Diamond Films Research Articles

Blue-white electroluminescence of diamond/WS2 quantum dot composite films

Two kinds of diamond films with completely different morphologies were prepared on N-type heavily doped silicon wafers by microwave plasma chemical vapor deposition (MPCVD) method, namely, micron-scale large grain polycrystalline diamond film dominated by (220) crystal plane (220DF) and nano-scale small grain polycrystalline diamond film dominated by (111) crystal plane (111DF). And WS2 quantum dot powder was obtained by aqueous liquid phase ultrasonic method. Then, the 111DF/WS2 quantum dot composite structure film (111DWSF) and 220DF/WS2 quantum dot composite structure film (220DWSF) were prepared by applying WS2 quantum dot powder uniformly on diamond film substrate. The results of electroluminescence (EL) detection show that the 220DWSF device emits visible blue light, and the main peak of EL spectrum is located at 443 nm in the blue region. The 111DWSF device emits white light, and the corresponding EL spectra show strong emission peaks in the blue region (454 nm), green region (536 nm) and red region (632 nm) respectively, meanwhile, the luminous intensity of 111DWSF device is much higher than that of 220DWSF device. In addition, it is also found that the 220DWSF EL device does not show obvious rectification characteristics, while the 111DWSF EL device has obvious rectification characteristics. After FN fitting of the IV characteristic curve of 111DWSF EL device, the tunneling characteristics of electrons are found in the region of high electric field intensity.

Microwave plasma CVD of diamond films on high concentration alloys: Microstructure, hardness and wear properties

Polycrystal diamond films were synthesized on high concentration alloys (HCAs) by microwave plasma chemical vapour deposition. It was found that the continuous diamond films formed in a short period, e.g., 10 min. The carbides including the stable MC [0 1 1] (M = Mo, Nb, Ta, Ti and Zr) and metastable carbides (e.g., Mo2C, Ti2C and Mo3C2) were identified by X-ray diffraction and transmission electron microscopy. The diamond/carbide interface had an orientation relationship as [0 1 1]Diamond//[0 1 0]Mo2C. The hardness of MoHfNbTaTiZr HCA at the CH4 concentration of 9% for 20 min was as high as 1238.2 HV0.3. The friction coefficient was 0.56–0.73 for the specimens with continuous diamond films. No spallation of films after friction indicated good wear resistance and adhesion.

Simultaneous Determination of Young's Modulus and Density of Ultrathin Low‐k Films Using Surface Acoustic Waves

The nondestructive testing (NDT) of mechanical properties in ultrathin low dielectric constant (low‐k) films is a major challenge in integrated circuit manufacturing. Young's modulus and density are closely related parameters for low‐k films. This study presents a method for NDT of Young's modulus and density of porous low‐k black diamond (SiOC:H, BD) films. A linear frequency modulation (LFM) surface acoustic wave (SAW) interdigital transducer (IDT) with a frequency range of 20–250 MHz is designed to generate SAW signals on the samples. The series of SAW waveforms obtained on the samples are processed to obtain experimental SAW dispersion curves across a broad frequency range. By comparing these experimental curves with theoretical dispersion curves, as well as their first‐order derivatives, Young's modulus and density of porous low‐k BD films with thicknesses of 100, 300, 500, and 1000 nm are characterized. To verify Young's modulus measurements from the SAW method, a control experiment using nanoindentation is conducted. The results demonstrate that the SAW method can reduce the impact of the substrate and is independent of the film thickness. This study presents a highly accurate measuring method for simultaneous multiparameter evaluation of ultra‐thin low‐k films.

Subsurface nitrogen bonding, thermal stability, and retention of 200 eV N2+ implanted polycrystalline diamond studied by in situ X-ray photoelectron spectroscopy

The properties of ultra-shallow nitrogen layers (<1 nm thick) in diamonds produced by very low energy (200 eV) N2+ implantation in polycrystalline diamond films at different doses (1.25×1014, 3.50×1014, 7.85×1014, 1.30×1015 and 9×1015 ions·cm−2), followed by thermal annealing, are investigated by in situ X-ray photoelectron spectroscopy. Spectral analyses of C(1s) and N(1s) peaks reveal that a chemical effect occurs depending on nitrogen local concentration and annealing temperature. Nitrogen exists in a predominant CN/C–N bonding configuration, followed by minor contributions of C≡N and quaternary-N configurations. Annealing (300–1000 °C) imparts complex effects that depend on local nitrogen concentration and bonding. The onset of nitrogen thermal desorption increases with ion dose: 300 °C for 1.25×1014 and 3.50×1014, 400 °C for 7.85×1014, and ∼650 °C for 1.30×1015 and 9×1015 ions·cm−2. Upon annealing to 1000 °C, the remaining nitrogen concentration in the diamond subsurface region increases with ion dose. The CN/C–N configuration was more thermally stable than the C≡N, while the quaternary-N is constant with annealing temperature. The nitrogen ion retention probability increased for 1.25×1014 and 3.50×1014 and decreased for the higher doses due to recombination-assisted desorption. This study may have important implications for stabilizing near-surface NV- centers for quantum sensing applications.

An investigation into low-temperature HFCVD and derivative techniques for the enhancement of diamond-coated cemented carbide tool performance

The performance of diamond-coated cemented carbide tools manufactured via the conventional hot filament chemical vapor deposition (HFCVD) technique exhibits certain limitations, including issues with poor toughness and reduced adhesive strength of film-substrate systems, primarily attributed to the cobalt diffusion at elevated temperatures (> 800 °C). In this study, a pioneering exploration of a low-temperature diamond film deposition technique on cemented carbide is developed, and a comprehensive evaluation of the film properties is conducted. The results indicate that owing to constraints related to growth rate and diamond film purity, it may not serve as an effective approach for enhancing the performance of conventional coated tools. Nonetheless, the inherent capability of this technique in inhibiting cobalt diffusion is strategically harnessed to pioneer the development of a derivative technique referred to as the “low-temperature to high-temperature HFCVD (LT-HT-HFCVD)”. This innovative method leverages a low-temperature deposited diamond layer as an intermediate layer to impede cobalt diffusion while serving as a densely nucleated layer for subsequent diamond growth. Subsequently, the conventional technique is employed to facilitate an effective growth rate and maintain high growth purity. The diamond-coated tools generated by this technique are subject to a comprehensive comparative analysis against those generated by low-temperature HFCVD (LT-HFCVD) and conventional HFCVD (CT-HFCVD) techniques. The results reveal that tools fabricated using the LT-HT-HFCVD combine the advantages inherent to both the LT-HFCVD and CT-HFCVD techniques, thereby manifesting superior toughness, enhanced film-substrate adhesive strength, and outstanding cutting performance.

Explore the growth mechanism of high-quality diamond under high average power density in the MPCVD reactor

Investigating the mechanism behind the high-efficiency deposition of high-quality diamond has always been a prominent topic in related research. This paper investigates the CH4-H2 plasma characteristics and related chemical reaction kinetics in the average power density range of 18–100 W·cm−3, which is a typical range for large-area diamond film deposition. The number densities of H, CH3 and C2H2 increase linearly with the average power density. C2H2 is the main hydrocarbon in the discharge, and CH3 is the main single-carbon hydrocarbon. The number density and radial uniformity of CH3 and C2H2 increase with the average power density, which is necessary for the high rate and uniform deposition of diamond films. The plasma's optical emission spectra indicate an acceleration in the C2 production rate at high power density. The diamond film deposition experiment demonstrates the efficacy of high average power density in achieving high-quality diamond deposition at a high growth rate.

Controlled boron content in lightly B-doped single crystal diamond films by variation of methane concentration

Obtaining desirable electrical properties from B-doped single crystal diamond (SCD) films hinges on precise control of boron incorporation into the crystal lattice structure. In this study, the impact of methane concentration during plasma deposition on boron incorporation of lightly B-doped SCD films is investigated. SCD layers are grown successively by microwave plasma enhanced chemical vapor deposition (CVD) at different methane-to-hydrogen concentrations (1%, 2%, and 3%), with residual boron atoms present in the CVD reactor. An increase in methane concentration leads to surface defects such as unepitaxial crystallites and pyramidal hillocks. The charge carrier mobility, electrical conductivity, and boron content of samples are evaluated and discussed. The temperature-dependent mobility is analyzed through theoretical modeling, revealing dominant scattering mechanisms at different temperatures. At 300 K, the maximum hole mobility reached 1200 cm2/V·s for the 1% methane concentration sample, transitioning to hopping conduction at lower temperatures. An increase in boron-doping level with rising methane concentration is detected by Fourier transform infrared spectroscopy, cathodoluminescence spectroscopy, Hall effect, and X-ray photoelectron spectroscopy measurements. These findings highlight the potential of methane concentration in plasma feedgas to control boron concentration in CVD diamond and open avenues for crafting efficient high-power electronic applications using p-type SCD films.

Preparation of HFCVD spherical diamond films and the effect of crystal orientations on adhesion and tribological properties

The different coefficients of thermal expansion of WC-Co cemented carbide and diamond have limited the development of spherical diamond-coated tools. In this study, diamond sphere films with different crystal orientation and texturing were successfully prepared by hot filament chemical vapor deposition (HFCVD). The adhesion and friction characteristics of the films were investigated by indentation and friction tests. The results show that the adhesion of the (111) orientation micron diamond (111MDF) spherical film, (110) orientation micron diamond (110MDF) spherical film, and (110) orientation texturized micron diamond (110TDF) spherical film increase sequentially at the same position. Under dry friction conditions, the average coefficient of friction of 110TDF spherical film was reduced by 28%, the wear resistance was increased by 80%, the surface roughness of the workpiece was reduced by 23%, and the material removal rate was reduced by 23.6% compared with that of 111MDF spherical film.

High performance field emission cathode based on the diamond nanowires prepared by nanocrystalline diamond films annealed in air

This paper reports the field emission (FE) characteristics of a diamond nanowires (DNWs) array. The nanocrystalline diamond (NCD) film was deposited on silicon by microwave plasma chemical vapor deposition (MPCVD) and then annealed in air forming DNWs and hydrogenated at last. A high-field flat-plate emission test structure with a 1.03 μm gap between anode and cathode was prepared and the electrical properties proved it feasible. The FE performance of DNWs array was measured in a vacuum test system and that of NCDs film as a comparison. Finally, their FE parameters were analyzed and extracted based on the Fowler–Nordheim (F-N) theory. The results show that transforming NCDs film into DNWs array can improve the FE characteristics greatly. The turn-on field is as low as 1.36 V μm−1 dropping by one order of magnitude, while the field enhancement factor and FE current density are up to 156.68 and 484.75 mA cm−2 respectively rising both by two orders of magnitude. This excellent FE performance stems from the characteristics of large aspect ratio, very small tip radius and high density of DNWs.

Maximizing visible Raman resolution of nanodiamond grains fabricated by coaxial arc plasma deposition through oxygen plasma etching optimization

Among the nondestructive carbon material characterization tools, the prominence of visible Raman spectroscopy has surged remarkably for many years due to its ability to explore a diverse array of carbon bonding configurations. However, to fully unlock the distinctive features concealed within carbon composite materials, additional specimen treatments or precise spectroscope calibrations are necessary. In the same regard, the tiny diamond grain size (5–10 nm) and the pronounced amount of sp2 carbon in the ultrananocrystalline diamond film represent major challenges in visible light excitation. In this work, we employ calibrated oxygen plasma reactive ion etching conditions to manifest the nanodiamond visible Raman signature from ultrananocrystalline diamond/amorphous carbon composite (UNCD/a‐C) films fabricated by coaxial arc plasma deposition. Upon plasma etching, the broad defect band in the visible Raman spectra converged toward the diamond characteristic Raman peak at 1332 cm−1. A detailed explanation of band components of the Raman spectra is extracted through peak fitting procedures. The results of Raman spectroscopy are further correlated with the electrical characteristics of the nitrogen‐doped UNCD/a‐C films due to the optimized oxygen plasma etching processes.

The improvement in heat transfer performance of single crystal silicon carbide with diamond film

In order to reduce the temperature of SiC-based electronic power devices during operation, the diamond films of different thickness were grown on 4H-SiC substrates by microwave plasma chemical vapor deposition (MPCVD) method. The thermal conductivity of the composite with 92 μm thick diamond film was measured to be 429.97 W/(m·K) by laser flash method, which is 53.56 % higher than that of individual 4H-SiC. The diamond/SiC composite was heated on the heat stage to investigate its heat transfer characteristics. The heat spread performance was improved by more than 10 %, which benefits the reliability and the service life of the electronic power device. The solid heat transfer was also simulated by COMSOL software. It was found that the thicker diamond film, the higher thermal conductivity. The thermal resistance of the interface between diamond and single crystal SiC would lead to the decrease of thermal conductivity of the composite.

Nano- and micro-crystalline diamond film structuring with electron beam lithography mask

Direct current plasma enhanced chemical vapor deposition (CVD) was employed to create polycrystalline diamond films from CH4/H2 gaseous mixture at 98 mbar pressure and various substrate temperatures between 720 °C and 960 °C. The Si chips with patterns of periodic masked and open seeded zones were used as substrates. The mask free seeded areas evolved into polycrystalline diamond films after CVD process. The diamond crystallites of the films featured single crystal ordering individually with distinct cubic (100) or octahedral (111) facets on the film surfaces. Notably, specific growth conditions were determined for obtaining diamond films composed of the crystallites of nanometre and micrometre scale. These conditions are differing from those observed for non-pattern-prepared Si substrates. The nano-crystalline diamonds emerged within the 4.5–5 A current range, with growth conditions involving 3% CH4/H2 mixture at 98 mbar. The micro-crystalline diamonds (MCDs) predominantly characterized by well-developed rectangular (100) crystal faces on the film surface were successfully grown with current settings of 5.5–6 A, under 3% CH4/H2 mixture at 98 mbar. Furthermore, MCDs characterized by entirely crystalline (111) diamond faces forming CVD film surface were attained within a growth parameter range of 4.5–5.8 A, employing 3% CH4/H2 mixture for certain samples, or alternatively, utilizing 5 A with a 1.5% CH4/H2 mixture for others. Upon thorough evaluation, it was established that SiO2, TiO2, and Cr masks are well-suited materials for the planar patterning of both nano- and micro-crystalline diamond films, and the bottom-up approach can pave the way for the production of diamond planar structures through CVD, facilitated by electron beam lithography (EBL).

Structure and properties of Si3N4-based diamond/MoS2-TiN composite films

This study aims to optimize the performance of silicon nitride (Si3N4) ceramic bearings in high-temperature and heavy-duty environments and to address the issues of insufficient lubrication and heat generation in vacuum environments. To this end, we prepared diamond and MoS2-TiN composite films on silicon nitride ceramic substrates using a hot-wire chemical vapor deposition system and a physical vapor deposition system. The experimental results show that increasing the deposition time of the diamond films can significantly improve their hardness and elastic modulus, enhance the bonding of the films with the substrate, reduce the friction coefficient, and increase the thermal conductivity. Furthermore, by appropriately reducing the sputtering power of the MoS2 film, we can effectively minimize damage to the diamond film and further enhance the overall performance of the composite film. This study offers valuable insights for addressing lubrication and heat dissipation challenges in vacuum environments.

Angular dependent terahertz emission from the interplay between nanocrystal diamond film and plasmonic metasurface

Composite structures integrated with metasurfaces and nonlinear films have emerged as alternative candidates to enhance nonlinear response. The cooperative interaction between the two components is complicated. Herein, a split-ring resonator (SRR)-type metasurface was fabricated on a free-standing nanocrystal diamond (NCD) film utilizing electron beam lithography, electron beam evaporation, and a lift-off process. The terahertz (THz) radiation from the SRR-NCD under normal incidence originates from the high-order magnetic resonance of SRR because the NCD film cannot produce detectable THz radiation at this incident angle. As increasing the incident angle, the contribution of the THz radiation from the NCD film gradually increases until reaching 40° incident angle limitation. The results indicate that this angular-dependent THz radiation is induced by the interplay between the NCD film and SRR. This study offers a new approach to investigate nonlinear processes in composite structures.

Micromechanical properties of micro- and nanocrystalline CVD diamond thin films with gradient microstructures and stresses

Chemical vapor deposition produced diamonds attract considerable scientific and industrial interest due to their exceptional mechanical and functional properties. Here, hot filament (HF) chemical vapor deposition was used to synthesize two diamond thin films with different cross-sectional microstructure and residual stresses. Structural characterization by scanning electron microscopy, Raman spectroscopy, and cross-sectional synchrotron x-ray nanodiffraction revealed different diamond morphologies. While the microcrystalline diamond film exhibits pronounced microstructural gradients expressed by gradually increasing (i) intensities of the 111 Debye-Scherrer rings, (ii) ⟨110⟩ fiber texture sharpness, (iii) grain size, and (iv) slightly oscillating residual stress at the level of −0.5 GPa, the nanocrystalline diamond film showed no pronounced cross-sectional variation of microstructure above the nucleation zone of ∼0.5 μm and a steady stress level of 0.25 GPa. In situ micromechanical cantilever bending tests revealed highly different mechanical properties of the two films. In detail, Young's modulus of 830 ± 53 and 459 ± 53 GPa, fracture stress of 12.4 ± 0.8 and 7.8 ± 1.0 GPa, and fracture toughness values of 6.9 ± 0.4 and 3.6 ± 0.3 MPa⋅m½ were evaluated for the micro- and nanocrystalline diamond films, respectively. In summary, this study provides valuable insights into the microstructure-residual stress correlation in micro- and nanocrystalline diamond films, especially illuminating their influence on micromechanical properties.

Diamond deposition on AlN using Q-carbon interlayer through overcoming the substrate limitations

Q-carbon, a quenched form of carbon, is a recently discovered carbon structure that has tremendous properties, compatibility, and potential for use in device fabrication and other electronic and mechanical applications. However, the non-equilibrium nature of the synthesis process and a very small window of growth parameters have limited the formation of Q-carbon to only low thermal conductive substrates. This study aims to overcome these limitations through extensive tuning of the parameters of diamond-like-carbon (DLC), the base structure required for the formation of Q-carbon. The as-deposited DLC films demonstrate ID/IG ratios ranging from 0.12 to 1.67, which are obtained through the optimization of laser energy density, rep rate, and deposition temperature during pulsed laser deposition. Utilizing Simulation of Laser Interaction with Materials, pulsed laser annealing (PLA) was used to directly transform the DLC films into Q-carbon while varying the PLA energy density from 0.3 J/cm2 to 1.2 J/cm2. Findings of Q-carbon formation on sapphire using different DLC films assisted in the preparation of a roadmap for overcoming the substrate limitations for Q-carbon formation. Further, Q-carbon is formed on AlN substrates for the direct deposition of diamond films without the requirement of a non-carbon interfacial layer or nanodiamond seeding layer. The large-area and uniform diamond growth on Q-carbon shows well-faceted and five-fold twinned growth with a 70 % improvement in the residual compressive stress of diamond on AlN. Such a method of diamond deposition on AlN provides the opportunity to address the thermal management issues in wide- and ultra-wide bandgap high-power electronic devices.

Processing of diamond films with azimuthal texture on silicon wafer for quantum systems

Processing of diamond films with azimuthal texture on silicon wafer for quantum systems

Effects of methane concentration on tribological properties of diamond films prepared on different ceramic substrates

ABSTARCT Diamond films were prepared on silicon nitride and zirconia ceramic substrates using hot filament chemical vapor deposition (HFCVD). The surface morphology, friction, and wear properties of the diamond films prepared with different methane concentrations (2%, 4%, and 6%) were compared using scanning electron microscopy, Raman spectroscopy, X-ray diffraction, and friction and wear testing machines. The results showed that, with an increase in the methane concentration, the diamond particles gradually changed from micro- to nanodiamonds, and the grain size first increased and then decreased. The diamond films on silicon nitride substrates were of excellent quality, with good wear resistance, strong adhesion, and wear rates of 2.857 × 10−8 mm−3•m−1•N−1, 5.151 × 10−8 mm−3•m−1•N−1, and 1.334 × 10−7 mm−3•m−1•N−1, respectively. The diamond films on zirconia substrates had more impurities on the surface, higher internal stress, poorer wear resistance, and weaker adhesion, with wear rates of 3.789 × 10−8 mm−3•m−1•N−1, 5.899 × 10−8 mm−3•m−1•N−1, and 2.074 × 10−7 mm−3•m−1•N−1, respectively. Hence, the deposition of diamond films on ceramic substrates significantly reduced the friction coefficient, and the performance of diamond films on silicon nitride substrates was excellent.

Growth and surface structrue of hydrogen terminal diamond thin films

The conductivity of hydrogen-terminated diamond is a limiting factor in its application in field-effect transistor devices. The traditional preparation process hinders the improvement of the electrical properties of hydrogen-terminated diamond due to impurity elements in the diamond bulk and surface damage caused by processing near the diamond surface. To overcome this, researchers have explored the epitaxial growth of a high-purity and flat-surfaced diamond thin film on a diamond substrate. However, this approach still faces challenges in film characterization and achieving high surface smoothness. In this study, microwave plasma chemical vapor deposition technology is used to epitaxially grow a sub-micron thick diamond film on a nitrogen-doping chemical vapor deposition diamond substrate of 10 mm × 10 mm × 0.5 mm in size. The influence of methane concentration on the growth and conductivity of diamond film is investigated. The test results reveal that the growth thickness of the diamond film ranges from 230 to 810 nm, and the nitrogen concentration in the epitaxial layer is lower than 1×10&lt;sup&gt;16&lt;/sup&gt; atom/cm&lt;sup&gt;3&lt;/sup&gt;. Three growth modes are observed for the homoepitaxial growth of the diamond thin film under different methane concentrations. A methane concentration of 4% enables two-dimensional planar growth of diamond, resulting in a smooth and flat surface with a roughness of 0.225 nm (10 μm×10 μm). The formation of different surface morphologies is attributed to the growing process and etching process of diamond. Surface low-energy electron diffraction testing indicates that the surface of the diamond film undergoes a structural transition from oxygen terminal (1×1: O) to hydrogen terminal (2×1: H) when grown for a short period of time. X-ray photoelectron spectroscopy analysis reveals an extremely low ratio of oxygen element to nitrogen element, giving the grown diamond film P-type conductivity characteristics. The Hall test results demonstrate that the hydrogen-terminated diamond film grown with a methane concentration of 4% exhibits the highest conductivity, with a square resistance of 4981 Ω/square and a hole mobility of 207 cm&lt;sup&gt;2&lt;/sup&gt;/(V·s). This enhanced conductivity can be attributed to the lower defect density observed under these specific conditions. The findings of this study effectively improve the electrical properties of hydrogen-terminated diamond, and contribute to the development and practical application of high-power diamond devices.

Sub-diffraction limited nanogroove fabrication of 30 nm features on diamond films using 800 nm femtosecond laser irradiation

By controlling the 800 nm fs laser energy and applying an isopropyl alcohol environment, controlled sub-diffraction limited lithography with a characteristic structure of approximately 30 nm was achieved on the surface of diamond films, and diamond gratings with a period of 200 nm were fabricated. The fabrication of single grooves with a feature size of 30 nm demonstrates the potential for patterning periodic or nonperiodic structures, and the fabrication of 200 nm periodic grating structures demonstrates the ability of the technique to withstand laser proximity effects. This enhances the technology of diamond film nanofabrication and broadens its potential applications in areas such as optoelectronics and biology.