Vertical structure Schottky barrier diode fabrication using insulating diamond substrate

To obtain high current operation of the diamond SBDs, the device should be designed in a vertical type structure in order to minimize the device on-resistance. In this research, we have designed and developed the technology for fabrication of diamond vertical structure Schottky barrier diodes (vSBD) by utilizing Inductively Coupled Plasma etching technique. Free standing CVD grown epilayers (p⁺/p^? = 100 μm/5 μm) were obtained by removing the base Ib substrate on which the epi-layers were grown, using ICP etching process. After ICP etching, ohmic contact (Ti/Pt/Au) was made at the bottom of p⁺ layer, and Schottky contact (Mo) was made at top side on oxidized surface of p^? layer, to realize Diamond/Mo vSBDs and were analyzed for their electrical characteristics. The SBDs showed a reproducible ideality factor close to 1.0, and a barrier height of 1.4 eV, with a small standard deviation of 0.06 and 0.12 eV respectively. Diodes in the vertical structure exhibited R_on with a battery uniformity irrespective of their location on the wafer, compared the diodes in a pseudo-vertical structure. Room temperature I–V analysis of the fabricated vSBDs (70 μm size) exhibited a high forward current density of 2980 A/cm² (= 0.115 A) with a low R_onS of 8 mΩ cm², which could be attained due to the vertical geometry of the diodes. At the high temperature operation, still higher current density could be obtained. Satisfactory reverse blocking characteristics also could be achieved with a breakdown field of 2.7 MV/cm for small size diodes.     

Power high-voltage and fast response Schottky barrier diamond diodes

We developed and investigated a set of packaged vertical diamond Schottky barrier diodes (SBDs) with a large crystal area of up to 25 mm². All devices show forward current above 5 A and the blocking voltage over 1000 V in the temperature range from 20 °C to 250 °C. Due to the large crystal area and finite thermal resistance of the crystal-case interface the forward current self-heating effect results in a good diamond SBDs performance not only at elevated temperatures but also at normal conditions. As a result we measured about 4 V forward voltage drop, 35 mΩ × cm² specific on-resistance and 100 nA/cm² leakage current for the diode case at room temperature. At a case temperature of 250 °C the forward voltage drop was less than 2.5 V, the specific on-resistance about 40 mΩ × cm² and the leakage current about 100 μA/cm². The Baliga's figure of merit was 25–30 MW/cm² in the temperature range of 20-250 °C. The typical value of the reverse recovery time less than 10 ns while switching from 2 A forward current to 100 V blocking voltage meets the requirements for practical use of diamond SBDs in effective switch-mode power converters operating at frequencies higher than 1 MHz. Further device design optimization and the diamond epitaxial layer quality improvement will help to reduce the power losses in on-state and make diamond SBDs competitive with SiC diodes even at room temperature.     

Characterization of vertical Mo/diamond Schottky barrier diode from non-ideal I–V and C–V measurements based on MIS model

In this study, we investigated non-ideal characteristics of a diamond Schottky barrier diode with Molybdenum (Mo) Schottky metal fabricated by Microwave Plasma Chemical Vapour Deposition (MPCVD) technique. Extraction from forward bias I–V and reverse bias C^− 2–V measurements yields ideality factor of 1.3, Schottky barrier height of 1.872 eV, and on-resistance of 32.63 mΩ·cm². The deviation of extracted Schottky barrier height from an ideal value of 2.24 eV (considering Mo workfunction of 4.53 eV) indicates Fermi level pinning at the interface. We attributed such non-ideal behavior to the existence of thin interfacial layer and interface states between metal and diamond which forms Metal-Interfacial layer-Semiconductor (MIS) structure. Oxygen surface treatment during fabrication process might have induced them. From forward bias C–V characteristics, the minimum thickness of the interfacial layer is approximately 0.248 nm. Energy distribution profile of the interface state density is then evaluated from the forward bias I–V characteristics based on the MIS model. The interface state density is found to be uniformly distributed with values around 10¹³ eV^− 1·cm^− 2.     

Microstructure,optical and electrical properties of sputtered HfTiO high-k gate dielectric thin films

The microstructure, optical and electrical properties of HfTiO high-k gate dielectric thin films deposited on Si substrate and quartz substrate by RF magnetron sputtering have been investigated. Based on analysis from x-ray diffraction (XRD) measurements, it has been found that the as-deposited HfTiO films remain amorphous regardless of the working gas pressure. Meanwhile, combined with characterization of ultraviolet-visible spectroscopy (UV–vis) and spectroscopy ellipsometry (SE), the deposition rate, band gap and optical properties of sputtered HfTiO gate dielectrics were determined. Besides, by means of the characteristic curves of high frequency capacitance–voltage (C–V) and leakage current density–voltage (J–V), the electrical parameters, such as permittivity, total positive charge density, border trap charge density, and leakage current density, have been obtained. The leakage current mechanisms are also discussed. The energy band gap of 3.70 eV, leakage current density of 1.39×10⁻⁵ A/cm² at bias voltage of 2 V, and total positive charge density and border trap charge density of 9.16×10¹¹ cm⁻² and 1.3×10¹¹ cm⁻², respectively render HfTiO thin films deposited at 0.6 Pa, potential high-k gate dielectrics in future CMOS devices.     

Structural and electrical properties of H-terminated diamond field-effect transistor

A dielectric barrier separating hydrogen induced p-type channel and Al gate metal contact of diamond FET has been investigated. The separation barrier is necessary to prevent tunneling current between the H-induced channel and the gate contact. In this investigation, CV measurements, fitting of forward IV characteristics, TEM and SIMS profiles have been used to obtain a more detailed picture of this barrier layer. While the composition of this layer is not clear, TEM and SIMS measurements indicate that this layer may be connected to a diamond phase or aluminium oxide. Using material properties of these materials, thickness of the separation layer extracted from the CV measurements was between 5–10 nm and the channel sheet change density was above 1 × 10¹³ cm^? 2. This thickness is in good agreement with the TEM observations. Frequency dependent CV measurements showed almost no frequency dependence, and no UV light dependence has been observed. Temperature dependent CV measurements showed a decrease of the dielectric constant at 100 °C. Fitting of the forward tunnelling current indicated a thickness of the barrier layer of about 5 nm with a barrier height of 2.4 eV.     

Growth of a three-dimensional complex carbon nanoneedle electron emitter for fabrication of field emission device

A three-dimensional complex carbon nanoneedle electron emitter film with high emission current density at low electric field has been developed by a direct current plasma chemical vapor deposition system. Sample grown on stainless wire substrate pretreated with the mixing powders of diamond and molybdenum exhibited novel film morphology. The scanning electron microscopy image taken from this film indicated a three-dimensional complex nanostructure emitter, the center of which was a carbon nanoneedle, and many small carbon nanowalls growing from the needle. The density of unique nanostructure emitters was about 5 × 10⁷/cm². The I–V characteristic addressed an emission current density of 251 mA/cm² at the electric field of 2.2 V/μm, and the field emission current was stable, making it possibly suitable for developing field emission device.     

Electron emission characteristics of needle type semiconductor diamond electron emitters by pulsed bias operation and X-ray generation

Electron emission characteristics of needle-type semiconductor diamond electron emitters with pulsed bias operation were evaluated. An X-ray generation experiment was performed. Fowler–Nordheim plotting confirmed that field emission completely governed the electron emission. Maximum emission current of 4.2 mA was achieved using an n-type diamond needle. The needle tip, with area smaller than 1 μm², had estimated electron emission density greater than 4.2 × 10⁵ A/cm². The effective emission area obtained from the Fowler–Nordheim plot was several 10^? 13 cm². For adopting and emission area of 1 × 10^? 12 cm², the estimated electron emission density was higher than 4.2 × 10⁹ A/cm². Furthermore, the average emission current was 0.5–0.6 mA. This large electron emission was continued for several seconds and repeatable. A threshold electric field existed for electron emission higher than 50 kV/mm; pulsed electron emissions of less than 30 ms were created by slow triangular waveform shaped bias voltage supplied at frequencies of 5–10 Hz. An improved vacuum level and pulsed bias operation prevented damage to diamond electron emitters and steady electron emission better than with thermoelectronic emission and high bias voltage supply in DC mode; continuous X-ray generation of 1 h was achieved.     

Homoepitaxial diamond p–n+ junction with low specific on-resistance and ideal built-in potential

We have realized low specific on-resistance and ideal built-in potential simultaneously for a (111)-oriented homoepitaxial diamond p–n⁺ junction. As the p–n⁺ junction, the heavily phosphorus doped n⁺-type layer, which shows variable range hopping conduction, was formed on the (111)-oriented boron doped p-type one. By using this hopping conduction, the resistivity of the n⁺-type layer becomes lower by three orders of magnitude than that of a lightly P-doped layer. Current density–voltage characteristics showed a rectification ratio of 10⁶ at ± 15 V at room temperature. The current density and the specific on-resistance at forward bias voltage of 15 V at room temperature are over 100 A/cm² and 8 × 10^− 2 Ωcm², respectively. This low specific on-resistance corresponds to the lower resistivity of the n⁺-type layer by three orders of magnitude than that of conventional lightly P-doped n-type layer. The existence of the space-charge layer at the vicinity of the p–n⁺ junction was confirmed from capacitance–voltage (C–V) characteristics. From C⁻²–V characteristics at 200 °C, the built-in potential was estimated as approximately 4.4 eV, which is identical to that of conventional diamond p–n junction.     

The effect of annealing on electrical properties of fluorinated amorphous carbon films

Fluorinated amorphous carbon (a–C:F) films have been deposited by electron cyclotron resonance chemical vapor deposition (ECR–CVD) at room temperature using C₄F₈ and CH₄ as precursor gases. The chemical compositions and electrical properties of a–C:F films have been studied by X-ray photoelectron spectroscopy (XPS), capacitance–voltage (C–V) and current-voltage (I–V) measurements. The results show that C–CF_x and C–C species of a–C:F films increase and fluorine content decreases after annealing. The dielectric constant of the annealed a–C:F films increases as a result of enhancement of film density and reduction of electronic polarization. The densities of fixed charges and interface states decrease from 1.6 × 10¹⁰ cm^− 2 and (5–9) × 10¹¹ eV^− 1 cm^− 2 to 3.2 × 10⁹ cm^− 2 and (4–6) × 10¹¹ eV^− 1 cm^− 2 respectively when a–C:F films are annealed at 300 °C. The magnitude of C–V hysteresis decreases due to reduced dangling bonds at the a–C:F/Si interfaces after heat treatment. The conduction of a–C:F films shows ohmic behavior at lower electric fields and is explained by Poole–Frankel (PF) mechanism at higher electric fields. The PF current increases indicative of reduced trap energy when a–C:F films are subjected to higher annealing temperatures.     

Effect of anodic and cathodic treatments on the charge transfer of boron doped diamond electrodes

This paper is concerned with the study of the influence of electrochemical pre-treatments on the behavior of highly boron doped diamond electrodes. Anodic and cathodic preconditioning, performed during 10 s either with 10^− 4 A/cm^− 2 (10^− 3 C cm^− 2) or 10^− 1 A/cm^− 2 (1 C cm^− 2), has been studied. Cyclic voltammetry at as-deposited, anodically and cathodically treated electrodes, in presence of 2 redox couples serving as electrochemical probes is analyzed in the light of the surface characterization given by XPS chemical analysis. Ce^4+/3+ redox couple in 0.5 M H₂SO₄ medium and Fe(CN)₆^3−/4− redox couple in 0.1 M KOH medium, have been studied before and after the different treatments. The results of Mott–Schottky plots and current voltage curves are reported and show that the electrochemical response of BDD electrodes is very dependent on the current density involved in the electrochemical preconditioning. The modification of surface bond termination – either hydrogen or oxygen – studied by XPS analyses is also strongly dependent on electrochemical pre-treatment. In particular, it is evidenced that the most important conversion of surface functionalities from hydrogen to oxygen is obtained when the anodic treatment is performed with the smallest current density. Finally, a correlation between surface terminations and charge transfer is evidenced.     

Nucleation and growth surface conductivity of H-terminated diamond films prepared by DC arc jet CVD

High-quality polycrystalline diamond film has been extremely attractive to many researchers, since the maximum transition frequency (f_T) and the maximum frequency of oscillation (f_max) of polycrystalline diamond electronic devices are comparable to those of single crystalline diamond devices. Besides large deposition area, DC arc jet CVD diamond films with high deposition rate and high quality are one choice for electronic device industrialization. Four inch free-standing diamond films were obtained by DC arc jet CVD using gas recycling mode with deposition rate of 14 μm/h. After treatment in hydrogen plasma under the same conditions for both the nucleation and growth sides, the conductivity difference between them was analyzed and clarified by characterizing the grain size, surface profile, crystalline quality and impurity content. The roughness of growth surface with the grain size about 400 nm increased from 0.869 nm to 8.406 nm after hydrogen plasma etching. As for the nucleation surface, the grain size was about 100 nm and the roughness increased from 0.31 nm to 3.739 nm. The XPS results showed that H-termination had been formed and energy band bent upwards. The nucleation and growth surfaces displayed the same magnitude of square resistance (R_s). The mobility and the sheet carrier concentration of the nucleation surface were 0.898 cm/V s and 10¹³/cm² order of magnitude, respectively; while for growth surface, they were 20.2 cm/V s and 9.97 × 10¹¹/cm², respectively. The small grain size and much non-diamond carbon at grain boundary resulted in lower carrier mobility on the nucleation surface. The high concentration of impurity nitrogen may explain the low sheet carrier concentration on the growth surface. The maximum drain current density and the maximum transconductance (g_m) for MESFET with gate length L_G of 2 μm on H-terminated diamond growth surface was 22.5 mA/mm and 4 mS/mm, respectively. The device performance can be further improved by using diamond films with larger grains and optimizing device fabrication techniques.     

Ion implantation and anneal to produce low resistance metal–diamond contacts

Contacts to boron-doped, (100)-oriented diamond implanted with Si or with Si and B were formed and the effects of dose, implantation energy and anneal treatment on the specific contact resistance were examined. Ti/Au contacts on heavily implanted diamond (10¹⁶ Si ions cm⁻², E_i=30 keV or 10¹⁷ Si and B ions cm⁻², E_i=15 keV (Si) and E_i=10 keV (B)) had a specific contact resistance lower than the best contacts produced on unimplanted diamond. A specific contact resistance of (1.4±6.4)×10⁻⁷ Ω cm⁻² was achieved following a 450°C anneal. The results were consistent with a reduction in barrier height brought about by silicide formation. Light silicon implantation (10¹³ ions cm⁻²) or relatively light dual implantation (B, Si<10¹⁶ ions cm⁻²) did not reduce the specific contact resistance. Increasing the diamond conductivity by 4×10⁴ decreased the specific contact resistance by over three orders of magnitude, in agreement with the trend observed by Prins (J.F. Prins, J. Phys. D 22 (1989) 1562).     

Diamond based field-effect transistors with SiNx and ZrO2 double dielectric layers

A diamond-based field-effect transistor (FET) with SiN_x and ZrO₂ double dielectric layer has been demonstrated. The SiN_x and ZrO₂ gate dielectric are deposited by plasma-enhanced chemical vapor deposition (PECVD) and radio frequency (RF) sputter methods, respectively. SiN_x layer is found to have the ability to preserve the conduction channel at the surface of hydrogen-terminated diamond film. The leakage current density (J) of SiN_x/ZrO₂ diamond metal-insulator-semiconductor FET (MISFET) keeps lower than 3.88 × 10^− 5 A·cm^− 2 when the gate bias was changed from 2 V to − 8 V. The double dielectric layer FET operates in a p-type depletion mode, whose maximum drain-source current, threshold voltage, maximum transconductance, effective mobility and sheet hole density are determined to be − 28.5 mA·mm^− 1, 2.2 V, 4.53 mS·mm^− 1, 38.9 cm²·V^− 1·s^− 1, and 2.14 × 10¹³ cm^− 2, respectively.     

Raman scattering by defect-induced excitations in boron-doped diamond single crystals

Polarized Raman spectra of the oriented boron-doped diamond with a different content of boron (≤ 200 ppm) were obtained with 514.5 and 1064 nm excitations. The additional bands were found in the region below 1200 cm^− 1. Their intensity increased with doping. It was shown that in polarized spectra these bands were in agreement with the singularities of density of phonon states (DOS) of diamond for the A_1g, E_g and F_2g symmetries. It was assumed that the ~ 900 cm^− 1 band which does not coincide with any DOS peak and has the highest resonance character may be attributed to the localized mode of boron in a diamond lattice. The spectra were accompanied by continuum that had the same symmetry F_2g as optical phonon at 1333 cm^− 1.     

Electrochemical performance of intermediate temperature micro-tubular solid oxide fuel cells using porous ceria barrier layers

We describe the manufacture and electrochemical characterization of micro-tubular anode supported solid oxide fuel cells (mT-SOFC) operating at intermediate temperatures (IT) using porous gadolinium-doped ceria (GDC: Ce_0.9Gd_0.1O_2−δ) barrier layers. Rheological studies were performed to determine the deposition conditions by dip coating of the GDC and cathode layers. Two cell configurations (anode/electrolyte/barrier layer/cathode): single-layer cathode (Ni–YSZ/YSZ/GDC/LSCF) and double-layer cathode (Ni–YSZ/YSZ/GDC/LSCF–GDC/LSCF) were fabricated (YSZ: Zr_0.92Y_0.16O_2.08; LSCF: La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ). Effect of sintering conditions and microstructure features for the GDC layer and cathode layer in cell performance was studied. Current density–voltage (j–V) curves and impedance spectroscopy measurements were performed between 650–800 °C, using wet H₂ as fuel and air as oxidant. The double-cathode cells using a GDC layer sintered at 1400 °C with porosity about 50% and pores and grain sizes about 1 μm, showed the best electrochemical response, achieving maximum power densities of up to 160 mW cm⁻² at 650 °C and about 700 mW cm⁻² at 800 °C. In this case GDC electrical bridges between cathode and electrolyte are preserved free of insulating phases. A preliminary test under operation at 800 °C shows no degradation at least during the first 100 h. These results demonstrated that these cells could compete with standard IT-SOFC, and the presented fabrication method is applicable for industrial-scale.     

Chemical modification of diamond surface with X–(C6H4)–COOH (X = F,Cl, Br,I) using benzoyl peroxide

The chemical reactivity of a hydrogenated diamond surface with X–(C₆H₄)–COOH (X = F, Cl, Br, I) when using benzoyl peroxide was investigated in this study. After the reaction processes the shapes of the IR spectra changed. It was confirmed from the XPS measurements that halogen atoms existed on the samples after the reaction process. The position of the IR peak at ca. 700 cm^? 1 depended on the kind of halogen in X–(C₆H₄)–COOH. Moreover, the peak position depended on the kind of constitutional isomer, that is, ortho-, meta-, or para-. It was confirmed from the experimental results of this study that halogen-containing organic functional groups can be introduced onto a diamond surface.     

Microstructure and electrical characteristics of ZnO–B2O3–PbO–V2O5–MnO2 ceramics prepared from ZnO nanopowders

A peculiar kind of ZnO–B₂O₃–PbO–V₂O₅–MnO₂ ceramics was produced from the ZnO nanopowders directly co-doped with the oxides instead of lead zinc borate frit in this investigation. The 8 wt.% (PbO+B₂O₃) co-doped ceramics sintered at 950 °C for 2 h displayed the optimum electrical properties, that is, leakage current density J_L=6.2×10⁻⁶ A/cm², nonlinear coefficient α=22.8 and breakdown voltage V_BK=331 V/mm. The co-doping of 8 wt.% (PbO+B₂O₃) resulted in an increase in nonlinear coefficient and a decrease in leakage current density of the ZnO–V₂O₅ varistors while the sintering temperature showed no evident influence on nonlinear coefficient and leakage current density at the range of 800–950 °C.     

Homoepitaxial single crystal diamond growth at different gas pressures and MPACVD reactor configurations

Homoepitaxial growth of single crystal diamond by microwave plasma chemical vapor deposition in a 2.45 GHz reactor was investigated at high microwave power density varied from 80 W/cm³ to 200 W/cm³. Two methods of achieving high microwave power densities were used (1) working at relatively high gas pressures without local increase of electric field and (2) using local increase of electric field by changing the reactor geometry (substrate holder configuration) at moderate gas pressures. The CVD diamond layers with thickness of 100–300µm were deposited in H₂–CH₄ gas mixture varying methane concentration, gas pressure and substrate temperature. The (100) HPHT single crystal diamond seeds 2.5 × 2.5 × 0.3 mm (type Ib) were used as substrates. The high microwave power density conditions allowed the achievement of the growth rate of high quality single crystal diamond up to 20 µm/h. Differences in single crystal diamond growth at the same microwave power density 200 W/cm³ for two process conditions—gas pressure 210 Torr (flat holder) and 145 Torr (trapezoid holder)—were studied. For understanding of growth process measurements of the gas temperature and the concentration of atomic hydrogen in plasma were made.     

Growth and electron field emission properties of ultrananocrystalline diamond on silicon nanostructures

The electron field emission (EFE) properties of Si nanostructures (SiNS), such as Si nanorods (SiNR) and Si nanowire (SiNW) bundles were investigated. Additionally, ultrananocrystalline diamond (UNCD) growth on SiNS was carried out to improve the EFE properties of SiNS via forming a combined UNCD/SiNS structure. The EFE properties of SiNS were improved after the deposition of UNCD at specific growth conditions. The EFE performance of SiNR (turn-on field, E₀ = 5.3 V/μm and current density, J_e = 0.53 mA/cm² at an applied field of 15 V/μm) was better than SiNW bundles (turn-on field, E₀ = 10.9 V/μm and current density, J_e < 0.01 mA/cm² at an applied field of 15 V/μm). The improved EFE properties with turn-on field, E₀ = 4.7 V/μm, current density, J_e = 1.1 mA/cm² at an applied field of 15 V/μm was achieved for UNCD coated (UNCD grown for 60 min at 1200 W) SiNR. The EFE property of SiNW bundles was improved to a turn-on field, E₀ = 8.0 V/μm, and current density, J_e = 0.12 mA/cm² at an applied field of 15 V/μm (UNCD grown for 30 min at 1200 W).     

Synthesis of diamond using ultra-nanocrystalline diamonds as seeding layer and their electron field emission properties

A modified nucleation and growth process was adopted so as to improve the electron field emission (EFE) properties of diamonds films. In this process, a thin layer of ultra-nanocrystalline diamonds (UNCD), instead of bias-enhanced-nuclei, were used as nucleation layer for growing diamond films in H₂-plasma. The morphology of the grains changes profoundly due to such a modified CVD process. The geometry of the grains transform from faceted to roundish and the surface of grains changes from clear to spotty. The Raman spectroscopies and SEM micrographs imply that such a modified diamond films consist of UNCD clusters (~ 10–20 nm in size) on top of sp³-bonded diamond grains (~ 100 nm in size). Increasing the total pressure in CVD chamber deteriorated the Raman structure and hence degraded the EFE properties of the films, whereas either increasing the methane content in the H₂-based plasma or prolonged the growth time improved markedly the Raman structure and thereafter enhanced the EFE properties of diamond films. The EFE properties for the modified diamond films can be turned on at E₀ = 11.1 V/μm, achieving EFE current density as large as (J_e) = 0.7 mA/cm² at 25 V/μm applied field.