Conductive diamond possesses unique features as compared to other solid electrodes, such as a wide electrochemical potential window, a low and stable background current, relatively rapid rates of electron-transfer for soluble redox systems without conventional pretreatment, long-term responses, stability, biocompatibility, and a rich surface chemistry. Conductive diamond microcrystalline and nanocrystalline films, structures and particles have been prepared using a variety of approaches. Given these highly desirable attributes, conductive diamond has found extensive use as an enabling electrode across a variety of fields encompassing chemical and biochemical sensing, environmental degradation, electrosynthesis, electrocatalysis, and energy storage and conversion. This review provides an overview of the fundamental properties and highlights recent progress and achievements in the growth of boron-doped (metal-like) and nitrogen and phosphorus-doped (semi-conducting) diamond and hydrogen-terminated undoped diamond electrodes. Applications in electroanalysis, environmental degradation, electrosynthesis electrocatalysis, and electrochemical energy storage are also discussed. Diamond electrochemical devices utilizing micro-scale, ultramicro-scale, and nano-scale electrodes as well as their counterpart arrays are viewed. The challenges and future research directions of conductive diamond are discussed and outlined. This review will be important and informative for chemists, biochemists, physicists, materials scientists, and engineers engaged in the use of these novel forms of carbon.

Conductive diamond: synthesis, properties, and electrochemical applications

We report on a detailed analysis of the transport properties and superconducting critical temperatures of boron-doped diamond films grown along the {100} direction. The system presents a metal-insulator transition (MIT) for a boron concentration $({n}_{B})$ on the order of ${n}_{c}\ensuremath{\sim}4.5\ifmmode\times\else\texttimes\fi{}{10}^{20}\phantom{\rule{0.3em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}3}$, in excellent agreement with numerical calculations. The temperature dependence of the conductivity and Hall effect can be well described by variable range hopping for ${n}_{B}l{n}_{c}$ with a characteristic hopping temperature ${T}_{0}$ strongly reduced due to the proximity of the MIT. All metallic samples (i.e., for ${n}_{B}g{n}_{c}$) present a superconducting transition at low temperature. The zero-temperature conductivity ${\ensuremath{\sigma}}_{0}$ deduced from fits to the data above the critical temperature $({T}_{c})$ using a classical quantum interference formula scales as ${\ensuremath{\sigma}}_{0}\ensuremath{\propto}{({n}_{B}∕{n}_{c}\ensuremath{-}1)}^{\ensuremath{\nu}}$ with $\ensuremath{\nu}\ensuremath{\sim}1$. Large ${T}_{c}$ values $(\ensuremath{\geqslant}0.4\phantom{\rule{0.3em}{0ex}}\mathrm{K})$ have been obtained for boron concentration down to ${n}_{B}∕{n}_{c}\ensuremath{\sim}1.1$ and ${T}_{c}$ surprisingly mimics a ${({n}_{B}∕{n}_{c}\ensuremath{-}1)}^{1∕2}$ law. Those high ${T}_{c}$ values can be explained by a slow decrease of the electron-phonon coupling parameter $\ensuremath{\lambda}$ and a corresponding drop of the Coulomb pseudopotential ${\ensuremath{\mu}}^{*}$ as ${n}_{B}\ensuremath{\rightarrow}{n}_{c}$.

/pdf/metal-insulator-transition-and-superconductivity-in-boron-1ohmgvk7tr.pdf

Metal-insulator transition and superconductivity in boron-doped diamond

We report superconductivity in heavily boron-doped bulk silicon carbide related to the diamond structure. The compound exhibits zero resistivity and diamagnetic susceptibility below a critical temperature T c of ∼1.4 K, and an effective boron doping concentration higher than 10 21 cm -3 . We present the H – T phase diagram of this new superconducting compound determined from AC susceptibility. In finite DC magnetic fields a clear hysteresis was observed between cooling and subsequent warming runs. This indicates, in contrast with the type-II superconductivity in boron-doped diamond and silicon, that a type-I superconductivity with a critical field H c (0) of about 100 Oe is realized in boron-doped SiC. Moreover, the specific-heat shows a clear jump at T c , demonstrating bulk nature of the superconductivity.

Superconductivity in boron-doped SiC

The experimental discovery of superconductivity in boron-doped diamond came as a major surprise to both the diamond and the superconducting materials communities. The main experimental results obtained since then on single-crystal diamond epilayers are reviewed and applied to calculations, and some open questions are identified. The critical doping of the metal-to-insulator transition (MIT) was found to coincide with that necessary for superconductivity to occur. Some of the critical exponents of the MIT were determined and superconducting diamond was found to follow a conventional type II behaviour in the dirty limit, with relatively high critical temperature values quite close to the doping-induced insulator-to-metal transition. This could indicate that on the metallic side both the electron-phonon coupling and the screening parameter depend on the boron concentration. In our view, doped diamond is a potential model system for the study of electronic phase transitions and a stimulating example for other semiconductors such as germanium and silicon.

/pdf/metal-to-insulator-transition-and-superconductivity-in-boron-56ffxin5yu.pdf

Metal-to-insulator transition and superconductivity in boron-doped diamond

Solid-State Nuclear Magnetic Resonance (NMR) Methods Applied to the Study of Carbon Materials

http://iopscience.iop.org/article/10.1016/j.stam.2006.03.010/pdf

11B-NMR study in boron-doped diamond films

We have investigated the superconductivity discovered in boron-doped diamonds by means of $^{11}\mathrm{B}\text{\ensuremath{-}}\mathrm{NMR}$ on heteroepitaxially grown (111) and (100) films. $^{11}\mathrm{B}\text{\ensuremath{-}}\mathrm{NMR}$ spectra for all of the films are identified to arise from the substitutional B(1) site as single occupation and lower symmetric B(2) site substituted as $\text{boron}+\text{hydrogen}$ $(\mathrm{B}+\mathrm{H})$ complex, respectively. Clear evidence is presented that the effective carriers introduced by B(1) substitution are responsible for the superconductivity, whereas the charge neutral B(2) sites does not offer the carriers effectively. The result is also corroborated by the density of states deduced by $1∕{T}_{1}T$ measurement, indicating that the evolution of superconductivity is driven by the effective carrier introduced by substitution at B(1) site.

https://arxiv.org/pdf/cond-mat/0610134.pdf

Microscopic evidence for evolution of superconductivity by effective carrier doping in boron-doped diamond: B11 -NMR study

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11B-NMR study in boron-doped diamond films

Microscopic evidence for evolution of superconductivity by effective carrier doping in boron-doped diamond: B11 -NMR study