Polycrystalline Diamond Films Research Articles

Annealing process and temperature effects on silicon-vacancy and germanium-vacancy centers in CVD grown polycrystalline diamond

The annealing treatment plays a crucial role in tailoring the properties of synthetic diamond materials, especially those doped with various elements in order to form specific color centers like nitrogen-vacancy (NV), silicon-vacancy (Si-V), germanium-vacancy (Ge-V), etc. This study delves into the annealing of 175 μm-thick Ge-doped polycrystalline diamond (PCD) films grown by microwave plasma-assisted chemical vapor deposition (MPCVD). Large-area PCD plate was cut into smaller equivalent 5 × 5 mm2 pieces, which were separately subjected to annealing in microwave plasma in H2 atmosphere, to annealing in vacuum or to annealing under high-pressure high-temperature conditions (HPHT, 5.9 GPa, 2000 °C). The structure, phase composition and photoluminescence (PL) of samples before and after various annealing processes were investigated. All applied types of annealing enhance both the Si-V and Ge-V lines in PL at room temperature. Increasing annealing temperature leads to gradual decrease of full widths at half-maxima (FWHM) of diamond Raman peak (1332.5 cm−1), as well as Si-V (738 nm) and Ge-V (602 nm) PL peaks. In addition, the limitations for each type of annealing are established. The obtained results are crucial for the design of CVD-grown Ge-doped and Si-doped PCD materials that can be used for applications in photonics such as single photon sources, biomarkers, as well as for the fabrication of optical diamond thermometers.

Growth of diamond in liquid metal at 1 atm pressure.

Natural diamonds were (and are) formed (thousands of million years ago) in the upper mantle of Earth in metallic melts at temperatures of 900-1,400 °C and at pressures of 5-6 GPa (refs. 1,2). Diamond is thermodynamically stable under high-pressure and high-temperature conditions as per the phase diagram of carbon3. Scientists at General Electric invented and used a high-pressure and high-temperature apparatus in 1955 to synthesize diamonds by using molten iron sulfide at about 7 GPa and 1,600 °C (refs. 4-6). There is an existing model that diamond can be grown using liquid metals only at both high pressure and high temperature7. Here we describe the growth of diamond crystals and polycrystalline diamond films with no seed particles using liquid metal but at 1 atm pressure and at 1,025 °C, breaking this pattern. Diamond grew in the subsurface of liquid metal composed of gallium, iron, nickel and silicon, by catalytic activation of methane and diffusion of carbon atoms into and within the subsurface regions. We found that the supersaturation of carbon in the liquid metal subsurface leads to the nucleation and growth of diamonds, with Si playing an important part in stabilizing tetravalently bonded carbon clusters that play a part in nucleation. Growth of (metastable) diamond in liquid metal at moderate temperature and 1 atm pressure opens many possibilities for further basic science studies and for the scaling of this type of growth.

Heavily boron-doped polycrystalline diamond films: Microstructure, chemical composition investigation and plasma in-situ diagnostics

The introduction of boron brings excellent electrical conductivity to diamond films, but also induces uncontrollability of the doping process. Therefore, it is crucial to the monitor of the growth and doping processes. In this work, to establish the correlation between the gas-phase chemical reactions and the microstructure characteristics of heavily boron-doped diamond (BDD) films, the plasma reactions in the chemical vapor deposition (CVD) process of BDD films were in-situ diagnosed and monitored using optical emission spectroscopy (OES), and the effect of different B/C ratios (from 10,000 to 60,000 ppm) on the microstructure, chemical composition were investigated comprehensively. As the B/C ratio increases, the insufficient gas-phase excitation and the “hydrogen abstraction” reaction of BH species lead to a massive loss of H species in the gas-phase of plasma, which is unfavorable for the diamond growth, weakens the etching on sp2 carbon, induces the development of defects and seriously damages the diamond films quality. The in-situ diagnostics and monitoring of the plasma state can realize the optimization of the growth and doping process for heavily doped polycrystalline BDD films, which is highly significant for its preparation and application.

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.

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.

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).

Fabrication of polycrystalline diamond films with various boron doping levels deposited on WC–Co electrode for organic pollutants oxidation

Fabrication of polycrystalline diamond films with various boron doping levels deposited on WC–Co electrode for organic pollutants oxidation

Low-volume-loss surface polishing with a krypton fluoride excimer laser for polycrystalline diamond films

Surface polishing of hard diamond coatings is a key technique for applying such coatings in industry. In this study, we demonstrated surface modification of polycrystalline diamond films with minimal volume loss of the films by vertical irradiation of KrF excimer laser beams. Optimized laser scanning selectively removed surface asperities and reduced the surface roughness from ∼0.1 to ∼0.05 μm. Raman spectroscopic measurements revealed that laser polishing involves the phase transformation of diamond to amorphous carbon phases and thermal oxidation or evaporation of the amorphous phases. The residual amorphous carbon was almost completely removed by subsequent laser irradiation at appropriate fluences. We consider that the surface texture inherent to polycrystalline diamond films plays an important role in the concentration of laser beams on the nearby film surface. From reciprocating slide-type friction tests, we found that laser polishing decreased the initial friction coefficient from 0.5 to 0.1–0.3 against alumina balls and reduced the abrasion of the mating materials.

Formation of Ge-V color centers in poly- and monocrystalline CVD diamond: A comparative study

Germanium-Vacancy (Ge-V) color centers in diamond have narrow-band photoluminescence (PL) at room temperature (RT) and attract considerable attention due to their possible application in quantum information technologies, biomedicine, and local optical thermometry. In this work, we used microwave plasma chemical vapor deposition (MPCVD) to synthesize Ge-doped polycrystalline diamond (PCD) films and single-crystal diamond (SCD) epitaxial layers in hydrogen-methane-germane gas mixtures. Thick (>100 μm) layers of both types were grown to analyze their structure and luminescence characteristics. The first demonstration of the absorption of Ge-V centers in both PCD and SCD materials at low temperatures is presented. The sufficient narrowing of the Ge-V PL line for the SCD sample in comparison with the PCD sample was observed. On the other hand, the intensity of the Ge-V signal was an order of magnitude higher in the PCD sample compared to the SCD sample. A set of single Ge-V centers formed during CVD has been demonstrated. The results obtained can be used to manufacture and design various photonic devices based on Ge-V color centers.

Secondary electron emission of B-doped/undoped double-layer heteroepitaxial single crystal diamond film

A B-doped/undoped double-layer single crystal diamond structure was proposed to enhance secondary electron emission (SEE), and the double-layer single crystal diamond film was heteroepitaxially grown on MgO substrate by microwave plasma chemical vapor deposition. The crystal quality, surface morphology and conductivity of the film were studied. It is found that the film has high crystal quality, the full width at half maximum of X-ray diffraction rocking curve is 0.14°, and the surface roughness is small. For these reasons, the B-doped/undoped double-layer single crystal diamond film has better SEE performance than the B-doped/undoped double-layer polycrystalline diamond film. At the incident electron energy of 2 keV, the SEE yield of B-doped/undoped double-layer single crystal diamond reached 22.4. The physical model calculation results indicate that at a low B doping concentration, less sp2 carbon and smaller surface roughness are beneficial to improve the SEE yield.

High-speed growth of high-quality polycrystalline diamond films by MPCVD

High-speed growth of high-quality polycrystalline diamond films by MPCVD

Synthesis of Polycrystalline Diamond Films in Microwave Plasma at Ultrahigh Concentrations of Methane

Polycrystalline diamond (PCD) films are usually grown by chemical vapor deposition (CVD) in hydrogen–methane mixtures. The synthesis conditions determine the structure and quality of the grown material. Here, we report the complex effect of the microwave plasma CVD conditions on the morphology, growth rate and phase composition of the resulting PCD films. Specifically, we focus on the factors of (i) increased methane concentrations (νc) that are varied over a wide range of 4%–100% (i.e., pure methane gas) and (ii) substrate temperatures (Ts) varied between 700–1050 °C. Using scanning electron microscopy, X-ray diffraction and Raman spectroscopy, we show that diamond growth is possible even at ultrahigh methane concentrations, including νc = 100%, which requires relatively low synthesis temperatures of Ts &lt; 800 °C. In general, lower substrate temperatures tend to facilitate the formation of higher-quality PCD films; however, this comes at the cost of lower growth rates. The growth rate of PCD coatings has a non-linear trend: for samples grown at Ts = 800 °C, the growth rate increases from 0.6 µm/h at νc = 4% to 3.4 µm/h at νc = 20% and then falls to 0.6 µm/h at νc = 100%. This research is a step toward control over the nature of the CVD-grown PCD material, which is essential for the precise and flexible production of diamond for various applications.

Effect of diamond seeds size on the adhesion of CVD diamond coatings on WC-Co instrument

In this study, we investigated the effect of the size of diamond seeds on the adhesion of multilayered polycrystalline diamond (PCD) films, grown by microwave plasma-assisted chemical vapor deposition (MPCVD). For that, identical WC-Co substrates were separately seeded by a set of diamond powders with various average particle sizes from water-based suspensions using similar seeding procedures. This investigation included powders with a difference in particle sizes of nearly 3 orders of magnitude: from 5 nm up to 2-4 μm. Seeded substrates were used to grow 8-10 μm thick multilayered PCD films using MPCVD with time-limited cycling injections of N2 gas. The Raman spectra and scanning electron microscopy (SEM) studies showed the similarity of microstructure and phase composition of all grown films, which confirmed that all films were grown in similar conditions. The performed scratch tests revealed sufficient differences in the adhesion of the films seeded with different diamond particles. The PCD film grown on 250-500 nm particles delaminated even before any mechanical investigations. The substrates seeded with 50 nm particles allowed the formation of the stable PCD film, but it started flaking under a load as small as 15 N. The 2-4 μm powder allowed the formation of PCD film with decent adhesion, which had local flaking under scratch test, which can be explained by the inhomogeneity of seeds distribution. Detonation nanodiamond (DND) powders allowed the formation of continuous diamond films with decent adhesion, however, powders with positive zeta potential were superior due to a much lower agglomeration of separate particles.

Thickness Effects on Boron Doping and Electrochemical Properties of Boron-Doped Diamond Film.

As a significant parameter in tuning the structure and performance of the boron-doped diamond (BDD), the thickness was focused on the mediation of the boron doping level and electrochemical properties. BDD films with different thicknesses were deposited on silicon wafers by the hot filament chemical vapor deposition (HFCVD) method. The surface morphology and composition of the BDD films were characterized by SEM and Raman, respectively. It was found that an increase in the BDD film thickness resulted in larger grain size, a reduced grain boundary, and a higher boron doping level. The electrochemical performance of the electrode equipped with the BDD film was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in potassium ferricyanide. The results revealed that the thicker films exhibited a smaller peak potential difference, a lower charge transfer resistance, and a higher electron transfer rate. It was believed that the BDD film thickness-driven improvements of boron doping and electrochemical properties were mainly due to the columnar growth mode of CVD polycrystalline diamond film, which led to larger grain size and a lower grain boundary density with increasing film thickness.

CVD Diamond Growth Enhanced by a Dynamic Magnetic Field

A dynamic magnetic field (DMF) with different angular frequencies (50, 100, and 150 π rad/s) was introduced during diamond growth via hot filament chemical vapor deposition (HFCVD). The effects of the dynamic magnetic field on the growth rate, diamond quality, growth orientation, and deposition uniformity of large-area diamond films were investigated with scanning electron microscopy (SEM), X-ray diffractometry (XRD), and Raman spectroscopy. The correlation between diamond growth and angular frequency was discussed. The results showed that a faster growth rate (about 2.5 times) and higher diamond quality were obtained by increasing the angular frequency of the DMF. A (100) textured polycrystalline diamond film was achieved, and the preferential orientation was found to evolve from (110) to (100), while the expected uniform deposition of a large-area diamond film under DMF was not achieved. The enhancement effect of the DMF was ascribed to the activation of more gas molecules, which participated in CVD diamond growth.

Combined HF+MW CVD Approach for the Growth of Polycrystalline Diamond Films with Reduced Bow

A combination of two methods of chemical vapor deposition (CVD) of diamond films, microwave plasma–assisted (MW CVD) and hot filament (HF CVD), was used for the growth of 100 µm-thick polycrystalline diamond (PCD) layers on Si substrates. The bow of HF CVD and MW CVD films showed opposite convex\concave trends; thus, the combined material allowed reducing the overall bow by a factor of 2–3. Using MW CVD for the growth of the initial 25 µm-thick PCD layer allowed achieving much higher thermal conductivity of the combined 110 µm-thick film at 210 W/m·K in comparison to 130 W/m·K for the 93 µm-thick pure HF CVD film.

High pressure and high temperature treatment of chemical vapor deposited polycrystalline diamond: From opaque to transparent

The enhanced optical properties of chemical vapor deposited (CVD) diamond have been pursued in academia and industry for many applications. However, the barrier of CVD technology limits the application field of diamond. Herein, the performance of CVD polycrystalline diamond thick films was improved by high-pressure and high-temperature (HPHT) treatment. The microstructures of CVD polycrystalline diamond films before and after HPHT treatments were thoroughly examined using optical microscope, UV–visible and infrared absorption, Raman spectroscopy, scanning electron microscope (SEM) and transmission electron microscope (TEM). It is found that the transparency of the CVD samples at 10 GPa increases dramatically with processing temperatures, from the original opacity to almost full optical transparency. Through spectroscopic and microstructural analyses, the modification mechanism of CVD polycrystalline diamond under HPHT conditions is proposed. The results show that the HPHT treatment can significantly enhance the optical properties of the starting CVD polycrystalline diamond films.

High Performance of Normally‐On and Normally‐Off Devices with Highly Boron‐Doped Source and Drain on H‐Terminated Polycrystalline Diamond

AbstractDiamond exhibits large application potential in the field of power electronics, owing to its excellent and desirable electronic properties. However, the main obstacles to its development originate from the small‐sized single‐crystal wafers and the instability of the electrical conductivity. This work presents a metal‐oxide‐semiconductor field‐effect transistor (MOSFET) on a diamond substrate derived from a five‐inch (110) highly preferred polycrystalline diamond film. The MOSFETs with excellent performance are fabricated by combining an H‐terminated channel and an epitaxially grown boron‐doped layer as the source/drain contacts of the diamond devices. According to the electrical statistical results of ≈110 devices on the polycrystalline diamond substrate, 44% of devices show normally‐off operation with a maximum current density of 400 mA mm−1, while 56% of devices demonstrate normally‐on operation with a maximum current density of 525 mA mm−1. The normally‐off characteristics are more related to the higher amounts of nitrogen concentration than the grain boundaries. The stable boron‐doped source and drain provide a high concentration of holes, which facilitate transport in the surface p‐type channel induced by the H‐termination. The characteristics of the MOSFETs are inspiring for the fabrication of complementary inverter circuits on large diamond wafers.

Capillary adhesion governs the friction behavior of electrochemically corroded polycrystalline diamond

The friction behavior of rough polycrystalline diamond (PCD) surfaces is important in many applications and devices that are required to operate in various harsh environments and it can be argued that a thorough understanding of the friction behavior is essential to the application performance. However, the interplay between electrochemical corrosion, capillary adhesion and friction behavior of PCD in multi-asperity contacts is still poorly understood. In this work, we quantify the interfacial capillary adhesion at contact interfaces and its effect on the friction response, between a colloidal microsphere and rough PCD films before and after electrochemical corrosion, for water-immersed, low RH, and humid air conditions. For these multi-asperity contacts, we demonstrate how electrochemical corrosion influences the surface hydrophilicity of the PCD surfaces, and how capillary adhesion due to water condensation contributes to the friction force. We estimate the capillary forces from both the microscopic lateral force experiments and elastoplastic boundary element method (BEM) contact calculations. The combined results indicate strongly that the observed increase in friction force on electrochemically-corroded PCD surfaces is governed by enhanced capillary adhesion at the contact interface, as affected by surface hydrophilicity and environmental humidity.

Light emission dynamics of silicon vacancy centers in a polycrystalline diamond thin film.

Diamond thin films can be, at a relatively low-cost, prepared with a high-density of light-emitting negatively charged silicon vacancy (SiV) centers, which opens up the possibility of their application in photonics or sensing. The films are composed of diamond grains with both the SiV centers and sp2-carbon phase, the ratio of these two components being dependent on the preparation conditions. The grain surface and the sp2-related defects might act as traps for the carriers excited within the SiV centers, consequently decreasing their internal photoluminescence (PL) quantum efficiency. Here, we show that in a 300 nm thick polycrystalline diamond film on a quartz substrate, the SiV centers in the diamond grains possess similar temperature-dependent (13-300 K) PL decay dynamics as the SiV centers in monocrystalline diamond, which suggests that most of the SiV centers are not directly interconnected with the defects of the diamond thin films, i.e. that the carriers excited within the centers do not leak into the defects of the film. The activation energy ΔE = 54 meV and the attempt frequency α = 2.6 were extracted from the measured data. These values corresponded very well with the published values for SiV centers in monocrystalline diamond. We support this claim by measuring the transient absorption via a pump and probe technique, where we separated the nanosecond recombination dynamics of carriers in SiV centers from the picosecond decay dynamics of polycrystalline diamond defects. Our results show that PL emission properties of SiV centers in polycrystalline diamond thin films prepared via chemical vapor deposition are very similar to those in monocrystalline diamond thereby opening the door for their application in diamond photonics and sensing.