapour deposition methods of deposition. RF magnetron sputtering has therefore been suggested as a viable alternative to the more widely adopted CVD methods for device applications of silicon nitride, where the use of hazardous process gases can be avoided.     

Indium tin oxide thin films by bias magnetron rf sputtering for heterojunction solar cells application

In this investigation ITO thin films were prepared by bias magnetron rf sputtering technique at substrate temperature of 180 °C and low substrate-target distance for future a-Si:H/c-Si heterojunction (HJ) solar cells application. Microstructure, surface morphology, electrical and optical properties of these films were characterized and analyzed. The effects of ion bombardments on growing ITO films are well discussed. XRD analysis revealed a change in preferential orientation of polycrystalline structure from (2 2 2) to (4 0 0) plane with the increase of negative bias voltage. Textured surface were observed on AFM graphs of samples prepared at high negative bias. Hall measurements showed that the carrier density and Hall mobility of these ITO films are sensitive to the bias voltage applied. We attributed these effects to the sensitivity of energy of Ar⁺ ions bombarding on growing films to the applied bias voltage in our experiments. At last the figure of merit was calculated to evaluate the quality of ITO thin films, the results of which show that sample prepared at bias voltage of −75 V is good to be used in HJ cells application.     

Effect of substrate temperature and annealing temperature on the structural, electrical and microstructural properties of thin Pt films by rf magnetron sputtering

Influence of both substrate temperature, T_s, and annealing temperature, T_a, on the structural, electrical and microstructural properties of sputtered deposited Pt thin films have been investigated. X-ray diffraction results show that as deposited Pt films (T_s = 300, 400 °C) are preferentially oriented along (1 1 1) direction. A little growth both along (2 0 0) and (3 1 1) directions are also noticed in the as deposited Pt films. After annealing in air (T_a = 500-700 °C), films become strongly oriented along (1 1 1) plane. With annealing temperature, average crystallite size, D, of the Pt films increases and micro-strain, e, and lattice constant, a₀, decreases. Residual strain observed in the as deposited Pt films is found to be compressive in nature while that in the annealed films is tensile. This change in the strain from compressive to tensile upon annealing is explained in the light of mismatch between the thermal expansion coefficients of the film material and substrate. Room temperature resistivity of Pt films is dependant on both the T_s and T_a of the films. Observed decrease in the film resistivity with T_a is discussed in terms of annihilation of film defects and grain-boundary. Scanning electron microscopic study reveals that as the annealing temperature increases film densification improves. But at an annealing temperature of ∼600 °C, pinholes appear on the film surface and the size of pinhole increases with further increase in the annealing temperature. From X-ray photoelectron spectroscopic analysis, existence of a thin layer of chemisorbed atomic oxygen is detected on the surfaces of the as deposited Pt films. Upon annealing, coverage of this surface oxygen increases.     

Preparation of boron carbon nitride thin films by radio frequency magnetron sputtering

Boron carbon nitride films were deposited by radio frequency magnetron sputtering using a composite target consisting of h-BN and graphite in an Ar-N₂ gas mixture. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The results suggest that the films are atomic-level hybrids composed of B, C and N atoms. The boron carbon nitride films prepared in the present experiment have a disordered structure. The sputtering power varied from 80 W to 130 W. This sputtering power was shown to have regular effect on the composition of boron carbon nitride films. The samples deposited at 80 W and 130 W are close to the stoichiometry of BC₃N. The sample deposited at 110 W is close to the stoichiometry of BCN. The samples deposited at 100 W and 120 W approach to BC₂N. It is very significant for us to synthesize boron carbon nitride compound with controllable composition by changing the sputtering power.     

Development of conductive transparent indium tin oxide (ITO) thin films deposited by direct current (DC) magnetron sputtering for photon-STM applications

Highly conductive and transparent indium tin oxide (ITO) thin films, each with a thickness of 100 nm, were deposited on glass and Si(100) by direct current (DC) magnetron sputtering under an argon (Ar) atmosphere using an ITO target composed of 95% indium oxide and 5% tin oxide for photon-STM use. X-ray diffraction, STM observations, resistivity and transmission measurements were carried out to study the formation of the films at substrate temperatures between 40 and 400 °C and the effects of thermal annealing in air between 200 and 400 °C for between1 and 5 h. The film properties were highly dependent on deposition conditions and on post-deposition film treatment. The films deposited under an Ar atmosphere pressure of ∼1.7×10^-3 Torr by DC power sputtering (100 W) at substrate temperatures between 40 and 400 °C exhibited resistivities in the range 3.0–5.7×10^-5 Ω m and transmissions in the range 71–79%. After deposition and annealing in air at 300 °C for 1 h, the films showed resistivities in the range 2.9–4.0×10^-5 Ω m and transmissions in the range 78–81%. Resistivity and transmission measurements showed that in order to improve conductive and transparent properties, 2 h annealing in air at 300 °C was necessary. X-ray diffraction data supported the experimental measurements of resistivity and transmission on the studies of annealing time. The surface roughness and film uniformity improve with increasing substrate temperature. STM observations found the ITO films deposited at a substrate temperature of 325 °C, and up to 400 °C, had domains with crystalline structures. After deposition and annealing in air at 300 °C for 1 h the films still exhibited similar domains. However, after deposition at substrate temperatures from 40 °C to 300 °C, and annealing in air at 300 °C for 1 h, the films were shown to be amorphous. More importantly, the STM studies found that the ITO film surfaces were most likely to break after deposition at a substrate temperature of 325 °C and annealing in air at 300 °C for 2 or 3 h. Such findings give some inspiration to us in interpreting the effects of annealing on the improvement of conductive and transparent properties and on the transition of phases. In addition, correlations between the conductive/transparent properties and the phase transition, the annealing time and the phase transition, and the conductive/transparent properties and the annealing time have been investigated. Received: 10 July 2000 / Accepted: 27 October 2000 / Published online: 9 February 2001     

Effects of the sputtering time of ZnO buffer layer on the quality of GaN thin films

ZnO thin films with different thickness (the sputtering time of ZnO buffer layers was 10 min, 15 min, 20 min, and 25 min, respectively) were first prepared on Si substrates using radio frequency magnetron sputtering system and then the samples were annealed at 900 °C in oxygen ambient. Subsequently, a GaN epilayer about 500 nm thick was deposited on ZnO buffer layer. The GaN/ZnO films were annealed in NH₃ ambient at 950 °C. X-ray diffraction (XRD), atom force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) were used to analyze the structure, morphology, composition and optical properties of GaN films. The results show that their properties are investigated particularly as a function of the sputtering time of ZnO layers. For the better growth of GaN films, the optimal sputtering time is 15 min.     

Thermochromic VO2 thin films synthesized by rf-inverted cylindrical magnetron sputtering

The novel physical vapor deposition called inverted cylindrical magnetron sputtering (also known as hollow cathode sputtering) is commonly used to coat wires, fibers, ribbons as well as all sides of three-dimensional substrates. It is a reproducible method for the production of nano-structured systems onto complex shapes substrates. This paper reports the first synthesis and feasibility of reliably reproduced stoichiometric pure textured VO₂ nano-structures by the rf-inverted cylindrical magnetron sputtering. Morphological, structural, elemental analysis and optical properties of synthesized VO₂ under optimized conditions are reported.     

Optical properties of hexagonal boron nitride thin films deposited by radio frequency bias magnetron sputtering

The optical properties of hexagonal boron nitride (h-BN) thin films were studied in this paper. The films were characterized by Fourier transform infrared spectroscopy, UV--visible transmittance and reflection spectra. h-BN thin films with a wide optical band gap E_g (5.86 eV for the as-deposited film and 5.97 eV for the annealed film) approaching h-BN single crystal were successfully prepared by radio frequency (RF) bias magnetron sputtering and post-deposition annealing at 970~K. The optical absorption behaviour of h-BN films accords with the typical optical absorption characteristics of amorphous materials when fitting is made by the Urbach tail model. The annealed film shows satisfactory structure stability. However, high temperature still has a significant effect on the optical absorption properties, refractive index n, and optical conductivity σ of h-BN thin films. The blue-shift of the optical absorption edge and the increase of E_g probably result from stress relaxation in the film under high temperatures. In addition, it is found that the refractive index clearly exhibits different trends in the visible and ultraviolet regions. Previous calculational results of optical conductivity of h-BN films are confirmed in our experimental results.     

Titanium oxynitride thin films sputter deposited by the reactive gas pulsing process

DC reactive sputtering was used to successfully make thin films of titanium oxynitride using titanium metallic target, argon as plasma gas and nitrogen and oxygen as reactive gases. The nitrogen partial pressure was kept constant during every deposition whereas oxygen flow rate was pulsed using a square pattern. The study consisted in analysing the influence of the shape of the pulsed rate on physical properties of these films. In order to adjust the metalloid concentration to get films with a wide range of oxygen-to-nitrogen ratios, the reactive gas pulsing process (RGPP) was used. In this process, the oxygen flow switches “on” and “off” periodically according to a duty cycle α = t_ON/T. Electrical conductivity of films measured against temperature was gradually modified from metallic (σ_300K = 4.42 × 10⁴ S m⁻¹) to semi-conducting behaviour (σ_300K = 7.14 S m⁻¹) with an increasing duty cycle. Mechanical properties like nanohardness (H_n) and reduced Young's modulus (E_r) of the films were investigated. Experimental values of H_n and E_r obtained by nanoindentation at 10% depth ranged from 15.8 to 5.2 GPa and from 273 to 142 GPa, respectively. Evolutions of H_n and E against duty cycle were similar. A regular decrease was observed for duty cycle α ≤ 25% corresponding to the occurrence of TiO_xN_y phase. Higher duty cycles led to the smallest values of H_n and E and correlated with TiO₂ compound composition. At last, the colour variation of these titanium oxynitrides was investigated as a function of α in the L^*a^*b^* colour space. It was related to the chemical composition of the films.     

Photoelectron-spectroscopic and reactivity investigation of thin Pd-Sn films prepared by magnetron sputtering

We have studied Pd-Sn layers with different composition prepared by magnetron sputtering. Layers were sputtered onto Al₂O₃ and SiO₂ substrates and studied by X-ray photoelectron spectroscopy (XPS). Spectra confirmed that after vacuum annealing residual oxygen and carbon have been removed and bimetallic bonds have been created. The shift of Pd 3d_5/2 core level to higher binding energy followed by the peak narrowing in dependence on the composition was observed, accompanied by the shift of the Pd 4d in the valence band region, induced by hybridization of Pd-d and Sn-s,p states. Experiments carried out on a gas-flow reactor indicate increasing temperature of the CO oxidation with tin ratio in the alloy.     

Effect of oxygen content and deposition temperature on the characteristics of thin silver films deposited by magnetron sputtering

Thin silver films were prepared by direct current magnetron sputtering in a single-ended in-line sputter system at various substrate temperatures and in O₂ contents in sputter gas, and their electrical, optical, structural and morphological properties together with the compositional properties were investigated. When deposited at room temperature, the electrical and optical properties of Ag films deteriorated with addition of O₂ to sputter gas. Deposition of Ag films in O₂ added sputter gas promoted the formation of Ag crystallites with (2 0 0) plane parallel to the substrate surface. The electrical resistivity and optical reflection of Ag films deposited above 100 °C were not affected by the sputtering plasma containing oxygen. X-ray photoelectron spectroscopic analysis showed that Ag films deposited above 100 °C in O₂ added sputter gas did not possess surplus oxygen in the film, and that the oxidation states of these films were almost identical to that of Ag films deposited in pure Ar gas.