Effect of ECR-assisted microwave plasma nitriding treatment on the microstructure characteristics of FCVA deposited ultra-thin ta-C films for high-density magnetic storage applications

There are higher technical requirements for protecting layer of magnetic heads and disks used in future high-density storage fields. In this paper, ultra-thin (2 nm thickness) tetrahedral amorphous carbon (ta-C) films were firstly prepared by filtered cathodic vacuum arc (FCVA) method, then a series of nitriding treatments were performed with nitrogen plasma generated using electron cyclotron resonance (ECR) microwave source. Here it highlighted the influence of nitrogen flow and applied substrate bias voltage on the structural characteristics of ta-C films during the plasma nitriding process. The chemical compositions, element depth distribution profiles, physical structures and bonding configurations of plasma-nitrided ta-C films were investigated by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and UV-vis Raman spectroscopy. The experimental results show that the carbon nitride compounds (CN_x) are formed in nitrogenated ta-C films in which the N content and its depth distribution depends on bias voltage to large extent rather than N₂ flow. The N content of nitrogenated ta-C films can reach 16 at.% for a substrate bias of −300 V and a N₂ flow of 90 sccm. With increasing nitrogen content, there is less G peak dispersion and more ordering of structure. Furthermore, appropriate nitriding treatment (substrate bias: −100 V, N₂ flow: 150 sccm) can greatly increase the fraction of sp³ and sp³C-N bonds, but the values begin to fall when the N content is above 9.8 at.%. All these indicate that suitable ECR-assisted microwave plasma nitriding is a potential modification method to obtain ultra-thin ta-C films with higher sp³ and sp³C-N fractions for high-density magnetic storage applications.     

The effect of applied negative bias voltage on the structure of Ti-doped a-C:H films deposited by FCVA

Ti-doped hydrogenated diamond-like carbon (DLC) films were deposited on Si(1 0 0) substrates by a filtered cathodic vacuum arc (FCVA) method using Ar and CH₄ as the feedstock. The composition and microstructure of the films were investigated by Raman spectroscopy, X-ray photoelectron spectroscopy and IR spectroscopy. The internal stress was determined by the radius of curvature technique. The influence of the bias voltage on the microstructure of the as-deposited films was investigated. It was found that the graphite-like bonds was dominated in the Ti-doped DLC film deposited at 0 V bias voltage. When bias voltage was increased to −150 V, more diamond-like bond were produced and the sp³ content in film reached the maximum value, after which it decreased and more graphite-like bonds feature produced with further increase of the negative bias voltage. The compressive internal in the Ti-doped DLC films also exhibited a maximum value at −150 V bias voltage. IR results indicated that CH bonded intensity reduced, and H atoms bonded with C atoms were substituted for the Ti atoms as the negative bias voltage increasing. All the composition and microstructure change can be explained by considering the plasma conditions and the effect of negative bias voltage applied to the substrate.     

X-ray photoelectron spectroscopic study of nitrogen incorporated amorphous carbon films embedded with nanoparticles

The effect of substrate bias on X-ray photoelectron spectroscopy (XPS) study of nitrogen incorporated amorphous carbon (a-C:N) films embedded with nanoparticles deposited by filtered cathodic jet carbon arc technique is discussed. High resolution transmission electron microscope exhibited initially the amorphous structure but on closer examination the film was constituted of amorphous phase with the nanoparticle embedded in the amorphous matrix. X-ray diffraction study reveals dominantly an amorphous nature of the film. A straight forward method of deconvolution of XPS spectra has been used to evaluate the sp³ and sp² contents present in these a-C:N films. The carbon (C 1s) peaks have been deconvoluted into four different peaks and nitrogen (N 1s) peaks have been deconvoluted into three different peaks which attribute to different bonding state between C, N and O. The full width at half maxima (FWHM) of C 1s peak, sp³ content and sp³/sp² ratio of a-C:N films increase up to −150 V substrate bias and beyond −150 V substrate bias these parameters are found to decrease. Thus, the parameters evaluated are found to be dependent on the substrate bias which peaks at −150 V substrate bias.     

Properties of K0.5Bi0.5TiO3 thin films deposited on different substrates

K_0.5Bi_0.5TiO₃ thin films were deposited on fused quartz, n-type Si(100) and Pt/TiO₂/SiO₂/Si substrates by repeated coating/dying cycles. X-ray diffraction analysis shows that the films annealed at 700 °C for 10 min present perovskite phase. Atomic force microscopy reveals that the surface morphology is smooth, the grain sizes of the films on Si(100) are quite larger than on fused quartz. The capacitance-voltage hysteresis loops at various sweeping speed are collected as are polarization types. The films in the ON and OFF states are relatively stable. The films also exhibit a hysteresis loop at an applied voltage of 4 V, with a remanent polarization of 9.3 μC/cm² and a coercive voltage of 2 V. The insulating property of negative bias voltage is better than that of positive bias voltage. The transmittance of the films is between 74 and 82% in the wavelength range of 200-2000 nm.     

Femtosecond Z-scan measurement of third-order optical nonlinearities in anatase TiO2 thin films

Anatase phase TiO₂ films have been grown on fused silica substrate by pulsed laser deposition technique at substrate temperature of 750 °C under the oxygen pressure of 5 Pa. From the transmission spectra, the optical band gap and linear refractive index of the TiO₂ films were determined. The third-order optical nonlinearities of the films were measured by Z-scan method using a femtosecond laser (50 fs) at the wavelength of 800 nm. The real and imaginary parts of third-order nonlinear susceptibility χ⁽³⁾ were determined to be −7.1 × 10⁻¹¹esu and −4.42 × 10⁻¹²esu, respectively. The figure of merit, T, defined by T=βλ/n₂, was calculated to be 0.8, which meets the requirement of all-optical switching devices. The results show that the anatase TiO₂ films have great potential applications for nonlinear optical devices.     

Structure and properties of DLC–MoS2 thin films synthesized by BTIBD method

Diamond-like carbon (DLC)–MoS₂ composite thin films were synthesized using a biased target ion beam deposition (BTIBD) technique in which MoS₂ was produced by sputtering a MoS₂ target using Ar ion beams while DLC was deposited by ion beam deposition with CH₄ gas as carbon source. The structure and properties of the synthesized films were characterized by X-ray diffraction, X-ray absorption near edge structure (XANES), Raman spectroscopy, nanoindentation, ball-on-disk testing, and corrosion testing. The effect of MoS₂ target bias voltage, ranging from −200 to −800 V, on the structure and properties of the DLC–MoS₂ films was further investigated. The results showed that the hardness decreases from 9.1 GPa to 7 GPa, the Young?s modulus decreases from 100 GPa to 78 GPa, the coefficient of friction (COF) increases from 0.02 to 0.17, and the specific wear rate coefficient (k) increases from 5×10⁻⁷ to 5×10⁻⁶ mm³ N⁻¹ m⁻¹, with increasing the biasing voltage from 200 V to 800 V. Also, the corrosion resistance of the DLC–MoS₂ films decreased with the raise of biasing voltage. Comparing with the pure DLC and pure MoS₂ films, the DLC–MoS₂ films deposited at low biasing voltages showed better tribological properties including lower COF and k in ambient air environment.     

C-V studies on metal-ferroelectric bismuth vanadate (Bi2VO5.5)-semiconductor structure

Ferroelectric bismuth vanadate Bi₂VO_5.5 (BVO) thin films have been successfully grown on p-type Si(100) substrate by using chemical solution decomposition (CSD) technique followed by rapid thermal annealing (RTA). The crystalline nature of the films has been studied by X-ray diffraction (XRD). Atomic force microscopy (AFM) was used to study the microstructure of the films. The dielectric properties of the films were studied. The capacitance-voltage characteristics have been studied in metal-ferroelectric-insulator-semiconductor (MFIS) configuration. The dielectric constant of BVO thin films formed on Si(100) is about 146 measured at a frequency of 100 kHz at room temperature. The capacitance-voltage plot of a Bi₂VO_5.5 MFIS capacitor subjected to a dc polarizing voltages shows a memory window of 1.42 V during a sweep of ±5 V gate bias. The flatband voltage (V_f) shifts towards the positive direction rather than negative direction. This leads to the asymmetric behavior of the C-V curve and decrease in memory window. The oxide trap density at a ramp rate of 0.2 V/s was estimated to be as high as 1.45×10¹² cm⁻².     

The effect of potential of impedance in the pulsed-laser-deposited SrBi2Ta2O9 thin film

Ferroelectrics SrBi₂Ta₂O₉ (SBTO) thin films were grown on a highly oriented Pt/Ti/SiO₂/Si substrates using the pulsed laser ablation. The ac impedance of SBTO thin films have been measured at room temperature both in the frequency range from 10⁻¹ to 10⁶ Hz and bias voltage range from −6 to 6 V. The ac impedance dispersion was observed at low frequency with increasing bias voltage, which was interpreted based on a blocked charge. We can explain that the blocking interface gives rise to constant phase element (CPE) response, and we give an impedance model function that can fit data along the low frequency range when such a CPE is found. The low frequency dispersion phenomena of SBTO thin film are related to a charge diffusion process at the surface of thin film.     

The effects of dc bias voltage on the crystal size and crystal quality. of cBN films

For the deposition of cubic boron nitride thin films in Ar–N₂–BF₃–H₂ system by dc jet plasma chemical vapor deposition, the role of dc substrate bias ranging from -70 V to -150 V was investigated. A critical bias voltage was observed for the formation of cBN phase. The cBN content in the film increased with bias voltage and reached a maximum at the bias voltage of -85 V. Increasing the bias voltage further caused a decrease in cBN content and peeling of the films from the substrate. By combining the results of infrared spectroscopy, Raman spectroscopy and X-ray diffraction, the bias voltage was also found to strongly affect the crystal size, crystal quality and residual stress of the deposited films. A bias voltage a little higher than the critical value was demonstrated to be favorable for the deposition of a high-quality cBN film with large crystal size and low residual stress. Received: 13 June 2000 / Accepted: 21 June 2000 / Published online: 23 August 2000     

The enhanced conductivity and stability of AZO thin films with a TiO2 buffer layer

Aluminum doped zinc oxide (AZO) films were substitutes of the SnO₂:F films on soda lime glass substrate in the amorphous thin-film solar cells due to good properties and low cost. In order to improve properties of AZO films, the TiO₂ buffer layer had been introduced. AZO films with and without TiO₂ buffer layer were deposited on soda lime glass substrates by r.f. magnetron sputtering. Subsequently, one group samples were annealed in vacuum (0.1 Pa) at 500 °C for 120 s using the RTA system, and the influence of TiO₂ thickness on the properties of AZO films had been discussed. The XRD measurement results showed that all the films had a preferentially oriented (0 0 2) peak, and the intensity of (0 0 2) peak had been enhanced for the AZO films with TiO₂ buffer layer. The resistivity of TiO₂ (3.0 nm)/AZO double-layer film is 4.76×10⁻⁴ Ω cm with the maximum figure merit of 1.92×10⁻² Ω⁻¹, and the resistivity has a remarkable 28.7% decrease comparing with that of the single AZO film. The carrier scattering mechanism of TiO₂ (3.0 nm)/AZO double-layer film had been described by Hall measurement in different temperatures. The average transmittance of all the films exceeded 92% in the visible spectrum. Another group samples were heat treated in the quartz tube in air atmosphere, and the effect of TiO₂ thickness on thermal stability of AZO films had been discussed.     

Influence of the active layer thickness on the electrical properties of ZnO thin film transistors fabricated by radio frequency magnetron sputtering

We report on the electrical properties of bottom-gate ZnO thin film transistors (TFTs) with different active layer thicknesses. The ZnO active layer films with thickness varied from 20 to 100 nm were deposited by radio frequency (rf) magnetron sputtering on SiO₂/p-Si substrate and annealed at a high temperature of 950 °C. The transistor with 40 nm thick ZnO exhibited the best performance, with a field effect mobility of 27.5 cm²/V s, a threshold voltage of −2.4 V and an on/off ratio of 7×10³.     

Magneto-optical spectroscopy of diluted magnetic oxides TiO2−δ: Co

We report an experimental study on transversal Kerr effect (TKE) in magnetic oxide semiconductors TiO_2−δ:Co. The TiO_2−δ: Co thin films were deposited on LaAlO₃ (0 0 1) substrates by magnetron sputtering in the argon-oxygen atmosphere at oxygen partial pressure of 2×10⁻⁶-2×10⁻⁴ Torr. It was obtained that TKE spectra in ferromagnetic samples are extremely sensitive to the Co-volume fraction, the crystalline structure, and technology parameters. The observed well-pronounced peaks in TKE spectra for anatase Co-doped TiO_2−δ films at low Co (<1%) volume fraction are not representative for bulk Co or Co clusters in TiO_2−δ matrix that indicates on intrinsic ferromagnetism in these samples. With increase of Co-volume fraction up to 5-8% the fine structure of TKE spectra disappears and magneto-optical response in reflection mode becomes larger than that for thick Co films     

Native oxidation of ultra high purity Cu bulk and thin films

The effect of microstructure and purity on the native oxidation of Cu was studied by using angle-resolved X-ray photoelectron spectroscopy (AR-XPS) and spectroscopic ellipsometry (SE). A high quality copper film prepared by ion beam deposition under a substrate bias voltage of −50 V (IBD Cu film at V_s = −50 V) showed an oxidation resistance as high as an ultra high purity copper (UHP Cu) bulk, whereas a Cu film deposited without substrate bias voltage (IBD Cu film at V_s = 0 V) showed lower oxidation resistance. The growth of Cu₂O layer on the UHP Cu bulk and both types of the films obeyed in principle a logarithmic rate law. However, the growth of oxide layer on the IBD Cu films at V_s = 0 and −50 V deviated upward from the logarithmic rate law after the exposure time of 320 and 800 h, respectively. The deviation from the logarithmic law is due to the formation of CuO on the Cu₂O layer after a critical time.     

Effects of substrate bias and nitrogen flow ratio on the surface morphology and binding state of reactively sputtered ZrNx films before and after annealing

ZrN_x films were sputtered in an Ar + N₂ atmosphere, with different substrate biases (0 to −200 V) at various nitrogen flow ratios (%N₂ = 0.5-24%). The surface morphology, resistivity, crystllinity, and bonding configuration of ZrN_x films, before and after vacuum annealing, were investigated. As compared with ZrN_x films grown without substrate bias, before and after annealing, the resistivity of 1% and 2% N₂ films decreases with increasing substrate biases. Simultaneously, if the applied bias is too high, the crystallinity of ZrN_x film will decrease. The surfaces of 1% and 2% N₂ flow films deposited without bias have small nodules, whereas the surface morphology of films deposited at −100 V of substrate bias exhibits large nodules and rugged surface. Once a −200 V of substrate bias is applied to the substrate, the surface morphology of ZrN_x films, grown at 1% and 2% nitrogen flow ratios, is smooth. Furthermore, there are two deconvoluted peaks in XPS spectra (i.e., Zr-O and Zr-N) of ZrN_x films deposited at −200 V of substrate bias before and after annealing. On the other hand, the surface morphology changes dramatically from rugged surfaces for film deposited at lower nitrogen flow ratio (%N₂ < 1%) to smoother and denser surfaces for film grown at higher nitrogen flow ratio (%N₂ ≥ 1%). The Zr-N bonding in 2% N₂ films still exist after annealing at 700 °C, while the Zr-N bonding in 0.5% and 16% N₂ flow film vanish at the same temperature. The connection between the resistivity, crystallinity, surface morphology, and bonding configuration of ZrN_x films and how they are influenced by the substrate bias and nitrogen flow ratio are discussed in this paper.     

The influence of titanium on the properties of zinc oxide films deposited by radio frequency magnetron sputtering

TiO₂-doped zinc oxide thin films were deposited on glass substrates by radio frequency (RF) magnetron sputtering with TiO₂-doped ZnO targets in an argon atmosphere. The structural properties of TiO₂-doped ZnO films doped with different TiO₂ contents were investigated. The experimental results show that polycrystalline TiO₂-doped ZnO films had the (0 0 2) preferred orientation. The deposition parameters such as the working pressure and substrate temperature of TiO₂-doped ZnO films were also investigated. The crystalline structure of the TiO₂-doped ZnO films gradually improved as the working pressure was lowered and the substrate temperature was raised. The lowest electrical resistivity for the TiO₂-doped ZnO films was obtained when the Ti addition was 1.34 wt%; its value was 2.50 × 10⁻³ Ω cm, smaller than that found in previous studies. The transmittance of the TiO₂-doped ZnO films in the visible wavelength range was more than 80%. The optical energy gap was related to the carrier concentration, and was in the range of 3.30-3.48 eV.     

Preparation of transparent conductive TiO2:Nb thin films by pulsed laser deposition

This study investigated the optical and electrical properties of Nb-doped TiO₂ thin films prepared by pulsed laser deposition (PLD). The PLD conditions were optimized to fabricate Nb-doped TiO₂ thin films with an improved electrical conductivity and crystalline structure. XRD analyses revealed that the deposition at room temperature in 0.92 Pa O₂ was suitable to produce anatase-type TiO₂. A Nb-doped TiO₂ thin film attained a resistivity as low as 6.7 × 10⁻⁴ Ω cm after annealing at 350 °C in vacuum (<10⁻⁵ Pa), thereby maintaining the transmittance as high as 60% in the UV-vis region.     

Control of electrical properties and gate bias stress stability in solution-processed a-IZO TFTs by Zr doping

Zr-doped indium zinc oxide (IZO) thin film transistors (TFTs) are fabricated via a solution process with different Zr doping ratios. The addition of Zr suppressed the carrier concentration in the IZO films, which was confirmed by Hall Effect measurements. As the amount of Zr was increased in the oxide active layer of TFTs, the subthreshold swing (S.S) reduced, the ON/OFF ratio improved, and the threshold voltage (V_th) shifted positively. Moreover, the starting points of the ON state for TFTs near the point zero gate voltage could be controlled by the addition of Zr. The 0.3% Zr-doped IZO TFT exhibited a high saturation mobility of 7.0 cm² V⁻¹ s⁻¹, ON/OFF ratio of 2.6 × 10⁶ and S.S of 0.57 V/decade compared the IZO TFT with 10.1 cm² V⁻¹ s⁻¹, 1.7 × 10⁶ and 0.75 V/decade. The Zr effect of the gate bias stability was examined. Zr-doped IZO TFTs were relatively unstable under a positive bias stress (PBS), whereas they showed good stability at a negative bias stress (NBS). The gate bias stability of the oxide TFTs were compared with the extracted parameters through a stretched-exponential equation. The characteristic trapping time under NBS of 0.3% Zr-doped IZO TFTs was improved from 8.3 × 10⁴ s for the IZO TFT to 3.1 × 10⁵ s.     

A magnetron sputtering technique to prepare a-C:H films: Effect of substrate bias

Amorphous hydrogenated carbon (a-C:H) films were deposited by magnetron sputtering with a mixture gas of Ar and CH₄. The a-C:H films deposited by this method have relatively low internal stress (<1 GPa) compared to some films deposited by conventional deposition process. The effects of substrate bias voltage on microstructure, surface morphology and mechanical properties of the films were investigated by various techniques. It has been found that the polymer-like structure is dominated at low bias voltage (−100 V), while the diamond-like structure with the highest hardness and internal stress is the main feature of the a-C:H films deposited under high bias voltage (−300 V). With increasing the bias voltage further, the feature of diamond-like structure decreases associating with the increase of graphitization. The frictional test shows that the friction coefficient and wear rate of the a-C:H films are depended strongly on structure and mechanical properties, which were ultimately influenced by the deposition method and bias voltage.     

Reversible local-modification of surface structure on clean Ge(0 0 1) by scanning tunneling microscopy below 80 K

The structure of the clean Ge(0 0 1) surface is locally and reversibly changed between c(4×2) and p(2×2) by controlling the bias voltage of a scanning tunneling microscopy (STM) below 80 K. It shows hysteresis for the direction of the sample bias voltage change. The c(4×2) structure is observed with the sample bias voltage V_b?−0.7 V. This structure is maintained at V_b?0.7 V with increasing the bias voltage from −0.7 V. When V_b is higher than 0.8 V, the structure changes to p(2×2). This structure is then maintained at V_b?−0.6 V with decreasing the bias voltage from +0.8 V. The area of the structure change can be confined in the single dimer row just under the STM tip using a bias voltage pulse. In particular, the minimum transformed length is four dimers along the dimer row in the transformation from p(2×2) to c(4×2). The observed local change of the reconstruction with hysteresis is attributed to the energy transfer process from the tunneling electron to the Ge lattice in the local electric field due to the STM bias voltage. A phenomenological model is proposed for the structure changes. It is based on a cascade inversion of the dimer buckling orientation along the dimer row.     

Characterization of Y2O3 gate dielectric on n-GaAs substrates

Physical and electrical properties of sputtered deposited Y₂O₃ films on NH₄OH treated n-GaAs substrate are investigated. The as-deposited films and interfacial layer formation have been analyzed by using X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS). It is found that directly deposited Y₂O₃ on n-GaAs exhibits excellent electrical properties with low frequency dispersion (<5%), hysteresis voltage (0.24 V), and interface trap density (3 × 10¹² eV⁻¹ cm⁻²). The results show that the deposition of Y₂O₃ on n-GaAs can be an effective way to improve the interface quality by the suppression on native oxides formation, especially arsenic oxide which causes Fermi level pinning at high-k/GaAs interface. The Al/Y₂O₃/n-GaAs stack with an equivalent oxide thickness (EOT) of 2.1 nm shows a leakage current density of 3.6 × 10⁻⁶ A cm⁻² at a V_FB of 1 V. While the low-field leakage current conduction mechanism has been found to be dominated by the Schottky emission, Poole-Frenkel emission takes over at high electric fields. The energy band alignment of Y₂O₃ films on n-GaAs substrate is extracted from detailed XPS measurements. The valence and conduction band offsets at Y₂O₃/n-GaAs interfaces are found to be 2.14 and 2.21 eV, respectively.