首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 0 毫秒
1.
This paper shows what structural properties of amorphous non-diamond phases in nanocrystalline diamond films are responsible for the transition from resistive to conductive films. The films incorporated with nitrogen, oxygen, and hydrogen are prepared by microwave plasma chemical vapor deposition using Ar-rich gas mixtures. The amount, composition, and bonding properties of non-diamond phases are studied mainly by Raman spectroscopy and compared with the electrical resistivity of the films. The addition of N2 gas decreases the resistivity down to the order of 10 2 Ω cm for deposition temperatures above a threshold of ∼ 1100 K. Non-diamond phases for high n-type conductivity are characterized by graphitic components with improved sp2 bond angle order for trivalent carbon atoms in addition to CN bonds. The addition of O2 or H2 gas promotes incorporation of oxygen or hydrogen into the films, not preferential etching of non-diamond phases. The resistivity increases or decreases largely by oxygen or hydrogen incorporation, respectively, then inversely changes by thermal annealing due to the deoxidization and dehydrogenation.  相似文献   

2.
We report on the effect of ambient conditions and UV irradiation on the subgap photoluminescence of nanocrystalline diamond prepared by microwave plasma enhanced chemical vapour deposition. We measured the photoluminescence of self-supporting membranes of thickness about 290 nm with the grain size up to 40 nm under variable ambient conditions – pressure, temperature, air, nitrogen and helium atmospheres. We have found that intensity of photoluminescence of samples kept under low pressure increases during the time. The photoluminescence intensity of samples under low pressure depends on sample temperature with maximum at about 260 K. The photoluminescence increase can be enhanced substantially by UV irradiation (325 nm) of the sample under certain conditions: temperature greater than ~ 280 K, low pressure of ambient atmosphere. We interpret the experimental results in terms of desorption of water molecules and their interaction with the of individual diamond nanocrystals in the membrane.  相似文献   

3.
Scanning Raman spectroscopic measurements were performed on nanocrystalline diamond thin films with 0.5 μm lateral steps and excitation spot limited to 1 μm in diameter using 488 nm and 785 nm excitation wavelengths. The comparison of the spectra measured with different excitation energies showed that in contrast to the well-known five bands in the 488 nm excited Raman spectra of nanocrystalline diamond a number of narrow peaks appears in the spectra when using near-infrared excitation. The intensity and position of the latter vary when moving the excitation spot along the sample. The detailed analysis of the sequences showed that the 785 nm excited Raman spectroscopy allows the detection and identification of the Raman peaks arising from individual diamond crystallites of the nanocrystalline diamond films.  相似文献   

4.
We use femtosecond photoluminescence spectroscopy to study the light-induced changes in the sub-gap energy states of nanocrystalline diamond samples (thickness ~ 500 and 1000 nm) prepared on a spectral-grade fused silica substrate by microwave plasma enhanced chemical vapour deposition technique. The decay of photoluminescence in the visible spectral interval excited by blue femtosecond light pulses (405 nm,70 fs) shows that photoexcited charge carrier dynamics depend strongly on the ambient air pressure and on the light irradiation by the laser pulses. Specifically, at lower ambient air pressure (0.5-300 Pa) the irradiation leads to the peak photoluminescence intensity increase and to its faster decay. At higher air pressures (> 600 Pa) the photoluminescence intensity slightly decreases with no change in decay rates. O- and H-termination of nanocrystalline diamond films had negligible effect on their photoluminescence dynamics. The photoluminescence decay curves are described very well by the power-law decay reflecting the importance of the carrier trapping in the dynamics. Based on our results we propose a model of surface and sub-surface structure of nanodiamond films.  相似文献   

5.
A. Tokura  F. Maeda  A. Yoshigoe  Y. Homma  Y. Kobayashi 《Carbon》2008,46(14):1903-1908
We have investigated the adsorption of atomic hydrogen on vertically aligned carbon nanotube (CNT) films using in situ synchrotron-radiation-based core-level (CL) photoelectron spectroscopy and Raman spectroscopy. From C 1s CL spectra, we identified a CL peak component due to C-H bonds of carbon atoms in single-walled carbon nanotubes (SWCNTs). We also found the suppression of π-plasmon excitation, indicating that the hydrogen adsorption deforms the bonding structure. Raman spectra of the SWCNT film indicated that the radial-breathing-mode intensities of SWCNTs decreased due to the adsorption-induced bonding-structure deformation. Moreover, the decrease for small-diameter SWCNTs was more severe than that for large-diameter SWCNTs. Our results strongly suggest that the hydrogen adsorption, which induces the structure deformation from sp2 to sp3-like bonding, depends on the diameter of SWCNTs.  相似文献   

6.
The nanocrystalline diamond (NCD) layers were grown by the large area (linear plasma) MWCVD on polished silicon substrates with and without intermediate mirror-like metallic coatings. The optical reflectance and Raman spectroscopy in the ultraviolet, visible and near infrared region (UV-VIS-NIR) reveals the thickness and the optical quality of NCD layers. The modified grazing angle reflectance (GAR) spectroscopy is applied in the mid infrared region 800-4000/cm to detect the molecular vibrations (functional groups) at the functionalized NCD surface. The optical absorbance of functionalized NCD surface is evaluated from p-polarized reflectance spectra measured at Brewster angle of incidence (BAR) to eliminate the interference fringes. We report a significant enhancement of sensitivity of BAR using NCD growth on metal mirrors.  相似文献   

7.
Nanocrystalline diamond (NCD) films were deposited on Si substrates by microwave plasma-enhanced chemical vapor deposition (MPECVD) using methane/hydrogen/oxygen (30/169/0.2 sccm) as process gases. Subsequently a thin (0.33 μm) and a thick (1.01 μm) NCD films were irradiated with XeF excimer laser (λ = 351 nm) with 300 and 600 mJ cm? 2 of energy densities in air. The NCD films became rougher after laser irradiations. Fraction of graphitic clusters decreased but oxygen content increased in the thin NCD film after laser irradiation. Opposite phenomena were observed for the thick NCD films. Effect of laser irradiation to oxygenation and graphitization of NCD films was correlated with structural properties of free surface and grain boundaries of the thin and thick NCD films.  相似文献   

8.
In this work we provide direct evidence of hydrogen, carbon and oxygen contamination of poly-crystalline diamond surfaces from ambient conditions and their thermal stability upon vacuum annealing. Deuterated diamond films were exposed to ambient conditions for ~ 3 months and then studied by high-resolution electron energy loss spectroscopy and X-ray photoelectron spectroscopy. Hydrocarbon contaminations posses at least two different binding states which desorb upon annealing to ~ 300 °C and ~ 600 °C. Oxygen contaminations gradually desorb upon annealing to 700–800 °C. It is shown that thermal desorption of contaminations creates sp2 carbon atoms on the diamond film surface.  相似文献   

9.
A self-contained research system based on the technique of confocal laser scanning microscopy (CLSM) was put up to quantitatively analyze the dynamics of protein adsorption to porous cation exchanger by mathematical modeling. Bovine serum albumin adsorption to the cation exchanger SP Sepharose FF was performed by batch adsorption and micro-flow cell in which protein concentration in single absorbent was visualized by CLSM. The effects of ionic strength and the protein concentration in liquid phase (50 mmol/L acetate buffer, pH 5.0) on the adsorption dynamics were examined. The intraparticle concentration profile data experimentally obtained from CLSM were quantitatively analyzed by three diffusive mass transfer models (i.e., pore diffusion, surface diffusion and Maxwell-Stefan models (MSM)) in virtue of the attenuation equation for the CLSM visualization developed earlier. The nuance between the model simulations and experimental results of the developing protein distribution in a single adsorbent particle could thus be found out. Without salt addition to the buffer, the adsorption isotherm was strongly favorable, and the pore diffusion model (PorDM) and MSM gave similarly good simulations of the experiments, whereas the surface diffusion model was unreasonable in the model presumption. Moreover, it was observed that the experimentally obtained adsorption front was relative flatter as compared with the calculated results from the PorDM, which implied the possible existence of surface diffusion. With increasing salt concentration, the simulations became to deviate from the experiments. Especially, when the salt concentration approached 50 mmol/L, all the three mass transfer models could hardly give good simulation of the experiment. This was considered due to the difference in adsorption behavior between the fluorescence labeled and unlabeled proteins therein.  相似文献   

10.
This paper reports a novel procedure to infiltrate nanocrystalline diamond films (NCD) on porous silicon (PS) substrate. The NCD/PS films resulted in a composite material, with great potential for electrochemical application, mainly due to its high active surface area. The Hot Filament Chemical Vapor Deposition reactor was changed to Hot Filament Chemical Vapor Infiltration reactor in order to grow NCD films infiltrated into deep holes of PS substrate. This procedure allowed the infiltration of the reacting gases into the porous structure where the nucleation takes place, followed by the coalescence and film formation at pore bottoms and walls. In this configuration an additional entrance of CH4 was located next to the PS substrate using two distinct positions called “underneath” and “above”, with the use of the additional flow accurately underneath or above of the samples. In general, the combination of these two configurations with additional carbon sources provided NCD film infiltration in PS substrate with success with only 60 min of growing time. Particularly, the films obtained from the positions called “above” presented the best morphology, with high quality and crystallinity, confirmed from its scanning electron microscopy, Raman scattering spectroscopy and high resolution X-ray diffraction spectra, respectively.  相似文献   

11.
Vacuum-sealed cavities featuring diamond membranes are fabricated using plasma-activated direct bonding technology. A chemical mechanical polished (CMP) silicon dioxide interlayer, deposited on diamond with a high temperature oxide (HTO) process at 850 °C in a low pressure chemical vapor deposition (LPCVD) furnace, is employed for successful direct bonding and vacuum cavity formation. The circular cavities are defined on the thermally grown oxide of the phosphorus-doped Si wafer (4-in, < 100>, 1.2 Ω/sq) using reactive ion etching (RIE). The same microfabrication steps are applied for low residual stress (i.e. < 50 MPa) nanocrystalline (NCD) and ultrananocrystalline (UNCD) diamonds to determine and compare membrane characteristics. For both diamond types, successful microfabrication of membranes is demonstrated using the optimized process flow. Profilometer measurements of membrane deflection are compared with finite element modeling (FEM), and indicate a Young's modulus of 1000 GPa for NCD and 850 GPa for UNCD. Furthermore, FEM analysis suggests the residual stress of UNCD membrane is approximately 100 MPa tensile, whereas NCD one does not show any significant residual stress (< 50 MPa). Our results show that NCD is a more promising choice than UNCD as a membrane material for electromechanical transducers.  相似文献   

12.
Recent spectroscopic results in the emerging area of transition-metal NIR-to-visible upconversion are related. The examples of Ti(2+)-, Re(4+)-, and Os(4+)-doped materials showing upconversion illustrate GSA/ESA, GSA/ETU, and photon avalanche multiphoton excitation mechanisms, respectively. Strategies for manipulation of such upconversion processes using the spectroscopic or magnetic properties of the host material are described. High-resolution low-temperature continuous-wave absorption and emission and time-resolved emission experiments combine to yield information about energy splittings, intensities, and excited-state dynamics, and assist in the design and development of luminescent materials showing novel multiphoton excitation properties.  相似文献   

13.
Green TD  Knappenberger KL 《Nanoscale》2012,4(14):4111-4118
The relaxation dynamics of electronically excited [Au(25)(SR)(18)](q), where q = 0 or -1 and SR = S(CH(2))(2)Ph, were studied using femtosecond time-resolved transient absorption spectroscopy. Nanoclusters excited by 400 nm light were probed using temporally delayed broad-bandwidth continuum probe pulses. Continuum pulses were generated in both the visible and near infrared (NIR) spectral regions, providing access to a wide range of transient spectral features. The use of NIR probe pulses allowed the relaxation dynamics of the excited states located near the HOMO-LUMO energy gap to be monitored in the probe step via the sp ← LUMO and sp ← LUMO+1 transitions. These NIR measurements yielded excited state absorption (ESA) data that were much less congested than the typical visible transient spectrum. For the neutral nanocluster, the time-domain data were composed of three components: (1) a few-picosecond decay, (2) a slower decay taking a few hundred picoseconds and (3) a non-decaying plateau function. Component 1 reflected energy relaxation to semi-ring ligand states; component 2 was attributed to relaxation via a manifold of states located near the HOMO-LUMO energy gap. Component 3 arose from slow radiative recombination. The dynamics of the anion depended upon the identity of the excited state from which the particle was relaxing. The LUMO+1 state of the anion exhibited relaxation dynamics that were similar to those observed for the neutral nanocluster. By comparison, the time-domain data observed for the LUMO state contained only two components: (1) a 3.3 ± 0.2 ps decay and (2) a 5 ± 1 ns decay. The amplitude coefficients of each component were also analyzed. Taken together, the amplitude coefficients and lifetimes were indicative of an activation barrier located approximately 100 meV above the HOMO-LUMO energy gap, which mediated a previously unobserved excited state decay process for [Au(25)(SR)(18)](0). These data suggested that NIR ESA measurements will be instrumental in describing the relaxation processes of quantum-confined nanoclusters.  相似文献   

14.
Plasma hydrogenation of polycrystalline diamond films results in a fully hydrogenated well-ordered diamond surface and etching of the amorphous phase located at grain boundaries. Vacuum annealing to 1000 °C followed by in-situ hydrogenation by thermal activated hydrogen of the bared diamond surface results in the formation of sp3-CHx adsorbed groups located on the top surface. Annealing of the in-situ hydrogenated surface to 600 °C results in desorption of these species and partial reconstruction of the film surface. Some irreversible surface degradation was detected in the in-situ annealed and hydrogenated surface compared to the state of the surface obtained upon plasma hydrogenation.  相似文献   

15.
Thin films of heavily B-doped nanocrystalline diamond (B:NCD) have been investigated by a combination of high resolution annular dark field scanning transmission electron microscopy and spatially resolved electron energy-loss spectroscopy performed on a state-of-the-art aberration corrected instrument to determine the B concentration, distribution and the local B environment. Concentrations of ~1 to 3 at.% of boron are found to be embedded within individual grains. Even though most NCD grains are surrounded by a thin amorphous shell, elemental mapping of the B and C signal shows no preferential embedding of B in these amorphous shells or in grain boundaries between the NCD grains, in contrast with earlier work on more macroscopic superconducting polycrystalline B-doped diamond films. Detailed inspection of the fine structure of the boron K-edge and comparison with density functional theory calculated fine structure energy-loss near-edge structure signatures confirms that the B atoms present in the diamond grains are substitutional atoms embedded tetrahedrally into the diamond lattice.  相似文献   

16.
The broad optical spectral range (0.2–6 eV) photoionization spectra of the nominally undoped, carefully oxidized and hydrogenated nanocrystalline diamond (NCD) thin films grown on silicon and sapphire substrates were measured using the dual-beam photoconductivity method (under constant UV light bias). The novel amplitude modulated step scan Fourier transform photocurrent spectroscopy (AMFTPS) was applied in IR region. The wet chemistry etching was used to open 6 × 6 mm window in Si substrate and to create NCD membrane in the silicon frame. In photoionization spectra we found localized defect states with the threshold around 1 eV in both hydrogenated and oxidized NCD films. The threshold of the photoionization cross section shifts towards lower photon energies in the hydrogenated samples. The photosensitivity increases by several orders of magnitude with hydrogenation. We suggest that the main deep defect is related to the nanocrystalline grain boundaries and it can be passivated by the hydrogen. In hydrogenated samples we detect at low temperature shallow defect states with photoionization threshold energies well below 1 eV, probably related to the hydrogenated surface.  相似文献   

17.
Detonation nanodiamond (ND) particles were dispersed on silicon nitride (SiNx) coated sc-Si substrates by spin-coating technique. Their surface density was in the 1010–1011 cm?2 range. Thermal stability and surface modifications of ND particles were studied by combined use of X-ray Photoelectron Spectroscopy (XPS) and Field Emission Gun Scanning Electron Microscopy (FEG SEM). Different oxygen-containing functional groups could be identified by XPS and their evolution versus UHV annealing temperature (400–1085 °C) could be monitored in situ. The increase of annealing temperature led to a decrease of oxygen bound to carbon. In particular, functional groups where carbon was bound to oxygen via one σ bond (C–OH, C–O–C) started decomposing first. At 970 °C carbon–oxygen components decreased further. However, the sp2/sp3 carbon ratio did not increase, thus confirming that the graphitization of ND requires higher temperatures. XPS analyses also revealed that no interaction of ND particles with the silicon nitride substrate occurred at temperatures up to about 1000 °C. However, at 1050 °C silicon nitride coated substrates started showing patch-like damaged areas attributable to interaction of silicon nitride with the underlying substrate. Nevertheless ND particles were preserved in undamaged areas, with surface densities exceeding 1010 cm?2. These nanoparticles acted as sp3-carbon seeds in a subsequent 15 min Chemical Vapour Deposition run that allowed growing a 60–80 nm diamond film. Our previous study on Si(100) showed that detonation ND particles reacted with silicon between 800 and 900 °C and, as a consequence, no diamond film could be grown after Chemical Vapour Deposition (CVD). These findings demonstrated that the use of a thin silicon nitride buffer layer is preferable insofar as the growth of thin diamond films on silicon devices via nanoseeding is concerned.  相似文献   

18.
Several examples are presented that illustrate how the internal and surface structure of oxide supported Pt nanoparticles can change under reaction conditions. High temperatures and the presence of adsorbates may lead to different effects: (1) changes in the particle size distribution (sintering or redispersion) that may affect the crystallographic and electronic structure of the nanoparticles, (2) restructuring of the particle surface facets, and (3) crystallization of large polycrystalline aggregates. Three different model systems are described that are well-suited for high resolution transmission electron microscopy (HRTEM) and/or surface science techniques. To examine the influence of high gas pressure on the structure of adsorbates, infrared-visible sum frequency generation (SFG) surface vibrational spectroscopy is applied to monitor CO adsorption on supported Pd nanoparticles from 10-7 to 200 mbar. The adsorption site occupancy of CO, in particular the on-top population, strongly depends on pressure and temperature preventing a simple extrapolation of low pressure results to reaction conditions.  相似文献   

19.
Hydrogen evolution reaction (HER) on a polycrystalline Pt electrode has been investigated in Ar-purged acids by surface-enhanced infrared absorption spectroscopy and electrochemical kinetic analysis (Tafel plot). A vibrational mode characteristic to H atom adsorbed at atop sites (terminal H) was observed at 2080-2095 cm−1. This band appears at 0.1 V (RHE) and grows at more negative potentials in parallel to the increase in hydrogen evolution current. Good signal-to-noise ratio of the spectra enabled us to establish the quantitative relation between the band intensity (equivalently, coverage) of terminal H and the kinetics of HER, from which we conclude that terminal H atom is the reaction intermediate in HER and the recombination of two terminal H atoms is the rate-determining step. The quantitative analysis of the infrared data also revealed that the adsorption of terminal H follows the Frumkin isotherm with repulsive interaction.  相似文献   

20.
A review of diamond synthesis by CVD processes   总被引:4,自引:0,他引:4  
Diamond has some of the most extreme mechanical, physical and chemical properties of all materials. Within the last 50 years, a wide variety of manufacturing methods have been developed to deposit diamond layers under various conditions. The most common process for diamond growth is the chemical vapor deposition (CVD). Starting from the first publications until the latest results today, a range of different developments can be seen. Comparing the basic conditions and the process parameters of the CVD techniques, the technical limitations are shown. Processes with increased pressure, flow rate and applied power are the general tendency.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号