Sulfur doped nanocrystalline diamond films as field enhancement based thermionic emitters and their role in energy conversion

Sulfur doped nanocrystalline diamond films, like other nanostructured carbon films, exhibit electron emission characterized by a spatial non-uniformity of the field enhancement factor. While field emission effects are observed at room temperature, an increase in emitter temperature is accompanied by an amplified emission current with a simultaneous drop in the threshold field. At low extraction fields a fit of the emission current to the Richardson equation indicates a material work function of 2.5 eV. The Schottky formula describes thermionic emission at a moderate field and is utilized to determine the work function at an electric field of 0.8 V/μm with a value of 1.7 eV and a concurrently reduced Richardson constant. This significant difference in the work function of 2.5 and 1.7 eV for 0.5 and 0.8V/μm, respectively can be attributed to field enhancement effects.     

Sulphur doped DLC films deposited by DC magnetron sputtering

Diamond‐like carbon (DLC) and sulphur doped diamond‐like carbon (S‐DLC) films were synthesised at different sulphur molar percentage of 0%, 2%, 5%, 8% and 10% by direct current (DC) magnetron sputtering process using novel compressed sulphur‐graphite targets at relatively low power density. Films were characterised for their morphologies, structural, electrical and optical properties. Scanning electron microscope images reveal changes in the quality of the obtained films shown by the denser packing of DLC grains at different sulphur percentage. The conductivities of S‐DLC films were found to be in the range of 6.0 × 10^?3–0.6/Ω cm. The optical band gap energies were found to be in the range of ～1.4–2.0 eV. Both electrical and optical measurements exhibit nonlinear responses with optimum at around 5% sulphur molar percentage (minimum for conductivity and maximum for optical band gap energy). These trends of change in both conductivity and optical band gap energy are consistent with the variation in bond characters of the films indicated by Raman spectroscopy. © 2011 Canadian Society for Chemical Engineering     

Boron-doped hydrogenated amorphous carbon films grown by surface-wave mode microwave plasma chemical vapor deposition

We report the effects of boron (B) doping on optical and structural properties of the hydrogenated amorphous carbon thin films grown by surface-wave mode microwave plasma (SW-MWP) chemical vapor deposition (CVD) on n-type silicon and quartz substrates at room temperature. Argon and acetylene were used as a carrier and carbon source gases respectively. Analytical methods such as X-ray photoelectron spectroscopy (XPS), Nanopics 2100/NPX200 surface profiler, JASCO V-570 UV/VIS/NIR spectroscopy, Fourier transform infrared spectroscopy (FT-IR) and Raman spectroscopy were employed to investigate the properties of the films. Low atomic concentration of B (0.08 at.%) was found in the doped film. The optical band gap of the undoped film was 2.6 eV and it decreased to 1.9 eV for the B-doped film. Structural property shows the crystalline structure of the film and it has changed after incorporating B as a dopant. The structural modifications of the films leading to being more graphite in nature were confirmed by the Raman and FT-IR characterization.     

Structural features of diamond layers photo-emitting at sub-band gap energies

The photoemission behaviour of a series of diamond-based polycrystalline films irradiated by the second (2.3 eV), third (3.5 eV) and fourth (4.7 eV) harmonics produced by a Q-switched-mode-locked Nd: Yag laser has been investigated and related to the structural and compositional characteristics of the layers. The materials were polycrystalline undoped diamond films as well as Nd- and N-containing diamond films grown by CVD techniques, diamond-like and amorphous carbon layers. The morphological and structural characteristics of the films were investigated by electron microscopy, Raman spectroscopy and electron diffraction. The analysis of the photoemission curves does not evidence any improvement of the emission efficiency in the case of Nd-containing films nor for the diamond films grown in the presence of N_2. The results evidence conversely a strong correlation between the characteristics of the photoemission process at sub-band gap energies and the presence of amorphous sp²-C patches located at the diamond film surfaces. The photoemitting properties of our samples are discussed and rationalized by considering charge emission occurring at the sp²-diamond-vacuum border and the emission process governed by the ratio of amorphous sp²-C to crystalline sp³-C. The rather high values of quantum efficiency measured in the course of the present research at 3.5 and 4.7 eV suggest that a proper distribution of amorphous carbon onto a good quality diamond surface is the key factor for the preparation of efficient and stable photocathode materials.     

Deposition of carbon nitride films by filtered cathodic vacuum arc combined with radio frequency ion beam source

Atomically smooth carbon nitride films were deposited by an off-plane double bend filtered cathodic vacuum arc (FCVA) technique. A radio frequency nitrogen ion source was used to supply active nitrogen species during the deposition of carbon nitride films. The films were characterized by atomic force microscopy (AFM), XPS and Raman spectroscopy. The internal stress was measured by the substrate bending method. The influence of nitrogen ion energy (0–1000 eV) on the composition, structure and properties of the carbon nitride films was studied. The nitrogen ion source greatly improves the incorporation of nitrogen in the films. The ratio of N/C atoms in the films increases to 0.40 with an increase in the ion beam energy to 100 eV. Further increase in the ion beam energy leads to a slight decrease in the N/C ratio. XPS results show that nitrogen atoms in the films are chemically bonded to carbon atoms as C---N, C=N, and CN bonds, but most of nitrogen atoms are bonded to sp² carbon. The increase in nitrogen ion energy leads to a decrease in the content of nitrogen atoms bonded to sp² carbon, and an increase in the content of nitrogen atoms bonded to sp³ and sp¹ carbon. Raman spectra indicate an increase in the sp² carbon phase in carbon nitride films with an increase in nitrogen ion energy. The increase in sp² carbon fraction is attributed to the decrease in internal stress with increasing nitrogen ion energy.     

Effect of ion bombardment and hydrogen pressure during deposition on the optical properties of hydrogenated amorphous carbon thin films

Carbon-based thin films are ideal materials for several state-of-the-art applications, such as protective materials and as active films for organic electronics, medical, optoelectronic devices. In this work, we study in detail the effect of the ion-bombardment and the hydrogen partial pressure during deposition on the optical properties of hydrogenated amorphous carbon (a-C:H) thin films grown onto c-Si substrates by rf magnetron sputtering. The optical properties of the a-C:H films were investigated by phase modulated Spectroscopic Ellipsometry in a wide spectral region from the NIR to the Vis-far UV (0.7-6.5 eV). A dispersion model based on two Tauc-Lorentz oscillators, has been applied for the analysis of the measured < ε(ω)> of the a-C:H films to describe the π-π* and σ-σ* interband electronic transitions, that can describe accurately the optical properties of all amorphous carbons. The applied V_b influences the bombardment of the growing thin films with Ar ions affecting the content of sp² and sp³ hybridized carbon bonds in the films. As it was found, the increase of the applied negative voltage reduces the optical transparency of the a-C:H films. Also, the H incorporation has been found to change only the energy position of the σ-σ* transitions. Finally, from the study of the refractive index n(ω = 0 eV) it has been found that the increase of the ion bombardment during the films deposition is correlated to an increase in the films density.     

Aging of fluorocarbon thin films deposited on polystyrene from hyperthermal C3F+5 and CF+3 ion beams

Fluorocarbon films grown on polystyrene (PS) in vacuum from 25-100 eV CF⁺ ₃ and C₃F⁺ ₅ ions are aged by exposure to atmosphere for 4 and 8 weeks, then analyzed by X-ray photoelectron spectroscopy, atomic force microscopy, and water contact angle measurements. These fluorocarbon films oxidize with time, showing an increase in their oxygen/ carbon ratio and a decrease in their fluorine/carbon ratio. The decrease in fluorine/carbon ratio with aging is due not only to increased oxygen content, but also to surface restructuring and release of low molecular weight oxidized material from the surface. The higher oxidation and surface restructuring observed upon aging for 100 eV C₃F⁺ ₅ and 50 eV CF⁺ ₃ ion-modified PS can be additionally attributed to higher surface bond breakage and active site formation. 100 eV C₃F⁺ ₅ and 50 eV CF⁺ ₃ ion-modified PS surfaces are rougher than the 50 eV C₃F⁺ ₅ ion-modified PS. Overall, the aging process of these ion-deposited films appears similar to that of plasma-deposited films.     

Polymeric semiconducting carbon from fullerene by pulsed laser ablation

The polymeric semiconducting carbon films are grown on silicon and quartz substrates by excimer (XeCl) pulsed laser deposition (PLD) technique using fullerene C₆₀ precursor. The substrate temperature is varied up to 300 °C. The structure and optical properties of the films strongly depend on the substrate temperature. The grain size is increased and uniform polymeric film with improved morphology at higher temperature is observed. The Tauc gap is about 1.35 eV for the film deposited at 100°C and with temperature the gap is decreased upto 1.1 eV for the film deposited at 250 °C and increased to about 1.4 eV for the film deposited at 300 °C. The optical absorption properties are improved with substrate temperature. Raman spectra show the presence of both G peak and D peak and are peaked at about 1590 cm^− 1 and 1360 cm^− 1, respectively for the film deposited at 100 °C. The G peak position remains almost unchanged while D peak has changed only a little with temperature might be due to its better crystalline structure compared to the typical amorphous carbon films and might show interesting in device such as, optoelectronic applications.     

Cathodoluminescence of the a-C:N films deposited by a filtered cathodic arc plasma system

Amorphous carbon nitride (a-C:N) films were successfully synthesized on silicon using a 90°-bend magnetic filtered cathodic arc plasma (FCAP) system. ESCA analysis demonstrated that the N/C ratios reached 1.08. Many investigations on photoluminescence (PL) spectra of diamondlike carbon films have been performed, but cathodoluminescence (CL) spectra have seldom been discussed. This work investigated a-C:N films using the CL spectra at 300 K. This work presents CL spectra of a-C:N films obtained at 1.5–3.5 eV and verifies luminescence from the a-C:N films in the visible region. The most prominent luminescence in the CL spectra from the a-C:N films has two peaks centered ∼2.67 eV (blue light) and ∼1.91 eV (red light), but the a-C film yielded only the band at ∼1.91 eV. These optical emissions are intrinsic and extrinsic to the a-C:N film and are sensitive to the content of nitrogen.     

Molecular dynamics simulations for the growth of diamond-like carbon films from low kinetic energy species

In this study, molecular dynamics simulations using the Brenner potential for hydrocarbons have been used to simulate the formation of diamond-like carbon (DLC) films grown from low-energy hydrocarbon radicals (<2 eV). With these simulations, insight is gained in the processes occurring in this type of deposition. The initial surface is a previously deposited DLC surface; impinging particles include Ar⁺ ions, with an energy of 2 eV, as well as several carbon radicals and molecules, and hydrogen atoms, with an energy of 1 eV. Two different radical flux compositions were examined: in the first condition, only C, C₂, and CH were used as growth species, as well as a large flux of H atoms. In the second condition, the same carbon radicals were considered, as well as the C₂H radical and C₂H₂, C₄H₂, and C₆H₂ molecules, but without the H atom flux. These fluxes are similar to different experimental conditions in an expanding thermal Ar/C₂H₂ plasma (expanding thermal plasma, or ETP), using different influxes of acetylene. Several properties of the resulting films will be presented, focusing mainly on the carbon coordination and the bonding network. The simulations suggest that lowering the acetylene influx results in films having a more extensive bonding network, but with more H incorporated. This leads to more polymeric films having a less diamond-like character, as is expected also from experiments. The aim of this work is twofold. The first objective is to compare the structural composition of the simulated films to the structure of the experimentally deposited films by applying similar conditions. Second, the simulations can give us valuable information about the key mechanisms in the deposition process.     

Cathodoluminescence of fluorine doped amorphous carbon nanoparticles deposited by a filtered cathodic arc plasma system

The fluorine doped amorphous carbon nanoparticles (a-C:F NPs) films with sizes 50-100 nm were deposited on polyethylene terephthalate in an atmosphere of CF₄ by a 90°-bend magnetic filtered cathodic arc plasma system. The surface morphology of a-C:F NPs films was observed by field emission scanning electron microscope and atomic force microscope. The microstructure and chemical bonding nature of the a-C:F NPs films were investigated by Raman, X-ray diffraction and X-ray photoelectron spectroscopy. This work presents cathodoluminescence (CL) spectra of a-C:F NPs films obtained at 1.9-2.4 eV and verifies luminescence from a-C:F NPs films in the visible region. The incorporation of fluorine into the carbon network results in orange emission (∼2.03 eV) due to the transitions between fluorine-related electron levels and σ* states, and the red emission (∼1.97 eV) results from the recombination of carriers in the valence π and conduction π* states. The peak at ∼2.10 eV may result from the defects of the structures in a-C:F NPs films.     

Piezoresistive,optical and electrical properties of diamond like carbon and carbon nitride films

In the present study diamond like carbon (DLC) and carbon nitride (a-CN_x:H) films were deposited by closed drift ion source from the acetylene and nitrogen gas mixture. The piezoresistive, electrical and optical properties of ion beam synthesized DLC films were investigated. Piezoresistive properties of the diamond like carbon and carbon nitride films were evaluated by four point bending test. The piezoresistors were fabricated on crystalline alumina substrates using Al-based interdigitated finger type electrodes. Effects of the nitrogen concentration on the piezoresistive gauge factor were investigated. The dependence of the resistance of the metal/a-CN_x:H/metal structures on temperature has been studied. Current–voltage (I–V) and capacitance–voltage characteristics were measured for a-CN_x:H/Si heterostructures. The main current transport mechanisms were analyzed. Optical parameters of the synthesized films such as optical bandgap and B parameter (slope of the linear part of the Tauc plot) were investigated to study possible correlation with the piezoresistive properties.     

Deep level transient spectroscopy of CVD diamond: the observation of defect states in hydrogenated films

Hydrogenated polycrystalline CVD diamond films support a number of defect states within the range 0.03–1.0 eV, as determined by charge-based deep level transient spectroscopy (Q-DLTS). The observation of a 30-meV state is direct evidence for such a shallow level in this material, and is most likely to be the acceptor state that gives rise to the p-type character of these films. Deeper levels, at 0.11 eV, 0.39 eV, 0.65 eV and 0.70 eV–1.0 eV can also be observed and again appear to be associated with the hydrogenation level within the near surface region of the CVD diamond film. The loss of the 0.11 eV level at temperatures greater than 417 K is most easily explained if adsorbates are being removed from the surface at this temperature.     

Electrochemical characteristics of amophous carbon coated silicon electrodes

The properties of carbon films deposited by the radio frequency plasma sputtering of a fullerene C₆₀ target were investigated to elucidate the dependence on the plasma power. A radio frequency argon plasma power ranging from 50 to 300W at a pressure of 1.3 Pa was applied for sputtering. This corresponds to a self-bias potential on the target ranging from −95 to −250 V and a maximum argon ion energy ranging from 240 to 575 eV. The analysis of the G and D peaks in the Raman spectra shows that the films are similar to tetragonal hydrogenated amorphous carbon annealed at 600–1,000 °C. The electron band structure of the carbon films deposited by the sputtering of C₆₀ depends on the plasma power. The coating effect of these carbon films on the capacity performance of the silicon film electrode of lithium secondary batteries was significant in our experimental range. An electrochemical test revealed that such carbon thin film on the silicon electrode plays an important role in mitigating the capacity fading during the charge and discharge processes. The test revealed that the film formed at a plasma power of 300 W is the most effective.     

Formation of nanodots and nanostripes of carbon nitride on silicon by plasma and thermal treatments

Amorphous carbon nitride (a-CN) films on Si(100) were grown by plasma-enhanced chemical vapor deposition at room temperature, followed by H₂ plasma and thermal annealing treatments, which produced densely and uniformly distributed nanodot- and nanostripe-like structures. The as-grown CN films showed two weak emission peaks at 2.1 and 2.4 eV, but the a-CN nanostructures showed a strong peak at 2.2 eV.     

Surface morphology and evolution of amorphous carbon thin films

The surface morphology of disordered carbon films grown by nanosecond pulsed laser ablation of graphite is reviewed. It is shown that the presence of a background gas can have a profound effect on the plume of material ejected during ablation. At low pressures smooth films are produced but at higher pressures rough films with an evolution from a nodular morphology to a large area cluster-assembled morphology occurs. The surface morphology changes with increasing background pressure as a result of collisions, which reduce the kinetic energy of the ejected material and allow for cluster formation within the plume. It is shown that the energy of some of the carbon ablated species in vacuum can exceed 100 eV. The nature of the species present in the plume is discussed in terms of electron–ion recombination and impact ionisation/excitation. The cluster-assembled films are shown to be useful as a scaffold for supporting metal nanoparticles to produce substrates for surface enhanced Raman spectroscopy.     

On the reaction kinetics of Ni with amorphous carbon

The kinetics of the graphitisation of thin films of amorphous carbon (a-C) by supported Ni particles was investigated by in situ transmission electron microscopy. Ni particles were deposited on a-C films at temperatures from 350 to 500 °C, and reactions with the support were recorded at 600 up to 720 °C. The activity was found to strongly depend on temperature. Reactions generally started with encapsulation of Ni particles with a graphite shell, out of which the metal was eventually expelled and spread on the substrate, which was then graphitised. The propagation speed of the reaction front, and the increase with time of its length and of the graphitised area were measured as function of temperature. Through this, an activation energy of 1.8 ± 0.2 eV was determined; such result is significantly comparable to the theoretical estimate of 1.6 eV, reported by other authors.     

Real-time monitoring,growth kinetics and properties of carbon based materials deposited by sputtering

The nucleation stages of growth of carbon-based materials such as amorphous carbon (a-C) and carbon nitride (a-CN_x) films control the bonding configuration, sp² and sp³ formation, N concentration in a-CN_x films and consequently their final properties. Thus, in order to obtain insights into the deposition mechanisms, the study of growth kinetics by applying real-time monitoring is required. We present here, the development of a-C and a-CN_x thin-films by conventional and unbalanced magnetron sputtering, studied by in situ spectroscopic ellipsometry (SE) and multi-wavelength ellipsometry (MWE) in the energy region 1.5–5.5 eV. SE and MWE were used to monitor the deposition processes and to study the films properties. The MWE provides the ability for simultaneous acquisition of the dielectric function, in 16 different wavelengths distributed in the VIS-UV energy region and to investigate the nucleation and growth stages, the deposition rate and films composition, as well as their optical properties during deposition. The results deduced either by real-time MWE monitoring, or by the analysis of in situ SE and MWE data, for the carbon based materials prepared by the above techniques, were certified by X-ray reflectivity studies and were correlated to various mechanisms taking place during film growth (e.g. diffusion, surface adsorption, chemical reactions, etc.), which were investigated by applying a phenomenological model of growth kinetics.     

The structural phases of non-crystalline carbon prepared by physical vapour deposition

The structure of non-crystalline carbon films produced using physical vapour deposition is studied as a function of ion impact energy and substrate temperature. The average ion energy was varied from 10 eV to 820 eV using magnetron sputtering and cathodic arc deposition systems while the substrate temperature was varied from room temperature to 640 °C. The intrinsic stress, film density and through-film electrical resistance were mapped in the ion energy-temperature plane. These contour plots show the deposition conditions which give rise to stressed tetrahedral amorphous carbon (ta-C), stress relieved ta-C and lower density films with a variety of structural forms. Electron microscopy revealed that the microstructure of the low-density forms ranges from highly disordered to various types of oriented graphitic material. The microstructure is determined by the local structural rearrangements that occur due to ion impacts on the picosecond timescale (thermal spikes) and slower relaxation processes which depend on the substrate temperature.     

Properties of Phosphorus‐Doped Silicon‐Rich Amorphous Silicon Carbide Film Prepared by a Solution Process

Using a polymeric precursor synthesized from a mixture of cyclopentasilane, white phosphorus, and 1‐hexyne, we deposited phosphorus‐doped silicon‐rich amorphous silicon carbide (a‐SiC) films via a solution‐based process. Unlike conventional polymeric precursors, this polymer requires neither catalysts nor oxidation for its synthesis and cross‐linkage. Therefore, the polymeric precursor is sufficiently pure for effective doping and fabricating semiconducting a‐SiC. This study presents the results of a detailed study of the effect of carbon and phosphorus concentrations on the structural, optical, and electrical properties of a‐SiC films. The lowest activation energy for these films is 0.39 eV, which leads to an optical gap and a dark conductivity of 2.1 eV and 10⁹ Ω cm, respectively. Moreover, these films satisfy the Meyer–Neldel rule for thermally activated conductivity, which indicates that white‐phosphorus doping of solution‐processed a‐SiC produces films with the same characteristics as phosphine‐doped vacuum‐processed a‐SiC.