High-temperature oxidation behaviors of CVD diamond films

In this study, high-temperature oxidation of single-crystal diamond and diamond films prepared by hot filament chemical vapor deposition (HF-CVD), were characterized using thermal analysis and high-temperature in-situ Raman analysis. The measurements were performed in various temperatures up to 1300 °C in air and N₂ atmospheres. The results indicate that the initial oxidization temperature of diamond film deposited at 700 °C (D700 film) is ≈629 °C, lower than those of diamond film deposited at 900 °C (D900 film, ≈650 °C) and single-crystalline diamond (≈674 °C) in air. Oxidation rate of D700 film at high temperatures appeared to be the highest among the samples studied. A likely cause lies in the fact that, compared to their D900 sample, D700 diamond film contains a larger amount of non-diamond carbon and grain boundaries. However, D900 and D700 diamond films as well as single-crystalline diamond showed no detectable weight loss and oxidization when they were heated up to 1300 °C in N₂ atmosphere.     

Optical and electrical properties of different oriented CVD diamond films

Due to different oriented diamond films having different properties, in this paper optical and electrical properties of different oriented diamond films have been investigated. The measured results indicate diamond films are of high quality and the properties of the (0 0 1)-oriented diamond film are better than those of the (1 1 1)-oriented one. Refractive index and extinction coefficient of (0 0 1)-oriented diamond film in the wavelength range of 2.5-12.5 μm is 2.391 and in the order of 10⁻⁵, respectively. And for the (1 1 1)-oriented one it is 2.375 and in the order of 10⁻⁴. The dark current of the (0 0 1)-oriented diamond film is 33.7 nA under an applied electric field of 100 kV/cm. The resistivity of the (0 0 1)-oriented diamond film obtained is about 2.33 × 10¹⁰ Ω cm. The current of (0 0 1)-oriented diamond film is almost no change with the time testing.     

Substitutional phosphorus incorporation in nanocrystalline CVD diamond thin films

Nanocrystalline diamond (NCD) thin films were produced by chemical vapor deposition (CVD) and doped by the addition of phosphine to the gas mixture. The characterization of the films focused on probing the incorporation and distribution of the phosphorus (P) dopants. Electron microscopy evaluated the overall film morphology and revealed the interior structure of the nanosized grains. The homogeneous films with distinct diamond grains featured a notably low sp²:sp³‐ratio as confirmed by Raman spectroscopy. High resolution spectroscopy methods demonstrated a homogeneous P‐incorporation, both in‐depth and in‐plane. The P concentration in the films was determined to be in the order of 10¹⁹ cm^–3 with a significant fraction integrated at substitutional donor sites. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

金刚石膜α粒子探测器的电学性能研究

从外加偏压、预辐照处理等方面对三明治结构金刚石膜探测器在α粒子辐照下的电学性能进行了研究.电流-电压特性和脉冲高度分布测试和分析表明，金刚石膜探测器在能量为5.5MeV的²⁴¹Am α粒子辐照一定时间后，其暗电流有所增加.探测器顶电极施加负偏压时，在α粒子辐照下得到的净电流和信噪比均较大.Raman光谱测试表明，造成上述现象的原因很可能是金刚石膜厚度方向的不均匀性分布.负偏压下探测器对α粒子的能量分辨率为25.0%，优于正偏压下的能量分辨率(38.4%).随着α粒子辐照时间的延长，探测器的净电流和电荷收集效率均有明显增加. 关键词： 金刚石薄膜 辐射探测器 电学性能 脉冲高度分布     

CVD diamond films for electronics

Mechanical, optical, thermal and electronic properties of diamond films and chemical vapour deposition (CVD) techniques are briefly reviewed. Some spectroscopical methods for the characterization of CVD diamond films are described (optical absorption, photothermal deflection spectroscopy, Raman spectroscopy and electron paramagnetic resonance), together with our recent results on investigation of electronic properties of the main defects in this material, relevant to the application of CVD diamond films for the future electronic devices. Presented at the 6th Joint Seminar “Development of Materials Science in Research and Education”, Karlštejn, Czech Republic, 17–19 September 1996. This work was supported by Grant Agency of the Czech Republic, Grant No. 202/06/0446 and by the NATO Scientific Exchange Programme, HTECH.LG 940890 and NFWO (National Fonds voor Wetenschappelijk Orderzoek, Brussel) Project G.0014.96.     

Characterization of soft-X-ray detectors fabricated with high-quality CVD diamond thin films

We have characterized the performance of soft-X-ray detectors fabricated with undoped and B-doped homoepitaxial diamond layers of high quality which were grown on a commercially available type Ib (1 0 0) substrate by means of a high-power microwave-plasma chemical-vapor-deposition (CVD) method. The signal currents of the diamond-based detectors with thin TiN electrodes formed vertically (along the homoepitaxial growth direction) were measured at room temperature as a function of the applied voltage, V_a, for irradiations of 500-1200 eV soft-X-ray beams ranging from ≈6 × 10⁹ to ≈1 × 10¹¹ photons/s. The deduced apparent quantum efficiencies increased with the increasing V_a and reached to 2.5 × 10³ at V_a = 60 V. As expected from the device structure, the detector performance depended only very slightly on the applied magnetic field up to 10 T. The excellently high sensitivities attained for soft-X-ray photons are discussed in relation to carrier amplification mechanisms which invested the above diamond detectors.     

Antireflection structures written by excimer laser on CVD diamond

Two-dimensional antireflective periodical microstructures for the IR range are fabricated on the surface of CVD diamond films. These structures are created using an ArF excimer laser (λ=193 nm) and a direct writing scheme consisting of a beam collimator and a microscope objective to focus the beam onto the sample. Two different arrays are investigated. One has a spacing of 3 μm and is produced with single shots and the other one has a spacing of 4 μm and is produced with three shots per spot. The hole depth and shape are measured with an atomic force microscope (AFM). The optical transmittance and the scattering properties of the structure at 10.6 μm are reported for a CO₂ laser beam. With a spectrometer further transmission measurements in the range of 5 to 20 μm are performed. Received: 16 September 1999 / Accepted: 11 October 1999 / Published online: 24 March 2000     

Structural,morphological, composition and optical properties of undoped zinc oxide thin films prepared by spray pyrolysis method: effect of solution concentrations

Abstract

The aim of this paper is the study of transparent undoped zinc oxide thin films obtained by spray pyrolysis technique on glass substrates heated at 350?°C from 0.1 to 0.4?mol solution concentrations using zinc acetate dehydrate as precursor. The X-ray diffraction patterns and Raman spectrometry with respect to Urbach energy and wurtzite structure, show that the maximum value of the high frequency intensity E₂ and the optimal value of the optical gap are obtained at 0.2?mol concentration. Furthermore, an appropriate transparency is obtained and that makes these films suitable for photovoltaic windows layer cells.     

Influence of deposition pressure on structural, optical and electrical properties of nc-Si:H films deposited by HW-CVD

Hydrogenated nanocrystalline silicon (nc-Si:H) thin films were deposited using HW-CVD technique at various deposition pressures. Characterisation of these films from Raman spectroscopy revealed that nc-Si:H thin films consist of a mixture of two phases, crystalline phase and amorphous phase containing small Si crystals embedded therein. We observed increase in crystallinity in the films with increase in deposition pressure whereas the size of Si nanocrystals was found ∼2 nm over the entire range of deposition pressure studied. The FTIR spectroscopic analysis showed that with increasing deposition pressure the predominant hydrogen bonding in the films shifts from, Si-H to Si-H₂ and (Si-H₂)_n complexes and the hydrogen content in the films was found in the range 6.2-9.3 at% over the entire range of deposition pressure studied. The photo and dark conductivities results also indicate that the films deposited with increasing deposition pressure get structurally modified. It has been found that the optical energy gap range was between 1.72 and 2.1 eV with static refractive index between 2.85 and 3.24. From the present study it has been concluded that the deposition pressure is a key process parameter to induce the crystallinity in the Si:H thin films using HW-CVD.     

Size effect in optical spectra of microcrystalline diamond powders and CVD films

Received: 24 March 1997/Accepted: 27 May 1997     

N离子注入对金刚石膜场发射特性的影响

不同剂量的N离子被注入到化学气相沉积金刚石膜内，研究了表面结构及场发射特性的变化.Raman谱和x射线光电子能谱分析表明，N离子的注入破坏了金刚石膜表面原有的sp3结构，并在膜内形成大量的sp2 C—C 和sp2 C—N 键.样品的场发射测试显示N离子的注入显著提高了金刚石膜场发射特性，膜的场发射阈值电场从注入前的18 V/μm下降到注入后的4 V/μm.金刚石膜场发射特性的提高归因于N离子注入后膜内sp2 C键含量的增加和体内缺陷带的形成，这些变化能改变膜的表面功函数，提高Feimi能级，降低电子隧穿表面的能量势垒. 关键词： 场致电子发射 N离子注入 金刚石膜 热丝化学气相沉积     

Optical properties of hydroxyapatite obtained by mechanical alloying

Calcium phosphate based bioceramics, mainly in the form of hydroxyapatite (HA), have been in use in medicine and dentistry for the last 20 years. Applications include coatings of orthopaedic and dental implants, alveolar ridge augmentation, maxillofacial surgery, otolaryngology, and scaffolds for bone growth and as powders in total hip and knee surgery. These materials exhibit several problems of handling and fabrication, which can be overcome by mixing with a suitable binder. In this paper, mechanical alloying has been used successfully to produce nanocrystalline powders of HA using five different experimental procedures. The milled HA were studied by X-ray powder diffraction, infrared and Raman scattering spectroscopy. For four different procedures, HA was obtained after a couple of hours of milling (on an average, 20 h of milling depending on the reaction procedure). The XRD patterns indicate that the grain size is within the range of 29-103 nm. This milling process, used to produce HA, presents the advantage that melting is not necessary and the powder obtained is nanocrystalline with extraordinary mechanical properties. The material can be compacted and transformed in solid ceramic samples. The high efficiency of the process opens a way to produce commercial amount of nanocrystalline HA. Due to the nanocrystalline character of this powder, their mechanical properties have changed and for this reason a pressure of 1 GPa is enough to shape the sample into any geometry.     

Control of composition and crystallinity in hydroxyapatite films deposited by electron cyclotron resonance plasma sputtering

Hydroxyapatite (HAp) films were deposited by electron cyclotron resonance plasma sputtering under a simultaneous flow of H₂O vapor gas. Crystallization during sputter-deposition at elevated temperatures and solid-phase crystallization of amorphous films were compared in terms of film properties. When HAp films were deposited with Ar sputtering gas at temperatures above 460 °C, CaO byproducts precipitated with HAp crystallites. Using Xe instead of Ar resolved the compositional problem, yielding a single HAp phase. Preferentially c-axis-oriented HAp films were obtained at substrate temperatures between 460 and 500 °C and H₂O pressures higher than 1×10⁻² Pa. The absorption signal of the asymmetric stretching mode of the PO₄³⁻ unit (ν₃) in the Fourier-transform infrared absorption (FT-IR) spectra was the narrowest for films as-crystallized during deposition with Xe, but widest for solid-phase crystallized films. While the symmetric stretching mode of PO₄³⁻ (ν₁) is theoretically IR-inactive, this signal emerged in the FT-IR spectra of solid-phase crystallized films, but was absent for as-crystallized films, indicating superior crystallinity for the latter. The Raman scattering signal corresponding to ν₁ PO₄³⁻ sensitively reflected this crystallinity. The surface hardness of as-crystallized films evaluated by a pencil hardness test was higher than that of solid-phase crystallized films.     

Local structure of hydroxy-peroxy apatite: A combined XRD, FT-IR, Raman, SEM, and solid-state NMR study

The synthesized hydroxyapatite (HAp) and hydroxy-peroxy apatite are studied using various techniques, such as X-ray powder diffraction, FT-IR and Raman spectroscopy, scanning electron microscopy, and solid-state NMR spectroscopy. The experimental data suggest that hydroxy-peroxy apatite contains a small amount of hydration of partially dehydroxylated hydroxyapatite phase and calcium hydroxide. The incorporation of peroxide ions into the lattice of HAp causes perturbations of the hydrogen environments and slight changes in its crystal morphology. The distance between H in some structural OH⁻ and adjacent O along the c-axis becomes longer instead of forming a hydrogen bond after the incorporation of peroxide ions.     

Controlling growth and Raman spectra of individual suspended single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) were prepared with ethanol chemical vapor deposition (CVD) on SiO₂ flat and pillar-patterned Si substrates. The effect of CVD temperatures from 600 to 800 °C on SWNTs yields was investigated. By virtue of its unperturbed environment, an individual suspended SWNT grown between two different SiO₂ pillars provides a possibility to study the phonon band structure of SWNT itself at a single-nanotube level. Raman spectra of individual SWNTs grown between pillars were investigated systematically.     

Micro-Raman and photoluminescence spectra of Sm-doped β-BaB2O4 crystal lines written by YAG laser irradiation in glass

Nonlinear optical β-BaB₂O₄ (β-BBO) crystal straight lines are written in 10Sm₂O₃·40BaO·50B₂O₃ glass by irradiation of a continuous wave Nd:YAG laser operating at 1064 nm. The linearly polarized micro-Raman scattering spectra for β-BBO crystal lines are consistent with those for commercially available y-cut β-BBO bulk single-crystals, supporting that β-BBO crystal straight lines with the c-axis orientation along the YAG laser scanning direction might be single-crystals. The photoluminescence spectra with large intensities and Stark splitting are observed for β-BBO crystal lines, and it is concluded that some amounts of Sm³⁺ ions in the glass are incorporated into β-BBO crystal lines. Two-dimensional β-BBO crystal curved lines with a bending angle of 30° are successfully written in 10Sm₂O₃·42BaO·48B₂O₃ glass.     

Raman spectroscopic analysis of sulphur-doped TiO2 by co-grinding with TiS2

Doping sulphur into titania has been tried using TiS₂ as a doper based on the mechanically induced solid-state reaction between TiO₂ and TiS₂. The prepared samples have been characterized by X-ray diffraction (XRD), Raman spectroscopy and UV-Vis reflectance spectroscopy. Raman analysis, particularly has been proved to be effective in assessing the sulphur doping by correlating the oxygen deficiency of the doped oxide with the change of active Eg mode of rutile phase.     

Raman and FTIR studies of the structural aspects of Nasicon-type crystals; AFeTi(PO4)3 [A=Ca, Cd]

Raman and FTIR spectra of CaFeTi(PO₄)₃ and CdFeTi(PO₄)₃ are recorded and analyzed. The observed bands are assigned in terms of vibrations of TiO₆ octahedra and PO₄ tetrahedra. The symmetry of TiO₆ octrahedra and PO₄ tetrahedra is lowered from their free ion symmetry. The presence of Fe³⁺ ion disrupts the Ti-O-P-O-Ti chain and leads to the distortion of TiO₆ octrahedra and PO₄ tetrahedra. The PO₄³⁻ tetrahedra in both crystals are linearly distorted. The covalency bonding factor of PO₄³⁻ polyanion of both the crystals are calculated from the Raman spectra and compared to that of other Nasicon-type systems. The numerical values of covalency bonding factor indicates that there is a reduction in redox energy and cell voltage and is attributed to strong covalency of PO₄³⁻ polyanionin.     

Evolution of structural and optical properties of rutile TiO2 thin films synthesized at room temperature by chemical bath deposition method

Nanocrystalline thin films of TiO₂ were prepared on glass substrates from an aqueous solution of TiCl₃ and NH₄OH at room temperature using the simple and cost-effective chemical bath deposition (CBD) method. The influence of deposition time on structural, morphological and optical properties was systematically investigated. TiO₂ transition from a mixed anatase–rutile phase to a pure rutile phase was revealed by low-angle XRD and Raman spectroscopy. Rutile phase formation was confirmed by FTIR spectroscopy. Scanning electron micrographs revealed that the multigrain structure of as-deposited TiO₂ thin films was completely converted into semi-spherical nanoparticles. Optical studies showed that rutile thin films had a high absorption coefficient and a direct bandgap. The optical bandgap decreased slightly (3.29–3.07 eV) with increasing deposition time. The ease of deposition of rutile thin films at low temperature is useful for the fabrication of extremely thin absorber (ETA) solar cells, dye-sensitized solar cells, and gas sensors.     

Effect of annealing on structural and electrical properties of the Li–Mn–O thin films, prepared by high frequency RF magnetron sputtering

Li–Mn–O thin film cathode materials are prepared by high frequency (27.12 MHz) RF magnetron sputtering. The high RF frequency gives higher deposition rates without compromising on the quality of the films. This investigation focuses on the effects of post-annealing on the micro-structural, morphological and electrical properties of Li–Mn–O films. It is observed that with the increase of annealing temperature the crystallinity as well as the electrical conductivity of the films increases. The films annealed at 600–700 °C are found to have high structural perfection and good electrical properties.