Deposition and characterization of smooth ultra-nanocrystalline diamond film in CH4/H2/Ar by microwave plasma chemical vapor deposition

The smooth ultra-nanocrystalline diamond (UNCD) films were prepared by microwave plasma chemical vapor deposition (MWCVD) using argon-rich CH₄/H₂/Ar plasmas with varying argon concentration from 96% to 98% and negative bias voltage from 0 to −150 V. The influences of argon concentration and negative bias voltage on the microstructure, morphology and phase composition of the deposited UNCD films are investigated by using scanning electron microscopy (SEM), X-ray diffraction (XRD), atom force microscopy (AFM), and visible and UV Raman spectroscopy. It was found that the introduction of argon in the plasma caused the grain size and surface roughness decrease. The RMS surface roughness of 9.6 nm (10 micron square area) and grain size of about 5.7 nm of smooth UNCD films were achieved on Si(100) substrate. Detailed experimental results and mechanisms for UNCD film deposition in argon-based plasma are discussed. The deposited highly smooth UNCD film is also expected to be applicable in medical implants, surface acoustic wave (SAW) devices and micro-electromechanical systems (MEMS).     

Characteristics of a well-adherent nanocrystalline diamond thin film grown on titanium in Ar/CH4 microwave CVD plasma

The fabrication of a well-adherent diamond film on titanium and its alloys is always problematical due to the different thermal expansion coefficients of the two materials, the complex nature of the interlayer formed during diamond deposition, and the difficulty in achieving very high nucleation density. In this work, well-adherent and smooth nanocrystalline diamond (NCD) thin film is successfully deposited on pure titanium substrate by microwave plasma-assisted chemical vapor deposition (MWPCVD) method in Ar/CH₄ environment. It is found that the average grain size is less than 20 nm with a surface roughness value as low as 12 nm. Morphology, surface roughness, diamond crystal orientation and quality are obtained by characterizing the sample with field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), X-ray diffraction (XRD) and Raman spectroscopy, respectively. Detailed experimental results and mechanisms for NCD film deposition are discussed.     

Effect of microwave power and C2 emission intensity on structural and surface properties of nanocrystalline diamond films

Nanocrystalline diamond (NCD) films are synthesized using microwave plasma enhanced chemical vapour deposition technique at 2 × 10⁴ Pa and 600 °C with microwave power of 600-1600 W. Deposition is carried out on n-type (100) silicon wafer with Ar/H₂/CH₄ gas mixtures. The film properties are analyzed using micro Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy and atomic force microscopy. Raman spectra show two predominant peaks centered around 1335 cm⁻¹ and 1560 cm^− 1 and two humps around 1160 cm^− 1 and 1450 cm^− 1, respectively. FTIR spectra show C:H stretching modes around 3000 cm^− 1. XRD patterns show a peak at 44° (2θ). In situ diagnostic of plasma is carried out using Optical Emission Spectroscopy. It has been observed that C₂ dimer plays an important role in the nucleation of diamond crystals during NCD film deposition and the emission intensity of C₂ can be adjusted by varying the microwave power. It has also been observed that the structural properties like growth rate, surface morphology and grain size of the growing film are dependent on the C₂ intensity during deposition.     

Growth of silicon carbide thin films by hot-wire chemical vapor deposition from SiH4/CH4/H2

Silicon carbide (SiC) thin films were prepared by hot-wire chemical vapor deposition from SiH₄/CH₄/H₂ and their structural properties were investigated by X-ray diffraction, Fourier transform infrared absorption and Raman scattering spectroscopies. At 2 Torr, Si-crystallite-embedded amorphous SiC (a-Si_1 − xC_x:H) grew at filament temperatures (T_f) below 1600 °C and nanocrystalline cubic SiC (nc-3C-SiC:H) grew above T_f = 1700 °C. On the other hand, At 4 Torr, a-Si_1 − xC_x:H grew at T_f = 1400 °C and nc-3C-SiC grew above T_f = 1600 °C. When the intakes of Si and C atoms into the film per unit time are almost the same and H radicals with a high density are generated, which takes place at high T_f, nc-3C-SiC grows. On the other hand, at low T_f the intake of Si atoms is larger than that of C atoms and, consequently, Si-rich a-Si_1 − xC_x:H or Si-crystallite-embedded a-Si_1 − xC_x:H grow.     

High-rate synthesis of microcrystalline silicon films using high-density SiH4/H2 microwave plasma

A high electron density (> 10¹¹ cm^− 3) and low electron temperature (1-2 eV) plasma is produced by using a microwave plasma source utilizing a spoke antenna, and is applied for the high-rate synthesis of high quality microcrystalline silicon (μc-Si) films. A very fast deposition rate of ∼ 65 Å/s is achieved at a substrate temperature of 150 °C with a high Raman crystallinity and a low defect density of (1-2) × 10¹⁶ cm^− 3. Optical emission spectroscopy measurements reveal that emission intensity of SiH and intensity ratio of H_α/SiH are good monitors for film deposition rate and film crystallinity, respectively. A high flux of film deposition precursor and atomic hydrogen under a moderate substrate temperature condition is effective for the fast deposition of highly crystallized μc-Si films without creating additional defects as well as for the improvement of film homogeneity.     

Linear antenna microwave plasma CVD deposition of diamond films over large areas

Diamond thin films were grown by linear antenna microwave plasma CVD process over large areas (up to 20 × 10 cm²) from a hydrogen based gas mixture. The influence of the gas composition (H₂, CH₄, CO₂) and total gas pressure (0.1 and 2 mbar) on the film growth is presented. For CH₄/H₂ gas mixtures, the surface crystal size does not show dependence on the methane concentration and total pressure and remains below 50 nm as observed by SEM. Adding CO₂ (up to 10%) significantly improves the growth rate. However, still no significant change of morphology is observed on films grown at 2 mbar. The crucial improvement of the diamond film purity (as detected by Raman spectroscopy) and crystal size is found for deposition at 0.1 mbar. In this case, crystals are as large as 500 nm and the growth rate increases up to 38 nm/h.     

Synthesis of boron-doped diamond films by DC plasma CVD using a CH4+CO2+H2 gas mixture at lower substrate temperature and formation of an n-Si/p-diamond heterojunction

Diamond films were synthesized by direct current plasma chemical vapour deposition using a CH₄+CO₂+H₂ gas mixture on Si substrates. The optimum deposition conditions were determined. It was found that 0.4 A/cm² current density, at applied voltage of 1 kV, resulted in good-quality diamond films. The substrate temperature was 750 K which is considerably lower than the conventional requirement of ∼1100 K. Boron doping was achieved by passing a portion of the gas mixture through boric acid dissolved in methanol. The boron-doped p-type diamond films were deposited on an n-type single crystalline Si substrate and an n-Si/p-diamond heterojunction was fabricated. The p-n junction was characterized in terms of current-voltage (I-V) and capacitance-voltage (C-V) measurements.     

Effect of doping elements on ZnO etching characteristics with CH4/H2/Ar plasma

Effect of doping elements on the etching characteristics of doped-ZnO (Ag, Li, and Al) thin films, etched with a positive photoresist (PR) mask, and an etch process window for infinite etch selectivity were investigated by varying the CH₄ flow ratio and self-bias voltage, V_dc, in inductively coupled CH₄/H₂/Ar plasmas. Increased doping of ZnO films decreased the etch rates significantly presumably due to lower volatility of reaction by-products of doped Li, Ag, and Al in CH₄/H₂/Ar plasmas. The etch rate of AZO (Al-doped ZnO) was most significantly decreased as the doping concentration is increased from 4 to 10 wt%. It was found that process window for infinite etch selectivity of the doped ZnO to the PR is closely related to a balance between deposition and removal processes of a-C:H (amorphous hydrogenated carbon) layer on the doped-ZnO surface. Measurements of optical emission of the radical species in the plasma and surface binding states by optical emission spectroscopy (OES) and X-ray photoelectron spectroscopy (XPS), respectively, implied that the chemical reaction of CH radicals with Zn atoms in doped-ZnO play an important role in determining the doped-ZnO etch rate together with an ion-enhanced removal mechanism of a-C:H layer as well as Zn(CH_x)_y etch by-products.     

The influence of CH4 addition on composition, structure and optical characteristics of SiCN thin films deposited in a CH4/N2/Ar/hexamethyldisilazane microwave plasma

Amorphous silicon carbonitride (a-SiCN) thin films were synthesized in a microwave plasma assisted chemical vapor deposition system using N₂, Ar, CH₄ and hexamethyldisilazane vapor (HMDSN). Composition, morphology and optical constants of the layers have been studied as a function of CH₄ rate in the range 0 to 9%. It was found that films are mainly composed of silicon nitride like compound whatever the CH₄ rate. However, CH₄ addition leads to less hydrogenated and denser films. In addition, a refractive index augmentation from 1.7 to 2.0 and a Tauc gap decrease from 5.2 eV to 4.8 eV is measured with CH₄ rate increase. It is believed that the refractive index augmentation is due to higher thin film density whereas hydrogen bonds decrease is assumed to contribute to the band gap narrowing. Besides, CH₄ addition to the gaseous mixture increases thin film oxidation resistance. These results show the ability of varying composition, structure and optical constants of a-SiCN films by modifying CH₄ rate in a N₂/Ar/HMDSN plasma.     

High rate growth highly crystallized microcrystalline silicon films using SiH4/H2 high-density microwave plasma

The plasma parameter for fast deposition of highly crystallized microcrystalline silicon (μc-Si) films with low defect density is presented using the high-density and low-temperature microwave plasma (MWP) of a SiH₄-H₂ mixture. A very high deposition rate of ∼ 65 Å/s has been achieved at SiH₄ concentration of 67% diluted in H₂ with high Raman crystallinity I_c / I_α > 3 and low defect density of 1-2 × 10¹⁶ cm^− 3 by adjusting the plasma condition. Contrary to the conventional rf plasma, the defect density of the μc-Si films strongly depend on substrate temperature T_s and it increased with increasing T_s despite T_s below 300 °C, suggesting that the real surface temperature at the growing surface was higher than the monitored value. The sufficient supply of deposition precursors such as SiH₃ at the growth surface under an appropriate ion bombardment was effective for the fast deposition of highly crystallized μc-Si films as well as the suppression of the incubation and transition layers at the initial growth stage.     

Effects of argon and oxygen addition to the CH4-H2 feed gas on diamond synthesis by microwave plasma enhanced chemical vapor deposition

In order to investigate the effects of argon and oxygen on diamond synthesis, the behaviors of diamond deposition using microwave plasma chemical vapor deposition method have been studied by varying the concentrations of argon and oxygen in the methane-hydrogen gas mixture. Diamond films were deposited on silicon wafer under the conditions of substrate temperatures: 1073 1173 K, total reaction pressure: 5333 Pa (40 Torr), methane concentrations: 0.5 5.0%, and they were characterized by scanning electron microscopy, Raman spectroscopy and optical emission spectroscopy. The deposition rates of diamond films were enhanced by adding argon into the methane-hydrogen system, but nondiamond carbon phases in the films also increased. It resulted from the increase of hydrocarbon radicals in the plasma. As oxygen was added, the quality of deposited diamond films was improved due to the decrease of C₂ radicals and increase of OH radicals in the plasma. Simultaneous addition of 0.3% oxygen and 20% argon has been able to effectively suppress the formation of nondiamond carbon components and increase the deposition rate of diamond films. It appears that the ionized argon (Ar⁺) and excited argon atoms (Ar*) may activate the various chemical species and promote the reactions between the gas phase species and oxygen in the plasma.     

Nanowhiskers formation by radio frequency Ar/O2 plasma etching of aluminum coated diamond films

Diamond nanowhiskers were fabricated by etching as-grown and aluminum coated diamond films in radio frequency (RF) Ar/O₂ plasma. It was found that diamond nanowhiskers could be obtained by anisotropic etching of both kinds of films. For the as-grown diamond film, the whiskers randomly formed on the diamond surface with higher etching rate. However, for the Al-coated diamond film, an energy dispersive X-ray spectroscopy measurement revealed that the distribution of the whiskers was the same as that of the coated Al particles. During the etching process, Al particles served as masks contributing to restraining the etching of the film underneath. It was found that the distribution of the whiskers was significantly influenced by the Al coating. The whiskers (1 μm in height and 50 nm in diameter) could be obtained under the optimum etching condition. In addition, the dependence of the distribution of the whiskers on Al coating time was demonstrated.     

Deep etch-induced damage during ion-assisted chemical etching of sputtered indium-zinc-oxide films in Ar/CH4/H2 plasmas

Plasma etch damage to sputtered indium-zinc-oxide (IZO) layers in the form of changes in the film stoichiometry was investigated using Auger Electron Spectroscopy (AES). While damage resulting from pure chemical etching processes is usually constrained to the surface vicinity, ion-assisted chemical etching of IZO in Ar/CH₄/H₂ plasmas produces a Zn-rich layer, whose thickness (∼ 50 nm) is well-above the expected stopping range of Ar ions in IZO (∼ 1.5 nm). Based on AES depth profiles as a function of plasma exposure time, it is concluded that the observed Zn enrichment and In depletion deep into the IZO film are driven by the implantation of hydrogen atoms.     

Growth of nanocrystalline diamond films in CCl4/H2 ambient

We investigated the growth characteristics of the nanocrystalline diamond films using CCl₄/H₂ as gas sources in a hot-filament chemical vapor deposition (CVD) reactor. Successful growth of nanocrystalline diamond at typical growth condition of 1.5-2.5% CCl₄ and 550-730 °C substrate temperature has been demonstrated. Glancing angle X-ray diffraction (XRD) clearly indicated the formation of diamond in the films. Typical root-mean-square surface roughness of 10-15 nm and an optimal root-mean-square surface roughness of 6 nm have been achieved. Transmission electron microscopy (TEM) analyses indicated that nanocrystalline diamond film with an average grain size in the range of 10-20 nm was deposited from 2.5% CCl₄/H₂ at 610 °C. Effects of different source gas composition and substrate temperature on the grain nucleation and grain growth processes, whereby the grain size of the nanocrystalline film could be controlled, were discussed.     

Formation and characterization of diamond crystals synthesized by microwave plasma CVD system

Abstract

Diamond crystals have been successfully synthesized on (100) Si wafer using microwave plasma CVD. The growth was conditioned in a flowing system in which the parameters, such as CH₄/H₂ ratio, pressure, temperature and microwave power were varied. Cubo‐octahedra or tetrakaidecahedra are the equilibrium shape of diamond single crystals obtained under all conditions and are therefore the basic unit for the formation of polycrystalline diamond films, mostly through repetitive twinning and secondary growth of diamond crystals on {100} habit planes of cubo‐octahedra. Both X‐ray diffraction and Raman spectroscopy were used to facilitate the analysis of the diamond crystallinity and purity. These qualities are similar to those of natural diamonds.     

Electrochemical studies of nano-structured diamond thin-film electrodes grown by microwave plasma CVD

In this paper, we report the investigation of the electrochemical properties of nano-structured diamond thin-film electrodes on porous silicon (PSi) synthesized by microwave plasma chemical vapor deposition (MPCVD). For the application, boron-doped and undoped diamond thin film has been performed and fabricated into an electrode device, and its microstructure, electrical and chemical properties have been studied. In order to enlarge the surface area of diamond electrodes, a negative bias was applied to the MPCVD process to deposit diamond thin film in a nano-structured form, so that its surface remained rough and nano-fine structured. Diamond thin films were analyzed by Raman spectroscopy and SEM. The morphology of boron-doped diamond thin films on PSi reveals nano-rods in the shape of diamond crystallites. Their electrochemical properties were evaluated by performing cyclic voltammetry (CV) measurement in inorganic K₄[Fe(CN)₆] in a K₂HPO₄ buffer solution. Boron-doped diamond thin film on PSi has demonstrated good electrochemical properties, with a larger redoxidation current of CV, due to its rough surface, which provides a more active electrochemical interface.     

Ion irradiation-induced modifications of diamond nanorods synthesised by microwave plasma chemical vapour deposition

Diamond nanorods (DNRs) synthesised by the high methane content in argon rich microwave plasma chemical vapour deposition (MPCVD) have been implanted with nitrogen ions. The nanorods were characterised by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. The DNRs consist of single-crystalline diamond cores of 3–5?nm in diameter and several tens of nanometres in length. For purification from non-diamond contents, hydrogen plasma etching of DNRs was performed. Structural modifications of etched DNRs were studied after irradiating with 50?keV nitrogen ions under the fluence of 5?×?10¹⁴, 1?×?10¹⁵, 5?×?10¹⁵ and 1?×?10¹⁶?ions?cm^?2. Nitrogen-ion implantation changes the carbon–carbon bonding and structural state of the nanocrystalline diamond (NCD). Raman spectroscopy was used to study the structure before and after ion irradiation, indicating the coexistence of diamond and graphite in the samples. The results indicated the increase in graphitic and sp²-related content, at the expense of decrease in diamond crystallinity, for ion implantation dose of 5?×?10^15?cm^?2 and higher. The method proves valuable for the formation of hybrid nanostructures with controlled fractions of sp³–sp² bonding.     

Deposition of hydrophobic nano-coatings with low-pressure radio frequency CH2F2/Ar plasma processing

In an attempt to perform hydrophobic nano-coating, this investigation examined various operational parameters including in RF plasma power, system gas pressure, and CH₂F₂:Ar ratio of low-pressure plasma processing. The low-pressure plasma, generated with radio frequency power at 13.56 MHz, was fed difluoromethane (CH₂F₂)/Ar gas mixture. The surface characteristics of the plasma polymerized films were studied by static contact angle measurement (CA) and atomic force microscopy (AFM). As a result, increasing deposition of CH₂F₂ plasma polymerized films was achieved in enhanced RF plasma power input. The CH₂F₂ plasma polymerized films also were conducted in a varying system gas pressure with enhanced hydrophobic surface property. The effects of CH₂F₂/Ar plasma on the surface characteristics of the plasma polymerized films were investigated as a function of the Ar content. The super hydrophobic coating under optimized operational parameters prepared in this study obtained water contact angles greater than 150°. It was found that the maximum water contact angles (161°) was obtained at 1.5:1 (CH₂F₂: Ar) ratio. In addition, AFM analysis shows that possible ion bombardment from CH₂F₂/Ar plasma can increase surface roughness, and effectively form a hydrophobic coating on the surface of heat sensitive materials.     

Comparison of line edge roughness and profile angles of chemical vapor deposited amorphous carbon etched in O2/N2/Ar and H2/N2/Ar inductively coupled plasmas

In this study, we compared the line edge roughnesses (LER) and profile angles of chemical vapor deposited (CVD) amorphous carbon (a-C) patterns etched in an inductively coupled plasma (ICP) etcher produced by varying process parameters such as the N₂ gas flow ratio, Q (N₂), and dc self-bias voltage (V_dc) in O₂/N₂/Ar and H₂/N₂/Ar plasmas. The tendencies of the LER and profile angle values of the etched CVD a-C pattern were similar in both plasmas. The LER was smaller in the O₂/N₂/Ar than in the H₂/N₂/Ar plasmas, and the profile angle was larger in the O₂/N₂/Ar than in the H₂/N₂/Ar plasmas under the same processes conditions. The use of O₂/N₂/Ar plasma was more advantageous than the H₂/N₂/Ar plasma for controlling LER and profile angle.     

Infinitely high etch selectivity during CH4/H2/Ar inductively coupled plasma (ICP) etching of indium tin oxide (ITO) with photoresist mask

Under certain conditions during ITO etching using CH₄/H₂/Ar inductively coupled plasmas, the etch rate selectivity of ITO to photoresist (PR) was infinitely high because the ITO films continued to be etched, but a net deposition of the α-C:H layer occurred on the top of the PR. Analyses of plasmas and etched ITO surfaces suggested that the continued consumption of the carbon and hydrogen in the deposited α-C:H layer by their chemical reaction with In and Sn atoms in the ITO resulting in the generation of volatile metal-organic etch products and by the ion-enhanced removal of the α-C:H layer presumably play important roles in determining the ITO etch rate and selectivity.