Electrical properties of B-doped homoepitaxial diamond (001) film

Relationship between growth condition and quality of homoepitaxially grown B-doped diamond (001) film has been studied using physical measurements of defect density as a function of doping concentration. In particular, electrical properties of the homoepitaxial diamond film were characterized using measurements of conductivity, carrier concentration and mobility. The highest mobility is found to be about 1000 cm²V⁻¹s⁻¹ at 293 K, indicating that the quality of the CVD diamond film is further improved through optimizing the growth condition. The density of the compensation donor was determined from the temperature-dependent hole concentration. The lowest donor density is found to be 8.4 × 10¹⁵ cm⁻³ in the present work. This is an order of magnitude greater than the lowest value measured in natural IIb diamond. Furthermore, it is also found that the donor density increases with increasing doping concentration during the growth. On the other hand, the mobility decreases rapidly with increasing doping concentration. From these results, we speculate that the compensation donor is an origin of an additional scattering center in diamond, and excessive B-doping makes the quality of the CVD diamond worse.     

Electrical characterization of phosphorus-doped n-type homoepitaxial diamond layers

Electrical properties of phosphorus (P)-related donors have been investigated for P-doped homoepitaxial diamond layers grown by microwave plasma CVD. Temperature-dependent current–voltage (I–V), capacitance–voltage (C–V) measurements and frequency-dependent C–V measurements have been carried out with lateral dot-and-plane (with ring-shaped gap) Schottky barrier diodes. N-type Schottky junction properties were obtained. The ideality factor and the rectification ratio of the Schottky junction were obtained to be 1.9 and 1.7×10⁵ at ±10 V and 473 K, respectively. Frequency-dependent measurements on these Schottky barrier diodes have shown that the capacitance is reduced at high frequency, most likely due to the inability of deep centers to maintain an equilibrium ionization state under a high-frequency modulation. C–V measurements deduced that the net donor concentration was 6.2×10¹⁷ cm⁻³ and the corresponding built-in potential was 4.0 eV, when the P concentration was 8.3×10¹⁷ cm⁻³. Phosphorus electrical activity was 0.75 in the P-doped diamond layer. The carrier thermal activation energy (the donor level) was evaluated to be 0.6 eV from the relation between the net donor concentration and the carrier concentration.     

Electrical characterization of homoepitaxial diamond p–n junction

Electrical properties of homoepitaxial diamond p–n⁺ junction of boron (B)-doped p-type layer and phosphorus-doped n-type layer on Ib (111) diamond single crystal have been characterized. Current–voltage characteristics show a clear rectifying property with rectification ratio of over 10⁵ at ± 10 V. From capacitance–voltage characteristics, it is found that a spatial distribution of space-charge density N_i of the p–n⁺ junction is not uniform and N_i at a middle region of the space-charge layer formed at zero bias voltage is higher than that of other region of the space-charge layer. This peculiar characteristic can be explained by superposition of two effects; one is the deep dopant effect due to B atoms in the p-type layer, which makes to reduce N_i at around the edge of the space-charge layer formed at zero bias voltage. The other is the compensation of B acceptors by impurity atoms diffusing during the p–n⁺ interface and incorporating during the growth of p-type layer, which makes to reduce N_i at the vicinity of the p–n⁺ interface.     

Feasibility of CVD diamond radiation energy conversion devices

We analyzed the feasibility of CVD diamond to operate as the main component in active devices for conversion of high-energy radiation into electrical power. A self-sustained radiation dosimeter based on the electron emission effect was designed and tested under low-energy X-ray beam (Mg X-ray tube). The device operative conditions (absence of applied bias voltage) represented also the first experimental test towards the development of diamond energy conversion systems. On this basis, we designed a CVD diamond vacuum radiation energy converter and analyzed it using electron beams. An analysis of the performance was obtained letting both electron flux I₀ and kinetic energy E₀ to vary. For E₀ = 1 keV the power exploited by a load was estimated as tenths of nW and the total conversion efficiency was between 0.2 and 0.4%. This performance makes the device nominally competitive if compared to other similar solid-state converters. A discussion about the device design and possible improvements was performed in order to rationalize the conditions able to maximize the energy conversion efficiency.     

High-pressure and high-temperature annealing effects on CVD homoepitaxial diamond films

High-pressure and high-temperature (HPHT) annealing effects on the chemical vapor-deposited (CVD) homoepitaxial diamond films were investigated. By the HPHT annealing, the intensity of free-exciton (FE)-related emission was increased by  2 times and the luminescence bands from 270 to 320 nm, which originate from 5RL and 2BD bands, were almost completely eliminated in the cathodoluminescence (CL) spectrum. The CL intensity of band-A emission, which is related to crystal defects in diamond, was also decreased. The hole mobility at room temperature was increased from 826 to 1030 cm²/Vs by HPHT annealing. These results suggest that HPHT annealing decreases the crystalline defects and improves the optical and electronic properties of homoepitaxial diamond films.     

Influence of the substrate type on CVD grown homoepitaxial diamond layer quality by cross sectional TEM and CL analysis

To assess diamond-based semiconducting devices, a reduction of point defect levels and an accurate control of doping are required as well as the control of layer thickness. Among the analyses required to improve such parameters, cross sectional studies should take importance in the near future. The present contribution shows how FIB (focused ion beam) preparations followed by electron microscopy related techniques as TEM or CL allowed to perform analysis versus depth in the layer, doping and point defect levels. Three samples grown along the same week in the same machine with identical growth conditions but on different substrates (CVD-IIIa (110) oriented, CVD-optical grade (100) oriented and a HPHT-Ib (100) oriented) are studied. Even though A-band is observed by CL, no dislocation is observed by CTEM. Point defect type and level are shown to substantially change with respect to the substrate type as well as the boron doping levels that vary within an order of magnitude. H3 present in the epilayer grown on HPHT type of substrate is replaced by T1 and NE3 point defects for epilayers grown on the CVD type one. An increase of excitonic transitions through LO phonons is also shown to take place near the surface while only TO ones are detected deeper in the epilayer. Such results highlight the importance of choosing the correct substrate.     

Anisotropic dry etching of boron doped single crystal CVD diamond

Semiconducting boron doped single-crystal CVD diamond has been patterned using aluminum masks and an inductively coupled plasma (ICP) etch system. For comparison insulating HPHT diamond samples were also patterned using the same process. Diamond etch rates above 200 nm/min were obtained with an O₂/Ar discharge for a gas pressure of 2.5 mTorr using 600 W RF power. We have accomplished the fabrication of structures with a minimum feature size of 1 μm with vertical sidewalls in both CVD and HPHT diamond. The ICP etching produced smooth surfaces with a typical root-mean-square surface roughness of 3 nm. The dependence of etch rate on bias voltage was somewhat different for the two types of diamond. However, for all samples both the etch rate and anisotropy were found to improve with increasing bias voltage.     

High-quality homoepitaxial diamond (100) films grown under high-rate growth condition

We present advantages of high-power microwave plasma chemical vapor deposition (MPCVD) in homoepitaxial diamond film deposition. Diamond films grown at comparatively high growth rate of 3.5 μm/h showed intense free-exciton recombination emission at room temperature. The free-exciton decay time of the diamond film at room temperature, 22 ns, was much longer than that of type-IIa single crystal, indicating electronically high quality of the homoepitaxial films. Dislocation-related emissions were locally observed, a part of which created by mechanical polishing process was successfully removed by surface etching process using oxygen plasma. Another advantage of the high-power MPCVD is effective impurity doping; boron-doped diamond films with high carrier mobility and high carrier concentration were reproducibly deposited. An ultraviolet photodetector fabricated using the high-quality undoped diamond film showed lower noise equivalent power as well as higher photoresponsivity for ultraviolet light with better visible-blind property, compared to those of standard Si-based photodetectors. The high-power MPCVD is, thus, indispensable technique for depositing high quality diamond films for electronic devices.     

CVD diamond for spintronics

The ability to minimise, control and manipulate defects in CVD diamond has grown rapidly over the last ten years. The application which best illustrates this is probably that of quantum information processing (QIP) or ‘diamond spintronics’. QIP is a rapidly growing area of research, covering diverse activities from computing and code breaking to encrypted communication. All these applications need ‘quantum bits’ or qubits where the quantum information can be maintained and controlled. Controlled defects in an otherwise high perfection diamond lattice are rapidly becoming a leading contender for qubits, and offer many advantages over alternative solutions. The most promising defect is the NV⁻ defect whose unique properties allow the state of its electron spin to be optically written to and read from. Substantial developments in the synthesis of CVD diamond have produced diamond lattices with a high degree of perfection, such that the electron spin of this centre exhibits very long room temperature decoherence times (T₂) in excess of 1 ms. This paper gives a brief review of the advantages and challenges of using CVD diamond as a qubit host. Lastly the various qubit applications being considered for diamond are discussed, highlighting the current state of development including the recent development of high sensitivity magnetometers.     

EPR study of hydrogen-related defects in boron-doped p-type CVD homoepitaxial diamond films

Boron-doped p-type single crystalline chemical vapor deposition (CVD) homoepitaxial diamond films were investigated by electron paramagnetic resonance (EPR). Carbon dangling bond defects, which were accompanied by a nearby hydrogen atom, were observed in boron-doped p-type CVD diamond films on a IIa substrate similar to those observed in undoped diamond. This result suggested that the energy level position of the defects is located below the Fermi energy of boron-doped diamond, at around 0.3 eV above the valence-band top. The reason why the Fermi energy could be changed by the incorporation of boron atoms at low density (10¹⁶–10¹⁷/cm³) in the film in spite of the existence of the large defect density of EPR centers (10¹⁸/cm³) is thought to be that the singly occupied electron states of defects are located near the band edge. As for the thermal annealing effect of the defects, it was revealed that the concentration of the defects and the mobility of the p-type film did not change after annealing up to 1200 °C which is much higher than the temperature of boron–hydrogen pair dissociation.     

Homoepitaxial single crystal diamond grown on natural diamond seeds (type IIa) with boron-implanted layer demonstrating the highest mobility of 1150 cm/V s at 300 K for ion-implanted diamond

The homoepitaxial single crystal diamond growth by microwave plasma assisted CVD at high microwave power density 200 W/cm³ in a 2.45 GHz MPACVD reactor using natural diamond seeds (type IIa) was investigated. The semiconductor CVD diamond of p-type was obtained by doping technique of ion implantation. Boron ions were implanted at the acceleration energy of 80 keV with two cases of dose: 5 · 10¹⁴ and 3 · 10¹⁵ cm^− 2. To recover the damage layer and activate dopants in CVD diamond the rapid annealing at nitrogen atmosphere at 1380° C was used. B-implanted diamond layer showing the mobility of 1150 cm²/V s at 300 K which is the highest for ion-implanted diamond was obtained.     

The effect of nitrogen addition during high-rate homoepitaxial growth of diamond by microwave plasma CVD

The effect of nitrogen addition on growth rate, morphology and crystallinity during high-rate microwave plasma chemical vapor deposition (MPCVD) of diamond was investigated. Epitaxial diamond was grown on type Ib diamond (100) substrates using a 5-kW, 2.45-GHz microwave plasma CVD system with nitrogen addition in the methane and hydrogen source gases. In order to obtain high growth rates, we designed the substrate holders to generate high-density plasma. The growth rates ranged from 30 to 120 μm/h. The nitrogen addition enhanced the growth rate by a factor of 2 and was beneficial to create a macroscopic smooth (100) face avoiding the growth of hillocks. However, the (100) surfaces looked microscopically rough by bunched steps as the effect of nitrogen addition. The macroscopic smoothing during the growth enabled the long-term stable deposition required to obtain large crystals. The deposited diamond was characterized by optical microscope, Raman spectroscopy, cathodoluminescence spectroscopy and X-ray diffraction.     

Ohmic contacts to semiconducting diamond using a Ti/Pt/Au trilayer metallization scheme

Ohmic contacts have been fabricated on a naturally occurring type IIb diamond crystal using an annealed Ti/Pt/Au trilayer metallization where the Pt served successfully as a barrier to Ti diffusion into the Au capping layer. However, a specific contact resistance could not be reliably determined using transmission line model measurements. Auger microanalysis revealed the presence of Ti on the diamond surface near the ohmic contact pads. The most likely origin of the Ti on the diamond surface was determined to be lateral diffusion from beneath the contact pads. This would have produced a nonuniform concentration of Ti across the diamond surface which, in turn, would have affected the diamond sheet resistance in a complicated way.     

Weak localization — Precursor of unconventional superconductivity in nanocrystalline boron-doped diamond

Analyzing the magnetotransport data obtained on nanocrystalline variety of heavily boron-doped diamond, we have proposed a new model of unconventional superconductivity in this material based on the very experimental fact that the symptoms of localization are precursors of superconducting transition. It is shown by quantitative arguments that the system treated as disordered Mott's metal in which the transport is controlled by weak localization of carriers should reveal, in the Kelvin range, superconducting transition just when the holes occupying neighbouring weakly localized orbits are paired by means of a spin-flip mechanism.     

Characterization of substrate off-angle effects for high-quality homoepitaxial CVD diamond films

We have studied the substrate off-angle effects for the crystalline quality of the homoepitaxial diamond films mainly by using steady-state cathodoluminescence (CL) and time-resolved photoluminescence (PL) measurements. By means of the microwave plasma chemical vapor deposition method under high-power microwave power with high methane concentrations, the homoepitaxial diamond films were grown on the high-pressure/high-temperature-synthesized (HPHT) Ib (001) substrates inclined along either <110> or <100> direction by different off-angles ranging from 2° to 5°. In spite of high growth rates, we have succeeded in improving crystalline quality by employing the HPHT substrates with considerably large off-angles. Both steady-state CL and time-resolved PL measurements clearly indicate that larger off-angles lead to better crystalline quality of the homoepitaxial film, suggesting that further improvements in crystalline quality can be expected when using substrates having even larger off-angles.     

UV Schottky photodiode on boron-doped CVD diamond films

We report on experimental study of photosensitivity and Q-DLTS spectra of polycrystalline CVD diamond UV photodetectors. The measured characteristics of Schottky photodiode on boron-doped diamond films are compared with those obtained for planar photoconductive structures (photoresistor type) based on undoped CVD diamond. The Schottky photodiode exhibited a sharp cut-off in photoresponse with spectral discrimination ratio (between wavelengths of 190 nm and 700 nm) as high as 5 · 10⁵ at zero bias voltage (at zero dark current). The photodiode showed the maximum of photoresponse at wavelength < 190 nm, and a low density of trapping and recombination centers as evaluated with the Q-DLTS technique. The devices demonstrated the photoresponsivity at 190 nm from 0.03 to 0.1 A/W with quantum yield of 0.20 to 0.67 in closed circuit, while the photovoltage ≥ 1.6 V was measured in open circuit regime. Another type of UV detector, the planar photoconductive structures with interdigitizing ohmic electrodes fabricated on undoped diamond film and operated under a bias voltage, revealed a higher density of (surface) defect centers and the maximum photoresponse at  210 nm wavelength. A strong influence of UV light illumination on the Q-DLTS spectra of the planar photoconductive structures was observed. This effect can be used for development of new UV detectors and dosimeters based on the Q-DLTS signal measurements.     

Reduced influences of the HPHT substrates on the electronic quality of homoepitaxial CVD diamond layers and on their ultraviolet detector performance

We have carried out a detailed estimation of the influences of the high-pressure/high-temperature-synthesized (HPHT) Ib substrate on the crystalline quality of the homoepitaxial diamond and on the performance of the ultraviolet (UV) detector. The H3 center related luminescence peaks were observed even from the homoepitaxial diamond film having a thickness of 250 μm on a HPHT Ib substrate, suggesting that carriers excited in the epitaxial diamond layer can diffuse over a rather long distance to the HPHT substrate when the quality of the epitaxial layer is sufficiently high. Furthermore, we have attempted to efficiently reduce the long-distance carrier diffusion phenomenon by inserting a boron-doped layer between the epitaxial layer for the detection and the HPHT Ib substrate. The electrically-floating B-doped layer inserted between the homoepitaxial layer and the HPHT substrate efficiently reduced the long-distance carrier diffusion phenomenon, and substantially improved the performance of the UV detector fabricated on a low-quality HPHT Ib substrate.     

The effect of CO2 on the high-rate homoepitaxial growth of CVD single crystal diamonds

In this paper, we report the effect of gaseous carbon dioxide (CO₂) introduced in the typical reaction atmosphere of CH₄/H₂/N₂ (60/500/1.8 in sccm) on the growth rate, morphology and optical properties of homoepitaxy single crystal diamonds (SCDs) by microwave plasma chemical vapor deposition. The additional carbonaceous sources supplied by CO₂ are favorable to increase the growth rate, and meanwhile, the oxygen related species generated would enhance the etching effect not only to eliminate the non-diamond phase of SCD but also to decrease the growth rate. The appropriate addition of CO₂ can increase the high growth rate, decrease the surface roughness, and reduce the concentration of N-incorporation. It is demonstrated that adding CO₂ strongly affects the contents of various reaction species in plasma, which would determine the growth features of CVD SCDs.     

Electrical properties of MgO/p-diamond junction fabricated on homoepitaxial single-crystalline diamond

Sufficiently flat and hillock-free insulating homoepitaxial diamond films were successfully grown on high-pressure–high-temperature-synthesized diamond using a 5-kW microwave-plasma chemical-vapor-deposition system with a 20-ppm-nitrogen-included source gas of 4% CH₄ diluted with H₂. Then, layered MgO/boron-doped (p-type) diamond structures were fabricated on the homoepitaxial insulating diamond. Current (I)–voltage (V) characteristics of these device structures showed strong nonlinear behaviors for both current directions, or those for two electrically-parallel, reversed diodes, with conduction limited mainly by sheet resistance of the p-diamond layer in a temperature range from 300 to 600 K. This suggests that the carrier transport occurred through different current passes in the junction region at both biases. Low-frequency capacitances measured were mainly dominated by the depletion capacitance which was influenced by the bias voltage. At relatively high frequencies, however, the total capacitance measured (C) was determined not only by the depletion capacitance but also by the series resistance and the dispersion capacitance. Equivalent circuits of the MgO/p-diamond structure were deduced to explain the measured I–V and C–V results. A possible conduction mechanism is proposed in relation to the electronic structure of the MgO/p-diamond junction.     

Comparative study of homoepitaxial single crystal diamond growth at continuous and pulsed mode of MPACVD reactor operation

Homoepitaxial growth of single crystal diamond by microwave plasma chemical vapor deposition in pulsed regime of a 2.45 GHz MPACVD reactor operation at pulse repetition rates of 150 and 250 Hz was investigated. The high quality CVD diamond layers were deposited in the H₂-CH₄ gas mixture containing 4% and 8% of methane, gas pressures of 250 and 260 Torr and substrate temperature of 900 °C without any nitrogen addition. The (100) HPHT single crystal diamond seeds 2.5 × 2.5 × 0.3 mm (type Ib) were used as substrates. At pulse repetition rate 150 Hz the high quality single crystal diamond was grown with growth rate of 22 μm/h. The comparison of the single crystal diamond growth rates in CW and pulsed wave regimes of MPACVD reactor operation at microwave power density 200 W/cm³ was made. It was found that at equal power density, the growth rate in pulsed wave regime was higher than in CW regime. Differences in single crystal diamond growth for two sets of experiments (with continuous and pulsed wave regimes) were explained.