Synthesis of nitrogen incorporated diamond-like carbon thin films using microwave surface-wave plasma CVD

Nitrogenated diamond-like (DLC:N) carbon thin films have been deposited by microwave surface wave plasma chemical vapor deposition on silicon and quartz substrates, using argon gas, camphor dissolved in ethyl alcohol composition and nitrogen as plasma source. The deposited DLC:N films were characterized for their chemical, optical, structural and electrical properties through X-ray photoelectron spectroscopy, UV/VIS/NIR spectroscopy, Raman spectroscopy, atomic force microscope and current–voltage characteristics. Optical band gap decreased (2.7 to 2.4 eV) with increasing Ar gas flow rate. The photovoltaic measurements of DLC:N / p-Si structure show that the open-circuit voltage (V_oc) of 168.8 mV and a short-circuit current density (J_sc) of 8.4 μA/cm² under light illumination (AM 1.5 100 mW/cm²). The energy conversion efficiency and fill factor were found to be 3.4 × 10^{− 4}% and 0.238 respectively.     

Characteristics of nitrogen doped diamond-like carbon thin films grown by microwave surface-wave plasma CVD

Nitrogen doped diamond-like carbon (DLC:N) thin films were deposited on p-type silicon (p-Si) and quartz substrates by microwave (MW) surface-wave plasma (SWP) chemical vapor deposition (CVD) at low temperature (< 100 °C). For films deposition, argon (Ar: 200 sccm), acetylene (C₂H₂:10 sccm) and nitrogen (N: 5 sccm) were used as carrier, source and doping gases respectively. DLC:N thin films were deposited at 1000 W microwave power where as gas composition pressures were ranged from 110 Pa to 50 Pa. Analytical methods such as X-ray photoelectron spectroscopy (XPS), UV-visible spectroscopy, FTIR and Raman spectroscopy were employed to investigate the chemical, optical and structural properties of the DLC:N films respectively. The lowest optical gap of the film was found to be 1.6 eV at 50 Pa gas composition pressure.     

Diamond-like carbon thin films by microwave surface-wave plasma CVD aimed for the application of photovoltaic solar cells

The nitrogen doped diamond-like carbon (DLC) thin films were deposited on quartz and silicon substrates by a newly developed microwave surface-wave plasma chemical vapor deposition, aiming the application of the films for photovoltaic solar cells. For film deposition, we used argon as carrier gas, nitrogen as dopant and hydrocarbon source gases, such as camphor (C₁₀H₁₆O) dissolved with ethyl alcohol (C₂H₅OH), methane (CH₄), ethylene (C₂H₄) and acetylene (C₂H₂). The optical and electrical properties of the films were studied using X-ray photoelectron spectroscopy, Nanopics 2100/NPX200 surface profiler, UV/VIS/NIR spectroscopy, atomic force microscope, electrical conductivity and solar simulator measurements. The optical band gap of the films has been lowered from 3.1 to 2.4 eV by nitrogen doping, and from 2.65 to 1.9 eV by experimenting with different hydrocarbon source gases. The nitrogen doped (flow rate: 5 sccm; atomic fraction: 5.16%) film shows semiconducting properties in dark (i.e. 8.1 × 10^{− 4} Ω^{− 1} cm^{− 1}) and under the light illumination (i.e. 9.9 × 10^{− 4} Ω^{− 1} cm^{− 1}). The surface morphology of the both undoped and nitrogen doped films are found to be very smooth (RMS roughness ≤ 0.5 nm). The preliminary investigation on photovoltaic properties of DLC (nitrogen doped)/p-Si structure show that open-circuit voltage of 223 mV and short-circuit current density of 8.3 × 10^{− 3} mA/cm². The power conversion efficiency and fill factor of this structure were found to be 3.6 × 10^{− 4}% and 17.9%, respectively. The use of DLC in photovoltaic solar cells is still in its infancy due to the complicated microstructure of carbon bondings, high defect density, low photoconductivity and difficulties in controlling conduction type. Our research work is in progress to realize cheap, reasonably high efficiency and environmental friendly DLC-based photovoltaic solar cells in the future.     

Bonding defects and optical band gaps of DLC films deposited by microwave surface-wave plasma CVD

The effects of CH₄ / C₂H₄ flow ratio and annealing temperature on the defect states and optical properties of diamond-like carbon (DLC) films deposited by novel microwave surface-wave plasma chemical vapour deposition (MW SWP CVD) are studied through UV/VIS/NIR measurements, atomic force microscopy, Raman spectroscopy and electron spin resonance analysis. The optical band gap of DLC has been tailored between a relatively narrow range, 2.65–2.5 eV by manipulating CH₄ / C₂H₄ flow ratio and a wide range, 2.5–0.95 by thermal annealing. The ESR spin density varied between 10¹⁹ to 10¹⁷ spins/cm³ depending on the CH₄ / C₂H₄ flow ratio (1 : 3 to 3 : 1). The defect density increased with increasing annealing temperature. Also, there is a strong dependence of spin density on the optical band gap of the annealed-DLC films, and this dependency has been qualitatively understood from Raman spectra of the films as a result of structural 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 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.     

Effects of iodine doping on optoelectronic properties of diamond-like carbon thin films deposited by microwave surface wave plasma CVD

We report the effects of iodine (I) doping on the electrical and optical properties of diamond-like carbon (DLC) thin films grown on silicon and quartz substrates by microwave surface wave plasma chemical vapor deposition at low temperature (<100 °C). For film deposition, we used argon gas with methane or camphor dissolved with ethyl alcohol composition as plasma source. The optical gap and photoconductivity measurements of the samples were carried out before and after the iodine doping. The results show that optical gap dropped from 3.4 to 0.9 eV corresponding to nondoping to iodine-doping conditions, respectively. The photovoltaic measurements show that the open-circuit voltage (V_oc) and short-circuit current density (J_sc) of I-doped DLC film deposited on n-type silicon substrate under light illumination (AM1.5, 100 mW/cm²) were approximately 177 mV and 1.15 μA, respectively, and the fill factor was found to be 0.217.     

Effect of substrate bias voltage on the properties of diamond-like carbon thin films deposited by microwave surface wave plasma CVD

Diamond-like carbon (DLC) thin films were deposited on silicon and ITO substrates with applying different negative bias voltage by microwave surface wave plasma chemical vapor deposition (MW SWP-CVD) system. The influence of negative bias voltage on optical and structural properties of the DLC film were investigated using X-ray photoelectron spectroscopy, UV/VIS/NIR spectroscopy, Fourier transform infrared spectroscopy and Raman spectroscopy. Optical band gap of the films decreased from 2.4 to 1.7 with increasing negative bias voltage (0 to − 200 V). The absorption peaks of sp³ CH and sp² CH bonding structure were observed in FT-IR spectra, showing that the sp²/sp³ ration increases with increasing negative bias voltage. The analysis of Raman spectra corresponds that the films were DLC in nature.     

Thermal stability of the optical properties of plasma deposited diamond-like carbon thin films

In present paper we studied the optical constants of the diamond-like carbon (DLC) films and their changes with annealing. The multisample modification of combined variable angle spectroscopic ellipsometry and near normal spectroscopic reflectometry was used. The optical constants of the DLC films were simulated by our recently published six-parameter dispersion model employing a parameterization of the density of electronic states (DOS). Based on the dispersion model parameters the density of π and σ electrons were evaluated. We showed that from our model and the independently determined hydrogen atomic fraction of the films before and after annealing the ratio between momentum matrix elements of π → π* and σ → σ* transitions and the correct sp³-to-sp² carbon bonding configuration ratio can be calculated. It is worth to notice that the first quantity is usually assumed to be equal to unity but we showed that this assumption may cause a significant error in the determination of the sp³-to-sp² ratio. Therefore, our suggested method represents a novelty in this field.     

Influence of technological conditions on mechanical stresses inside diamond-like carbon films

In this paper the influences of the technological conditions, i.e. the influences of the hydrogen flow rate and deposition time, on the values of the intrinsic mechanical stresses inside the diamond-like carbon (DLC) thin films prepared by plasma enhanced chemical vapor deposition onto silicon substrates are studied. These stresses are measured by two-beam interferometry and optical profilometry based on chromatic aberration through the measurements of deformations of the silicon substrates originating in consequence of the film stresses. It is shown that the influence of the deposition time (i.e. film thickness) on the film stress is relatively slight in contrast to the influence of the hydrogen flow rate on this quantity. It is namely shown that the film stresses are influenced by the hydrogen flow rate values in a pronounced way within the interval of interest, i.e. within the interval 1–7 sccm. Moreover, it is shown that the method of optical profilometry used can be competitive to the method of two-beam interferometry from the practical point of view.     

Characterization of amorphous carbon films deposited by surface wave plasma CVD

Many dangling bonds in hydrogenated amorphous carbon (a-C:H) films are usually generated by bombardments of high-energy ion precursors in typical chemical vapor deposition (CVD). To generate low dangling bonds, a-C:H films should be deposited from low-energy radical species. Surface wave plasma (SWP) generates low-energy and high-density radicals. We prepare a-C:H films using SWP and investigate the relationship between the plasma characteristics and structures of a-C:H films. The microwave of the TM01 mode was introduced through the dielectric window and SWP generate under the dielectric window. An Ar and C₂H₂ plasma mixture mainly consists of neutral radical species, and the electron temperature is as low as 1 eV. Electron density significantly decreases with increasing distance from the dielectric window. The a-C:H films are prepared from these hydrocarbon and carbon low-energy radicals as main precursors. The sp² bonded network cluster size in a-C:H films increase with electron density in SWP. This structure change is the influence of the termination structure of clusters changing to CH from CH₃ and CH₂.     

Optoelectronic properties of nitrogenated amorphous carbon films synthesized by microwave surface wave plasma chemical vapor deposition system

The n-type nitrogen doped amorphous carbon (a-C:N) thin films have been grown by microwave (MW) surface wave plasma (SWP) chemical vapor deposition (CVD) system on silicon, quartz and ITO substrates at different nitrogen flow rates (1 to 4 sccm). The effects of nitrogen doping on chemical, optical, structural and electrical properties were studied through X-ray photoelectron spectroscopy, Nanopics 2100/NPX200 surface profiler, UV/VIS/NIR spectroscopy, Raman spectroscopy and solar simulator measurements. Argon, acetylene and nitrogen are used as plasma sources. Optical band gap decreased and nitrogen atomic concentration (%) increased with increasing nitrogen flow rate as a dopant. The a-C:N/p-Si based device exhibits photovoltaic behavior under illumination (AM 1.5, 100 mW/cm²), with a maximum open-circuit voltage (V_oc), short-circuit current (J_sc) and fill factor of 4.2 mV, 7.4 μA/cm² and 0.25 respectively.     

Vibrational properties of nitrogen-doped ultrananocrystalline diamond films grown by microwave plasma CVD

Ultrananocrystalline diamond (UNCD) films grown in an argon-rich Ar/CH₄/H₂ microwave plasma with nitrogen gas added in amounts of 0%–20% were studied by Raman spectroscopy with multiple excitation wavelengths in the range of 244–647 nm and by optical absorption in UV–visible. The Raman spectra have demonstrated the presence of diamond, amorphous carbon and polyacetylene in the UNCD films. Analysis of vibrational and optical properties of amorphous carbon phase proves that nitrogen stimulates the transition from amorphous carbon into an ordered graphite-like structure with narrowed optical band gap, which is supposed to be responsible for the high electrical conductivity of the N-doped UNCD.     

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.     

Effect of temperature on sulfur-doped diamond-like carbon films deposited by pulsed laser ablation

In this study, S-DLC films were deposited using pulsed laser ablation of a novel sulfur-graphite (SG) mixture target using an ArF excimer laser (193 nm). The SG targets were made by mixing sulfur and graphite powders at different sulfur molar percentages from 0% to 25%. The S-DLC films were deposited at room temperature, 150 °C and 250 °C. The optical and electronic properties of the doped films were studied. Laser Raman spectroscopy indicated increased graphitic behavior with temperature but decreased with higher sulfur content. Spectroscopic ellipsometry analyses found that the optical band-gap energy, extinction coefficient and reflective index, clearly depended on deposition temperature and sulfur content. Hall Effect measurements indicated n-type carrier with concentration in the range of 1 × 10¹⁴ to 2 × 10¹⁷ cm^− 3, strongly depended upon the deposition temperature and amount of sulfur.     

Stress and structural properties of diamond-like carbon films deposited by electron beam excited plasma CVD

Diamond-like carbon (DLC) films prepared using CH₄ or C₆H₆ with varying deposition parameters by an electron beam excited plasma CVD system were investigated for the internal stress, dynamic hardness and structural properties such as the film density, total, bonded and unbound hydrogen contents, sp³ ratio and graphite crystallite. From the correlations between internal stress and structural properties, the following conclusions were derived. The fraction of unbound hydrogen to total hydrogen content was the most influential factor for the compressive stress of the DLC films deposited from CH₄. It is suggested that unbound hydrogen may be trapped into the disordered microstructure of graphite crystallites embedded in the network of film. For the DLC films deposited from C₆H₆, it was shown that the compressive stress was correlated with not only the fraction of unbound hydrogen content but also the degree of cross-linking between graphite crystallites in the film.     

Study of photoconductivity in thin amorphous diamond-like carbon (a:DLC) films prepared by r.f. glow discharge technique

Thin a:DLC films were deposited by r.f. plasma system in which methane (CH₄) was admitted. Photoconductivity measurements were performed on an Al-a:DLC-Cu sandwich structure and an Al-a:DLC-Al planar structure. The photocurrent was measured in a wide interval of temperatures. The photocurrent signal of the sandwich device is about 100 times higher than the dark current measured under He-Ne laser incident light (2.5 mW) at 160 K. A photocurrent response time of τ_o ≈ 8 ms was measured at this temperature. In the planar device, under the same conditions, the photocurrent signal was twice the dark current. The maximum mobility-lifetime product of a:DLC (sandwich device) was about 2 × 10⁻¹⁰ cm²/V.     

Synthesis of cobalt/diamond-like carbon thin films by biased target ion beam deposition

Cobalt/diamond-like carbon (Co/DLC) composite thin films were synthesized on silicon wafers by biased target ion beam deposition (BTIBD) in which Co was deposited by sputtering a negatively biased Co target using an Ar ion beam and DLC was produced simultaneously by a second ion beam with CH₄ as carbon source. The surface morphology, chemical composition and binding states of the synthesised thin films were studied. The as-deposited Co/DLC films are continuous and smooth with a thickness of approximately 150 nm for an hour of deposition. The average roughness is 3.5 ± 0.3 Å and the root-mean squared roughness is 5.3 ± 1.1 Å. The films are low in contaminations and the mass concentration of Co is approximately 24%. Fourier transform infrared spectroscopy and Raman spectroscopy results indicate the Co did not react with C and barely changed the microstructure of DLC. X-ray photoelectron spectroscopy and synchrotron based near-edge X-ray absorption fine structure studies indicate that the Co is in metallic form in the as-deposited films. The preliminary results demonstrate the promise to synthesize high quality Co/DLC composite films by BTIBD.     

液相沉积类金刚石膜的沉积机理研究

根据电化学的相关理论,提出了钛合金表面液相沉积DLC膜的反应机理,给出了可能电极过程,认为膜是通过甲基阳离子的亲电取代反应而不断生长。讨论了氢原子对金刚石结构的稳定作用,并解释了实验条件对膜结构和性能的影响。     

Effect of microwave power on diamond-like carbon films deposited using electron cyclotron resonance chemical vapor deposition

Diamond-like carbon (DLC) films have been deposited using electron cyclotron resonance chemical vapor deposition (ECR-CVD) under various microwave power conditions. Langmuir probe measurement and optical emission spectroscopy (OES) were used to characterize the ECR plasma, while the films were characterized using Raman and infrared (IR) spectroscopies, hardness and optical gap measurements. It was found that the ion density and all signal peaks in the optical emission (OE) spectra increased monotonously following the increase in microwave power. Raman spectra and optical gap measurements indicate that the films become more graphitic with lower content of sp³-hybridized carbon atoms as the microwave power was increased. IR and hardness measurements indicate a reduction in hydrogen content and decrease in hardness for the film produced at relatively high microwave powers. A deposition mechanism is described which involved the ion bombardment of film surfaces and hydrogen–surface interactions. The deposition rate of DLC film is correlated to the ion density and CH₃ density.     

液相沉积类金刚石膜的结构与性能研究

探讨了液相沉积法制备类金刚石的新工艺,并采用XPS,Raman光谱和SEM等对所得膜的结构进行表征,证实所得的是类金刚石膜。液相沉积得到的类金刚石膜与钛合金基材之间具有较强的结合强度,并具有较低的摩擦系数和一定的耐磨损能力。