A study of the mobility and trapping of minor hydrogen concentrations in diamond in three dimensions using quantitative ERDA microscopy

Two direct and two indirect nuclear methods are used for the analysis of hydrogen in diamond of different types. Exploiting the power of two-dimensional position sensitive detectors, the distribution of hydrogen in and on diamond in three dimensions has been measured by elastic recoil detection analysis, supplementing the earlier resonant nuclear techniques. Indirect methods of muonium spin rotation and time differential perturbed angular distribution measurements prove to be very informative. In a series of dynamic experiments, hydrogen has been implanted and the diffusion thereof sought as a function of temperature. Unlike the equivalent case for silicon, no migration of the hydrogen in diamond is found up to 1473 K. This striking result is considered in regard to existing theoretical calculations. It is concluded that the implanted hydrogen is self-trapped. Arguments are presented as to the location of hydrogen in natural diamond, in diamond grown at high pressure and high temperature, and in diamond grown by chemical vapour deposition.     

Structural investigation of nanocrystalline diamond/amorphous carbon composite films

Nanocrystalline diamond/amorphous carbon (NCD/a-C) composite films have been prepared by microwave plasma chemical vapor deposition (MWCVD) from methane/nitrogen mixtures. The complex nature of the coatings required the application of a variety of complementary analytical techniques in order to elucidate their structure. The crystallinity of the samples was studied by selected-area electron diffraction (SAED). The diffraction patterns revealed the presence of diamond crystallites within the films. From the images taken by transmission electron microscopy (TEM) the crystallite size was determined to be on the order of 3–5 nm. The results were confirmed by X-ray diffraction (XRD) measurements exhibiting broad (111) and (220) peaks of diamond from which the average size of the crystallites was calculated. The grain boundary width is 1–1.5 nm as observed by TEM images which corresponds to a matrix volume fraction of about 40–50%. This correlates very well with the crystalline phase content of about 50% in the films estimated from their density (2.75 g/cm³ as determined by X-ray reflectivity). The bonding structure of the composite films was studied by electron energy loss spectroscopy (EELS) in the region of carbon core level. The spectra were dominated by a peak at 292 eV indicating the diamond nature of the investigated films. In addition, the spectra of NCD/a-C films possessed a shoulder at 284 eV due to the presence of a small sp² bonded fraction. This phase was identified also by X-ray photoelectron spectroscopy (XPS). The sp²/sp³ ratio was on the order of 10% as determined by deconvolution of the C1s XPS peak.     

Thermal chemical vapor deposition of fluorocarbon polymer thin films in a hot filament reactor

Formation of fluorocarbon polymer films with a linear (CF₂-CF₂)_n molecular structure similar to polytetrafluoroethylene, PTFE is described by a hot filament chemical vapor deposition method. Growth process is analyzed by infrared absorption and C(1s), O(1s) and F(1s) core level electron spectroscopy of films deposited at −5 and +70 °C. Absorption doublet at 1220 and 1160 cm⁻¹ assigned to C-F₂ asymmetric and symmetric stretches, rock at 518 cm⁻¹ and wag at 637 cm⁻¹ indicate formation of linearly organized CF₂ groups with minimum hindrance to molecular vibration modes in CVD grown films. Absorption bands at 1660 and 3389 cm⁻¹ show O and OH groups in the films which diminish on annealing. The C(1s) components, CF₃, CF and C-CF bonding show branching, cross-liking and defects sites which increase as substrate temperature is increased. The O(1s) line analysis shows O₂ in fluorocarbon films is chemically bonded as C-O and F₂CO with relative ratio depending on the film growth temperature. Both O₂ and OH are the result of additional reaction pathways involving the species generated from fragmentation of CF₃C(O)F. Molecular structure of fluorocarbon polymer films involving these species are discussed which are in conformity with the XPS and IR absorption data.     

Development of a TOF measurement system of charge carrier dynamics in diamond thin films using a UV pulsed laser

A fast TOF measurement system with 150 ps time resolution for transport behavior of free charge carriers in an intrinsic diamond film by using a UV pulsed laser was developed. The 213 nm UV laser light narrowed to approximately 80 μm widths could locally create hole–electron pairs in selected locations on a diamond film between two parallel electrodes on the surface. This system measured accurate charge transport characteristics in a diamond film, because created charge carriers moved in a part of the diamond film where they did not get any influence from the laser irradiation. Diamond samples used for verification of the TOF system were intrinsic CVD diamond films with thickness between 4 and 10 μm grown on HP/HT diamond substrates. Transit time of holes for one diamond film was 4.7 ns with a traverse distance of 250 μm. The local irradiation of laser made it possible to measure transport characteristics of electrons and holes separately. In addition, it substantially reduced the influence of photoelectron, because the laser beam did not irradiate electrodes. Through several examinations, excellent reliability of the TOF system was confirmed.     

Ex-situ spectroscopic ellipsometry studies of micron thick CVD diamond films

Micron thick diamond films have been studied by spectroscopic ellipsometry (SE). The films were grown, on previously prepared Si(100) substrates, by the plasma enhanced chemical vapor deposition (PECVD) technique. Ex situ SE measurements were carried out on samples grown under different conditions, such as substrate temperature and methane fraction in the gas mixture. An optical model consisting of five layers was constructed in order to explain the SE spectra and to provide the optical and structural parameters of the films. This model was deduced from results of various measurements performed by other characterization techniques (Raman spectroscopy, scanning electron microscopy, atomic force microscopy and positron annihilation spectroscopy) which have revealed the optical and structural parameters of the samples. Its sensitivity to the surface and interface roughness as well as to the absorption of the nondiamond phase of the film is demonstrated. Several values of the percentage of the nondiamond phase can be obtained, with the same fit quality, however, depending on the amorphous carbon reference used in the model. These references were obtained by performing SE measurements on various amorphous carbon films. Finally, our SE analysis has allowed us to monitor the lateral homogeneity of the thickness, surface and interface roughness and nondiamond phase concentration over the diamond film.     

EPR study of hydrogen-related defects in boron-doped p-type CVD homoepitaxial diamond films

Boron-doped p-type single crystalline chemical vapor deposition (CVD) homoepitaxial diamond films were investigated by electron paramagnetic resonance (EPR). Carbon dangling bond defects, which were accompanied by a nearby hydrogen atom, were observed in boron-doped p-type CVD diamond films on a IIa substrate similar to those observed in undoped diamond. This result suggested that the energy level position of the defects is located below the Fermi energy of boron-doped diamond, at around 0.3 eV above the valence-band top. The reason why the Fermi energy could be changed by the incorporation of boron atoms at low density (10¹⁶–10¹⁷/cm³) in the film in spite of the existence of the large defect density of EPR centers (10¹⁸/cm³) is thought to be that the singly occupied electron states of defects are located near the band edge. As for the thermal annealing effect of the defects, it was revealed that the concentration of the defects and the mobility of the p-type film did not change after annealing up to 1200 °C which is much higher than the temperature of boron–hydrogen pair dissociation.     

Adhesion of CVD diamond films on silicon substrates of different crystallographic orientations

In order to gain insight into the adhesion mechanisms of diamond films, we examine Si substrates with three different crystallographic orientations at the various stages of the deposition process. This allows one to distinguish the surface phenomena involved in diamond deposition from those due to gaseous plasma processes. We find that the initial ultrasonic scratching treatment produces partial graphitization of the diamond powder, and it controls the crystallite size through the carbon residues. On the other hand, an increased surface roughness due to H-atom etching correlates with increased adhesion. The deposited film adhesion is found to increase in the sequence Si(111)相似文献   

Grain boundary effect on the superconducting transition of microcrystalline boron-doped diamond films

Microcrystalline boron-doped diamond (BDD) films were prepared on silicon substrates by hot-filament chemical vapor deposition method. Different grain sizes of the boron-doped diamond films with nearly the same boron concentration were obtained by changing the nuclei concentration on the silicon substrates. The electrical transport behaviors of as-prepared boron-doped diamond films were measured, and the results revealed that with the increase of the grain sizes on the BDD films, the superconducting transition temperature was evidently increased. This phenomenon indicates that the superconducting transition of microcrystalline BDD films is influenced by the inhomogeneity aroused by the grain boundary effect. Our results could expand our understanding of the superconducting mechanism of microcrystalline BDD films, and are also significant to conventional applications of BDD materials.     

Secondary electron emission from CVD diamond films

Secondary electron emission from boron doped diamond polycrystalline membranes (hole concentration 5×10¹⁸ cm⁻³), prepared by microwave plasma assisted CVD, was investigated in both the reflection and transmission configurations. The model of secondary electrons behavior taking into account the distribution and diffusion mechanism of secondary electrons is proposed to explain the yield dependencies on primary electron energy in both configurations. The model predicts the SEE yield K=19 at the primary electron energy E₀ close to 1 keV for reflection configuration and K=3–7 at E₀=15–30 keV for transmission configuration for polycrystalline films used in the study. Experimental measurements of the SEE yield vs. primary electron energy (18 at E₀=950 eV for the reflection scheme and 3.5–4 at E₀=25 keV for the transmission one) are found to accord well with the theoretical results. Estimations, which were made using the model, show that SEE yield in transmission configuration can be increased up to 60 for the primary electron energy of about 10 keV. Since such high yields in transmission scheme may be obtained in monocrystalline membrane, another approach using porous polycrystalline diamond membranes is considered. Porous diamond membranes having SEE yield in transmission scheme of more than 10 at the primary electron energy E₀=1 keV were fabricated.     

Effect of properties of MWPECVD polycrystalline diamond films on photoemissive response

Diamond is an extremely interesting material for photoemission applications, due to the negative electron affinity of its surface, which can be obtained after suitable treatments. In the present work two sets of polycrystalline diamond films, characterized by different thicknesses and deposition conditions, are analyzed. In particular, in the examined films the relationship among the grain size, the amount of non-diamond carbon (sp²) located at the grain boundaries and their efficiency as photocathodes has been found and carefully investigated. The photoemission yield in the UV range is evaluated for all the samples, before and after hydrogenation, and after air exposure. The crucial parameter for the photocathode performances has been found not to be the film thickness, but the properties of polycrystalline diamond films, tunable with the plasma modulation and the methane percentage in the gas mixture.     

Determination of the optical constants of diamond films with a rough growth surface

The determination of the optical constants n and k for polycrystalline diamond films with typical growth surface roughness σ of the order of tens to hundreds of nanometers is both an important and a difficult procedure. A method for determining n, k and σ for rough diamond films is presented here. It is based on theoretical expressions for the optical reflectance R and transmittance T for a free-standing thin film incorporating the effects of surface scattering at one surface. The usefulness and validity of this approach are illustrated using experimental R and T data for diamond films. Simplified expressions for R and T are also presented which are valid when scattering or absorption are sufficiently strong to cause interference effects in the films to be averaged out.

Prime novelty: Simple expressions for n, k and σ are presented which will enable researchers to extract this important information about the optical constants and surface roughness of their CVD diamond films.     

Mechanical properties of nanocrystalline diamond/amorphous carbon composite films prepared by microwave plasma chemical vapour deposition

Nanocrystalline diamond films (NCD) have been deposited by microwave plasma chemical vapour deposition from CH₄/N₂ mixtures with varying methane content. They consist of diamond nanocrystallites with sizes of 3–5 nm embedded in an amorphous matrix with grain boundary widths of 1–1.5 nm. The CH₄ content in the gas phase has almost no influence on the microscopic structure but a strong effect on the macroscopic structure and morphology. The mechanical and tribological properties of these films have been investigated by nanoindentation, nano tribo tests, and nano scratch tests. The hardness of a 4-μm-thick film deposited with 17% methane was about 40 GPa, the indentation modulus 387 GPa, and the elastic recovery 75%. Ball-on-disk tests against an Al₂O₃ ball revealed, after initially higher values, a friction coefficient of ≤0.1. Tribo tests and scratch tests proved a strong adhesion and a protective effect on silicon substrates. Finally, the correlations between the macroscopic structure of the films and their mechanical and tribological properties are discussed.     

Nitrogenated nanocrystalline diamond films: Thermal and optical properties

Ultrananocrystalline diamond films have been grown by microwave plasma CVD using CH₄/H₂/Ar mixtures with N₂ added in plasma in amounts up to 25%. The films were characterized with AFM, Raman, XRD, and UV–IR optical absorption spectroscopy mainly focusing on optical and thermal properties. In comparison with polycrystalline CVD diamond the UNCD are very smooth (R_a < 10 nm), have low thermal conductivity ( 0.10 W/cm K), high optical absorption ( 10³ cm^− 1 at 500 nm) and high concentration of bonded hydrogen ( 9 at.%). The nitrogen presence in the plasma has a profound impact on UNCD structure and properties, particularly leading to a decrease in resistivity (by 12 orders of magnitude), thermal conductivity, Tauc band gap, optical transmission and H content. The UNCD demonstrated rather good thermal stability in vacuum: the diamond phase still was present in the films subjected to annealing to 1400 °C.     

Cool plasma functionalization of nano-crystalline diamond films

It was demonstrated that an atmospheric pressure dielectric barrier glow discharge system is a powerful tool for the surface functionalization of nano-crystalline diamond films. Diamond film functionalization was performed in minutes using plasma discharges generated with fluorine containing gases. The chemical bonds formed between reactive species generated in the plasma and diamond surface were confirmed by FTIR and XPS analysis. Following plasma treatment, XPS analysis revealed a high concentration of F on the diamond surface, nearly 50 atomic percent. FTIR analysis revealed the presence F-bands related to CF₃ (CF₂) stretching vibrations and symmetric and asymmetric CF₂ vibrations. It was concluded that atmospheric pressure dielectric barrier glow discharge is a highly effective means to fluorinate diamond surfaces within a modest time.     

Free-standing diamond films deposited by DC arc plasma jet on graphite substrates with a destroyable Ti interlayer

A destroyable Ti interlayer on graphite substrate was used for fabrication of crack-free free-standing diamond films by high-power DC Arc Plasma Jet. Ti interlayer was arc ion plated on the polycrystalline graphite substrate. The thickness, morphology and composite phase of the Ti interlayer were examined by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Titanium carbide (TiC) was detected in both sides of the interlayer, which played an important role with respect to reasonable adhesion and diamond nucleation. Semi-translucent and crack-free diamond films were obtained and characterized by SEM and Raman spectroscopy. It is shown that the diamond films so obtained have excellent Raman signature. The overall results suggest that plating Ti interlayer on graphite substrate is an effective way to obtain potentially crack-free free-standing diamond films.     

砷化镓上生长金刚石薄膜的研究

以CH4和H2为气源,用微波辅助等离子体装置,在10.0 mm×7.0 mm的砷化镓基底上沉积了CVD金刚石薄膜,用扫描电子显微镜观察沉积效果,拉曼光谱表征沉积质量,分析薄膜附着力与砷化镓材料性能的关系。结果表明,当基体温度为600℃,气压为5 kPa,甲烷浓度为2.0%时,在砷化镓片表面上沉积出了CVD金刚石薄膜,晶粒尺寸均匀,晶形完整、规则,晶界非常清晰。     

Superconductivity in heavily B-doped diamond layers deposited on highly oriented diamond films

We deposited a [100]-oriented B-doped diamond layer by three methods to clarify the effects of film morphology on the transition from metallic to superconducting diamond. Heavily B-doped [100]-oriented diamond layers were deposited on [first method] undoped polycrystalline diamond films with [111] faces, [second method] highly oriented undoped diamond (HOD) thin films with a pyramidal surface, and [third method] thick undoped HOD films with a pyramidal surface. We confirmed that the B-doped layer in the third method was oriented in the [100] direction by scanning electron microscopy (SEM). The highest transition temperatures were T_c(onset) = 5.0 K and T_c(zero) = 3.1 K for the B-doped layer deposited on a thick HOD film with a pyramidal surface under a zero magnetic field. By contrast, T_c(onset) was 4.1 K for a heavily B-doped diamond layer deposited on a thin HOD film with a pyramidal surface, and was 3.9 K for a heavily B-doped diamond layer deposited on an undoped polycrystalline diamond film. These differences in T_c for our samples are affected by disorder and effective hole-carrier doping in each sample. Using the third method, we successfully deposited a high-quality B-doped [100] layer in three steps: (first step) depositing a [100] HOD film on a Si [100] substrate, (second step) depositing an HOD film with a pyramidal surface, and (third step) depositing a [100]-oriented B-doped layer. The change in the electronic states due to the B-doping of diamond films and the film morphology were investigated by x-ray photoelectron spectroscopy (XPS) measurements and band calculations.     

CVD金刚石薄膜技术发展现状及展望(下)

简要描述了CVD金刚石薄膜技术的发展历程。介绍了纳米特别是超纳米金刚石膜、CVD金刚石大单晶的技术特点及其应用。超纳米金刚石膜在MEMS(微机电系统)、电化学和生物医学上的应用和CVD金刚石大单晶是当前的研究热点。简言之,金刚石的发展向着更大或者更小的方向深入进行,即"非大即小"。     

Superconductivity in polycrystalline diamond thin films

Superconductivity was discovered in heavily boron-doped diamond thin films deposited by the microwave plasma assisted chemical vapor deposition (MPCVD) method. Advantages of the MPCVD deposited diamond are the controllability of boron concentration in a wide range, and a high boron concentration, especially in (111) oriented films, compared to that of the high-pressure high-temperature method. The superconducting transition temperatures are determined to be 8.7 K for T_c onset and 5.0 K for zero resistance by transport measurements. And the upper critical field is estimated to be around 7 T.     

UV Schottky photodiode on boron-doped CVD diamond films

We report on experimental study of photosensitivity and Q-DLTS spectra of polycrystalline CVD diamond UV photodetectors. The measured characteristics of Schottky photodiode on boron-doped diamond films are compared with those obtained for planar photoconductive structures (photoresistor type) based on undoped CVD diamond. The Schottky photodiode exhibited a sharp cut-off in photoresponse with spectral discrimination ratio (between wavelengths of 190 nm and 700 nm) as high as 5 · 10⁵ at zero bias voltage (at zero dark current). The photodiode showed the maximum of photoresponse at wavelength < 190 nm, and a low density of trapping and recombination centers as evaluated with the Q-DLTS technique. The devices demonstrated the photoresponsivity at 190 nm from 0.03 to 0.1 A/W with quantum yield of 0.20 to 0.67 in closed circuit, while the photovoltage ≥ 1.6 V was measured in open circuit regime. Another type of UV detector, the planar photoconductive structures with interdigitizing ohmic electrodes fabricated on undoped diamond film and operated under a bias voltage, revealed a higher density of (surface) defect centers and the maximum photoresponse at  210 nm wavelength. A strong influence of UV light illumination on the Q-DLTS spectra of the planar photoconductive structures was observed. This effect can be used for development of new UV detectors and dosimeters based on the Q-DLTS signal measurements.