n-type phosphorus-doped polycrystalline diamond on silicon substrates

The microwave plasma-assisted deposition of reproducible and homogeneously n-type phosphorus-doped polycrystalline (microcrystalline) diamond films on silicon substrates is described. The phosphorus incorporation is obtained by adding gaseous phosphine (PH₃) to the gas mixture during growth. The low CH₄/H₂ ratio (0.15%) and the use of the same growth parameters as for homoepitaxial {111} films, led to a good crystalline quality of the continuous polycrystalline diamond layers, confirmed by SEM images and Raman spectroscopy measurements.Secondary-ion mass spectrometry (SIMS) analysis measured a phosphorus concentration [P] of at least 7 × 10¹⁷ cm^− 3. Cathodoluminescence spectroscopy in our P-doped polycrystalline films shows a phosphorus bound exciton (BE^TO_P) peak between 5.142 and 5.181 eV. Cathodoluminescence and Raman-effect spectroscopy confirmed the improvement of the crystalline quality of our films as well as a decrease in the intensity of the internal strain when the grain size was decreased. Cathodoluminescence imaging and SIMS depth profile of phosphorus demonstrated a very good homogeneity of phosphorus incorporation in the films.     

Light penetration depth dependence of photocarrier life time and the Hall effect in phosphorous-doped and boron-doped homoepitaxial CVD diamond films

Photocurrent in phosphorous-doped CVD diamond film of the bandgap of 5.5 eV with the density of 2 × 10¹⁸ cm^− 3 decreases with increasing photon energy in the energy range higher than 5.8 eV at room temperature (RT). The photocarrier life time is 0.3 ms at the excitation energy of 5.8 eV and decreases with increasing excitation energy. These show that the photocarriers, ascertained to be electrons by the Hall effect of the photocurrent, are trapped near the surface. The life time of photo-excited holes in Boron-doped CVD diamond film with the density of 9 × 10¹⁷ cm^− 3 is 35 ms at RT and decreases with decreasing Boron density, which is explained from the relation between the Fermi energy and the density.     

Growth of thick and heavily boron-doped (113)-oriented CVD diamond films

Diamond as a wide band-gap semiconductor exhibits unrivalled figures of merit for power electronics. However this application has been held back by the poor availability of thick large-area electrically-conductive diamond material that is a prerequisite for developing elemental devices. Efforts have been devoted to optimizing CVD growth and doping on conventional (100) and more rarely (111) crystal orientations but (113) has yet almost never been considered. In this work we report the growth of thick CVD diamond films on (113)-oriented substrates with various boron doping levels. We found that high-quality films can be obtained on this orientation with a 5-times improved doping efficiency as compared to (100). A thick freestanding CVD plate with a low resistivity and a doping level of 4 × 10²⁰ cm^− 3 is demonstrated which paves the way to the fabrication of efficient Schottky diodes based on this orientation.     

Effect of total reaction pressure on electrical properties of boron doped homoepitaxial (100) diamond films formed by microwave plasma-assisted chemical vapor deposition using trimethylboron

Boron was doped into diamond films which were synthesized homoepitaxially on polished (100) diamond substrates by means of microwave plasma-assisted chemical vapor deposition (MPCVD) using trimethylboron as the dopant at a constant substrate temperature of 1073 K. The morphologies and electrical properties of the synthesized diamond films were dependent on the total reaction pressure. A maximum Hall mobility, 760 cm² V⁻¹ s⁻¹, was obtained for the film synthesized at 10.7 kPa. The values of Hall mobility were comparable with those obtained for B₂H₆-doped films at corresponding hole concentrations.     

MOCVD doping technology for phosphorus incorporation in diamond: Influence of the growth temperature on the electrical properties

Phosphorus incorporation in diamond can be achieved either by phosphine gas or by gaseous or liquid organic precursors of phosphorus. The main advantage of organic precursors is their lower level of toxicity. In this work, we report on the influence of the growth temperature on the phosphorus incorporation rate, the compensation ratio and the electron mobilities of homoepitaxial phosphorus-doped diamond grown using liquid tertiarybutylphosphine (TBP) as the phosphorus precursor. The incorporation rate of phosphorus is maximum at 890 °C. The highest room temperature electron mobility is 350 cm²/V s for a phosphorus concentration of 6 × 10¹⁷ cm^− 3.     

Properties of boron-doped epitaxial diamond layers grown on (110) oriented single crystal substrates

Boron doped diamond layers have been grown on (110) single crystal diamond substrates with B/C ratios up to 20 ppm in the gas phase. The surface of the diamond layers observed by scanning electron microscopy consists of (100) and (113) micro-facets. Fourier Transform Photocurrent Spectroscopy indicates substitutional boron incorporation. Electrical properties were measured using Hall effect from 150 to 1000 K. Secondary ion mass spectrometry analyses are consistent with the high incorporation of boron determined by electrical measurements. A maximum mobility of 528 cm² V^− 1 s^− 1 was measured at room temperature for a charge carrier concentration of 1.1 10¹³ cm^− 3. Finally, properties of boron doped (110) diamond layers are compared with layers on (100) and (111) orientated substrates.     

Mechanistic study of ion-induced diamond nucleation

The effect of low-energy ion bombardment of silicon on diamond nucleation was investigated. By bombarding 100 eV ions of methane and hydrogen on a silicon substrate prior to diamond growth by chemical vapor deposition, diamond nucleation can be immensely enhanced. The ion beam treatment deposited a layer of nano-crystalline graphitic carbon embedded with amorphous SiC. Diamond then nucleated on the graphite overlayer; the nucleation density increased with increasing ion dose. At 1×10¹⁹ ions cm⁻², a nuclei density of 4×10⁸ cm⁻² was obtained. These results show that ion bombardment of the substrate enhances diamond nucleation.     

A cathodoluminescence study of boron doped {111}-homoepitaxial diamond films

In this work we use cathodoluminescence (CL) at liquid helium temperature to investigate the boron incorporation in {111}-homoepitaxial diamond films, grown outside the visible plasma ball by the Microwave plasma-assisted chemical vapor deposition (MPCVD) technique. The boron concentration of this set of films covers the whole possible doping range divided into four parts: Low doping (5 × 10¹⁶ < [B] < 1.5 × 10¹⁹ cm^? 3), high doping (1.5 × 10¹⁹ < [B] < 3 × 10²⁰ cm^? 3), heavy doping (3 × 10²⁰ < [B] < 2 × 10²¹ cm^? 3), and phase separation range ([B] > 2 × 10²¹ cm^? 3). The phase separation occurs for very high boron concentrations, between the diamond phase (sp³ carbon) and the other components of the layer, namely sp² carbon and boron. A part of them is accumulated outside the diamond lattice.This detailed cathodoluminescence investigation of {111}-homoepitaxial diamond films has led to determining the doping range of the films and following the evolution of their crystalline quality when the boron concentration increases. In addition, a comparison between {111} and {100} films in the same doping ranges has been undertaken.     

Photoelectron emission from heavily B-doped homoepitaxial diamond films

We discuss the energy band structure near the valence band maximum based on photoemission yield spectroscopy experiments using a hydrogen-terminated heavily boron-doped homoepitaxial diamond film with concentration of 3 × 10²⁰ cm^− 3. The experimental results showed a metallic photoemission behavior with a negative electron affinity surface. Based on the fitting as metallic photoemission behavior with a Fowler plot, the Fermi level should be at 5.35 eV below the conduction band minimum, which means that the Fermi level lies at 0.12 eV (5.47–5.35 eV) above the valence band maximum. Thus the film shows metallic conduction by the Mott transition, but not as degenerate semiconductor.     

The role of nitrogen in the deposition of polycrystalline diamond films

The role of nitrogen in the formation of polycrystalline diamond films prepared using a microwave plasma CVD system has been studied using micro-Raman spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy (XPS). Although the nitrogen concentration in the films was too low to be detected by XPS, the Raman spectrum was found to be significantly affected by the nitrogen flow ratio. The intensity of the Raman peak at 1480 cm⁻¹ significantly decreases, whereas that of 1190 cm⁻¹ peak remains almost unchanged in comparison with the 1350 and 1550 cm⁻¹ peaks with increasing nitrogen flow ratio. In contrast, the preferentially (111)-orientated growth and the growth rate were little influenced by the nitrogen flow ratio. These results indicate that nitrogen plays a special role in the formation and structure of the polycrystalline diamond films studied in this report.     

Characterization of specific contact resistance on heavily phosphorus-doped diamond films

Specific contact resistance of Ti contact on phosphorus-doped diamond film has been characterized by means of circular type transfer length method. The resistance was significantly reduced down to ～ 10^? 3 Ω cm² orders using heavily phosphorus-doped diamond film (n⁺) with phosphorus concentration over ～ 10²⁰ cm^? 3, although an ideal ohmic property was not obtained. The results are explained by a narrowing of the Schottky barrier width of Ti/n⁺ interface for tunneling through the barrier to take place, indicating that the heavily doping is promising method for reducing the contact resistance for n-type diamond.     

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.     

Cathodoluminescence of boron-doped heteroepitaxial diamond films on platinum

Cathodoluminescence (CL) spectra of diamond films epitaxially grown on single crystal platinum (111) have been investigated at room temperature and 89 K. It was found that the CL spectra of the heavily boron-doped (>3×10²⁰ cm⁻³) diamond films of more than 16 μm thickness consist only of a near-edge emission at 248±1 nm (5.00±0.02 eV), while any other emissions are absent. It was also found that the temperature dependence of the 248 nm band is very unusual, since its intensity increases as temperature increases. This result is in strong contrast to CL intensities of both the free exciton and the bound exciton, which decrease significantly with temperature. It is concluded that a new electronic band due to heavily-doped boron is the origin of the 248 nm emission.     

Incorporation of lithium and nitrogen into CVD diamond thin films

High concentrations of lithium (~ 5 × 10¹⁹ cm^− 3) and nitrogen (~ 3 × 10²⁰ cm^− 3) have been simultaneously incorporated into single-crystal and microcrystalline diamond films using Li₃N and gaseous ammonia as the sources of Li and N, respectively. Using sequential deposition methods, well-defined localised layers of Li:N-doped diamond with a depth spread of less than ± 200 nm have been created within the diamond. The variation in Li:N content and amount of diffusion within the various types of diamond suggests a model whereby these atoms can migrate readily through the grain-boundary network, but do not migrate much within the grains themselves where the diffusion rate is much slower. However, the high electrical resistivity of the doped films, despite the high Li and N concentrations, suggests that much of the Li and N are trapped as electrically inactive species.     

The CH stretching features on diamonds of different origins

Surface CH stretching features on diamonds from various sources have been explored using Fourier transform infrared spectroscopy and Raman spectroscopy. The exploration encompasses the samples of natural, meteoritic, and synthetic diamond crystallites produced by high-pressure/high temperature, and detonation methods. To obtain the infrared spectra, the diamond samples are first surface-cleaned by oxidation and then hydrogenated using atomic hydrogen created by hot tungsten filaments under vacuum. Sharp and distinct features, corresponding to the CH stretch of tertiary C on C(111)-1 × 1, are observed at 2835 cm^− 1 for samples of different origins, but the peak shape depends on the surface morphology. For meteoritic and detonation-synthesized diamonds, however, the 2835 cm^− 1 peak is completely missing. We attribute this observation to a domain size effect, where the sizes of the C(111)-1 × 1 facets created on these two diamond samples (3 and 5 nm in diameter, respectively) by H-etching are too small to yield the characteristic CH stretching feature. This study gives a detail analysis on the IR spectra of the CH stretching feature on various diamond and diamond films.     

Nano- and micro-crystalline diamond growth by MPCVD in extremely poor hydrogen uniform plasmas

It is well established that argon rich plasmas (> 90% Ar) in Ar/CH₄/H₂ gas mixtures lead to (ultra)nanodiamond nucleation and growth by microwave plasma chemical vapour deposition (MPCVD). Nonetheless, in the present work, both microcrystalline and nanocrystalline diamond deposits developed under typical conditions for ultrananocrystalline (UNCD) growth by MPCVD. Silicon substrates were pretreated by abrasion using two different diamond powder types, one micrometric (< 0.5 μm) and the other nanometric (∼ 4 nm), the latter obtained by detonation methods. Samples characterization was performed by SEM (morphology), AFM (roughness and morphology) and micro-Raman (structure).For all samples, Raman analysis revealed good crystalline diamond quality with an evident ∼ 1332 cm^− 1 peak. The Raman feature observed at ∼ 1210 cm^− 1 is reported to correlate with two other common bands at ∼ 1140 cm^− 1 and ∼ 1490 cm^− 1 characteristic of nano- and ultra-nanocrystalline diamond.A new growth process is proposed to explain the observed morphology evolution from nano- to microcrystalline diamond. Based on this, the microcrystalline morphology is in fact a crystallographically aligned construction of nanoparticles.     

Maximum hole concentration for Hydrogen-terminated diamond surfaces with various surface orientations obtained by exposure to highly concentrated NO2

NO₂ exposure drastically increases the hole concentration on the surface of hydrogen (H)-terminated diamond. When the NO₂ gas concentration is higher than 300 ppm, the saturated hole sheet concentration p_s stays the same. Therefore, the p_s value is regarded as the high limit of the concentration of holes on H-terminated diamond surface, p_s,max. In this work, we compared p_s,max, mobility μ, and sheet resistance R_s for (100), (110), and (111) H-terminated surfaces of chemical-vapor-deposited single-crystal diamond. On (110), (111), (100) surfaces, the p_s,max values are 1.717 × 10¹⁴ and 1.512 × 10¹⁴ cm^− 2, and 0.981 × 10¹⁴, respectively. This result supports the first-principle calculations: the hole concentration depends on the energy difference between the valence band maximum and the unoccupied orbitals of adsorbent NO₂ molecules. We have achieved R_s of 719.3 Ω/sq (p_s = 1.456 × 10¹⁴ cm^− 2 and μ = 59.6 cm² V^− 1 s^− 1), the lowest reported so far, on (111) surfaces under 20,000-ppm NO₂ atmosphere.     

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).     

Characteristics of boron δ-doped diamond for electronic applications

Boron delta-doped profiles with peak concentrations above the full activation limit have been grown on (100)-oriented single crystal diamond substrates by microwave assisted CVD using a solid doping source technique. The growth process was optimized targeting electronic device applications. Up to now these profiles could only be analyzed by chemical/physical profiling and it had been difficult to relate these profiles to the electrical characteristics. For the first time, ERD (Electron Recoil Detection) profiles could be correlated with free carrier profiles extracted by electrochemical profiling based on electrochemical impedance analysis. The comparison shows, that it is possible to incorporate boron on acceptor site with high efficiency even for concentrations in the order of 10²¹ cm^− 3 by the doping technique developed.     

Structural and optical characterization of Zn0.95−xMg0.05AlxO nanoparticles

The structural and optical properties of ZnO nanoparticles doped simultaneously with Mg and Al were investigated. XRD results revealed the hexagonal wurtzite crystalline structure of ZnO. The FE-SEM study confirmed the formation of nano-sized homogeneous grains whose sizes decreased monotonously with increasing doping concentrations of Mg and Al. The absorption spectra showed that band gap increased from 3.20 to 3.31 eV with Mg doping. As the Al concentration changed from x=0.01 to x=0.06 mol% at constant Mg concentration the band gap observed to be decreased. Particle sizes estimated from effective mass approximation using absorption data and these values are in good agreement with the crystallite sizes calculated from XRD data. Raman spectra of ZnO showed a characteristic peak at 436 cm⁻¹ correspond to a non-polar optical phonon E₂ (high). With increase of the Al doping concentrations, E₂ (high) phonon frequency shifted to 439 cm⁻¹ from to 436 cm⁻¹. The origin of E₂ (high) peak shift in ZnO nanoparticles is attributed to optical phonon confinement effects or the presence of intrinsic defects on the nanoparticles. PL spectra indicated that with increase of Al co-doping along with Mg into ZnO, intensity of the peak positioned at 395 nm was initially increased at x=0 and then decreased with increase of the Al concentrations from x=0.01 to x=0.06 mol%.