Properties Of Diamond Research Articles

Covalently‐Bonded Diaphite Nanoplatelet with Engineered Electronic Properties of Diamond

AbstractDiamond, as a highly promising “extreme” semiconductor material, necessitates electronic property engineering to unleash its full potential in electronic and photonic devices. In this work, the diaphite nanoplatelet, consisting of (11) planes of diamond nanoplatelet covalently bonded with graphite (0001) planes, is facilely synthesized using one‐step microwave plasma enhanced chemical vapor deposition method. The high‐energy plasma created by the pillar plays a crucial role in the formation. Importantly, altered electronic and optical properties are determined in the diaphite nanoplatelet through electron energy loss spectrum, density functional theory calculations, and cathodoluminescence spectroscopy. It is revealed that the strong sp3/sp2‐hybridized interfacial covalent bonding in the diaphite nanoplatelet induces the electron transfer from diamond to graphite. This modulates the electronic structure of the near‐interface layer of diamond and triggers a new local trapping band below the conduction band minimum within the bandgap. Consequently, the covalently‐bonded diaphite exhibits a different optical emission characteristic ranging from 2.5 to 3.64 eV, featuring a significant peak blueshift of 430 meV compared to the H‐terminated diamond. This work demonstrates a novel method to engineer the electronic properties of diamond, opening avenues for functional semiconductor device applications of diamond.

Covalently Bonded Heterostructures with Mixed-Dimensional Carbons for Suppressing Mechanochemical Wear of Diamond under Heavy Loads.

Diamond is widely acknowledged as the hardest naturally occurring material. Nevertheless, when exposed to friction against ferrous metals, it is prone to graphitization or amorphization, which limits the utilization of its extremely high hardness and wear resistance. These issues have persisted for decades without an effective solution. Here, we report that a covalently bonded heterostructure with mixed-dimensional carbons as a high-performance solid lubricant could effectively reduce diamond surface friction and mechanochemical wear with excellent load capacity and durability. When subjected to dry friction and heavy loads (20-150 N), the heterostructure exhibited a notable improvement over pristine diamond with reduced friction coefficients and relative wear rates by 22-45 and 67-91%, respectively. Especially under a 20 N load, the relative wear rate was an order of magnitude lower than that of pristine diamond. Additionally, experiments and molecular dynamics simulations revealed that the heterostructure integrated the outstanding properties of diamond (three-dimensional (3D)), nanographite (3D), and graphene (two-dimensional (2D)), resulting in improved lubrication and antiwear performance that could not be achieved by the individual carbon materials. The findings in this work will be beneficial to overcome the ferrous metal forbidden zone of diamond and are expected to expand the applications of engineered diamond surfaces and graphite/graphene in tribology, mechanics, and electronic fields.

Mechanical quenching phenomenon in diamond

The structure of dislocation cores, the fundamental knowledge on crystal plasticity, remains largely unexplored in covalent crystals. Here, we conducted atomically resolved characterizations of dislocation core structures in a plastically deformed diamond anvil cell tip that was unloaded from an exceptionally high pressure of 360 GPa. Our observations unveiled a series of nonequilibrium dislocation cores that deviate from the commonly accepted "five-seven-membered ring" dislocation core model found in FCC-structured covalent crystals. The nonequilibrium dislocation cores were generated through a process known as "mechanical quenching," analogous to the quenching process where a high-energy state is rapidly frozen. The density functional theory-based molecular dynamic simulations reveal that the phenomenon of mechanical quenching in diamond arises from the challenging relaxation of the nonequilibrium configuration, necessitating a large critical strain of 25% that is difficult to maintain. Further electronic-scale analysis suggested that such large critical strain is spent on the excitation of valance electrons for bond breaking and rebonding during relaxation. These findings establish a foundation for the plasticity theory of covalent materials and provide insights into the design of electrical and luminescent properties in diamond, which are intimately linked to the dislocation core structure.

Effect of Nitrogen on Growth and Optical Properties of Single-Crystal Diamond Synthesized by Chemical Vapor Deposition.

Concurrently achieving high growth rate and high quality in single-crystal diamonds (SCDs) is significantly challenging. The growth rate of SCDs synthesized by microwave plasma chemical vapor deposition (MPCVD) was enhanced by introducing N2 into the typical CH4-H2 gas mixtures. The impact of nitrogen vacancy (NV) center concentration on growth rate, surface morphology, and lattice binding structure was investigated. The SCDs were characterized through Raman spectroscopy, photoluminescence (PL) spectroscopy, and X-ray photoelectron spectroscopy. It was found that the saturation growth rate was increased up to 45 μm/h by incorporating 0.8-1.2% N2 into the gas atmosphere, which is 4.5 times higher than the case without nitrogen addition. Nitrogen addition altered the growth mode from step-flow to bidimensional nucleation, leading to clustered steps and a rough surface morphology, followed by macroscopically pyramidal hillock formation. The elevation of nitrogen content results in a simultaneous escalation of internal stress and defects. XPS analysis confirmed chemical bonding between nitrogen and carbon, as well as non-diamond carbon phase formation at 0.8% of nitrogen doping. Furthermore, the emission intensity of NV-related defects from PL spectra changed synchronously with N2 concentrations (0-1.5%) during diamond growth, indicating that the formation of NV centers activated the diamond lattice and facilitated nitrogen incorporation into it, thereby accelerating chemical reaction rates for achieving high-growth-rate SCDs.

One-dimensional diamond nanostructures: Fabrication, properties and applications

Diamonds exhibit a unique combination of numerous excellent physical and chemical properties, such as the highest hardness, high Young's modulus, wide bandgap, high carrier mobility, negative electron affinity, and high thermal conductivity. Especially, diamond has attracted significant attention in recent years for its outstanding performance in high-frequency and high-power electronic devices and thermal management. Inheriting the intrinsic physical and chemical properties of diamonds, one-dimensional (1D) diamond nanostructures exhibit many additional properties that are unavailable for bulk diamond or thin films, e.g., large specific surface area, ultrahigh elasticity, and some plasticity, tip effect as well as direct transport for photon or photo-induced carriers. These properties make 1D diamond nanostructures an ideal candidate for applications ranging from micro/nano-electromechanical systems (MEMS/NEMS) to field electron emission, optical, electrochemical, and biological areas. This review will first introduce the development of controlled synthesis methods of 1D diamond nanostructure, including bottom-up chemical vapor deposition growth and top-down selective etching of bulk diamond. Subsequently, we will summarize recent advances in the mechanical, electron field emission, optical, and biological properties of 1D diamond nanostructures and their applications in electron and photon emitter, MEMS, sensing, intracellular delivery, etc.

Achieving ultrahigh hole mobility in hydrogen-terminated diamond via boron nitride modifications

Wide-bandgap semiconductors with high carrier mobility are in great demand for high-power radio-frequency applications. In the past decades, extensive efforts have been devoted to investigating the carrier transport properties of hydrogen-terminated diamond (H-diamond), however, achieving its high hole mobility remains a challenge, thereby limiting the development of diamond electronic devices. Herein, we propose a novel strategy to increase the hole mobility of H-diamond by boron nitride (BN) clusters modifications. Amorphous BN clusters were deposited on high-quality H-diamond surfaces using magnetron sputtering. The modified H-diamond exhibits an ultrahigh hole mobility of 1100 cm2 V−1 s−1, over 10-fold higher than that of H-diamond prior to BN modification. Moreover, the BN-modified H-diamond also exhibits outstanding high-temperature tolerance and excellent thermal stability benefitting from the passivation effect of BN. At 380 K, it still maintains a hole mobility of 385 cm2 V−1 s−1. Even after annealing at 350 K for over 8 h, there are no noticeable variations in its carrier transport properties. The hole mobility enhancing mechanism and the factors influencing carrier transport properties of the BN-modified H-diamond are discussed using first principles calculations analysis. The developed BN-modified H-diamond opens up new possibilities for diamond-based radio-frequency electronic devices operating in challenging temperature environments.

First-principles prediction of n-type diamond: novel co-doped structure using N and Be impurities

To address the limitation of diamond-based electronic devices, a comprehensive study on n-type diamond is crucial. A novel dopant structure, nitrogen–beryllium co-doping, is proposed for achieving n-type doping. The dopant structure, electronic property, synthesis route and internal strain are analyzed using first-principles density functional theory. The formation energy and ionization energy of xN–Be (x = 1–4) are compared to elucidate the distinct doping effects associated with varying numbers of N atoms. The formation energy initially decreases and then gradually increases with an incensing number of N atoms. Notably, 3N–Be and 4N–Be exhibit appealing n-type diamond properties, with low ionization energies of 0.30–0.41 eV (3N–Be) and 0.23–0.37 eV (4N–Be). To facilitate the preparation of 3/4N–Be co-doped diamond, a non-molecular synthetic route is proposed, involving the prior generation of the 3N-V and 4N-V. The 3/4N–Be co-doped diamond exhibits relatively small strain energy. Finally, this investigation highlights the potential of 3/4N–Be co-doping as excellent choices for n-type dopants, providing a greater variety of n-type structures with similar ionization energy compared to 4N–Li co-doping.

Diamond Nanostructures at Different Dimensions: Synthesis and Applications

AbstractDiamond materials at different nanoscales provide them various characteristics such as elastic mechanical properties in needle‐like nanotips, flexibility of 2D films having atomic thicknesses and constant hardness under high pressures, superior field electron emission properties of vertically wall‐like composites, unprecedented hardness and improved toughness of nanotwin diamond (nt‐diamond), while the inherent excellent properties of bulk diamond (e.g., high Young's modulus, robustness, biocompatibility) can be maintained. In this paper, the newly born 1D diamond nanothreads, 2D diamanes, as well as 3D nt‐diamond are briefly reviewed. The innovations, progresses and achievements of different dimensional diamond nanostructures, covering lines, planes and volumes are overviewed. The topical problems and future outlooks of diamond nanostructures are outlined and discussed.

Prediction of Compressive Behavior of Laser-Powder-Bed Fusion-Processed TPMS Lattices by Regression Analysis

Triply periodic minimal surface (TPMS) structures offer lightweight and high-stiffness solutions to different industrial applications. However, testing of these structures to calculate their mechanical properties is expensive. Therefore, it is important to predict the mechanical properties of these structures effectively. This study focuses on the effectiveness of using regression analysis and equations based on experimental results to predict the mechanical properties of diamond, gyroid, and primitive TPMS structures with different volume fractions and build orientations. Gyroid, diamond, and primitive specimens with three different volume fractions (0.2, 0.3, and 0.4) were manufactured using a laser powder bed fusion (LPBF) additive manufacturing process using three different build orientations (45°, 60°, and 90°) in the present study. Experimental and statistical results revealed that regression analysis and related equations can be used to predict the mass, yield stress, elastic modulus, specific energy absorption, and onset of densification values of TPMS structures with an intermediate volume fraction value and specified build orientation with an error range less than 1.4%, 7.1%, 19.04%, 21.6%, and 13.4%, respectively.

Tuning the Electronic and Mechanical Properties of Two-Dimensional Diamond through N and B Doping

Tuning the Electronic and Mechanical Properties of Two-Dimensional Diamond through N and B Doping

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<sup>16</sup> atom/cm<sup>3</sup>. 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<sup>2</sup>/(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.

Mechanical regulation to interfacial thermal transport in GaN/diamond heterostructures for thermal switch.

Gallium nitride offers an ideal material platform for next-generation high-power electronics devices, which enable a spectrum of applications. The thermal management of the ever-growing power density has become a major bottleneck in the performance, reliability, and lifetime of the devices. GaN/diamond heterostructures are usually adopted to facilitate heat dissipation, given the extraordinary thermal conduction properties of diamonds. However, thermal transport is limited by the interfacial conductance at the material interface between GaN and diamond, which is associated with significant mechanical stress at the atomic level. In this work, we investigate the effect of mechanical strain perpendicular to the GaN/diamond interface on the interfacial thermal conductance of heterostructures using full-atom non-equilibrium molecular dynamics simulations. We found that the heterostructure exhibits severe mechanical stress at the interface in the absence of loading, which is due to lattice mismatch. Upon tensile/compressive loading, the interfacial stress is more pronounced, and the strain is not identical across the interface owing to the contrasting elastic moduli of GaN and diamond. In addition, the interfacial thermal conductance can be notably enhanced and suppressed by tensile and compressive strains, respectively, leading to a 400% variation in thermal conductance. More detailed analyses reveal that the change in interfacial thermal conductance is related to the surface roughness and interfacial bonding strength, as described by a generalized relationship. Moreover, phonon analyses suggest that the unequal mechanical deformation under compressive strain in GaN and diamond induces different frequency shifts in the phonon spectra, leading to an enhancement in phonon overlapping energy, which promotes phonon transport at the interface and elevates the thermal conductance and vice versa for tensile strain. The effect of strain on interface thermal conductance was investigated at various temperatures. Based on the mechanical tunability of thermal conductance, we propose a conceptual design for a mechanical thermal switch that regulates thermal conductance with excellent sensitivity and high responsiveness. This study offers a fundamental understanding of how mechanical strain can adjust interface thermal conductance in GaN/diamond heterostructures with respect to mechanical stress, deformation, and phonon properties. These results and findings lay the theoretical foundation for designing thermal management devices in a strain environment and shed light on developing intelligent thermal devices by leveraging the interplay between mechanics and thermal transport.

(Invited) Heterogeneous Integration of Ultrawide Bandgap III-Nitrides and Diamond

Industry demands for power switching, amplification and photonic applications are continually pushing the limits of semiconductor device technologies leading to increasing applied voltages and, thus, higher electric fields while simultaneously requiring reduction in the size, weight and power consumption. In addition, recent heightened interest in higher temperature (and other extreme environment) applications, while simultaneously maintaining high-voltage and high-power performance, has inexorably led to ultrawide bandgap (UWBG) semiconductor materials. This interest in UWBG materials stems from superior properties that include high material hardness, breakdown strength to withstand large electric fields and mitigation of power dissipation during device switching, deliver high current density while operating at higher junction and ambient temperature. Among these materials are boron nitride in its hexagonal and cubic phases, gallium oxide, diamond, and aluminum gallium nitride. The versatile alloys of wurtzite AlxGa1-xN have long been demonstrated across the full composition range. The variation in Eg with AlGaN composition, along with select WBG and UWBG materials, is shown in Figure 1 versus (in-plane for non-cubic) lattice constant.Premier WBG materials to date for electronics and photonics are SiC (Eg = 3.3 eV) and GaN (Eg = 3.4 eV). The latter has been successfully applied to high-power transistors and near ultraviolet photonics. In both electronics and photonics applications, the polarization fields of the wurtzite crystal structure, generally grown along (0001) direction, produce design challenges. In photonics, for example, the fields and band alignment couple to spatially separate electrically injected electrons and holes to reduce wavefunction overlap in quantum wells. In electronics, the internal fields have contributed to difficulties in the design of logic and bipolar transistor devices based on these materials. Despite this, the inherent polarization field and band offsets were successfully employed in the design of high electron-mobility transistors (HEMTs). The inherent AlGaN/GaN HEMT band offset produces a high electron concentration at the interface that spontaneously forms a two-dimensional electron gas (2DEG). Because charge flow in these devices is restricted to the 2DEG, current crowding results in intense self-heating. The local heating decreases electrical conductivity to produce a runaway scenario for elevating the Joule heating. Dissipating this heat, therefore, is the principal limiting factor in operating at power higher than 40 W/mm.The various temperature dependences of semiconductor device parameters are the principal drivers in the operation of semiconductor devices. The physics has inextricably led to UWBGs for future high temperature applications, > 300 °C, due to their lower intrinsic carrier density and thus the effects of leakage are orders of magnitudes less than Si-based devices. Furthermore, AlGaN and diamond offer superior high temperature mechanical stability due to their structural hardness and chemical inertness. Thermal management is essential for achieving higher power densities. Diamond is highly attractive for many applications due to its high hardness, transparency, chemical inertness, promising semiconductor properties, and its high thermal conductivity (κ) to 2500 W/m·K in natural material. Factors related to the consequences of self-heating in devices have motivated extensive research to improve the properties of diamond and produce better approaches to determine the thermal properties. Laboratory-grown diamond films exhibit significantly poorer κ than natural diamond and, when integrated with other electronic materials, a low thermal boundary conductance (TBC in W/m2·K) that inhibits heat transfer between materials. The former originates from the ubiquitous polycrystalline nature of chemical vapor deposition (CVD) diamond and the presence of non-diamond carbon (NDC) in the layer. The low TBC stems from fundamental barriers to phonon propagation between two materials and from practical issues of poor diamond quality in the initial growth regime. Continued research is needed to improve κ in the polycrystalline diamond and mitigate the negative impact of the initial diamond layer on TBC.The current status of hetero-integration of UWBG AlGaN and diamond will be reviewed. Particular emphasis is given to high Al content AlGaN for near-bandgap matching with diamond. Patterned diamond grown using hot-filament CVD to realize unique three-dimensional lateral device structures in a self-aligned, as-grown fabrication process is employed. Engineering the AlGaN-diamond bandgap alignment is noteworthy at the nonpolar AlGaN – diamond interface including diamond surface terminations that produce either negative or positive electron affinity. The review will focus on improvements in material properties, especially the interfaces, that are critical to both charge and heat transport for UWBG device structures. Figure 1

Mechanical properties of cubic boron nitride and diamond at dynamical pressure and temperature

We report the mechanical properties of cubic boron nitride (c-BN) and diamond under the combined impact of dynamical pressure and temperature, calculated using ab initio molecular dynamics. Our study revealed a pronounced sensitivity of the mechanical properties of c-BN to applied pressure. Notably, c-BN undergoes a brittle-to-ductile transition at ∼220 GPa, consistent across various dynamical temperatures, while diamond exhibits no such transition. Furthermore, the Vickers hardness profile for c-BN closely mirrors that of diamond across a spectrum of temperature–pressure conditions, highlighting c-BN's significant mechanical robustness. These results underscore the superior resilience and adaptability of c-BN compared to diamond, suggesting its potential as an ideal candidate for applications in extreme environments.

First principles investigation of thermodynamic property of diamond under high pressure and high temperature

The present study utilizes the density functional theory to obtain the diamonds’ thermodynamic properties up to 2000 K and 100 GPa under the quasi-harmonic approximation. The results reveal that the variation of thermal expansion coefficient and heat capacity with temperature can be categorized into three distinct temperature regions within the range of 10–2000 K. These regions are accurately described by the Debye model, a combination of Debye and Einstein models, and the Einstein model, respectively. Additionally, high pressures raise the upper temperature limit applicable to the Einstein model. And the study successfully explained the variation of Grüneisen coefficient under high-temperature and high-pressure conditions using the proposed model. In the temperature range where both Einstein and Debye models yield accurate results, the influence of pressure enhances the contribution of the Debye model to the thermal expansion coefficient and heat capacity of diamond, resulting in a higher peak in the Grüneisen coefficient.

Novel Route for Preparing Diamond-Enhanced Cemented Carbides via Reactive Sintering

Hardmetals are cemented carbides consisting of the hard ceramic phase WC and the ductile metallic binder Co. They offer an outstanding combination of hardness and fracture toughness. Hence, they have a widespread use across the manufacturing industry. However, due to the increasing requirements for tool material, the combination of the beneficial properties of hardmetal and diamond is a long sought-after objective. In this work, a new approach was evaluated to reduce the formation of graphite due to the phase transformation of diamond during the sintering of compounds together with hardmetal. Earlier trials could not fully suppress the phase transformation despite using alternative Ni-instead of conventional Co-based binder systems and field-assisted sintering (FAST) to reduce required sintering temperatures and time. To lower the amount of graphite formed during sintering even further, a reactive sintering process was developed. The increased sinter activity due to the in situ synthesis of WC has the potential to decrease the needed temperature to achieve a pore-free compact. For the first time, a WC-Ni hardmetal produced from elemental powders was successfully used as a matrix in a diamond-enhanced cemented carbide (DECC). Different approaches regarding carbon sources and the extent of reactive material were pursued. The introduction of a carbon deficit by adding metallic W to a mixture of WC and Ni, which is essentially partial reactive sintering, leads to an increased relative density compared to the reference of 97.3%.

Customized boron-doped diamond electrodes for efficient water treatment via HF-CVD parameter optimization

Among the Design of Experiments (DoE) approaches available, the Taguchi method offers a methodical and effective way to optimize designs with fewer experimental trials. The effects of deposition conditions on the final properties of boron-doped diamond (BDD) films for water treatment applications deposited in a Hot Filament Chemical Vapor Deposition (HF-CVD) reactor were evaluated by applying a Taguchi Matrix. Methane to hydrogen (CH4/H2) ratio, argon mass flow, and total gas pressure were the controllable factors, each in three different levels. Diamond quality was affected by a combination of the three considered factors. A 0.02 CH4/H2 ratio was found as the optimal value to yield films with reduced non-diamond carbon inclusions in our CVD system. Resistivity, residual stress, double-layer capacitance, and surface roughness were mainly affected by total pressure and argon content. The methane content and the total pressure significantly influenced growth rate and grain size. The latter was primarily responsible for changes in the electrochemical potential window and the electron transfer process of the BDD films. Within the studied range of deposition conditions, the optimal deposition parameters to obtain BDD films for water treatment applications were: 0.02 CH4/H2 ratio, 25 mbar total gas pressure, and 30 sccm argon mass flow.

Effect of heat treatment on mechanical properties of CuCrZr triply periodic minimal surface structures fabricated by selective laser melting

CuCrZr alloy has excellent conductivity, thermal conductivity, friction reduction and abrasion resistance, which can satisfy in different fields. Copper alloy porous structure is a new multifunctional structure with both structural and functional properties. Selective laser melting (SLM) technology has certain advantages for the preparation of periodic porous structures with triply periodic minimal surfaces (TPMS). Under the background of SLM technique, the quasi-static compression properties of Diamond and Gyroid porous structures were studied. The whole deformation of structures was captured by digital camera, and the failure mechanism was analyzed by finite element software. The effects of different heat treatments on the microstructure and mechanical properties of the CuCrZr were studied by scanning electron microscopy and compression tests. The microstructure morphologies show that the number of curved grains decreases and the grains become more regular after heat treatment. Heat treatment can optimize the mechanical properties and energy absorption capacity of the material, which is most obvious at 500 °C. These results indicate that specific heat treatment can improve the stability and predictability of the CuCrZr porous structure.

Instantaneous formation of covalently bonded diamond–graphite–graphene with synergistic properties

Diamond and graphene are the most widely used carbon allotropes and offer great potential for developing mechanical, electronic, energy-storage, and sensor applications. Their combination, especially interfacial covalent bonding, can impart excellent properties. However, achieving interfacial covalent bonding with superior performance using flexible and low-power strategies remains challenging. This study developed a novel instantaneous transformation method from diamond to graphene to prepare a new covalent structure of diamond–nano-graphite–graphene (CDGG). That is, a nanosecond-pulse laser induces sp3-to-sp2 instantaneous transformations from diamond to graphite in air, and the subsequent mechanical cleavage overcomes the weak van der Waals forces to achieve the final transformation of graphite to graphene. First, the key factors influencing laser-induced graphitization and mechanical cleavage were investigated, and a covalent carbon structure with multidirectional graphene was obtained. Furthermore, the mechanisms encompassing the lattice transformation, interface relationships, transformation time, and interface bonding were elucidated. The obtained new structure synergized the excellent properties of diamond, nano-graphite, and graphene, exhibiting superior lubrication, mechanochemical wear resistance, durability, and load-capacity. Compared to polished diamond, the obtained structure exhibited a significant decrease in the stable coefficient of friction by 49–59 % and a reduction of more than one order of magnitude in the relative wear rate under high friction against ferrous metals with a normal load of 1–9 N. Even under a heavy load of 100 N, it still exhibited superior lubrication and mechanochemical wear resistance. Finally, the preparation and patterning of covalent carbon structures were achieved on various diamond surfaces with high efficiency, environmental friendliness, and low power. This study is expected to broaden the scope of developing and applying diamond, diamond films, and graphene devices.

Electrochemical Properties and Structure of Membranes from Perfluorinated Copolymers Modified with Nanodiamonds.

In this study, we aimed to design and research proton-conducting membranes based on Aquivion®-type material that had been modified with detonation nanodiamonds (particle size 4-5 nm, 0.25-5.0 wt. %). These nanodiamonds carried different functional groups (H, OH, COOH, F) that provided the hydrophilicity of the diamond surface with positive or negative potential, or that strengthened the hydrophobicity of the diamonds. These variations in diamond properties allowed us to find ways to improve the composite structure so as to achieve better ion conductivity. For this purpose, we prepared three series of membrane films by first casting solutions of perfluorinated Aquivion®-type copolymers with short side chains mixed with diamonds dispersed on solid substrates. Then, we removed the solvent and the membranes were structurally stabilized during thermal treatment and transformed into their final form with -SO3H ionic groups. We found that the diamonds with a hydrogen-saturated surface, with a positive charge in aqueous media, contributed to the increase in proton conductivity of membranes to a greater rate. Meanwhile, a more developed conducting diamond-copolymer interface was formed due to electrostatic attraction to the sulfonic acid groups of the copolymer than in the case of diamonds grafted with negatively charged carboxyls, similar to sulfonic groups of the copolymer. The modification of membranes with fluorinated diamonds led to a 5-fold decrease in the conductivity of the composite, even when only a fraction of diamonds of 1 wt. % were used, which was explained by the disruption in the connectivity of ion channels during the interaction of such diamonds mainly with fluorocarbon chains of the copolymer. We discussed the specifics of the mechanism of conductivity in composites with various diamonds in connection with structural data obtained in neutron scattering experiments on dry membranes, as well as ideas about the formation of cylindrical micelles with central ion channels and shells composed of hydrophobic copolymer chains. Finally, the characteristics of the network of ion channels in the composites were found depending on the type and amount of introduced diamonds, and correlations between the structure and conductivity of the membranes were established.