Masahiko Ogura

The potential of diamond films for future semiconductor applications is partly limited by current growth techniques. This limitation can be addressed by achieving an atomic-level understanding of the growth processes. Using atomic force microscopy with atomic resolution, we examined diamond surfaces and observed specific structures, where odd numbers of dimers form ribbonlike configurations. Formed in the nonequilibrium environment of plasma, these structures were evaluated as the most stable configurations through density-functional-theory calculations. Our findings provide a crucial foundation for optimizing the film growth process.

Nitrogen-vacancy (NV) centers in phosphorus-doped diamond have potential applications in quantum technologies because their electron spin has the longest spin coherence time among those in solid systems at room temperature (RT) and because their negative charge state is more stable than that in undoped diamond. However, the conventional phosphorus source, phosphine, is toxic and explosive; a safer precursor is therefore preferred. We consequently attempted to synthesize phosphorus-doped diamonds using tert-butylphosphine (TBP), which has lower toxicity and explosivity than phosphine. However, controlling phosphorus incorporation during doping with TBP is difficult because it condenses easily and remains in the synthesis reactor due to its low boiling point. Here, we report controlling the incorporation of impurities by optimizing the synthesis conditions, such as the synthesis pressure. Comparing diamonds synthesized at 15 and 50 kPa reveals that the phosphorus concentration was reduced by 93% and the nitrogen concentration by 72% in the diamond synthesized at 50 kPa. For diamonds prepared under optimized conditions in our synthesis reactor, a long spin coherence time (T2 = 2.23 ms) for NV centers with almost perfect selective alignment of the NV axes was achieved. The T2 was comparable to the longest reported length for NV centers in a sample synthesized with phosphine, indicating that TBP is a promising phosphorus source for obtaining NV centers with excellent properties. We also achieved high electron mobility [580 cm2/(V s) at RT] in diamonds synthesized with TBP; this value is comparable to that for diamonds synthesized with phosphine.

A platform for heteroepitaxial (111) chemical vapor deposition (CVD) diamond quantum sensors with preferentially aligned nitrogen vacancy (NV) centers on a large substrate is developed, and its operation as an electric vehicle (EV) battery monitor is demonstrated. A self‐standing heteroepitaxial CVD diamond film with a (111) orientation and a thickness of 150 µm is grown on a non‐diamond substrate and subsequently separated from it. The high uniformity and crystallinity of the (111)‐oriented diamond is confirmed. A 150‐µm thick NV‐diamond layer is then deposited on the heteroepitaxial diamond. The T ₂ value measured by confocal microscopy is 20 µs, which corresponds to substitutional nitrogen defect concentration of 8 ppm. The nitrogen‐vacancy concentration and T ₂ ^* are estimated to be 0.05 ppm and 0.05 µs by continuous wave optically detected magnetic resonance (CW‐ODMR) spectroscopy in a fiber‐top sensor configuration. In a gradiometer, where two sensors are placed on both sides of the busbar, the noise floor is 17 nT/Hz ^0.5 in the frequency range of 10–40 Hz without magnetic shielding. The Allan deviation of the magnetic field noise in the laboratory is below 0.3 µT, which corresponds to a busbar current of 10 mA, in the accumulation time range of 10 ms to 100 s.

Our group developed the first inversion-type p-channel diamond metal–oxide–semiconductor field-effect transistor, which featured normally off properties by employing water vapor annealing treatments for the oxygen-terminated diamond surface. Despite the comprehensive device-grade characterization, the impact of water vapor annealing treatments on the Al2O3/diamond interface has not been investigated in detail. In this work, we fabricated four diamond metal–oxide–semiconductor (MOS) capacitors without and with water vapor annealing treatments for various times of 30 min, 1 h, and 2 h and conducted the cycle capacitance–voltage (C–V) and simultaneous C–V measurements. The large cycle C–V shift existed in the sample without water vapor annealing treatment, whereas it was significantly suppressed by water vapor annealing treatments, indicating the effective passivation of the traps with long time constants. The simultaneous C–V results showed a similar trend that the frequency dispersion of the simultaneous C–V was dramatically reduced with water vapor annealing treatments, and the interface quality of Al2O3/diamond had a slight dependence on the water vapor annealing times. Based on simultaneous C–V measurements, the interface state density (Dit) at an energy level of 0.2–0.6 eV from the valence band edge of diamond was extracted for the different MOS capacitors. The Dit was reduced by one order of magnitude with water vapor annealing treatments, and it almost did not change with the water vapor annealing times. Besides, the flat band voltage shift and effective fixed charge were also dramatically reduced by water vapor annealing. The possible physical reason for the interface improvement by water vapor annealing treatments was discussed.

Control of the charge state of the nitrogen-vacancy (NV) center is crucial because of its instability and its transitions between the negative (NV–) and neutral (NV0) NV charge states under laser irradiation In this study, we fabricated an n-i-n junction, with an i-layer sandwiched between two phosphorus-doped n-layers; then, we measured the charge state of NV centers under steady state and laser irradiation in a known band structure where the Fermi energy changes gradually. The steady-state charge state measured by a nondestructive single shot exhibited stable NV– and NV0 signals when the Fermi level was even slightly above and below the transition level, respectively. This result indicates that the charge state can be significantly stabilized through band engineering. Both charge-state populations were observed only when the Fermi level was close to the transition level. Under continuous green laser irradiation, the ratio of NV– measured by the photoluminescence spectra changed gradually with the Fermi level in the depletion layer because of the balance between excitation from the laser and the supply of charge from the band. This outcome agrees reasonably with the calculated bands. Furthermore, we measured the PL spectra of the ensemble NV centers and discovered that their charge state can be well-controlled, as in the single NV center. The charge state of the i-layer at the interface can be stabilized by depositing a thin n-layer on the surface. These results would contribute significantly to improve sensor performance.

The realization of electroluminescence (EL) of negatively charged nitrogen vacancy (NV⁻) centers is important toward all-electrical control of diamond quantum devices. In this study, we demonstrated electrical excitation and detection of EL of single NV⁻ centers by using lateral diamond p⁺–i(n⁻)–n⁺ diodes. It had been grown by homoepitaxy using the plasma enhanced chemical vapor deposition technique. We introduced a lightly phosphorus doped i(n⁻) layer to stabilize the negative state of NV centers. It was estimated that the efficiency of the electrical excitation rate of the NV center was more than 30 times enhanced by introducing lateral diamond p⁺–i(n⁻)–n⁺ diodes structure compared with the previous vertical diode. Furthermore, the EL of a single NV⁻ center embedded in the i(n⁻) layer region was characterized. The results show that the charge state of the single NV centers can be manipulated by the voltage applied to the p⁺–i(n⁻)–n⁺ diode, where the emission of EL is increasingly dominated by NV⁻ in the range of 30 to 50 V.

The longest spin coherence times for nitrogen-vacancy (NV) centers at room temperature have been achieved in phosphorus-doped n-type diamond. However, difficulty controlling impurity incorporation and the utilization of highly toxic phosphine gas in the chemical vapor deposition (CVD) technique pose problems for the growth of n-type diamond. In the present study, n-type diamond samples were synthesized by CVD using tert-butylphosphine, which is much less toxic than phosphine. The unintentional incorporation of nitrogen was found to be suppressed by incrementally increasing the gas flow rates of H₂ and CH₄. It was found that the spin coherence time (T₂) increased with decreasing the nitrogen concentration, which suggests that the nitrogen concentration limits the length of T₂. In the sample with the lowest nitrogen concentration, T₂ increased to 1.62 ± 0.10 ms. Optically detected magnetic resonance spectra indicated that all of the measured NV centers were aligned along the [111] direction. Hall measurements confirmed n-type conduction in three measured samples prepared under different growth conditions. The highest measured Hall mobility at room temperature was 422 cm²/(V s). This study provides appropriate CVD conditions for growing phosphorus-doped n-type diamond with perfectly aligned NV centers exhibiting long spin coherence times, which is important for the production of quantum diamond devices.

As diamond possesses only deep dopants, certain conventional physics and characterization methods are not applicable to diamond devices, owing to the explicit or implicit assumption of shallow dopants. To resolve this limitation, the capacitance–voltage (C–V) characteristics of metal–insulator–semiconductor (MIS) capacitors formed on a semiconductor substrate with deep and compensating dopants were successfully formulated. Based on these equations, methods for accurately estimating the MIS capacitor properties were developed and validated through their application in the analysis of an actual MIS capacitor formed on a boron-doped hydrogen-terminated diamond substrate. The high-frequency C–V characteristic of the capacitor exhibited a prominent dip specific to deep dopants. However, the dip depth was considerably shallower than theoretically expected. This C–V characteristic was accurately reproduced theoretically, assuming the presence of a surficial diamond layer that contains acceptors with an activation energy of 0.23 eV, which is less than the value 0.37 eV for boron, and has a thickness of the extrinsic Debye length (40 nm in this study) or larger. The insulator charge of the MIS capacitor was estimated as −4.6 × 10¹² cm⁻² in units of electronic charge, which is sufficiently large to induce two-dimensional hole gas. The interface-state density was 1.4 × 10¹² cm⁻² eV⁻¹ for interface-state energies of 0.3–0.5 eV above the valence band maximum. Hence, the proposed methodology and the possible presence of the reduced activation energy layer will guide the development of diamond-based devices.

A normally-off inversion p-channel metal-oxide-semiconductor field-effect transistor (MOSFET) with a nitrogen (N)-doped diamond body deposited using microwave plasma-enhanced chemical vapor deposition (MPECVD) was fabricated. The MOSFET exhibited a drain current density of −1.7 mA/mm. Thus far, this value is similar to the device performance of the inversion p-channel MOSFET fabricated using a phosphorus (P)-doped n-type diamond body. The N₂ used for N-doping is safer than the PH₃ used for P-doping; moreover, the doping concentration is highly controllable. Because the MOSFET, which is a classical electronic device, is driven by a gate voltage, smooth functioning was possible even at a deep donor level. The observed characteristics of the classic MOSFET operating via an N-doped body are crucial for the development of diamond power devices. In this paper, we discuss the significance of the N-doped diamond body and electrical characteristics of the inversion p-channel MOSFET fabricated using an N-doped diamond body.