Diamond Surface Research Articles

Nanocrystalline Diamond Lateral Overgrowth for High Thermal Conductivity Contact to Unseeded Diamond Surface

We demonstrate diamond lateral overgrowth as a way of increasing the thermal conductivity of thin layers of diamond. The technique can be used as a way of growing diamond on top of semiconductors, creating a thin layer of high thermal conductivity diamond in direct contact with semiconductors and allowing for the encasement of GaN in high thermal conductivity diamond.As we move to higher and higher power densities, the requirements for heat removal become extreme. The best passive way to remove heat from a semiconductor is to have a high thermal conductivity heat spreader near the heat source. Having diamond under the substrate is good. Having diamond under the epi is better and having diamond on top and bottom of the epi is better still.As-grown thin layers of diamond on non-diamond substrates have nano-diamond seeds as the starting material. The diamond thermal conductivity is a function of the grain size (Especially for small grain material) [1]. If we can increase the grain of the diamond near the junction, we can increase the thermal conductivity near the junction and more efficiently spread the heat away from the source before rejecting it into the surrounding material.In the experiment, we start with a bare silicon wafer seeded with nano-diamond seeds then grow about one micron of diamond. We coat it with a few nanometers of SiN. Then pattern the SiN layer with 2μm wide features to facilitate the coalescence of LOG-NCD over the SiN. Then we grow a 2μm thick microwave-plasma CVD NCD film (800W, 15Torr, 750°C, 0.3% CH4/H2) over the patterned SiN film initiating directly from the exposed areas of the host NCD. The diamond growth does not initiate on the patterned silicon nitride without seeds. The exposed diamond acts as a nucleating center initiating the diamond regrowth. The regrown diamond spreads from the diamond crystals exposed from the first growth. The edge crystals closest to the SiN patterned area expand over the silicon nitride forming diamond conformal to the SiN surface. This creates large crystals over the unseeded area. Figure 1 is a transmission electron microscope (TEM) image of the sample. The TEM, the image can be split into two regions. The left has no patterning, the called-out grain is 100nm wide. The right is patterned, and the diamond grains are between 1,000 to 2,000nm wide.We measured the thermal conductivity of the diamond on this samples using the TDTR method. This method uses a laser many times larger in diameter than the thickness of the film. As such, we probe the out-of-plane thermal conductivity. The initial diamond growth near the silicon had an average thermal conductivity of 100W/mK. We measured the second micron of growth without patterns to have Tc of 130W/mK. The diamond directly above the patterns had Tc of 260W/mK with grains 10X larger than the un-patterned diamond.Since the diamond grains are columnar, the difference in thermal conductivity between the patterned and un-patterned diamonds was 2X. Lateral measurements would likely show even larger changes in thermal conductivity. With grain sizes of 100 nm to 250 nm (as is the case with seeded diamond), the in-plane thermal conductivity will be dominated by the quality of the grain/grain interfaces and the lateral grain size dimensions rather than for the quality of the lattice. [1] We used lateral overgrowth to increase the grains to microns rather than 100s of nm. This means that we move into a regime where thermal conductivity is dominated by the quality of the diamond in the grains rather than the grain boundaries. As such the thermal conductivity is increased and can be further improved by improving the crystal quality - a parameter which is controlled by the diamond growth conditions. Typically, samples grown with more than 1% methane / hydrogen ratio show lower thermal conductivity [2]. However higher concentrations are important to establish the initial diamond film without damage to the underlying semiconductor. Here, the lateral overgrowth and methane concentration can be balanced to achieve both high thermal conductivity and low damage to the underlying substrate.

Small-scale roughness entraps water and controls underwater adhesion.

While controlling underwater adhesion is critical for designing biological adhesives and in improving the traction of tires, haptics, or adhesives for health monitoring devices, it is hindered by a lack of fundamental understanding of how the presence of trapped water impedes interfacial bonding. Here, by using well-characterized polycrystal diamond surfaces and soft, nonhysteretic, low-surface energy elastomers, we show a reduction in adhesion during approach and four times higher adhesion during retraction as compared to the thermodynamic work of adhesion. Our findings reveal how the loading phase of contact is governed by the entrapment of water by ultrasmall (10-nanometer-scale) surface features. In contrast, the same nanofeatures that reduce adhesion during approach serve to increase adhesion during separation. The explanation for this counterintuitive result lies in the incompressibility-inextensibility of trapped water and the work needed to deform the polymer around water pockets. Unlike the well-known viscoelastic contribution to adhesion, this science unlocks strategies for tailoring surface topography to enhance underwater adhesion.

Interface improvement of diamond/copper composites through a low-temperature high-efficiency coating method

A tungsten coating was formed by the in situ reaction of tungsten trioxide formed by the thermal decomposition of ammonium metatungstate in a molten salt (NaCl+BaCl2) environment with carbon atoms on the surface of diamond. Meanwhile, diamond/copper composites were prepared using the prepared tungsten-coated diamonds. The morphology and composition of the coatings and diamond/copper composites were observed using scanning electron microscopy, transmission electron microscopy, and energy-dispersive spectroscopy. The results revealed that the originally smooth diamond surface was uniformly covered by a tungsten coating after low-temperature salt bath treatment at 1050 °C, a temperature 50–100 °C lower than that of traditional methods. Compared to the directly added tungsten trioxide, the tungsten trioxide produced by the thermal decomposition of ammonium metatungstate was more active, and the coating was more uniform. The bending strength and thermal conductivity of tungsten-coated diamond/copper composites were 280.6 MPa and 516 W/(m·k), respectively, which were significantly higher than those of uncoated diamond/copper composites (128.6 MPa and 168 W/m·K). This indirectly confirms that the diamond surface coating can improve the interfacial bonding performance between diamond and copper.

Ultrathin Boron Growth onto Nanodiamond Surfaces via Electrophilic Boron Precursors.

Diamond as a templating substrate is largely unexplored, and the unique properties of diamond, including its large bandgap, thermal conductance, and lack of cytotoxicity, makes it versatile in emergent technologies in medicine and quantum sensing. Surface termination of an inert diamond substrate and its chemical reactivity are key in generating new bonds for nucleation and growth of an overlayer material. Oxidized high-pressure high temperature (HPHT) nanodiamonds (NDs) are largely terminated by alcohols that act as nucleophiles to initiate covalent bond formation when an electrophilic reactant is available. In this work, we demonstrate a templated synthesis of ultrathin boron on ND surfaces using trigonal boron compounds. Boron trichloride (BCl3), boron tribromide (BBr3), and borane (BH3) were found to react with ND substrates at room temperature in inert conditions. BBr3 and BCl3 were highly reactive with the diamond surface, and sheet-like structures were produced and verified with electron microscopy. Surface-sensitive spectroscopies were used to probe the molecular and atomic structure of the ND constructs' surface, and quantification showed the boron shell was less than 1 nm thick after 1-24 h reactions. Observation of the reaction supports a self-terminating mechanism, similar to atomic layer deposition growth, and is likely due to the quenching of alcohols on the diamond surface. X-ray absorption spectroscopy revealed that boron-termination generated midgap electronic states that were originally predicted by density functional theory (DFT) several years ago. DFT also predicted a negative electron surface, which has yet to be confirmed experimentally here. The boron-diamond nanostructures were found to aggregate in dichloromethane and were dispersed in various solvents and characterized with dynamic light scattering for future cell imaging or cancer therapy applications using boron neutron capture therapy (BNCT). The unique templating mechanism based on nucleophilic alcohols and electrophilic trigonal precursors allows for covalent bond formation and will be of interest to researchers using diamond for quantum sensing, additive manufacturing, BNCT, and potentially as an electron emitter.

What Are the Key Factors for the Detection of Peptides Using Mass Spectrometry on Boron-Doped Diamond Surfaces?

We investigated the use of boron-doped diamond (BDD) with different surface morphologies for the enhanced detection of nine different peptides by matrix-assisted laser desorption/ionisation mass spectrometry (MALDI-MS). For the first time, we compared three different nanostructured BDD film morphologies (Continuous, Nanograss, and Nanotips) with differently terminated surfaces (-H, -O, and -F) to commercially available Ground Steel plates. All these surfaces were evaluated for their effectiveness in detecting the nine different peptides by MALDI-MS. Our results demonstrated that certain nanostructured BDD surfaces exhibited superior performance for the detection of especially hydrophobic peptides (e.g., bradykinin 1-7, substance P, and the renin substrate), with a limit of detection of down to 2.3 pM. Further investigation showed that hydrophobic peptides (e.g., bradykinin 1-7, substance P, and the renin substrate) were effectively detected on hydrogen-terminated BDD surfaces. On the other hand, the highly acidic negatively charged peptide adrenocorticotropic hormone fragment 18-39 was effectively identified on oxygen-/fluorine-terminated BDD surfaces. Furthermore, BDD surfaces reduced sodium adduct contamination significantly.

Spectroscopic characterization of rare natural pink diamonds with yellow color zones

A set of 28 uncommon pink diamonds with yellow color zones are identified among thousands of natural pink diamonds examined. The pink color in these diamonds is caused by the 550 nm absorption band associated with plastic deformation, and is concentrated along straight lamellae (also known as deformation lines). These pink diamonds are type Ia with nitrogen concentrations ranging from 118 to 313 ppma, predominantly as A-centers, i.e., type IaA ≫ B (proportion of B-center < 10 %) to IaA > B (proportion of B-center = 11–26 %).Yellow color zones are observed on or beneath the surface of these faceted pink diamonds. Yellow fluorescence and occasionally yellow phosphorescence excited by long-wave (365 nm) or deep UV (<225 nm), corresponding to the yellow color zones, are commonly observed in yellow diamonds colored by the 480 nm absorption band. PL mapping conducted on the diamond surface and along the depth of the pink diamonds in this study reveals that the yellow color zones have features associated with the 480 nm absorption band. Some of these features are associated with nickel-related defects, and are only detected within the yellow color zones. This suggests that the yellow color zones formed in a different growth episode or from a different diamond-forming fluid than the remaining volume of the diamond with pink body color. Post-growth plastic deformation created defects giving rise to the 550 nm absorption band, producing a pink body color to diamond that was presumably colorless, and producing brown color in zones that may have had pre-existing yellow color. Three diamonds in this study contain eclogitic mineral inclusions, indicating that they formed in association with mantle eclogite, prior to plastic deformation.

Unveiling the Structure of Metal–Nanodiamonds Bonds: Experiment and Theory

In this study, we conducted a theoretical simulation to compare the effects of various factors on the atomic and electronic structures and the magnetic properties of copper and gadolinium ions bonded to carboxylated species of (111) diamond surfaces. It was experimentally found that in the temperature range above 120 K, the magnetic moments of chelated Gd3+ and Cu2+ equal 6.73 and 0.981 Bohr magnetons, respectively. In the temperature range from 12 to 2 K, these magnetic moments sharply decrease to 6.38 and 0.88 Bohr magnetons. Specifically, we examined the effects of the number of covalent adatom–diamond substrate bridges, coordination of water molecules, and shallow carbon-inherited spins in the substrate on the physical properties of the metal center. Our simulation predicted that increasing the number of bonds between the chelated metal ion and substrate while decreasing the number of coordinating water molecules corresponded to a decrease in the magnetic moment of metal ions in a metal–diamond system. This is due to the redistribution of the electron charge density in an asymmetric metal–diamond system. By comparing our theoretical results with experimental data, we proposed configurations involving one and, in a minor number of cases, two surface –COO− groups and maximum coordination of water molecules as the most realistic options for Cu- and Gd-complexes.

Overview of Patents on Diamond Polishing Apparatus

Diamond, with its unparalleled combination of physical and chemical attributes, occupies a critical role in future technological domains; yet, the caliber of its surface quality is decisively linked to its performance within advanced applications. Thus, engaging in super-precision processing to elevate the surface integrity of diamond constitutes a central tenet for broadening its application potential. This paper systematically dissects patents pertaining to diamond polishing apparatus, not only revealing the distinctive strengths and pragmatic features inherent in contemporary diamond polishing technology but also identifying limitations and avenues for refinement within current polishing methodologies. With the continuous expansion and deepening of modern industrial sectors, there is a growing demand for diversified and specialized material performance. Diamond, as a pivotal raw material, exhibits immense potential in its composite applications with a variety of other materials, forming an entire industrial chain that has permeated numerous industries. Throughout the comprehensive preparation process of diamond, from rough stone to finished product, polishing techniques play a critical role, representing an indispensable step in enhancing the surface quality and functional attributes of diamond products. This study provides a comprehensive review of representative patents in the field of diamond polishing apparatus, analyzing the distinctive functional attributes and performance characteristics of various diamond polishing devices. The study classifies polishing devices according to their design characteristics and application domains into five distinct categories: polishing apparatuses specifically designed for single-crystal diamonds, systems tailored for the polishing of complex curved surface diamonds, laser-assisted diamond polishing setups, structurally-enhanced diamond polishing equipment, and functionally-specialized diamond polishing tools. The analysis underscores the unique innovative aspects and advantages demonstrated by each patent in addressing the inherent limitations of traditional polishing devices. Moreover, it elucidates the technological constraints and developmental gaps that exist within each respective area. Presently, the essence of polishing technology research revolves around the precision and efficacy in polishing single-crystal diamonds and intricate curved diamond surfaces, alongside the structural innovation and functional refinement of polishing apparatuses. Predominant among these devices are those that largely depend on mechanical polishing methods integrated with laser-assisted and chemical mechanical polishing methodologies, where patent advancements are mainly geared towards boosting efficiency, guaranteeing surface integrity, fortifying adaptability across different operating scenarios, and incorporating multiple functionalities. Concurrently, considerable attention is given to enhancing the ecological performance of these systems. There remains a significant underdevelopment and limited widespread application of diamond polishing apparatus in advanced technologies such as thermal chemical polishing and ion beam polishing. This gap presents an enormous potential for innovation breakthroughs and diversified advancements in polishing techniques. There is an urgent need for increased investment to propel the development and integration of automated control systems, intelligent monitoring, and deeper exploration of new materials within polishing technology. The aim is to realize higher-level automated and intelligent diamond polishing solutions that can achieve more efficient, precise, and environmentally friendly polishing objectives.

Methods for Color Center Preserving Hydrogen‐Termination of Diamond

AbstractChemical functionalization of diamond surfaces by hydrogen is an important method for controlling the charge state of near‐surface fluorescent color centers, an essential process in fabricating devices such as diamond field‐effect transistors and chemical sensors, and a required first step for realizing families of more complex terminations through subsequent chemical processing. In all these cases, termination is typically achieved using hydrogen plasma sources that can etch or damage the diamond, as well as deposited materials or embedded color centers. This work explores alternative methods for lower‐damage hydrogenation of diamond surfaces, specifically the annealing of diamond samples in high‐purity, non‐explosive mixtures of nitrogen and hydrogen gas, and the exposure of samples to microwave hydrogen plasmas in the absence of intentional stage heating. The effectiveness of these methods are characterized by x‐ray photoelectron spectroscopy (XPS), and comparison of the results to density‐functional modelling of the surface hydrogenation energetics implicates surface oxygen ligands as the primary factor limiting the termination quality of annealed samples. Finally, photoluminescence (PL) spectroscopy is used to verify that both the annealing and reduced sample temperature plasma methods are non‐destructive to near‐surface ensembles of nitrogen‐vacancy (NV) centers, in stark contrast to plasma treatments that use heated sample stages.

Enhancement of Flow Boiling Heat Transfer Characteristics on Diamond/Cu Heterogeneous Surface

Surface treatment is an effective method of enhancing the heat transfer performance of flow boiling. Diamond/Cu, as a particle‐reinforced composite, exhibits heterogeneous surface properties and surface microstructures that play distinct roles in heat transfer. To elucidate the synergistic effect of heterogeneous material surfaces and microstructures, pure copper surface (PC), untreated diamond/Cu surface (DC), and surface‐treated diamond/Cu surface (SDC) are prepared for this experiment. These surfaces demonstrate various combinations of diamond, copper, and their corresponding surface microstructures. DC, characterized by heterogeneous wetting properties, demonstrates a heat transfer coefficient (HTC) that is 9%–24% higher than that of PC. The surface treatment of SDC results in the formation of a superhydrophilic CuO nanosheet structure, significantly enhancing both surface roughness and energy. SDC develops microcracks on the surface of diamond. The increased roughness provides numerous nucleation areas for the hydrophobic diamond, enhancing the overall wettability of the surface when combined with the superhydrophilic CuO region. SDC demonstrates the advantage of enhanced flow boiling on the surface of heterogeneous materials. At the identical heat flux, SDC exhibits a reduction of 5–10 °C in wall superheat and an increase of 38%–47% in HTC.

Photoinduced Charge Injection from Shallow Point Defects in Diamond into Water.

Thanks to its low or negative surface electron affinity and chemical inertness, diamond is attracting broad attention as a source material of solvated electrons produced by optical excitation of the solid-liquid interface. Unfortunately, its wide bandgap typically imposes the use of wavelengths in the ultraviolet range, hence complicating practical applications. Here, we probe the photocurrent response of water surrounded by single-crystal diamond surfaces engineered to host shallow nitrogen-vacancy (NV) centers. We observe clear signatures of diamond-induced photocurrent generation throughout the visible range and for wavelengths reaching up to 594 nm. Experiments as a function of laser power suggest that NV centers and other coexisting defects─likely in the form of surface traps─contribute to carrier injection, though we find that NVs dominate the system response in the limit of high illumination intensities. Given our growing understanding of near-surface NV centers and adjacent point defects, these results open new perspectives in the application of diamond-liquid interfaces to photocarrier-initiated chemical and spin processes in fluids.

Oxygen-Terminated Polycrystalline Boron-Doped Diamond Superhydrophobic Surface with Excellent Mechanical and Thermal Stabilities.

Superhydrophobic surfaces are of great interest because of their remarkable properties. Due to its maximal hardness and chemical inertness, diamond film has great potential in fabricating robust superhydrophobic surfaces. In the present study, an oxygen-terminated polycrystalline boron-doped diamond (O-PBDD) superhydrophobic surface with micro/nano-hierarchical porous structures is developed. The preparation method is very simple, requiring only sputtering and dewetting procedures. The former involves sputtering gold and copper particles onto the hydrogen-terminated polycrystalline boron-doped diamond (H-PBDD) to form gold/copper films, whereas the latter involves placing the samples in an atmospheric tube furnace to form hierarchical pores. By controlling the etching parameters, the wettability of the O-PBDD surface can be adjusted from hydrophilic to superhydrophobic, which is significantly different to the normal hydrophilicity feature of O-termination diamonds. The water contact angle of the obtained O-PBDD surface can reach 165 ± 5°, which is higher than the superhydrophobic diamond surfaces that are reported in the literature. In addition, the O-PBDD surface exhibits excellent durability; it can maintain satisfactory superhydrophobicity even after high-pressure, high-temperature, and sandpaper friction tests. This work provides a new research direction for fabricating robust superhydrophobic materials with diamond film.

Study on hydrogen retention resistance of diamond film by HFCVD

To explore the potential application of diamond coating on the surface modification of graphite-based plasma-facing components in nuclear fusion, the retention of hydrogen irradiated into diamond film deposited by HFCVD was studied. After being attacked with 200 eV hydrogen ions for 10 h at 200 °C, this diamond layer was observed to maintain the stability of crystal structure. The C-H absorption peaks in the FTIR spectrum that were conspicuous in the sole graphite were absent in the diamond surface subjected to the same quantity of hydrogen irradiation, suggesting that the implanted hydrogen was difficult to penetrate or persist in the diamond covering. Further computational studies have demonstrated that hydrogen atoms exhibit a low propensity for retention within the diamond (111), in contrast to reside stably in graphite or graphite-like structures. The above shows that HFCVD diamond film has strong resistance to hydrogen retention and structural stability under hydrogen irradiation.

Effect of different titanium addition methods on the properties of diamond/Cu composites

Due to the low bonding strength between diamond and copper, the thermal conductivity and mechanical strength of diamond/copper composites are affected. In order to improve the interface bonding strength, this paper prepared diamond/Cu composites with titanium element in two forms: adding titanium to the copper matrix and using titanium coated diamond particles, respectively. The microstructure and composition analysis of the materials were carried out through SEM, EDS, AFM, etc. The bending strength and thermal conductivity of titanium coated diamond/copper composites reached 230 MPa and 480 W/(m·K), respectively, which were higher than the bending strength and thermal conductivity of diamond/Cu composites with added titanium in the matrix (208 MPa and 127 W/(m·K) and significantly higher than the corresponding properties of pure diamond/Cu composites (69 MPa and 108 W/(m·K)). Pre coating a layer of titanium carbide on the surface of diamond can serve as a connecting bridge, effectively reducing interfacial thermal resistance and improving mechanical properties, which is more effective than adding titanium powder to the matrix to improve the bending strength and thermal conductivity of diamond/Cu composites.

Enhancing colloidal stability of nanodiamond via surface modification with dendritic molecules for optical sensing in physiological environments

Pre-treatment of diamond surface in low-temperature plasma for oxygenation and in acids for carboxylation was hypothesized to promote the branching density of the hyperbranched glycidol polymer. This was expected to increase the homogeneity of the branching level and suppress interactions with proteins. As a result, composite nanodiamonds with reduced hydrodynamic diameters that are maintained in physiological environments were anticipated. Surfaces of 140-nm-sized nanodiamonds were functionalized with oxygen and carboxyl groups for grafting of hyperbranched dendritic polyglycerol via anionic ring-opening polymerization of glycidol. The modification was verified with Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. Dynamic light scattering investigated colloidal stability in pH-diverse (2–12) solutions, concentrated phosphate-buffered saline, and cell culture media. Thermogravimetric analysis of nanodiamonds-protein incubations examined non-specific binding. Fluorescence emission was tested across pH conditions. Molecular dynamics simulations modeled interparticle interactions in ionic solutions. The hyperbranched polyglycerol grafting increased colloidal stability of nanodiamonds across diverse pH, high ionic media like 10 × concentrated phosphate-buffered saline, and physiological media like serum and cell culture medium. The hyperbranched polyglycerol suppressed non-specific protein adsorption while maintaining intensive fluorescence of nanodiamonds regardless of pH. Molecular modelling indicated reduced interparticle interactions in ionic solutions correlating with the improved colloidal stability.

Microstructure and finite element analysis of Mo2C-diamond/Cu composites by spark plasma sintering

Abstract Mo2C layer was generated on the diamond surface via vacuum micro-evaporating, which was used as the reinforcement particles to fabricate diamond/Cu composites by spark plasma sintering (SPS). The effect of evaporation parameters on the forming of Mo2C, and the holding time on diamond/Cu composites fabrication is studied. Combined with the experiment and finite element analysis (FEA), the holding time on diamond/Cu composites influence on the thermal conductivity (TC) of composites is further discussed. The results show that the Mo2C area on the diamond surface would gradually enlarge and cover the diamond surface evenly with the increment in evaporation time and temperature, better vacuum micro-evaporating parameters were given as 1,000°C for 60 min. The fractures in the diamond/Cu composites are mainly ductile fractures on copper and diamond falling out from the Mo2C interface. It was found that sintering time would significantly influence the dissipation property of diamond/Cu composites. A comprehensive parameter for SPS was obtained at 900°C, 80 MPa for 10 min, the relative density (RD) and TC of the composites obtained under the parameter were 96.13% and 511 W/(m K). A longer sintering time would damage the Mo2C interlayer and further decrease the bonding between copper matrix and diamond particles, which would lower the RD and TC of composites. It can be obtained from the comparison of simulation results and experimental results that the FEA result is closer to the experimental results due to the gaps with low heat conduction, and the air in the gaps is added in the simulation process.

Prehydrated Electrons Activated by Continuous Electron Transfer Stemmed from Peracetic Acid Homolysis Mediated by Diamond Surface Defects for Enhanced PFOA Destruction.

Research on the use of peracetic acid (PAA) activated by nonmetal solid catalysts for the removal of dissolved refractory organic compounds has gained attention recently due to its improved efficiency and suitability for advanced water treatment (AWT). Among these catalysts, nanocarbon (NC) stands out as an exceptional example. In the NC-based peroxide AWT studies, the focus on the mechanism involving multimedia coordination on the NC surface (reactive species (RS) path, electron reduction non-RS pathway, and singlet oxygen non-RS path) has been confined to the one-step electron reaction, leaving the mechanisms of multichannel or continuous electron transfer paths unexplored. Moreover, there are very few studies that have identified the nonfree radical pathway initiated by electron transfer within PAA AWT. In this study, the complete decomposition (kobs = 0.1995) and significant defluorination of perfluorooctanoic acid (PFOA, deF% = 72%) through PAA/NC has been confirmed. Through the use of multiple electrochemical monitors and the exploration of current diffusion effects, the process of electron reception and conduction stimulated by PAA activation was examined, leading to the discovery of the dynamic process from the PAA molecule → NC solid surface → target object. The vital role of prehydrated electrons (epre-) before the entry of resolvable electrons into the aqueous phase was also detailed. To the best of our knowledge, this is the first instance of identifying the nonradical mechanism of continuous electron transfer in PAA-based AWT, which deviates from the previously identified mechanisms of singlet oxygen, single-electron, or double-electron single-path transfer. The pathway, along with the strong reducibility of epre- initiated by this pathway, has been proven to be essential in reducing the need for catalysts and chemicals in AWT.

Oxygen functionalized diamond nanocone arrays coupling cobalt phthalocyanine for enhanced electrochemical CO2 reduction

The development of high-efficiency catalysts plays a crucial role in advancing CO2 electroreduction techniques. Among potential candidates, diamond-based electrocatalysts show promise due to their broad electrochemical windows, which effectively suppress competitive hydrogen evolution and ensure high CO2 reduction efficiency. In this study, we report an integrated electrode composed of oxygen-terminated diamond nanocone (ODcone) with CoPc-molecules anchoring (CoPc/ODcone). The CoPc/ODcone electrodes exhibited remarkable performance, achieving a maximum Faradaic efficiency (FE) of 94.1% for CO at −0.97 V vs reversible hydrogen electrode (RHE), and maintaining an FECO higher than 80% over a wide potential range of −0.67 V to −1.07 V vs RHE. The outstanding performance of the CoPc/ODcone electrode can be attributed to the synergistic effects between the nanostructured diamond surface and the CoPc catalyst. The hydroxyl-rich nature of the diamond surface facilitates the anchoring of CoPc molecules and bonding with Co atoms in CoPc. Simultaneously, the nanostructured diamond with sharp tips enhances CO2 adsorption, thereby improving the catalyst's performance. This study provides valuable insights into the utilization of non-metallic carbon materials, particularly diamond, as metal-free catalysts in CO2 electrochemical reduction and tackles challenges such as low current density and poor Faradaic efficiency, thus contributing to the advancement of more effective catalysts for CO2 electroreduction.

Formation of low-dimensional nanopit structures on atomically flat surfaces of diamond (111) by nickel nanoparticles

Diamond nanoprocessing technologies are essential for the development of diamond-based devices. However, the existing etching processes damage the diamond crystal, adversely affecting the characteristics of the corresponding device. Herein, we focused on the Ni–C solid-solution reaction as a nondamaging fabrication method. Ni films (10, 3, and 1 nm) were deposited on atomically flat surfaces (AFSs) of diamond (111) and annealed under H2 gas flow. The Ni film aggregated into particles, and as the particle size decreased, Ni particles moved around, etching the diamond surface. Interestingly, when the diameter of the Ni nanoparticles was less than a few tens of nanometers, they dug one-dimensional (1D) nanopits with a linear trench shape on diamond AFS. We discuss the mechanism for the formation of these 1D nanopits in detail from the perspective of the etching-morphology dependence on the annealing time, Ni thickness, and gas atmosphere. The results of this study will improve our understanding of the Ni–C solid-solution reaction at the nanoscale and promote the development of damage-free nanofabrication techniques for diamond-based device applications.

A theoretical study on dopants substituted on the H-terminated surface regulating the threshold concentration of nitrogen for accelerating diamond growth

Nitrogen is widely believed to accelerate the diamond growth by chemical vapor deposition (CVD). While there is currently no consensus on the reaction mechanism of nitrogen increasing the growth rate of CVD diamond. In this work, we have proposed a chemical adsorption model formed by substitutional nitrogen on the H-terminated surface of diamond. The first principles calculations based on density functional theory are used to systematically study the effects of substitutional nitrogen on several key features (i.e., surface absorption energy, geometric structure, atomic charge, electron bond population, and electron density) of the H-terminated surfaces. The results indicate that nitrogen substituted on the H-terminated surface are probably more favorable for hydrogen desorption, which can not only affect the properties of directly bonding adjacent species, but also cause changes in the geometric and electronic properties around the surface by electron transfer or forming additional covalent bonds. Furthermore, compared with single nitrogen doping, the co-doped structures formed by adding boron or phosphorus at a relatively low N/H ratio on the H-terminated surface could enhance or weaken the stability of the diamond surface, that is, weaken or enhance the desorption process of hydrogen. It is therefore proved the existence of a regulatory effect on the threshold concentration required for nitrogen to accelerate diamond growth.