Single Crystal Diamond Substrates Research Articles

An interior damage free approach for nanosecond pulsed laser ablation of single crystal diamond via metal film induced self-maintaining graphitization

When laser ablation was conducted on an uncoated single-crystal diamond (SCD) substrate, interior damage and random ablation were observed. Metal film-induced self-maintaining graphitization (MISG) was proposed as a generic approach to solve this problem. MISG was realized through coating a ∼ 100-nm-thick metal film on an SCD substrate. Experiments involving laser irradiation of metal films, such as Au-, Al-, Ti-, and Pt-coated SCD substrates, revealed that the material removal depths were the same when the output power was the same and that the surface was covered by graphite after laser irradiation. In addition, the laser-induced damage to the upper or lower surface in the case of the uncoated SCD substrate disappeared. A semitransparent model based on Beer-Lambert law and an opaque model based on modified Level-Set method were built to simulate laser irradiation on uncoated and metal–coated SCD substrates. In the case of the uncoated sample, the laser energy was largely absorbed by the areas with high-concentration defects, leading to preferential graphitization. In the case of the metal-coated sample, a graphite layer was thermally induced on the SCD surface via heat transition during the period of laser irradiation of the metal film. Subsequently, the graphite layer was self-maintaining, and the material removal acted like a graphite piston sinking to the interior of the SCD substrate. This study demonstrates the feasibility of MISG as a universal approach for avoiding interior damage during laser ablation of SCD substrates.

(Invited) Preparation of N-Type and P-Type Doped Single Crystal Diamonds with Laser-Induced Doping and Microwave Plasma Chemical Vapor Deposition

In this study, n-type doped single crystal diamonds were successfully prepared under normal temperature and pressure conditions using laser-induced doping. 248nm pulsed laser beams with nanosecond duration were irradiated on the single crystal diamond substrate immersing in an 85% phosphoric acid solution and it introduced phosphorus doping to form an n-type doped thin layer. The resistivity of the doped region significantly decreased compared to that of the single crystal diamond. After depositing a titanium electrode, the resistivity of the doped film obtained by Van der Pauw Technique was determined to be 1.3×10-6 Ω·m. Raman spectroscopy confirmed the absence of carbon or graphite phases in the laser-induced doped diamond, indicating that the enhanced conductivity was due to phosphorus incorporation.Furthermore, p-type doped single crystal diamonds were successfully prepared by introducing boron during the growth process using Microwave Plasma Chemical Vapor Deposition（MPCVD）. It was demonstrated that the proposed technique can introduce impurities into single crystal diamonds to form doped conductive thin layers, which has potential applications in the field of microdevices and integrated circuits.

Evaluation of the effect of oxygen addition on charge carrier transport properties in single-crystal diamond growth

The effects of oxygen addition during single-crystal diamond growth by microwave plasma CVD method on crystal surface morphology and charge carrier transport properties were evaluated. Diamond single-crystals were homoepitaxially grown on (001) surface of high-pressure and high-temperature (HPHT) synthesized type IIa single-crystal diamond substrates with a fixed methane concentration of 1 % and oxygen concentrations of 0–0.8 %. Inverted pyramid-shaped pits were generated as the oxygen concentration increased. The free exciton recombination emission intensity in the cathodoluminescence spectrum reached a maximum at oxygen concentration of 0.5 %. The samples with oxygen concentrations of 0.5 % and 0.8 % showed excellent charge collection efficiency and energy resolution. On the other hand, the mobility-lifetime (μτ) product was only (7.1 ± 1.7) × 10−5 cm2/V, which is approximately 1/4 of that of the sample with 0.2 % methane and no oxygen addition.

Acoustic-assisted deposition of ordered self-assembled silica opal layers on hydrophilic single crystal diamond substrates

We deposited self-assembled films of a few monolayers of silica spheres from the water-based colloid on vertically moving hydrophilic single crystal diamond substrates. The use of acoustic agitation of the water suspension with the SiO2 nanospheres significantly improved the long-range order of the films with opal structure. The study examines the evolution of the structure, specifically the size of single crystal domains, with the assistance of sound frequency (0–2500 Hz) and intensity (0–125 dB). Optimal (resonance) parameters are determined based on scanning electron microscopy and optical reflection spectroscopy of the films. The production of high-quality photonic crystals, including templates for diamond-based ordered composites and inverse opal structures, is a promising application of acoustic crystallization of opals on diamond substrates.

(Invited) Preparation of N-Type and P-Type Doped Single Crystal Diamonds with Laser-Induced Doping and Microwave Plasma Chemical Vapor Deposition

In this study, n-type doped single-crystal diamonds were successfully prepared under normal temperature and pressure conditions using laser-induced doping. 248nm pulsed laser beams with nanosecond duration were irradiated on the single crystal diamond substrate immersing in an 85% phosphoric acid solution and it introduced phosphorus doping to form an n-type doped thin layer. The resistivity of the doped region significantly decreased compared to that of the single-crystal diamond. After depositing a titanium electrode, the resistivity of the doped film obtained by Van der Pauw Technique was determined to be 1.5×10-4 Ω·cm. Furthermore, p-type doped single-crystal diamonds were successfully prepared by introducing boron during the growth process using Microwave Plasma Chemical Vapor Deposition（MPCVD）. It was demonstrated that the proposed technique can introduce impurities into single crystal diamonds to form doped conductive thin layers.

Determination of optical properties of single crystal diamond substrates grown via welding-assisted microwave plasma enhanced chemical vapour deposition

Lab grown single crystal diamonds (SCDs) offer unrivalled hardness, a wide range of optical transparency, and supremely high thermal conductivity reliable materials to be a part of devices run at high frequency, temperature, and power. Effective synthesis techniques are essential in enhancing the potential applications of high-quality SCDs. This study aims to decrease the thermal contact resistance between diamond seeds and the molybdenum holder by utilizing welding material. Quality of grown diamond substrates (plates) were assessed by analysing optical properties through Raman, UV-Vis, and FT-IR spectroscopic methods. The findings revealed that the grown single-crystal diamonds have excellent transmittance (>70%) and absorption at 270 nm. Calculations also showed an average absorption coefficient of 1.1 cm−1, indicating the high quality of the grown SCDs with nitrogen impurities below 10 ppm. The absorption observed in the FTIR spectra, ranging from 1600 cm−1 to 2700 cm−1 with a peak at 2354.13 cm−1, is referred to as the “two phonon region,” which is a distinctive feature of the diamond phase.

Superconducting nanowire single-photon detectors with saturated quantum efficiency at 1550 nm on single-crystal diamond substrates

Single-crystal diamond possesses exceptional physical and optical properties, rendering it an ideal platform for integrated quantum optics. The direct integration of broadband-sensitive and high-performance single-photon detectors on diamond holds significant implications for the realization of integrated diamond quantum optical circuits. In this study, we polished the diamond surface with RMS (root mean square) below 0.6 nm suitable for the deposition and patterning of NbN thin films through ion beam etching. Subsequently, we fabricated superconducting nanowire single-photon detectors directly on the polished diamond substrates and characterized for their electrical and optical properties. The NbN-SNSPD exhibited a high critical current density (2 MA cm−2), a saturated quantum efficiency (QE) below 2.5 K, and a maximum value of QE up to 88% at 4 K. These findings offer a promising solution for fully integrated quantum optical chips on single-crystal diamond substrates.

Full-field measurement of residual stress in single-crystal diamond substrates based on Mueller matrix microscopy

In this work, a method has been proposed for fast-measuring full-field residual stress of diamond substrates based on Mueller Matrix (MM) microscopy. The measurement system features a polarization camera and a fixed compensator at 45° orientation, and real-time birefringence imaging can be performed. The magnitude and orientation of residual stress have been characterized by the stress-optical law. Optical-grade synthetic diamond substrates after laser-cutting and grinding have been measured. After laser-cutting samples exhibit a central region where stress orientation is shifted by −90° from the x-axis. After double-sided fine grinding, the average stress value is relatively low at 0.094 GPa, while single-sided fine grinding yields average stress of 0.142 Gpa, whereas double-sided rough grinding leads to 0.157 Gpa. Full-field stress distributions obtained from Raman images show consistent patterns. The research indicates that the MM-based method is a promising technique for detecting diamond substrate birefringence and characterizing its stress variation during fabrication.

Modulation of annealing process for the direct growth of multi-layered graphene on diamond with high uniformity

In this paper, graphene with good uniformity was successfully grown on (100)-orientation single crystal diamond substrate directly by regulating the annealing and cooling temperature. A medium annealing temperature of 1000 °C and duration of 20 s can trade-off the thickness and uniformity. In addition, the stress condition and thickness of graphene also present a dependence on cooling temperature. Under the cooling temperature of 500 °C, the multi-layered graphene (30 nm thickness) with high electron mobility (737 cm2/Vs at room temperature) was obtained. The surface roughness was 2.36 nm for the graphene layer and 0.85 nm for the etched diamond substrate, indicating a good surface flatness. By comparing with the Ti/Au electrode, it was found that the graphene directly synthesized on diamond presented improved ohmic contact with the diamond substrate.

Insights into the atomic-scale removal mechanism of single crystal diamond in plasma-assisted polishing with quartz glass

The atomic removal mechanism in plasma-assisted polishing (PAP) of single crystal diamond (SCD) substrate is investigated using ReaxFF molecular dynamics simulation. For comparison, another two simulations, polishing without O radical irradiation, polishing with the O atoms’ oxidation action omitted, are conducted. C atoms in PAP are removed by attachment to quartz glass via C-O-Si bonds or transformation into non-diamond. Such removals are achieved by the synergistic action of O atoms’ oxidation and Si-O-C bonds’ dragging force provided by plasma and quartz glass. As a result, material removal rate in PAP is much higher than that in another two cases. Thus, promoting the oxidizing properties of polishing plates and atmospheres is proposed as a route to accelerate diamond polishing efficiency.

Probe beam deflection technique with liquid immersion for fast mapping of thermal conductance

Frequency-domain probe beam deflection (FD-PBD) is an experimental technique for measuring thermal properties that combines heating by a modulated pump laser and measurement of the temperature field via thermoelastic displacement of the sample surface. In the conventional implementation of FD-PBD, the data are mostly sensitive to the in-plane thermal diffusivity. We describe an extension of FD-PBD that introduces sensitivity to through-plane thermal conductance by immersing the sample in a dielectric liquid and measuring the beam deflection created by the temperature field of the liquid. We demonstrate the accuracy of the method by measuring (1) the thermal conductivity of a 310 nm thick thermally grown oxide on Si, (2) the thermal boundary conductance of bonded interface between a 3C-SiC film and a single crystal diamond substrate, and (3) the thermal conductivities of several bulk materials. We map the thermal boundary conductance of a 3C-SiC/diamond interface with a precision of 1% using a lock-in time constant of 3 ms and dwell time of 15 ms. The spatial resolution and maximum probing depth are proportional to the radius of the focused laser beams and can be varied over the range of 1–20 μm and 4–80 μm, respectively, by varying the 1/e2 intensity radius of the focused laser beams from 2 to 40 μm. FD-PBD with liquid immersion thus enables fast mapping of spatial variations in thermal boundary conductance of deeply buried interfaces.

Fabrication of self-standing large (111) single crystal diamond using bulk growth of (100) CVD diamond and lift-off process

Diamond (111) plane is superior in impurity doping and quantum spin control to (100) plane, however, there are many technical issues in mass production of the substrate, such as a smaller seed substrate size, low removal rate of polishing, and low growth rate. In this study, a large (111) single crystal diamond substrate of 7 mm × 6 mm was fabricated by growing and processing bulk (100) CVD single crystal. Furthermore, using this as a seed substrate, a (111) self-standing plate was fabricated using the lift-off method. The FWHM of the X-ray rocking curve was 46 arcsec and that of the Raman peak was 2 cm−1. This method can be applied to fabrication of any high index plane such as (113) and can be utilized to fabrication of substrate for electronic and quantum devices, device processing to fabricate vertical structure.

Nucleation of cubic boron nitride on boron-doped diamond via plasma enhanced chemical vapor deposition

Cubic boron nitride (c-BN), with a small 1.4% lattice mismatch with diamond, presents a heterostructure with multiple opportunities for electronic device applications. However, the formation of c-BN/diamond heterostructures has been limited by the tendency to form hexagonal BN at the interface. In this study, c-BN has been deposited on free standing polycrystalline and single crystal boron-doped diamond substrates via electron cyclotron resonance plasma enhanced chemical vapor deposition (ECR-PECVD), employing fluorine chemistry. In situ x-ray photoelectron spectroscopy (XPS) is used to characterize the nucleation and growth of boron nitride (BN) films as a function of hydrogen gas flow rates during deposition. The PECVD growth rate of BN was found to increase with increased hydrogen gas flow. In the absence of hydrogen gas flow, the BN layer was reduced in thickness or etched. The XPS results show that an excess of hydrogen gas significantly increases the percent of sp2 bonding, characteristic of hexagonal BN (h-BN), particularly during initial layer growth. Reducing the hydrogen flow, such that hydrogen gas is the limiting reactant, minimizes the sp2 bonding during the nucleation of BN. TEM results indicate the partial coverage of the diamond with thin epitaxial islands of c-BN. The limited hydrogen reaction is found to be a favorable growth environment for c-BN on boron-doped diamond.

The Optical Properties of V2O5 Films Deposited on Single Crystal Diamond Under Homogenizing Preparation Technology

In this article, the V2O5 films’ temperature stratification theoretical model was built, and then the films were deposited on single crystal diamond substrates using homogenizing preparation technology. The results show that the films prepared under homogenizing preparation technology have higher optical-mutation properties than normal preparation technology. More interestingly, the optical phase-transition time was 1.5 ms under homogenizing preparation technology compared to 1.9 ms under normal preparation technology, showing a dramatic decline. In addition, the transmittance before and after phase change under homogenizing preparation technology were 78% and 11% respectively, much better than normal preparation technology of 74% and 17%. Furthermore, the laser-induced damage threshold was from 60 W/mm2 under normal technology up to 70.8 W/mm2 under homogenizing preparation technology.

Highly efficient finishing of large-sized single crystal diamond substrates by combining nanosecond pulsed laser trimming and plasma-assisted polishing

Diamond is an ideal material for fabricating functional components applied in power devices, heat spreaders, and surface acoustic wave. However, diamond's extreme hardness and brittleness nature makes it difficult to grind and polish to meet the roughness requirement for such applications. In this study, a novel hybrid process combining nanosecond pulsed laser trimming comprising a series of selective laser plane ablation (LPA) and plasma-assisted polishing (PAP) was proposed to flatten and smooth large-sized single-crystal diamond (SCD) substrate. When LPA was performed on an uncoated SCD substrate, deep explosion caverns and cracks were generated. Meanwhile, the material was uniformly removed by a few microns when an Au-coated SCD substrate was processed by LPA with the same conditions, in which a self-maintaining graphite layer on SCD surface was generated, and material was removed as a graphite “piston” penetrated into SCD substrate. In the validation of the proposed hybrid process, 10 and 20-mm square Au-coated SCD substrates were flattened by laser trimming for 79 and 538 s, reducing the p–v value of the entire SCD surface by ∼70 and ∼150 μm, respectively. Subsequently, the laser-trimming-processed SCD substrates were smoothed by PAP for 6.5 and 34 h, obtaining flatness of 0.2 and 1 μm or less, and surface roughness of 0.51 and 0.53 nm for SCD substrates of 10 and 20-mm square sizes, respectively. Proven by spectrophotometer and Raman results, no non-diamond phase was generated in the bulk of SCD during laser trimming and diamond surface was detected after hybrid process.

Microporous poly- and monocrystalline diamond films produced from chemical vapor deposited diamond-germanium composites.

We report on a novel method for porous diamond fabrication, which is based on the synthesis of diamond-germanium composite films followed by etching of the Ge component. The composites were grown by microwave plasma assisted CVD in CH4-H2-GeH4 mixtures on (100) silicon, and microcrystalline- and single-crystal diamond substrates. The structure and the phase composition of the films before and after etching were analyzed with scanning electron microscopy and Raman spectroscopy. The films revealed a bright emission of GeV color centers due to diamond doping with Ge, as evidenced by photoluminescence spectroscopy. The possible applications of the porous diamond films include thermal management, surfaces with superhydrophobic properties, chromatography, supercapacitors, etc.

In situ doping of epitaxial diamond with germanium by microwave plasma CVD in GeH4-CH4-H2 mixtures with optical emission spectroscopy monitoring.

We report the growth of Ge-doped homoepitaxial diamond films by microwave plasma CVD in GeH4-CH4-H2 gas mixtures at moderate pressures (70-100 Torr). Optical emission spectroscopy was used to monitor Ge, H, and C2 species in the plasma at different process parameters, and trends for intensities of those radicals, gas temperature, and excitation temperature, with variations of GeH4 or CH4 precursor concentrations, were investigated. The film deposited on (111)-oriented single crystal diamond substrates in a high growth rate regime revealed a strong emission of a germanium-vacancy (GeV) color center with a zero-phonon line at ≈604 nm wavelength in photoluminescence (PL) spectra, confirming the successful doping. The observed PL shift for the GeV defect is caused by stress in the films, as evidenced and quantified by Raman spectra. These results suggest that in situ doping with Ge using a GeH4 precursor is a convenient method of controlling the formation of GeV centers in epitaxial diamond films for photonic applications.

Microstructure and Magnetic Properties Dependence on the Sputtering Power and Deposition Time of TbDyFe Thin Films Integrated on Single-Crystal Diamond Substrate

As giant magnetostrictive material, TbDyFe is regarded as a promising choice for magnetic sensing due to its excellent sensitivity to changes in magnetic fields. To satisfy the requirements of high sensitivity and the stability of magnetic sensors, TbDyFe thin films were successfully deposited on single-crystal diamond (SCD) substrate with a Young’s modulus over 1000 GPa and an ultra-stable performance by radio-frequency magnetron sputtering at room temperature. The sputtering power and deposition time effects of TbDyFe thin films on phase composition, microstructure, and magnetic properties were investigated. Amorphous TbDyFe thin films were achieved under various conditions of sputtering power and deposition time. TbDyFe films appeared as an obvious boundary to SCD substrate as sputtering power exceeded 100 W and deposition time exceeded 2 h, and the thickness of the films was basically linear with the sputtering power and deposition time based on a scanning electron microscope (SEM). The film roughness ranged from 0.15 nm to 0.35 nm, which was measured by an atomic force microscope (AFM). The TbDyFe film prepared under a sputtering power of 100 W and a deposition time of 3 h possessed the coercivity of 48 Oe and a remanence ratio of 0.53, with a giant magnetostriction and Young’s modulus effect, suggesting attractive magnetic sensitivity. The realization of TbDyFe/SCD magnetic material demonstrates a foreseeable potential in the application of high-performance sensors.

High charge collection efficiency detector based on plasma purified high-quality diamond

Diamond radiation detector is an ideal choice for the next-generation radiation detection in harsh environments, due to its small size, high irradiation resistance and fast response. However, high-purity single crystal diamond is hard to be prepared at the high growth rate due to the inevitable impurity incorporation. In this paper, based on the high-quality high-temperature/high-pressure (HPHT) single crystal diamond substrate, detector-grade single crystal diamonds material with high purity and low defect density were epitaxially grown at growth rate of about 4 μm/h by using plasma environment purification technology. It showed that the full width at half maximum of X-ray rocking curve of high-quality single crystal diamond could reach 0.007°, there was no nitrogen related impurity in PL spectrum, and the substitutional nitrogen content estimated by UV absorption spectrum was less than 10 ppb. After metallization and packaging process, the diamond detectors were prepared and the detector response under irradiation with 241 Am α-particles was realized. For the sample with fewer dislocations, the charge collection efficiency and energy resolution of this detector were 86.8 % and 7.85 % for electrons, and 96.7 % and 2.48 % for holes. The product of mobility and lifetime of electrons and holes were 1.7 × 10 −4 cm 2 V −1 and 3.7 × 10 −4 cm 2 V −1 , respectively. The high performances of the detector indicate that the current diamond detector can meet the application requirements of commercial diamond detectors. • Detector-grade diamond was prepared by plasma environment purification technology. • The high-purity single crystal diamond was grown at growth rate of about 4 μm/h. • The diamond detector with charge collection efficiency of 96.7 % was realized. • The products of mobility and lifetime of electrons and holes were 1.7 × 10 −4 and 3.7 × 10 −4 cm 2 V −1 .

Process design for the manufacturing of soft X-ray gratings in single-crystal diamond by high-energy heavy-ion irradiation

This paper describes in detail a novel manufacturing process for optical gratings suitable for use in the UV and soft X-ray regimes in a single-crystal diamond substrate based on highly focused swift heavy-ion irradiation. This type of grating is extensively used in light source facilities such as synchrotrons or free electron lasers, with ever-increasing demands in terms of thermal loads, depending on beamline operational parameters and architecture. The process proposed in this paper may be a future alternative to current manufacturing techniques, providing the advantage of being applicable to single-crystal diamond substrates, with their unique properties in terms of heat conductivity and radiation hardness. The paper summarizes the physical principle used for the grating patterns produced by swift heavy-ion irradiation and provides full details for the manufacturing process for a specific grating configuration, inspired in one of the beamlines at the ALBA synchrotron light source, while stressing the most challenging points for a potential implementation. Preliminary proof-of-concept experimental results are presented, showing the practical implementation of the methodology proposed herein.