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1.
A modified nucleation and growth process was adopted so as to improve the electron field emission (EFE) properties of diamonds films. In this process, a thin layer of ultra-nanocrystalline diamonds (UNCD), instead of bias-enhanced-nuclei, were used as nucleation layer for growing diamond films in H2-plasma. The morphology of the grains changes profoundly due to such a modified CVD process. The geometry of the grains transform from faceted to roundish and the surface of grains changes from clear to spotty. The Raman spectroscopies and SEM micrographs imply that such a modified diamond films consist of UNCD clusters (~ 10–20 nm in size) on top of sp3-bonded diamond grains (~ 100 nm in size). Increasing the total pressure in CVD chamber deteriorated the Raman structure and hence degraded the EFE properties of the films, whereas either increasing the methane content in the H2-based plasma or prolonged the growth time improved markedly the Raman structure and thereafter enhanced the EFE properties of diamond films. The EFE properties for the modified diamond films can be turned on at E0 = 11.1 V/μm, achieving EFE current density as large as (Je) = 0.7 mA/cm2 at 25 V/μm applied field.  相似文献   

2.
We report on the preparation and characterisation of boron (B) doped nano-crystalline diamond (B-NCD) layers grown over large areas (up to 50 cm × 30 cm) and at low substrate temperatures (< 650 °C) using microwave plasma enhanced linear antenna chemical vapour deposition apparatus (MW-LA-PECVD). B-NCD layers were grown in H2/CH4/CO2 and H2/CH4 gas mixtures with added trimethylboron (TMB). Layers with thicknesses of 150 nm to 1 μm have been prepared with B/C ratios up to 15000 ppm over a range of CO2/CH4 ratios to study the effect of oxygen (O) on the incorporation rate of B into the solid phase and the effect on the quality of the B-NCD with respect to sp3/sp2 ratio. Experimental results show the reduction of boron acceptor concentration with increasing CO2 concentration. Higher sp3/sp2 ratios were measured by Raman spectroscopy with increasing TMB concentration in the gas phase without CO2. Incorporation of high concentrations of B (up to 1.75 × 1021 cm3) in the solid is demonstrated as measured by neutron depth profiling, Hall effect and spectroscopic ellipsometry.  相似文献   

3.
Carbon thin films were deposited on Si substrates by microwave-assisted chemical vapor deposition (CVD) using variable CH4 levels in an Ar/H2 (Ar-rich) source gas mixture. The relationship between the CH4 concentration (0.5 to 3 vol.%) in the source gas and the resulting film morphology, microstructure, phase purity and electrochemical behavior was investigated. The H2 level was maintained constant at 5% while the Ar level ranged from 92 to 94.5%. The films used in the electrochemical measurements were boron-doped with 2 ppm B2H6 while those used in the structural studies were undoped. Boron doping at this level had no detectable effect on the film morphology or microstructure. Relatively smooth ultrananocrystalline diamond (UNCD) thin films, with a nominal grain size of ca. 15 nm, were only formed at a CH4 concentration of 1%. At the lower CH4 concentration (0.5%), faceted microcrystalline diamond was the predominant phase formed with a grain size of ca. 0.5 µm. At the higher CH4 concentration (2%), a diamond-like carbon film was produced with mixture of sp2-bonded carbon and UNCD. Finally, the film grown with 3% CH4 was essentially nanocrystalline graphite. The characteristic voltammetric features of high quality diamond (low and featureless voltammetric background current, wide potential window, and weak molecular adsorption) were observed for the film grown with 1% CH4, not the films' grown with higher CH4 levels. The C2 dimer level in the source gas was monitored using the Swan band optical emission intensity at 516 nm. The emission intensity and the film growth rate both increased with the CH4 concentration in the source gas, consistent with the dimer being involved in the film growth. Importantly, C2 appears to be involved in the growth of the different carbon microstructures including microcrystalline and ultrananocrystalline diamond, amorphous or diamond-like carbon, and nanocrystalline graphite. In summary, the morphology, microstructure, phase purity and electrochemical properties of the carbon films formed varied significantly over a narrow range of CH4 concentrations in the Ar-rich source gas. The results have important implications for the formation of UNCD from Ar-rich source gas mixtures, and its application in electrochemistry. Characterization data by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), visible-Raman spectroscopy and electrochemical methods are presented.  相似文献   

4.
This review focuses on a status report on the science and technology of ultrananocrystalline diamond (UNCD) films developed and patented at Argonne National Laboratory. The UNCD material has been developed in thin film form and exhibit multifunctionalities applicable to a broad range of macro to nanoscale multifunctional devices. UNCD thin films are grown by microwave plasma chemical vapor deposition (MPCVD) or hot filament chemical vapor deposition (HFCVD) using new patented Ar-rich/CH4 or H2/CH4 plasma chemistries. UNCD films exhibit a unique nanostructure with 2–5 nm grain size (thus the trade name UNCD) and grain boundaries of 0.4–0.6 nm for plain films, and grain sizes of 7–10 nm and grain boundaries of 2–4 nm when grown with nitrogen introduced in the Ar-rich/CH4 chemistry, to produce UNCD films incorporated with nitrogen, which exhibit electrical conductivity up to semi-metallic level. This review provides a status report on the synthesis of UNCD films via MPCVD and integration with dissimilar materials like oxides for piezoactuated MEMS/NEMS, metal films for contacts, and biological matter for a new generation of biomedical devices and biosensors. A broad range of applications from macro to nanoscale multifunctional devices is reviewed, such as coatings for mechanical pumps seals, field-emission cold cathodes, RF MEMS/NEMS resonators and switches for wireless communications and radar systems, NEMS devices, biomedical devices, biosensors, and UNCD as a platform for developmental biology, involving biological cells growth on the surface. Comparisons with nanocrystalline diamond films and technology are made when appropriate.  相似文献   

5.
For the purpose of improving the electron field emission properties of ultra-nanocrystalline diamond (UNCD) films, nitrogen species were doped into UNCD films by microwave plasma chemical vapor deposition (MPCVD) process at high substrate temperature ranging from 600° to 830 °C, using 10% N2 in Ar/CH4 plasma. Secondary ion mass spectrometer (SIMS) analysis indicates that the specimens contain almost the same amount of nitrogen, regardless of the substrate temperature. But the electrical conductivity increased nearly 2 orders of magnitude, from 1 to 90 cm 1 Ω 1, when the substrate temperature increased from 600° to 830 °C. The electron field emission properties of the films were also pronouncedly improved, that is, the turn-on field decreased from 20 V/μm to 10 V/μm and the electron field emission current density increased from less than 0.05 mA/cm2 to 15 mA/cm2. The possible mechanism is presumed to be that the nitrogen incorporated in UNCD films are residing at grain boundary regions, converting sp3-bonded carbons into sp2-bonded ones. The nitrogen ions inject electrons into the grain boundary carbons, increasing the electrical conductivity of the grain boundary regions, which improves the efficiency for electron transport from the substrate to the emission sites, the diamond grains.  相似文献   

6.
It is well established that argon rich plasmas (> 90% Ar) in Ar/CH4/H2 gas mixtures lead to (ultra)nanodiamond nucleation and growth by microwave plasma chemical vapour deposition (MPCVD). Nonetheless, in the present work, both microcrystalline and nanocrystalline diamond deposits developed under typical conditions for ultrananocrystalline (UNCD) growth by MPCVD. Silicon substrates were pretreated by abrasion using two different diamond powder types, one micrometric (< 0.5 μm) and the other nanometric (∼ 4 nm), the latter obtained by detonation methods. Samples characterization was performed by SEM (morphology), AFM (roughness and morphology) and micro-Raman (structure).For all samples, Raman analysis revealed good crystalline diamond quality with an evident ∼ 1332 cm 1 peak. The Raman feature observed at ∼ 1210 cm 1 is reported to correlate with two other common bands at ∼ 1140 cm 1 and ∼ 1490 cm 1 characteristic of nano- and ultra-nanocrystalline diamond.A new growth process is proposed to explain the observed morphology evolution from nano- to microcrystalline diamond. Based on this, the microcrystalline morphology is in fact a crystallographically aligned construction of nanoparticles.  相似文献   

7.
A 30 kW-powered DC Arcjet Plasma enhanced chemical-vapor deposition (CVD) system was applied to grow diamonds which included the nano-crystal free-standing film, the nano-/micro-crystal layered free-standing film, the gradient micro-crystal free-standing film and the millimeter-sized grain. The free-standing film quality, such as the roughness, the sp2 content, the residual stress and the grain morphology, was studied by an atomic force microscope (AFM), Raman spectra, a scanning electron microscope (SEM) and a high resolution electron microscope (HREM). In large-sized grain deposition, as-grown deposit was obtained about 1 × 1 × 1 mm3 in size under the condition of 10 μm/h of the substrate moving speed without Nitrogen enhancement. Characterized by Raman spectra and Laue back reflection X-ray diffraction, the deposit was proven to be single crystal diamond with small grains coving its surfaces. The growth rate was about 30 μm/h. Optical emission spectrum (OES) was utilized to characterize gas phases in the plasma for diamond deposition. The mean electron temperature (Te) in the plasma was calculated based on the value of the emission intensity ratio of IHγ/IHβ. Te varied from 0.33 eV to 0.5 eV depending on the concentration of CH4 in H2 from 1.0% to 25%. C2 radical was found to be the dominant carbon source compared with CH radical. The influence of the radical on the morphology of diamond was discussed. It was found that the nano-crystal could be grown when the ratio of the emission intensity, IC2/ICH, was larger than 8.  相似文献   

8.
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   

9.
Nitrogen-doped ultrananocrystalline diamond (UNCD)/hydrogenated amorphous carbon (a-C:H) films were deposited by pulsed laser deposition (PLD). Nitrogen contents in the films were controlled by varying a ratio in the inflow amount between nitrogen and hydrogen gases. The film doped with a nitrogen content of 7.9 at.% possessed n-type conduction with an electrical conductivity of 18 Ω? 1 cm? 1 at 300 K. X-ray photoemission spectra, which were measured using synchrotron radiation, were decomposed into four component spectra due to sp2, sp3 hybridized carbons, C=N and C–N. A full-width at half-maximum of the sp3 peak was 0.91 eV. This small value is specific to UNCD/a-C:H films. The sp2/(sp3 + sp2) value was enhanced from 32 to 40% with an increase in the nitrogen content from 0 to 7.9 at.%. This increment probably originates from the nitrogen incorporation into an a-C:H matrix and grain boundaries of UNCD crystallites. Since an electrical conductivity of a-C:H does not dramatically enhance for this doping amount according to previous reports, we believe that the electrical conductivity enhancement is predominantly due to the nitrogen incorporation into grain boundaries.  相似文献   

10.
Hot filament and microwave plasma CVD micro- nanocrystalline diamond films are analysed by visible and ultra-violet excitation source Raman spectroscopy. The sample grain size varies from 20 nm to 2 μm. The hydrogen concentration in samples is measured by SIMS and compared to the grain size, and to the ratio of sp2 carbon bonds determined by Raman spectroscopy from the 1332 cm 1 diamond peak and the sp2 1550 cm 1 G band. Hydrogen concentration appears to be proportional to the sp2 bonds ratio. The 3000 cm 1 CHx stretching mode band intensity observed on the Raman spectra is decreasing with the G band intensity. Thermal annealing modifies the sp2 phase structure and concentration, as hydrogen outdiffuses.  相似文献   

11.
DLC films were deposited on silicon and quartz glass substrates by pulsed discharge plasma chemical vapor deposition (CVD), where the plasma was generated by pulsed DC discharge in H2–CH4 gas mixture at about 90 Torr in pressure, and the substrates were located near the plasma. The repetition frequency and duty ratio of the pulse were 800 Hz and 20%, respectively. When CH4 / (CH4 + H2) ratio, i.e. methane concentration (Cm), increased from 3 to 40%, C2 species in the plasma was increased, and corresponding to the increase of C2, deposition rate of the film was increased from about 0.2 to 2.4 μm/h. The absorption peaks of sp3C–H and sp2C–H structures were observed in the FT-IR spectra, and the peak of sp2C–H structure was increased with increasing Cm, showing that sp2 to sp3 bonding ratio was increased when Cm was increased. Corresponding to these structural changes due to the increase of Cm, optical band gap (Eg) was decreased from 3 to 0.5 eV continuously when Cm was increased from 3 to 40%.  相似文献   

12.
Recent developments of a piezoresistive sensor prototype based on n-type conductive ultrananocrystalline diamond (UNCD) are presented. Samples were deposited using hot filament chemical vapor deposition (HFCVD) technique, with a gas mixture of H2, CH4 and NH3, and were structured using multiple photolithographic and etching processes. Under controlled deposition parameters, UNCD thin films with n-type electrical conductivity at room temperature (5 × 10 3  5 × 101 S/cm) could be grown. Respective piezoresistive response of such films was analyzed and the gauge factor was evaluated in both transverse and longitudinal arrangements, also as a function of temperature from 25 °C up to 300 °C. Moreover, the gauge factor of piezoresistors with various sheet resistance values and test structure geometries was evaluated. The highest measured gauge factor was 9.54 ± 0.32 at room temperature for a longitudinally arranged piezoresistor with a sheet resistance of about 30 kΩ/square. This gauge factor is well comparable to that of p-type boron doped diamond; however, with a much better temperature independency at elevated temperatures compared to the boron-doped diamond and silicon. To our best knowledge, this is the first report on piezoresistive characteristics of n-type UNCD films.  相似文献   

13.
We revisit here how Raman spectroscopy can be used to estimate the H content in hard hydrogenated amorphous carbon layers. The H content was varied from 2 at.% to 30 at.%, using heat treatments of a a-C:H, from room temperature to 1300 K and was determined independently using ion beam analysis. We examine the correlation of various Raman parameters and the consistency of their thermal evolution with thermo-desorption results. We identify a weak band at 860 cm 1 attributed to H bonded to C(sp2). We show that the HD/HG parameter (height ratio between the D and G bands) is quasi-linear in the full range of H content and can thus be used to estimate the H content. Conversely, we show that the m/HG parameter (ratio between the photoluminescence background, m, and the height of the G band), often used to estimate the H content, should be used with care, first because it is sensitive to various photoluminescence quenching processes and second because it is not sensitive to H bonded to C(sp2).  相似文献   

14.
The electron field emission (EFE) properties of Si nanostructures (SiNS), such as Si nanorods (SiNR) and Si nanowire (SiNW) bundles were investigated. Additionally, ultrananocrystalline diamond (UNCD) growth on SiNS was carried out to improve the EFE properties of SiNS via forming a combined UNCD/SiNS structure. The EFE properties of SiNS were improved after the deposition of UNCD at specific growth conditions. The EFE performance of SiNR (turn-on field, E0 = 5.3 V/μm and current density, Je = 0.53 mA/cm2 at an applied field of 15 V/μm) was better than SiNW bundles (turn-on field, E0 = 10.9 V/μm and current density, Je < 0.01 mA/cm2 at an applied field of 15 V/μm). The improved EFE properties with turn-on field, E0 = 4.7 V/μm, current density, Je = 1.1 mA/cm2 at an applied field of 15 V/μm was achieved for UNCD coated (UNCD grown for 60 min at 1200 W) SiNR. The EFE property of SiNW bundles was improved to a turn-on field, E0 = 8.0 V/μm, and current density, Je = 0.12 mA/cm2 at an applied field of 15 V/μm (UNCD grown for 30 min at 1200 W).  相似文献   

15.
Hydrogenated amorphous carbon nitride (a-C:N:H) has been synthesised using a high plasma density electron cyclotron wave resonance (ECWR) technique using N2 and C2H2 as source gases, at different ratios and a fixed ion energy (80 eV). The composition, structure and bonding state of the films were investigated and related to their optical and electrical properties. The nitrogen content in the film rises rapidly until the N2/C2H2 gas ratio reaches 2 and then increases more gradually, while the deposition rate decreases steeply, placing an upper limit for the nitrogen incorporation at 30 at%. For nitrogen contents above 20 at%, the band gap and sp3-bonded carbon fraction decrease from 1.7 to 1.1 eV and ∼65 to 40%, respectively. The transition is due to the formation of polymeric CN, CN and NH groups, not an increase in CH bonds. Films with higher nitrogen content are less dense than the original hydrogenated tetrahedral amorphous carbon (ta-C:H) film but, because they have a relatively high band gap (1.1 eV), high resistivity (109 Ω cm) and moderate sp3-bonded carbon fraction (40%), they should be classed as polymeric in nature.  相似文献   

16.
In this study, structure and mechanical properties of doped diamond-like carbon (DLC) films with oxygen were investigated. A mixture of methane (CH4), argon (Ar) and oxygen (O2) was used as feeding gas, and the RF-PECVD technique was used as a deposition method. The thin films were characterized by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy (RS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and a combination of elastic recoil detection analysis and Rutherford backscattering (ERDA-RBS). Nano-indentation tests were performed to measure hardness. Also, the residual stress of the films was calculated by Stoney equation. The XPS and ERDA-RBS results indicated that by increasing the oxygen in the feeding gas up to 5.6 vol.%, the incorporation of oxygen into the films' structure was increased. The ratio of sp2 to sp3 sites was changed by the variation of oxygen content in the film structure. The sp2/sp3 ratios are 0.43 and 1.04 for un-doped and doped DLC films with 5.6 vol.% oxygen in the feeding gas, respectively. The Raman spectroscopy (RS) results showed that by increasing the oxygen content in doped DLC films, the amount of sp2 CC aromatic bonds was raised and the hydrogen content reduced in the structure. The attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) confirmed the decrease of hydrogen content and the increase the ratio of CC aromatic to olefinic bonds. Hardness and residual stress of the films were raised by increasing the oxygen content within the films' structure. The maximum hardness (19.6 GPa) and residual stress (0.29 GPa) were obtained for doped DLC films, which had the maximum content of oxygen in structure, while the minimum hardness (7.1 GPa) and residual stress (0.16 GPa) were obtained for un-doped DLC films. The increase of sp3 CC bonds between clusters and the decrease of the hydrogen content, with a simultaneous increase of oxygen in the films' structure is the reason for increase of hardness and residual stress.  相似文献   

17.
The nitrogen incorporated nanocrystalline diamond (NCD) films were grown on n-silicon (100) substrates by microwave plasma enhanced chemical vapor deposition (MPECVD) using CH4/Ar/N2 gas chemistry. The effect of surface passivation on the properties of NCD films was investigated by hydrogen and nitrogen-plasma treatments. The crystallinity of the NCD films reduced due to the damage induced by the plasma treatments. From the crystallographic data, it was observed that the intensity of (111) peak of the diamond lattice reduced after the films were exposed to the nitrogen plasma. From Raman spectra, it was observed that the relative intensity of the features associated with the transpolyacetylene (TPA) states decreased after hydrogen-plasma treatment, while such change was not observed after nitrogen-plasma treatment. The hydrogen-plasma treatment has reduced the sp2/sp3 ratio due to preferential etching of the graphitic carbon, while this ratio remained same in both as-grown and nitrogen-plasma treated films. The electrical contacts of the as-grown films changed from ohmic to near Schottky after the plasma treatment. The electrical conductivity reduced from ~ 84 ohm 1 cm 1 (as-grown) to ~ 10 ohm 1 cm 1 after hydrogen-plasma treatment, while the change in the conductivity was insignificant after nitrogen-plasma treatment.  相似文献   

18.
The effect of surface plasma treatment on the nature of the electrical contact to the nitrogen incorporated nanocrystalline diamond (n-NCD) films is reported. Nitrogen incorporated NCD films were grown in a microwave plasma enhanced chemical vapor deposition (MPECVD) reactor using CH4 (1%)/N2 (20%)/Ar (79%) gas chemistry. Raman spectra of the films showed features at ∼ 1140 cm 1, 1350 cm 1(D-band) and 1560 cm 1(G-band) respectively with changes in the bonding configuration of G-band after the plasma treatment. Electrical contacts to both untreated and surface plasma treated films are formed by sputtering and patterning Ti/Au metal electrodes. Ohmic nature of these contacts on the untreated films has changed to non-ohmic type after the hydrogen plasma treatment. The linear current–voltage characteristics could not be obtained even after annealing the contacts. The nature of the electrical contacts to these films depends on the surface conditions and the presence of defects and sp2 carbon.  相似文献   

19.
The electron field emission (EFE) properties of Si-nanowires (SiNW) were improved by coating a UNCD films on the SiNWs. The SiNWs were synthesized by an electroless metal deposition (EMD) process, whereas the UNCD films were deposited directly on bare SiNW templates using Ar-plasma based microwave plasma enhanced chemical vapor deposition (MPE–CVD) process. The electron field emission properties of thus made nano-emitters increase with MPE–CVD time interval for coating the UNCD films, attaining small turn-on field (E0 = 6.4 V/μm) and large emission current density (Je = 6.0 mA/cm2 at 12.6 V/μm). This is presumably owing to the higher UNCD granulation density and better UNCD-to-Si electrical contact on SiNWs. The electron field emission behavior of these UNCD nanowires emitters is significantly better than the bare SiNW ((E0)SiNWs = 8.6 V/μm and (Je)SiNWs < 0.01 mA/cm2 at the same applied field) and is comparable to those for carbon nanotubes.  相似文献   

20.
Effects of an ultrathin (~ 1 nm) diamond-like carbon (DLC) layer in single-layer organic light-emitting devices (OLEDs) that consist of ITO/(TPD-Alq3 doped PVK)/Al were investigated. DLC layers deposited by using Nd:YAG laser at laser wavelengths of 355 nm were high in sp3 content and resistivity (DLCUV) while that of 1064 nm laser were lower in sp3 content and resistivity (DLCIR), as characterized by Raman spectroscopy and resistivity measurements. Although emission were obtained for all the devices, only the device of ITO/DLCUV/(TPD-Alq3 doped PVK)/Al exhibited enhanced current density and brightness with lower turn-on voltage as compared to a standard device. Devices of ITO/DLCIR/(TPD-Alq3 doped PVK)/Al and ITO/(TPD-Alq3 doped PVK)/DLCUV/Al showed poor current and brightness characteristics but failed at higher applied voltage. The enhance performance of device with high resistivity/sp3 DLC film suggests the mechanisms of barrier reduction by sufficiently thin insulating layer which increase the probability of tunneling of carriers at ITO and PVK interface.  相似文献   

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