Mosaic growth and characteristics of 2-inch single-crystal diamond

Introduction Diamond, owing to its exceptional impact resistance, high thermal conductivity, broad-spectrum optical transparency, elevated breakdown field strength, and superior carrier mobility, finds widespread application in diverse fields such as high-power laser windows, efficient heat spreader, and high-performance semiconductor devices. Experimental 1. Heteroepitaxial Growth of Polycrystalline Diamond on Si, SiC, and Mo Substrates:In this part, substrates employed include double-side polished 4H-polytype SiC, (100) single-side polished single-crystal Si wafers, and Mo substrates. Ultrasonic grinding of substrates using diamond powder ethanol suspension to promote the dispersion of nucleation seeds, followed by sequential ultrasonic cleaning in acetone, ethanol, and deionized water.Subsequently, MPCVD was used for diamond growth, using hydrogen, methane, oxygen, and a mixture of hydrogen and nitrogen as reaction gases. Using different processes to produce efficient heat sinks and high-power laser windows. 2. Homoepitaxial Growth of Single-Crystal Diamond on Diamond Substrates:In the homoepitaxial growth process, (100) double-side polished single-crystal diamond substrates are utilized. No need for ultrasonic grinding steps, cleaning steps are the same as above. Then use MPCVD for homogeneous epitaxial growth of single-crystal diamond. 3. Investigation of Graphitized Surface Devices on Diamond:This study also investigated the graphitization devices on diamond surfaces. A high-temperature metal-catalyzed method is employed to promote surface graphitization of diamond. Firstly, polish and clean the diamond. Subsequently, a 300 nm thick nickel layer is deposited on the diamond surface. Rapid thermal annealing is then performed at 1300°C to form a highly conductive graphite layer. This process successfully prepares capacitor samples with a graphite-diamond-graphite three-layer structure. Results and Discussion 1. High-Power Laser Window Plates:The fabricated laser window plates utilize Si, SiC and Mo substrates, employing an ultra-low nitrogen growth process with a growth rate of approximately 3.7 µm/h. After double-sided polishing, the thickness reaches 1 mm. At room temperature, the transmittance at 10.6 µm wavelength approaches the theoretical maximum, reaching 67.9%. The overall thermal conductivity exceeds 1950 W/mK, approximating that of single-crystal diamond.Raman spectroscopy and XRD results indicate that the primary component is polycrystalline diamond with a (110) crystallographic orientation. Laser testing results demonstrate that these window plates possess a high laser-induced damage threshold with a peak energy of 60 J/cm2 and a peak power of 12 MW/mm2, capable of withstanding high-power CO2 laser output. 2. Heat Spreader:This study involves depositing diamond on Si and SiC substrates, forming diamond-based composite materials. This significantly improves the heat dissipation efficiency of the devices, bringing their performance closer to theoretical limits. The deposition process employs a low-nitrogen technique to balance growth rate and defect density, achieving a growth rate of approximately 5 µm/h.Raman spectroscopy and XRD results indicate that the primary component is polycrystalline diamond with a (110) crystallographic orientation. Although the increased nitrogen content results in lower optical transmittance compared to optical window plates, the grain size can be increased from 124 nm to 22 μm through production process adjustments, thereby enhancing thermal conductivity.Test results demonstrate that the thermal conductivity of the Si-diamond composite material reaches 450 W/mK,3 times that of single-crystal Si. The SiC-diamond composite material achieves a thermal conductivity of 500 W/mK,3.5 times that of SiC. 3. Single-Crystal Diamond:The transmittance and thermal conductivity of single-crystal diamond grown by homoepitaxial growth are superior to those of polycrystalline diamond. However, limitations in size and growth conditions restrict its large-scale application in heat spreaders and optical windows. Single-crystal diamond is more suitable for manufacturing semiconductor devices such as diamond capacitors, Schottky diodes, and hydrogen-terminated MOSFETs.The author has conducted research on doping of single-crystal diamond. Characterization through Raman spectroscopy, XRD, and TEM confirms that the primary component is single-crystal diamond with a (100) crystallographic orientation. The dislocation density is below 103/cm2, meeting the stringent requirements for semiconductor devices. 4. Graphite-Diamond-Graphite Capacitors:Utilizing prepared diamond, graphite-diamond-graphite capacitors were fabricated. Measurements using a semiconductor parameter analyzer revealed a high capacitance value of 4 nF. TCAD simulation indicated a breakdown voltage as high as 1100 V. This research explores a novel method for diamond capacitor fabrication. Conclusions Diamond heteroepitaxial grown on Si, SiC, and Mo substrates has prepared high-power laser windows with 67.9% optical transmittance at 10.6 μm wavelength, and composite materials with thermal conductivity enhanced to 3-3.5 times that of the original materials. Homoepitaxially grown diamond on single-crystal diamond substrates exhibits a dislocation density below 10³/cm², meeting the requirements for semiconductor device substrates. Furthermore, this research has developed a novel diamond capacitor fabrication technique, yielding capacitors with a capacitance of 4 nF and a breakdown voltage of 1100 V.

Diamond offers a range of unique properties, including wide band of optical transmission, highest thermal conductivity, stiffness, wear resistance and superior electronic properties. Such high-end properties are not found in any other material, so theoretically it can be used in many technological applications. But the shortcoming has been the synthesis of the diamond material in the laboratory for any meaningful use. Although microwave plasma chemical vapour deposited (MPCVD) has been in practice since 1980s for the diamond growth but it is in the past 7-8 years that its potential has been realised by the industry due to capability of MPCVD to deposit diamond, pure and fast, for commercial uses. There are many CVD techniques for growing diamond but among them MPCVD can only make single crystal diamond (SCD) effectively. SCD grown by MPCVD is also superior to other forms of diamond produced in the laboratory. For example, SCD is necessary for the best electronic properties - often outperforming the polycrystalline diamond (PCD), the high pressure high temperature (HPHT) diamond and the natural diamond. In many applications the short lateral dimensions of the lab-grown diamond available is a substantial limitation. Polycrystalline CVD diamond layers grown by hot filament CVD solved this problem of large area growth, but the presence of grain boundaries are not appropriate for many uses. On the other hand, there is still limitation in the area over which SCDs are grown by MPCVD, only upto 10-15 mm lateral sizes could have been achieved so far, while there are recipes which rapidly grow several mm thick bulk SCDs. This lateral size limitation of SCDs is primarily because of the small seed substrate dimension. Although natural and HPHT diamonds may not be suitable for the intended application, still they are routinely used as substrates on which SCD is deposited. But the problem lies in the availability of large area natural SCD seeds which are extremely rare and expensive. Moreover, large diamond substrate plates suitable for CVD diamond growth have not been demonstrated by HPHT because of the associated high economic risk in their fabrication and use. Other than lateral dimension, purity of SCD is also very important for technological use. Natural diamond is often strained and defective, and this causes twins and other problems in the CVD overgrowth or fracture during synthesis. In addition, dislocations which are prevalent in the natural diamond substrate are replicated in the CVD layer, also degrading its electronic properties. HPHT synthetic diamond is also limited in size, and generally is of poorer quality in the larger stones, with inclusions being a major problem. There will be much research interest in the next 10 years for the MPCVD growth of SCD. Purer and bigger SCDs will be tried to grow with faster and reproducible MPCVD recipes. Here the MPCVD growth of SCD is being reviewed keeping in mind its huge technological significance in the next decades or so. Discoveries of the commercial productions of silicon, steel, cement different materials have built modern societies but higher scales will be achieved with the advent of lab-grown diamond.

The intrinsic properties of diamond make this material theoretically very suitable for applications in medical physics. Until now ionization chambers have been fabricated from natural stones and are commercialized by PTW, but their fairly high costs and long delivery times have often limited their use in hospital. The properties of commercialized intrinsic polycrystalline diamond were investigated in the past by many groups. The results were not completely satisfactory due to the nature of the polycrystalline material itself. In contrast, the recent progresses in the growth of high mobility single crystal synthetic diamonds prepared by chemical vapor deposition (CVD) technique offer new alternatives. In the framework of the MAESTRO project (Methods and Advanced Treatments and Simulations for Radio Oncology), the CEA-LIST is studying the potentialities of synthetic diamond for new techniques of irradiation such as intensity modulated radiation therapy. In this paper, we present the growth and characteristics of single crystal diamond prepared at CEA-LIST in the framework of the NoRHDia project (Novel Radiation Hard CVD Diamond Detector for Hadrons Physics), as well as the investigations of high mobility single crystal CVD diamond for radiotherapy photon beam monitoring: dosimetric analysis performed with the single crystal diamond detector in terms of stability and repeatability of the response signal, signal to noise ratio, response speed, linearity of the signal versus the absorbed dose, and dose rate. The measurements performed with photon beams using radiotherapy facilities demonstrate that single crystal CVD diamond is a good alternative for air ionization chambers for beam quality control.

Clinical studies of optimised single crystal and polycrystalline diamonds for radiotherapy dosimetry

High-rate homoepitaxial growth of CVD single crystal diamond by dc arc plasma jet at blow-down (open cycle) mode

Fabrication and characterizations of large homoepitaxial single crystal diamond grown by DC arc plasma jet CVD

ABSTRACTGrowth of large area, single or almost single crystal diamond is of great importance to the electronics industry. In this work, single crystal diamonds were implanted with C+ ions, inducing a subsurface damage layer in the diamond lattice. Homoepitiaxial diamond films were then grown on the implanted crystals using a microwave plasma CVD reactor. Films grown on on-axis substrates were dominated by large numbers of hillocks, renucleation and penetration twins, while miscut substrates exhibited stepflow growth. The homoepitaxial layers were separated from the substrate by a water-based etch which selectively attacks the subsurface damage layer of the diamond lattice. The films were analyzed by Raman scattering, scanning electron microscopy (SEM), optical microscopy, photo- and cathodoluminescence, and x-ray diffraction. CVD growth on adjacent, oriented substrates formed a single, continuous diamond layer. The resulting homoepitaxial film quality, orientation, defect density and it's relationship to the underlying substrates were compared at various points on the surface, particularly the region which overgrew the gap between different substrates.

The epitaxial lateral growth of single-crystal diamond (SCD) using a plate-to-plate microwave plasma chemical vapor deposition (MPCVD) reactor under high pressure is investigated. The radicals’ distribution in H2/CH4 plasma as a function of pressure was locally detected by optical emission spectroscopy (OES). Raman spectroscopy and optical microscope were employed to analyze the properties of SCD deposited in different pressure. The OES results show that radicals’ distribution along the substrate direction is symmetrical under 20 kPa pressure. The symmetrical distribution of radicals at 20 kPa is in favor of epitaxial lateral growth SCD around the seed and without polycrystalline diamond (PCD) rim. When the pressure is increased to 21.5 kPa, the optical emission spectra center of plasma shifts close to the microwave reflector where is far away from the microwave source. The contact state between the diamond seed and the plasma is deteriorated and the PCD rim occurs in the plasma uncovered area. While the epitaxial lateral growth pattern occurs in the plasma covered area and the lateral growth rate of this region improves with the increase of pressure. A higher growth rate does not result in good quality; meanwhile, the diamond growth step spacing and direction become inconsistent in the transition zone as a function of pressure increasing. Finally, the overall effective lateral expansion area does not increase with the improvement of pressure. Therefore, the uniform and symmetrical distributed plasma is more conducive to the epitaxial lateral growth of SCD, and the effective expansion growth SCD can be realized at 20 kPa.

A comparative study of the growth dynamics and tribological properties of nanocrystalline diamond films deposited on the (110) single crystal diamond and Si(100) substrates

Step growth in single crystal diamond grown by microwave plasma chemical vapor deposition

Single crystal diamond (SCD) growth was performed in optimized pocket substrate holders at a high pressure (240 Torr) and a high power density (∼1000 W/cm3). In an effort to overcome the challenges of growing large area SCD substrates without a corresponding polycrystalline diamond (PCD) rim, a growth recipe using these pocket holders was developed. This growth recipe controls the substrate temperature (Ts) and the incident microwave power (Pinc) in a prescribed function of growth time. Through this process, the feasibility to enlarge the SCD substrate in situ, i.e., during the growth itself is shown. By allowing the temperature to increase from ∼980 °C to 1040 °C, then reducing the temperature, and then allowing it to drift up again, the deposition process alternates between the fast growth of the different crystal directions (i.e., 〈110〉, 〈111〉, and 〈100〉) and a slow growth to smoothen the top surface. This leads to an increased lateral SCD growth. The slow growth of the crystal faces in turn leads to a smooth and enlarged top surface. Certain strategies such as the termination of the growth process at the appropriate time are critical in obtaining flat and smooth SCD surfaces without the formation of any PCD rim. The SCD substrates grown via this method have been analyzed by optical and scanning electron microscopies. The lateral SCD surface area increased between 1.7 and 2 times greater than the initial seed surface area during one continuous run. The deposited SCDs have high growth rates of ∼30 μm/h resulting in smooth, flat and rimless substrates, hence indicating the improvement in the quality and morphology of the deposited substrates.

Exploring constant substrate temperature and constant high pressure SCD growth using variable pocket holder depths

Homoepitaxial lateral growth of single-crystal diamond with eliminating PCD rim and enlarging surface area

Investigation of homoepitaxial growth by microwave plasma CVD providing high growth rate and high quality of diamond simultaneously

Structural transformation of C+ implanted diamond and lift-off process