Hydrogen incorporation,bonding and stability in nanocrystalline diamond films

The hydrogen concentration in hot filament and microwave plasma CVD nanocrystalline diamond films is analysed by secondary ion mass spectrometry and compared to the film grain size. The surface and bulk film carbon bonds are analysed respectively by X-ray photoelectron spectroscopy (XPS) and ultra-violet Raman spectroscopy. XPS results show the presence of the hydrogenated p-type surface conductive layer. The respective intensities of the 1332 cm^− 1 diamond peak, of the G and D bands related to sp² phases, and of the 3000 cm^− 1 CH_x stretching mode band, are compared on Raman spectra. The samples are submitted to thermal annealing under ultra-high vacuum in order to get hydrogen out-diffusion. XPS analysis shows the surface desorption of hydrogen. Thermal annealing modifies the sp² phase structure as hydrogen out diffuses.     

Electrical properties of thick boron and nitrogen contained CVD diamond films

The acceptor and donor defects of thick (approx. 0.4 mm) free-standing boron and nitrogen containing microwave plasma CVD polycrystalline diamond films were investigated. Charge-based deep level transient spectroscopy (Q-DLTS) was applied to study impurity-induced defects, their density and energy distribution in the energy range of 0.01 eV≤E−E_v≤1.1 eV above the valence band. It was shown, that differential capacitance–voltage, and Hall effect measurements combined with DLTS data can be used to determine the degree of compensation, and the concentration of compensating donors (mostly the positively charged single-substitutional nitrogen (N⁺)) in p-type CVD polycrystalline diamond films. It was found, that incorporated boron atoms induce three levels of electrically active defects. Two of them with concentration (2–3)×10¹⁶ cm⁻³ each have activation energies of 0.36 and 0.25 eV with capture cross-sections of 1.3×10⁻¹³ and 4.5×10⁻¹⁹ cm², respectively. The third type of defect has an activation energy of 0.02 eV, capture cross-section 3×10⁻²⁰ cm² and concentration 10¹⁵ cm⁻³, this shallow trap being a probable general caterer of holes in low-doped films. The total concentration of electrically active uncompensated acceptors in all p-type diamond samples was approximately 2×10¹⁷ cm⁻³ with hole concentration of approximately 1.5×10¹⁴ cm⁻³ and hole mobility in the range of 30–40 cm² V⁻¹ s⁻¹ at room temperature. If assumed that compensating donors are mostly nitrogen, the films contained no less than 3×10¹⁶ cm⁻³ of N⁺.     

High-current electron emission characteristics of cathodes based on diamond films

Using different gas source, four types of diamond thin films were prepared on silicon substrate by microwave plasma chemical vapor deposition (MPCVD) technology, and characterized in detail through scanning electron microscopy (SEM), Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy. High-current pulsed emission characteristics, tested with a 2 MeV line-inducing injector, showed that all of CVD diamond films had high emission current density (> 70 A/cm²) and [100] textured B-doped microcrystalline diamond film possessed the largest emission current density of 115.1 A/cm². No obvious bright light and luminescent zones from side view CCD images indicated a possible pure field-emission mechanism of these diamond cathodes. Simultaneously, large decrease in the electron emission capability, above 15%, could be observed after several pulsed measurements, but this decrease could be completely recovered through the treatment of surface re-hydrogenation for emitted diamond cathodes, suggesting that emission performance of CVD diamond cathodes was closely relevant to hydrogen coverage ratio. The present data indicated that as-deposited CVD diamond films could be a potential candidate as cold cathode for the application in high-current electron emission field.     

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.     

Effect of titanium metal in the prenucleation of ultrananocrystalline diamond film growth at low substrate temperature

Ultrananocrystalline diamond (UNCD) film is usually grown in methane–argon plasma unlike methane–hydrogen plasma conventionally used to deposit microcrystalline diamond film. The prenucleation and growth mechanism of these two types of diamond films are different as well. The present study introduces titanium metal powder during ultrasonication of silicon substrate to enhance the nucleation density of UNCD. A titanium thin film was also used at the interface to find the effect of metal on the growth of diamond film. The nucleation density of as-grown film was estimated from the FE-SEM images. After 20 min of growth, nucleation density reaches to 10¹¹/cm² on a surface pretreated by titanium mixed nanodiamond powder. Raman study was carried out for qualitative analysis of different carbon phase present in the UNCD films. X-ray photoelectron spectroscopy (XPS) was used to understand the growth mechanism by detecting the formation of carbon phase and metal carbide formation at the surface after stopping the growth at different time intervals.     

Surface morphology and electrical properties of boron-doped diamond films synthesized by microwave-assisted chemical vapor deposition using trimethylboron on diamond (100) substrate

Prime novelty: The smoothness of the synthesized boron-doped diamond was improved by the pre-treatment of a hydrogen plasma. Moreover, the Hall mobility also increased with this pre-treatment.Surface morphology and electrical properties, such as electrical conductivity, hole concentration and Hall mobility, were investigated for boron-doped diamond films, which were synthesized by microwave-assisted chemical vapor deposition (MPCVD) on a (100) diamond substrate. Trimethylboron (TMB) was used as a dopant source and methane (CH₄) was used as a carbon source. The morphology of the synthesized diamond surface depended on the MPCVD conditions such as TMB and CH₄ concentrations in the gas phase, and lower concentrations of TMB and CH₄ lead to a smoother surface. When the substrate was treated in a hydrogen plasma, the electrical properties of the boron-doped diamond films, as well as the smoothness of the surface, were improved. After optimizing the synthesis conditions, Hall mobility reached to 2020 cm² V⁻¹ s⁻¹ at 243 K for a diamond film with a hole concentration of 5×10¹² cm⁻³.     

Nucleation and growth of diamond films on aluminum nitride by hot filament chemical vapor deposition

Nucleation and growth of diamond films on aluminum nitride (ALN) coatings were investigated by scanning electron microscopy, Raman spectroscopy and scratch test. ALN films were grown in a magnetron sputtering deposition. The substrates were Si(111) and tungsten carbide (WC). Chemical vapor deposition (CVD) diamond films were deposited on ALN films by hot filament CVD. The nucleation density of diamond on ALN films was found to be approximately 10⁵ cm⁻², whereas over 10¹⁰ cm⁻² after negative bias pre-treatment for 35 min was −320 V, and 250 mA. The experimental studies have shown that the stresses were greatly minimized between diamond overlay and ALN films as compared with WC substrate. The results obtained have also confirmed that the ALN, as buffer layers, can notably enhance the adhesion force of diamond films on the WC.     

Study the effect of O2 addition on hydrogen incorporation in CVD diamond

The effect of a small amount of O₂ addition on film quality and hydrogen incorporation in chemical vapour deposition (CVD) diamond films was investigated and the films were grown using a 5-kW microwave plasma CVD reactor. Film quality and bonded hydrogen were characterized using micro-Raman and Fourier transform infrared (FTIR) spectroscopy, respectively. It was found that in general for films grown using CH₄/H₂ plasma both without and with O₂ addition, the hydrogen incorporation increases with increasing substrate temperature, while a small amount of O₂ addition (O₂/CH₄=0.1) into CH₄/H₂ (4%) plasma strongly suppresses the incorporation of hydrogen into the film. Raman spectra show that the added oxygen improved film quality by etching and suppressing the amorphous carbon component formed in the film. The above effect of oxygen addition on hydrogen incorporation and film quality is discussed according to the growth mechanism of CVD diamond. The CVD diamond specific hydrogen related IR vibration at 2828 cm⁻¹ appears as a sharp and strong peak only in the FTIR spectra of poor quality films grown at high temperature both without and with O₂ addition, but it appears much stronger in the film grown without O₂ addition. This result experimentally excludes the assignment of the 2828 cm⁻¹ peak arises from hydrogen bonded to oxygen related defect in the literature.     

Influence of nucleation density on film quality,growth rate and morphology of thick CVD diamond films

The optimum growth parameters of our 5 kW microwave plasma CVD reactor were obtained using CH₄/H₂/O₂ plasma and high quality transparent films can be produced reproducibly. Among the films prepared in this system, the film of best quality has very smooth crystalline facets free of second nucleation and the full width at half maximum (FWHM) of the diamond Raman peak is 2.2 cm⁻¹, as narrow as that of IIa natural diamond. For this study, diamond films were grown on silicon substrates with low (10⁴–10⁵ cm⁻²) and high nucleation densities (>10¹⁰ cm⁻²), respectively. From the same growth run, a highly 〈110〉 textured 300 μm thick white diamond film with a growth rate of 2.4 μm/h was obtained from high nucleation densities (>10¹⁰ cm⁻²), and a white diamond film of 370 μm in thickness with a higher growth rate of 3 μm/h was obtained from low nucleation densities (5×10⁴–10⁵ cm⁻²) too. The effect of nucleation density on film quality, growth rate, texture and morphology was studied and the mechanism was discussed. Our results suggest that under suitable growth conditions, nucleation density has little effect on film quality and low nucleation density results in higher growth rate than high nucleation density due to less intense grain growth competition.     

Evolution and properties of adherent diamond films with ultra high nucleation density deposited onto alumina

In this work, we report on adherent diamond films with thickness of up to 4.5 μm grown on polycrystalline alumina substrates. Prior to deposition, alumina substrates were ultrasonically abraded with mixed poly-disperse slurry that allows high nucleation density of values up to ∼5×10¹⁰ particles/cm². It was estimated that the minimal film thickness achieved for continuous films was ∼320 nm, obtained after a deposition time of 15 min with diamond particles density (DPD) of ∼4×10⁹ particles/cm². Continuous adherent diamond films with high DPD (∼10⁹ particles/cm²) were obtained also on sapphire surface after abrasion with mixed slurry and 15 min of deposition. However, after longer deposition time, diamond films peeled off from the substrates during cooling.The poor adhesion between the diamond and sapphire is attributed to the weak interface interaction between the film and the substrate and to difference in coefficient of thermal expansion. On the other hand, it is suggested that the reason for good adhesion between diamond film and alumina substrate is that high carbon diffusivity onto alumina grain boundaries allows strong touch-points at the grooves of alumina grains, and this prevents the delamination of diamond film. This adhesion mechanism, promoted by sub-micron diamond grain-size, is allowed by initial high nucleation density.The surface properties, phase composition and microstructure of the diamond films deposited onto alumina were examined by electron energy loss spectroscopy (EELS), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and high-resolution scanning electron microscopy (HR-SEM). The residual stress in the diamond films was evaluated by diamond Raman peak position and compared to a theoretical model with good agreement. Due to the sub-micron grain-size, the intrinsic tensile stress is high enough to partially compensate the thermal compressive stress, especially in diamond films with thickness lower than 1 μm.     

Investigation of specific contact resistance of ohmic contacts to B-doped homoepitaxial diamond using transmission line model

In this study, metal (Ti/Pt/Au) contacts to mesa of boron-doped (boron concentration: 10¹⁸ cm⁻³) homoepitaxial diamond were fabricated by metal deposition followed by thermal annealing at 450 °C. Specific contact resistance was determined by characterizing the current–voltage (I–V) relations from transmission line model (TLM) measurement. The specific contact resistances determined from linear TLM corresponding to different lengths of rectangular contacts were in the order of 10⁻⁴ Ω cm². The results suggest that it is possible to reduce the specific contact resistance to 10⁻⁵–10⁻⁶ Ω cm², which would satisfy the operational requirements of diamond electronic devices, provided the dopant concentration in diamond can be increased to 10¹⁹–10²⁰ cm⁻³.     

Nucleation and growth of diamond films on single crystal and polycrystalline tungsten substrates

Silicon has been the most widely studied substrate for the nucleation and growth of CVD diamond films. However, other substrates are of interest, and in this paper, we present the results of a study of the biased nucleation and growth of diamond films on bulk single and polycrystalline tungsten. Diamond films were nucleated and grown, using a range of bias and reactor conditions, and characterized by Raman spectroscopy and scanning electron microscopy (SEM). High-quality (100) textured films (Raman FWHM<4 cm⁻¹) could be grown on both single and polycrystalline forms of the tungsten substrate. On carefully prepared substrates, by varying the bias treatment, it was possible to determine the nucleation density over a 4–5 order range, up to ∼10⁹ cm⁻². Raman measurements indicated that the diamond films grown on bulk tungsten exhibited considerable thermal stress (∼1.1 GPa), which, together with a thin carbide layer, resulted in film delamination on cooling. The results of the study show that nucleation and growth conditions can be used to control the grain size, nucleation density, morphology and quality of CVD diamond films grown on tungsten.     

A study of the crystalline growth of highly boron-doped CVD diamond: preparation of graded-morphology diamond thin films

An investigation was made of graded-morphology diamond thin films deposited on Si substrates by use of the microwave plasma chemical vapor deposition (CVD) technique. The preparation of graded diamond thin films not only offers new perspectives into functional materials, but it also gives clues to the growth mechanism of CVD diamond. Although it is clear that the substrate temperature and the deposition time affect the grain size in particular, the difference depending on the boron concentration in the growing process was studied in the present work. As a result, in highly boron-doped (10⁴ ppm) diamond films, the Raman peak which was ascribed to the boron-doping was not observed at the very initial growth stage. However, the crystal growth process was almost irrelevant for the boron-doping quantity. Furthermore, we showed the morphology dependence of electrochemical properties as one example of the excellent functions of the graded-morphology highly boron-doped diamond film.     

Deposition of diamond films on sapphire: studies of interfacial properties and patterning techniques

Polycrystalline diamond films were grown on single crystal sapphire substrates using hot filament chemical vapour deposition (CVD). Problems with poor adhesion, stress and film cracking became severe for deposited areas greater than about (100 μm)². Scanning electron microscopy analysis showed the films to be failing both at the interface and in the diamond layer itself. Transmission electron microscopy cross-sections of the interface showed that the interface was clean and free from non-diamond carbon impurities. Spallation problems in the diamond film could be reduced by introducing a barrier layer of epitaxial silicon grown on the sapphire prior to the diamond CVD step. Patterned silicon-on-sapphire wafers were then used as substrates for CVD of diamond in order to define features of linewidth more than 10 μm in the diamond films. Two methods were used: selective nucleation and lift off.     

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 pressure on thin amorphous carbon films deposited using microwave surface wave plasma CVD

We report the effects of gas composition pressure (GCP) on the optical, structural and electrical properties of thin amorphous carbon (a-C) films grown on p-type silicon and quartz substrates by microwave surface wave plasma chemical vapor deposition (MW SWP CVD). The films, deposited at various GCPs ranging from 50 to 110 Pa, were studied by UV/VIS/NIR spectroscopy, atomic force microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and current–voltage characteristics. The optical band gap of the a-C film was tailored to a relatively high range, 2.3–2.6 eV by manipulating GCPs from 50 to 110 Pa. Also, spin density strongly depended on the band gap of the a-C films. Raman spectra showed qualitative structured changes due to sp³/sp² carbon bonding network. The surfaces of the films are found to be very smooth and uniform (RMS roughness < 0.5 nm). The photovoltaic measurements under light illumination (AM 1.5, 100 mW/cm²) show that short-circuit current density, open-circuit voltage, fill factor and photo-conversion efficiency of the film deposited at 50 Pa were 6.4 μA/cm², 126 mV, 0.164 and 1.4 × 10^− 4% respectively.     

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.     

Effect of gas composition on the growth and electrical properties of boron-doped diamond films

Boron-doped diamond films are synthesized by the hot-filament chemical vapor deposition (HFCVD) method via introduction of the gas mixtures of methane and hydrogen, as well as the boron precursor carried by H₂ through a B(OCH₃)₃ liquid, into the chamber. Boron-doping level in as-grown diamond films can be well controlled in the range from 10¹⁹ to 10²¹ cm^? 3 by adjusting the B/C ratios of gas mixtures. The morphology, structure and resistivity of as-grown diamond films are investigated with scanning electron microscopy (SEM), X-ray diffraction (XRD) and Hall measurement system. The results show that the crystal quality and carrier concentration and resistivity of the as-grown films are obviously dependent on the B/C ratio of the gas mixtures during the deposition process. A critical B/C ratio of 3:4 is found to correspond to the highest crystal quality, highest carrier concentration and smallest film resistivity of as-grown boron-doped diamond films, which should be mainly related with the effective doping ability. In addition, based on the growth kinetics of the diamond films, the effect of the boron-doping on the growth process is discussed in detail.     

The influences of oxygen ion implantation on the structural and electrical properties of B-doped diamond films

The oxygen ion with a dose of 10¹⁴ (called CVDBO14) and 10¹⁵ cm^− 2 (called CVDBO15) was implanted into boron doped diamond films synthesized in chemical vapor deposition. The structural and electrical properties of different samples were characterized by XPS, Raman spectroscopy and 4-probe resistivity measurements. The results show that oxygen ion exists both in the diamond surface and the subsurface of the films. The FWHM values of CVDBO15 samples are higher than those of CVDBO14 samples, indicating that more damages existed in CVDBO15 samples. The resistivity of CVDBO15 sample series is smaller than those of CVDBO14 sample series, and the film with a larger FWHM value exhibits low resistivity. In the 1150 °C annealed sample, the activation energy decreases from 0.50 eV to 0.39 eV with the oxygen ion dose increasing from 10¹⁴ to 10¹⁵ cm^− 2. It is indicated that oxygen ion and the defects produced by ion implantation give contributions to the conductivity in diamond films. Some surface hydrogen is removed and pi-bonded carbon as well as C-H vibration is formed after annealing, which is also relative to the lower resistivity in the samples.     

Transmission electron microscopy study of diamond nucleation and growth on smooth silicon surfaces coated with a thin amorphous carbon film

Amorphous carbon (a-C) films with high contents of tetrahedral carbon bonding (sp³) were synthesized on smooth Si(100) surfaces by cathodic arc deposition. Before diamond growth, the a-C films were pretreated with a low-temperature methane-rich hydrogen plasma in a microwave plasma-enhanced chemical vapor deposition system. The evolution of the morphology and microstructure of the a-C films during the pretreatment and subsequent diamond nucleation and initial growth stages was investigated by high-resolution transmission electron microscopy (TEM). Carbon-rich clusters with a density of ∼10¹⁰ cm⁻² were found on pretreated a-C film surfaces. The clusters comprised an a-C phase rich in sp³ carbon bonds with a high density of randomly oriented nanocrystallites and exhibited a high etching resistance to hydrogen plasma. Selected area diffraction patterns and associated dark-field TEM images of the residual clusters revealed diamond fingerprints in the nanocrystallites, which played the role of diamond nucleation sites. The presence of non-diamond fingerprints indicated the formation of Si–C-rich species at C/Si interfaces. The predominantly spherulitic growth of the clusters without apparent changes in density yielded numerous high surface free energy diamond nucleation sites. The rapid evolution of crystallographic facets in the clusters observed under diamond growth conditions suggested that the enhancement of diamond nucleation and growth resulted from the existing nanocrystallites and the crystallization of the a-C phase caused by the stabilization of sp³ carbon bonds by atomic hydrogen. The significant increase of the diamond nucleation density and growth is interpreted in terms of a simple three-step process which is in accord with the experimental observations.