Single-crystal Boron-doped Diamond Research Articles

Heat capacity of bulk boron-doped single-crystal HPHT diamonds in the temperature range from 2 to 400 K

The heat capacity, Cp, of boron-doped single-crystal diamonds grown by the temperature gradient method was studied. The boron contents were < 1016, ~ 1018, and ~ 1020 cm–3. The heat capacity data for all tested crystals match well (within the measurement accuracy 1%) in the temperature range of 150–400 K and obey the Debye law. At low temperatures the heat capacity follows linear law possibly due to metallic inclusions in diamond bulk. Using this data the amount of metal can be calculated for each sample.

Intermittent‐contact Scanning Electrochemical Microscopy (IC‐SECM) as a Quantitative Probe of Defects in Single Crystal Boron Doped Diamond Electrodes

AbstractWe demonstrate, for the first time, the use of electrochemical imaging to identify defect and defect free areas in single crystal boron doped diamond (BDD) electrodes. Specifically, we show that defects contain different boron dopant concentrations than the surrounding single crystal matrix and that these variations can be visualized using intermittent contact−scanning electrochemical microscopy (IC‐SECM). The measured IC‐SECM tip currents provide quantitative information on the rates of electron transfer across the single crystal BDD electrodes, which correlate with variations in boron doping levels. In some instances, IC‐SECM outperforms alternative methods such as Raman microscopy and cathodoluminescence imaging, due to its intrinsic surface‐sensitivity, expanding the application and impact of electrochemical microscopy for materials characterization. The results obtained, and procedure outlined, are particularly valuable for the assessment and screening of single crystal BDD electrodes.

Thermal conductivity of synthetic boron-doped single-crystal HPHT diamond from 20 to 400 K

Abstract

Weak superconductivity in the surface layer of a bulk single-crystal boron-doped diamond

We have grown and investigated bulk single-crystal heavily boron-doped diamonds possessing superconductivity with . Only the surface layer with the thickness less than showed the degenerate semiconductor behavior with transition to the superconducting state, while the bulk of the crystal was a typical doped semiconductor. The morphology of the surface layer is dendritic polycrystalline with an average boron content of 2.5–2.9 at.%. The typical Josephson junction current-voltage characteristic was observed. The degenerate semiconductor-superconductor transition as in single-crystal high-temperature superconductors and the structural data analysis of the surface layer indicate the two-dimensional character of superconductivity, and the actual superconducting structure is a set of few-nanometer thick boron carbide layers embedded in a diamond structure.

Studies on synthesis of boron-doped Gem-diamond single crystals under high temperature and high presure

In this paper, by choosing catalyst of FeNiMnCo alloy, boron-doped diamond single crystals are synthesized under 5.1–5.6 GPa and 1230–1600℃; the temperature field is studied by finite element method (FEM). First, the P-T phase diagram for diamond single crystal growth, in the synthesis system of FeNiMnCo-C-B, is obtained, and the lowest synthesis conditions of 5.1 GPa and 1230℃ is found in the studies. By simulation with FEM, it is found that the content of boron element should be less and less in the growth of diamond single crystal in the {111} sector, and the reason is that the growth speed is reduced in the sectors. By growing diamond crystals with {111} faces, it is also found that the content of boron element in {111} secondary sector is greater than that in {111} primary sector, which is duo to the rapid growth of {111} secondary sector. Compared with the synthesis of diamond single crystal by film growth method, the diamond crystals thus obtained has no pits, the doping content of boron can be greater, and the diamond can be synthesized by temperature gradient method.

Effect of Nitrogen on the Growth of Boron Doped Single Crystal Diamond

Boron-doped single crystal diamond films were grown homoepitaxially on synthetic (100) Type Ib diamond substrates using microwave plasma assisted chemical vapor deposition. A modification in surface morphology of the film with increasing boron concentration in the plasma has been observed using atomic force microscopy. Use of nitrogen during boron doping has been found to improve the surface morphology and the growth rate of films but it lowers the electrical conductivity of the film. The Raman spectra indicated a zone center optical phonon mode along with a few additional bands at the lower wavenumber regions. The change in the peak profile of the zone center optical phonon mode and its downshift were observed with the increasing boron content in the film. However, sharpening and upshift of Raman line was observed in the film that was grown in presence of nitrogen along with diborane in process gas.

Boron-doped diamond single crystals for probes of the high-vacuum tunneling microscopy

The results of studying the structure of diamond single crystals grown by the temperature gradient method with the aim to obtain samples having maximum uniform characteristics for manufacturing probes for scanning electron microscopes with a specified axial orientation and controlled distribution of the dopant have been considered. It has been shown that the use of similar probes in scanning tunneling microscopy decreases the probability of incidental tunneling channels with participation of the surface states caused by the presence of boron atoms in the diamond structure and increases the reliability of experimental data. The high stability of monocrystalline diamond probes and the possibility to attain the atomic resolution with the help of them have been demonstrated by the investigations of the (0001) graphite plane using scanning tunneling microscopy.

Measuring the local resistivity by the nanoindentation and force-spectroscopy methods

Methods for measuring the resistivity of materials during elastic and elastoplastic interactions of a current-conducting indenter and a studied sample are described. Analytical methods that describe the dependences of the contact ohmic resistance on the pressure force and the contact stiffness are proposed. The considered models are experimentally tested with a NanoScan scanning nanohardness tester using indenters made of boron-doped diamond single crystals.

Synthesis and Characterization of Boron-Doped Single Crystal Diamond

ABSTRACTThe boron-doped single crystal diamond films were grown homoepitaxially on synthetic (100) oriented Type Ib diamond substrates using a Microwave Plasma Chemical Vapor Deposition (MPCVD) technique. Raman spectrum showed a few additional bands at the lower wavenumber regions along with the zone center optical phonon mode for diamond. The change in the peak profile of the zone center optical phonon mode and its downshift were observed with the increasing boron content in the film. A modification in surface morphology of the film with increasing boron content had been observed by atomic force microscopy. Four point probe electrical measurement indicated that different conduction mechanisms are operating in various temperature regions for these semiconducting films.

Hall Effect Measurement System for Characterization of Doped Single Crystal Diamond

ABSTRACTA temperature dependent Hall Effect measurement system with software based data acquisition and control was built and tested. Transport measurements are shown for boron-doped single crystal diamond (SCD) films deposited in a microwave plasma-assisted chemical vapor deposition (MPCVD) reactor. The influence of Ohmic contacts and temperature control accuracy are studied. For a temperature range of 300K-700K IV curves, Hall mobilities and carrier concentrations are presented.

Raman scattering in boron-doped single-crystal diamond used to fabricate Schottky diode detectors

Thanks to its exceptional physical and electronic properties, diamond is an attractive material for electronic devices working at high temperature and in harsh chemical environment. Its use as a semiconducting material for electronics is related to the possibility of doping it in order to control its conductivity. Semiconducting p-type diamond films can be grown when boron is introduced into the film. In this work, boron-doped (B-doped) homoepitaxial diamond films are grown by Microwave Plasma Enhanced Chemical Vapor Deposition. Raman and electrical characterizations are carried out on the films as a function of boron doping level. As the boron content increases, we observe systematic modifications in the Raman spectra of single-crystal diamonds. A significant change in the lineshape of the first-order Raman peak, as well as a wide and structured signal at lower wavenumbers, appears simultaneously in samples grown with higher boron content. A single crystal diamond Schottky diode based on a metal/intrinsic/p-type diamond junction is analysed.

Evaluation of freestanding boron-doped diamond grown by chemical vapour deposition as substrates for vertical power electronic devices

In this study, 4 × 4 mm2 freestanding boron-doped diamond single crystals with thickness up to 260 μm have been fabricated by plasma assisted chemical vapour deposition. The boron concentrations measured by secondary ion mass spectroscopy were 1018 to 1020 cm−3 which is in a good agreement with the values calculated from Fourier transform infrared spectroscopy analysis, thus indicating that almost all incorporated boron is electrically active. The dependence of lattice parameters and crystal mosaicity on boron concentrations have also been extracted from high resolution x-ray diffraction experiments on (004) planes. The widths of x-ray rocking curves have globally shown the high quality of the material despite a substantial broadening of the peak, indicating a decrease of structural quality with increasing boron doping levels. Finally, the suitability of these crystals for the development of vertical power electronic devices has been confirmed by four-point probe measurements from which electrical resistivities as low as 0.26 Ω cm have been obtained.

Dopant Uniformity and Concentration in Boron Doped Single Crystal Diamond Films

ABSTRACTHigh quality single crystal boron-doped diamond films are deposited in a microwave plasma-assisted CVD reactor with feedgas mixtures including hydrogen, methane, diborane, and carbon dioxide at reactor pressures of 160 Torr. The effect of diborane levels and other growth parameters on the incorporated boron levels are investigated, and the doping efficiency is calculated over a wide range of boron concentrations. The boron level is investigated using infrared absorption, and compared to SIMS measurements, and defects are shown to affect the doping uniformity.

Conducting boron-doped single-crystal diamond films for high pressure research

Epitaxial boron-doped diamond films were grown by microwave plasma chemical vapor deposition for application as heating elements in high pressure diamond anvil cell devices. To a mixture of hydrogen, methane and oxygen, diborane concentrations of 240–1200 parts per million were added to prepare five diamond thin-film samples. Surface morphology has been observed to change depending on the amount of diborane added to the feed gas mixture. Single-crystal diamond film with a lowest room temperature resistivity of 18 mΩ cm was fabricated and temperature variation of resistivity was studied to a low temperature of 12 K. The observed minima in resistivity values with temperature for these samples have been attributed to a change in conduction mechanism from band conduction to hopping conduction. We also present a novel fabrication methodology for monocrystalline electrically conducting channels in diamond and present preliminary heating data with a boron-doped designer diamond anvil to 620 K at ambient pressure.

Synthesis and characterization of p-type boron-doped IIb diamond large single crystals

High-quality p-type boron-doped IIb diamond large single crystals are successfully synthesized by the temperature gradient method in a china-type cubic anvil high-pressure apparatus at about 5.5 GPa and 1600 K. The morphologies and surface textures of the synthetic diamond crystals with different boron additive quantities are characterized by using an optical microscope and a scanning electron microscope respectively. The impurities of nitrogen and boron in diamonds are detected by micro Fourier transform infrared technique. The electrical properties including resistivities, Hall coefficients, Hall mobilities and carrier densities of the synthesized samples are measured by a four-point probe and the Hall effect method. The results show that large p-type boron-doped diamond single crystals with few nitrogen impurities have been synthesized. With the increase of quantity of additive boron, some high-index crystal faces such as {113} gradually disappear, and some stripes and triangle pits occur on the crystal surface. This work is helpful for the further research and application of boron-doped semiconductor diamond.

Electronic surface barrier properties of fluorine-terminated boron-doped diamond in electrolytes

The surface bond structure and electronic surface barrier in electrolytes were analysed for fluorinated boron-doped single crystal diamond. The diamond surface was exposed to a CF 4 RF-plasma combined with in-situ pre-heating in ultra-high vacuum to remove adsorbates. This treatment resulted in full surface coverage by mixed carbon–fluorine functionalities of 2 nm in thicknesses and possibly with cross-linked or branched structures, leaving no traces of carbon-oxygen groups and non-diamond carbon phase, as determined by high-resolution X-ray photoemission spectroscopy. The capacitance-voltage, impedance spectroscopy and redox characteristics of the fluorinated diamond were investigated in various electrolytes. The analysis of data showed that electronic barrier at the fluorinated surface was close to zero at equilibrium, meaning no surface depletion of the boron-doped diamond. In comparison, the surface barrier of identical oxygen-terminated diamond was approx. 1.6 eV using the same evaluation methods. The low surface barrier of the fluorinated surface remained stable after anodic polarisation and did not depend on pH or ion species.

Determination of Boron Concentration in Doped Diamond Films

ABSTRACTThe electrical characteristics of high quality single crystal boron-doped diamond are studied. Samples are synthesized in a high power-density microwave plasma-assisted chemical vapor deposition (CVD) reactor at a pressure of 160 Torr. The boron-doped diamond films are grown using diborane in the feedgas at concentrations of 0-0.25 ppm, and are compared to those grown previously with 1-10 ppm. The boron acceptor concentration is investigated using infrared absorption, and compared to the boron concentration obtained by SIMS. A four point probe is used to study the conductivity. The temperature dependent conductivity is analyzed to determine the boron dopant activation energy.

Scanning Probe Microscopy with Diamond Tip in Tribo-nanolithography

ABSTRACTThe results obtained by direct nano-patterning demonstrate the potential of the SPM-based techniques that include surface scratching to create 3D nanostructures. Such techniques became known as tribo-nanolithography and have prospects of being successfully implemented in the future nanofabrication industry. An important obstacle to this, however, is the effect of wear at the nanometer scale which is critical to the stability of tribo-nanolithoraphic processes. Such stability is achievable via in-depth theoretical and experimental studies of friction at the nanoscale along with the development of pioneering equipment. Our work presents the results of experimental fabrication of nanostructures formed by nanoscratching with the use of the multifunctional scanning tunneling microscopy previously developed by the authors. The authors attempted scratching the silicon surface by using a boron-doped diamond tip. This operation was undertaken in the same direction sequentially with the tip sliding a side of the groove by one of the tip’s facets and the consequent surface scanning. Although not being applicable to non-conductive surfaces, the proposed technique has significant advantages. One advantage is related to the high stiffness of the tunneling probe as compared to the stiffness of the AFM cantilever. High stiffness and perpendicularity of the tip to the surface during surface processing eliminates bending beam effects on the typical AFM and ensures machining effectiveness. Purposely synthesized boron-doped single-crystal diamonds were used as a tip material. The results of experimental fabrication of nanostructures formed by nanoscratching with the use of the multifunctional scanning probe are demonstrated and discussed.

Growth of thick heavily boron-doped diamond single crystals: Effect of microwave power density

The fabrication of diamond-based vertical power devices which are the most suited for high current applications requires the use of thick heavily boron-doped (B-doped) diamond single crystals. Although the growth of thin B-doped diamond films is well controlled over a large concentration range, little is known about the growth conditions leading to heavily doped thick single crystals. In this paper, it was found that the microwave power densities (MWPD) coupled to the plasma used to synthesize B-doped diamond by chemical vapor deposition is one of the key parameters allowing tuning doping efficiencies over two orders of magnitude. At high MWPD (above 100 W cm−3) the boron doping efficiency (DE) is extremely low while further increasing the boron concentration in the gas phase is no use as this leads to plasma instability. On the other hand, when low MWPD are used (&amp;lt;50 W cm−3), DE can be strongly increased but twinning and defects formation hampers the surface morphology. The use of intermediate MWPD densities has been demonstrated as the key in obtaining thick heavily B-doped diamond crystals (&amp;gt;1020 cm−3) with good morphologies.

Superconductivity in diamond

We survey methods of synthesis of boron doped diamond with high pressure-high temperature techniques. New route is proposed for synthesis of relatively large heavily boron doped diamond single crystals, which exhibit superconductivity. Superconducting boron-doped diamond samples were synthesized with isotopes of 10B, 11B, 13C and 12C. We claim the presence of a carbon isotope effect on the superconducting transition temperature, which supports the “diamond–carbon”-related nature of superconductivity and the importance of the electron–phonon interaction as the mechanism of superconductivity in diamond. Isotope substitution permits us to relate almost all bands in the Raman spectra of heavily boron-doped diamond to the vibrations of carbon atoms. The 500 cm − 1 Raman band shifts with either carbon or boron isotope substitution and may be associated with vibrations of paired or clustered boron.