Preparation and properties of CO<Subscript>x</Subscript> films

New types of amorphous graphite-like CO_x films were obtained by two ways: (i) magnetron sputtering of a graphite target in the gas mixture Ar+O₂; and (ii) air annealing at 250–300 °C of a-C films deposited by magnetron sputtering in Ar. These films contain at most 18–22% atomic oxygen, depending on the way of preparation. They remain stable in air and vacuum up to 300 °C. The transition from graphite-like a-C to a-CO_0.2 is accompanied by a sharp increase in electrical resistivity and IR transmittance. Two characteristic absorption bands at approximately 1700 and 1605 cm^-1 appear and the G band in the Raman spectrum shifts to approximately 1605 cm^-1. Electron diffraction reveals that only those films with 002 interlayer distance increased with respect to that of graphite may be saturated with oxygen up to approximately 22 at.%, until they become strongly vaporized. PACS 61.43.Dq; 78.30.Ly; 81.15.Cd; 81.40.Ef     

Structure and hardness of a-C:H films prepared by middle frequency plasma chemical vapor deposition

a-C:H films were prepared by middle frequency plasma chemical vapor deposition (MF-PCVD) on silicon substrates from two hydrocarbon source gases, CH₄ and a mixture of C₂H₂ + H₂, at varying bias voltage amplitudes. Raman spectroscopy shows that the structure of the a-C:H films deposited from these two precursors is different. For the films deposited from CH₄, the G peak position around 1520 cm⁻¹ and the small intensity ratio of D peak to G peak (I(D)/I(G)) indicate that the C-C sp³ fraction in this film is about 20 at.%. These films are diamond-like a-C:H films. For the films deposited from C₂H₂ + H₂, the Raman results indicate that their structure is close to graphite-like amorphous carbon. The hardness and elastic modulus of the films deposited from CH₄ increase with increasing bias voltage, while a decrease of hardness and elastic modulus of the films deposited from a mixture of C₂H₂ + H₂ with increasing bias voltage is observed.     

Hydrogenated diamond-like carbon film deposited on UHMWPE by RF-PECVD

In this work, investigations were conducted to analyze the properties of diamond-like carbon (DLC) film deposited on ultra-high molecular weight polyethylene (UHMWPE) by radio frequency plasma enhanced chemical vapor deposition (RF-PECVD) at a low temperature of 50 °C. Composition and structure of the films were characterized by scanning electron microscopy (SEM) and Raman spectroscopy. Hardness and wettability of the film were tested. Tribological characterizations were carried out on a universal micro-tribometer, and reciprocating friction against ZrO₂ ball was adopted with 25% bovine serum as lubrication. Results show that DLC film was successfully deposited on UHMWPE surface by RF-PECVD and the sp³ content was about 20% in the film. The film increased the macrohardness of the substrate by about 42% and the wettability was improved too. Tribology test showed a higher friction coefficient but a much smaller wear volume after the deposition due to the surface roughening and strengthening.     

Opto-electrical properties of amorphous carbon thin film deposited from natural precursor camphor

A simple thermal chemical vapor deposition technique is employed for the pyrolysis of a natural precursor “camphor” and deposition of carbon films on alumina substrate at higher temperatures (600-900 °C). X-ray diffraction measurement reveals the amorphous structure of these films. The carbon films properties are found to significantly vary with the deposition temperatures. At higher deposition temperature, films have shown predominately sp²-bonded carbon and therefore, higher conductivity and lower optical band gap (Tauc gap). These amorphous carbon (a-C) films are also characterized with Raman and X-ray photoelectron spectroscopy. In addition, electrical and optical properties are measured. The thermoelectric measurement shows these as-grown a-C films are p-type in nature.     

Effects of flow ratios on surface morphology and structure of hydrogenated amorphous carbon films prepared by microwave plasma chemical vapor deposition

A series of hydrogenated amorphous carbon (a-C:H) films were deposited on silicon substrates by microwave plasma chemical vapor deposition technique with a mixture of hydrogen and acetylene. The effects of flow ratio of hydrogen to acetylene on surface morphology and structure of a-C:H films were investigated using surface-enhanced Raman spectroscopy and scanning probe microscope (SPM) in the tapping AFM mode. Raman data imply a transition from graphite-like phase to diamond-like bonding configurations when the flow ratio increases. AFM measurements show that the increase in hydrogen content, to some extent, can smoothen the surface morphology and decrease the RMS roughness. Excessive hydrogen is found to cause the formation of polymeric hydrocarbon clusters in the films and reduce deposition rate.     

Electron field emission from amorphous carbon with N-doped nanostructures pyrolyzed from polyaniline

Carbon-based materials have been of great interest due to their potential application in cold cathodes for field emission displays and other vacuum microelectronic devices. Pyrolyzed polyaniline (PPANI) with N-doped nanostructures was prepared by pyrolysis of polyaniline at high temperature of 900 °C. The morphologies and microstructures were investigated by scanning electron microscopy, transmission electron microscopy, AFM, Raman spectroscopy, and X-ray photoelectron spectroscopy. It was found that there were sp²C-N and sp³C-N bonds between the nitrogen and the carbon atoms in the nanostructures of the PPANI obtained. The electron field emission investigations showed that the turn-on field and effective work function ?_e of PPANI were 1.7 V/μm and 0.010 eV which were lower than N-doped amorphous carbon films obtained by other methods.     

The study of magnetic properties and microstructures of nano-size FePt islands on amorphous carbon film

This work focuses on the formation mechanisms of nano-island FePt film on commercial copper grids covered with an amorphous carbon film. FePt films of different thickness (1-7.5 nm) were deposited on amorphous carbon film and then post-annealed at 700 °C for 30 min. The configuration of the film was changed during the annealing process due to the surface energy difference between the amorphous carbon films and FePt alloy. We have prepared nanometer-size island-shaped FePt films on the amorphous carbon films and investigated their magnetic properties and microstructures. A discontinuous nano-size island magnetic film can reduce the exchange coupling of the media and increase the recording density.     

A magnetron sputtering technique to prepare a-C:H films: Effect of substrate bias

Amorphous hydrogenated carbon (a-C:H) films were deposited by magnetron sputtering with a mixture gas of Ar and CH₄. The a-C:H films deposited by this method have relatively low internal stress (<1 GPa) compared to some films deposited by conventional deposition process. The effects of substrate bias voltage on microstructure, surface morphology and mechanical properties of the films were investigated by various techniques. It has been found that the polymer-like structure is dominated at low bias voltage (−100 V), while the diamond-like structure with the highest hardness and internal stress is the main feature of the a-C:H films deposited under high bias voltage (−300 V). With increasing the bias voltage further, the feature of diamond-like structure decreases associating with the increase of graphitization. The frictional test shows that the friction coefficient and wear rate of the a-C:H films are depended strongly on structure and mechanical properties, which were ultimately influenced by the deposition method and bias voltage.     

The electrochemical and mechanical properties of Ti incorporated amorphous carbon films in Hanks’ solution

Ti incorporated amorphous carbon (a-C) films with variant Ti contents were prepared by the unbalanced magnetron sputtering process. Scanning electron microscopy, ultraviolet Raman spectroscopy, X-ray photoelectron spectroscopy and transmission electron microscopy were used to characterize the microstructure of a-C films. The hardness and lubricated tribological properties were assessed using nanoindentation and ball-on-disk tribometer. As the Ti content in a-C films increases from 0 to 15.2 at.%, the sp³ volume fraction, the internal stress and the hardness of the films decreases gradually, while the disorder of sp² bond increases. The electrochemical tests reveal that the a-C films with lower than 1.5 at.% Ti possess good corrosion resistance in Hanks’ solution, while the a-C film with 15.2 at.% Ti is susceptible to crevice corrosion. The reduced friction of the a-C films is due to the sp² bonded film surface and boundary lubrication of the Hanks’ solution. The a-C film with 3.1 at.% Ti exhibits the best wear resistance in Hanks’ solution among the studied films.     

Field electron emission from amorphous carbon thin films grown by RF magnetron sputtering

Using a RF magnetron sputtering, amorphous carbon (a-C) and N-doped a-C (a-C:N) thin films were fabricated as field electron emitter. These thin films were deposited on Si(0 0 1) substrate at several temperatures. The field emission property was improved for a-C thin films grown at higher substrate temperatures. Furthermore, a-C:N film exhibits field emission property better than that of undoped a-C film. These results are explained in terms of the change in surface morphology and structural properties of a-C film.     

Field emission properties of a-C and a-C:H films deposited on silicon surfaces modified with nickel nanoparticles

The a-C and a-C:H films are deposited on silicon surfaces modified with and without nickel nanoparticles by using mid-frequency magnetron sputtering. The microstructures and morphologies of the films are analyzed by Raman spectroscopy and atomic force microscopy. Field emission behaviors of the deposited films with and without nickel nanoparticles modification are comparatively investigated. It is found that the hydrogen-free carbon film exhibits a high field emission current density and low turn-on electric field compared with the hydrogenated carbon film. Nickel modifying could increase the current density, whereas it has no significant effect on the turn-on electric field. The mechanism of field electron emission of a sample is discussed from the surface morphologies of the films and nickel nanoparticle roles in the interface between film and substrate.     

Raman light scattering in hydrogenated metal-carbon composite films

We have used Raman scattering, elemental analysis, and structural analysis to study the effect of the concentration of incorporated metals (Cu, Ni) on the ratio of sp²/sp³ carbon bonds in composite hydrogen-containing films a-C:H/Cu and a-C:H/Ni, formed by combining plasma-enhanced vapor phase deposition of carbon and sputtering of the metal, using a mixture of argon and methane or acetylene gases. We have shown that formation of a nanosized structure of metallic crystallites (2–5 nm) in the composite films leads to a significant increase in the fraction of disordered sp³-bonded carbon clusters and a decrease in the linear dimensions of the graphite-like carbon clusters. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 344–348, May–June, 2006.     

Thermal stability of ultrathin amorphous carbon films synthesized by plasma-enhanced chemical vapor deposition and filtered cathodic vacuum arc

Abstract

Ultrathin hydrogenated amorphous carbon (a-C:H) films deposited by plasma-enhanced chemical vapor deposition (PECVD) and hydrogen-free amorphous carbon (a-C) films of similar thickness deposited by filtered cathodic vacuum arc (FCVA) were subjected to rapid thermal annealing (RTA). Cross-sectional transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) were used to study the structural stability of the films. While RTA increased the thickness of the intermixing layer and decreased the sp³ content of the a-C:H films, it did not affect the thickness or the sp³ content of the a-C films. The superior structural stability of the FCVA a-C films compared with PECVD a-C:H films, demonstrated by the TEM and EELS results of this study, illustrates the high potential of these films as protective overcoats in applications where rapid heating is critical to the device functionality and performance, such as heat-assisted magnetic recording.     

Study of porous carbon thin films produced by pulsed laser deposition

Amorphous carbon is an interesting material and its properties can be varied by tuning its diamond-like (sp³) fractions. The diamond-like fractions in an amorphous carbon films depends on the kinetic energy of the deposited carbon ions. Porous amorphous carbon thin films were deposited onto silicon substrates at room temperature in a vacuum chamber by Glancing Angle Pulsed Laser Deposition (GAPLD). Krypton fluoride (248 nm) laser pulses with duration of 15 ns and intensities of 1-20 GW/cm² were used. In GAPLD, the angles between the substrate normal and the trajectory of the incident deposition flux are set to be almost 90°. Porous thin films consisting of carbon nanowires with diameters less than 100 nm were formed due to a self-shadowing effect. The kinetic energies of the deposited ions, the deposition rate of the films and the size of the nanowires were investigated. The sp³ fraction of the porous carbon films produced at intensity around 20 GW/cm² were estimated from their Raman spectra.     

Growth of hierarchical based ZnO micro/nanostructured films and their tunable wettability behavior

Hierarchical zinc oxide (ZnO) micro/nanostructured thin films were grown onto as-prepared and different annealed ZnO seed layer films by a simple two step chemical process. A cost effective successive ionic layer adsorption and reaction (SILAR) method was employed to grow the seed layer films at optimal temperature (80 °C) and secondly, different hierarchical based ZnO structured thin films were deposited over the seed layered films by chemical bath deposition (CBD). The influence of seed layer on the structural, surface morphological, optical and wettability behavior of the ZnO thin films were systematically investigated. The XRD analysis confirms the high crystalline nature of both the seed layer and corresponding ZnO micro/nanostructured films with a perfect hexagonal structure oriented along (0 0 2) direction. The surface morphology revels a complex and orientated hierarchical based ZnO structured films with diverse shapes from plates to hexagonal rod-like crystal to tube-like structure and even much more complex needle-like shapes during secondary nucleation, by changing the seed layer conditions. The water contact angle (WCA) measurements on hierarchical ZnO structured films are completely examined to study its surface wettability behavior for its suitability in future self-cleaning application. Photoluminescence (PL) spectra of the ZnO structured film exhibit UV and visible emissions in the range of 420-500 nm. The present approach demonstrates its potential for low-temperature, large-scale, controlled synthesis of crystalline hierarchical ZnO nanostructures films.     

Photoluminescence characteristics from amorphous SiC thin films with various structures deposited at low temperature

Hydrogenated amorphous SiC thin films deposited at low substrate temperature (100 °C) show the different bonding configurations and microstructures which depend on the carbon concentrations in the films controlled by the gas ratio R of methane to silane during the deposition. Photoluminescence characteristics are investigated for these samples with different structures. A strong luminescence in red light region can be observed for samples deposited with low gas ratio R which is significantly reduced its intensity with increasing the carbon concentrations in the films. On the other hand, the luminescence bands located at blue-green light region are detected under UV light excitation for samples deposited with high gas ratio R, which can be associated with the existence of amorphous SiC clusters in the films.     

Structure and gas-barrier properties of amorphous hydrogenated carbon films deposited on inner walls of cylindrical polyethylene terephthalate by plasma-enhanced chemical vapor deposition

The influence of radio-frequency (RF) power on the structure and gas permeation through amorphous hydrogenated carbon films deposited on cylindrical polyethylene terephthalate (PET) samples is investigated. The results show that a higher radio-frequency power leads to a smaller sp³/sp² value but produces fewer defects with smaller size. The permeability of PET samples decreases significantly after a-C:H deposition and the RF only exerts a small influence. However, the coating uniformity, color, and wettability of the surface are affected by the RF power. A higher RF power results in to better uniformity and it may be attributed to the combination of the high-density plasma and sample heating.     

In situ ellipsometry study of atomic hydrogen etching of extreme ultraviolet induced carbon layers

Atomic hydrogen based etching is generally considered an efficient method for the removal of carbon films resulting from photo-induced hydrocarbon dissociation, as occurs in extreme ultraviolet (EUV) photolithography environments. The etch rate of atomic hydrogen for three different kinds of carbon films was determined, namely for EUV-induced carbon, hot filament evaporated carbon and e-beam evaporated carbon. The etching process was monitored in situ by spectroscopic ellipsometry. The etch rate was found to depend on the type of carbon (polymer or graphite-like), on the layer thickness, and on the temperature. The EUV-induced carbon shows the highest etch rate, with a value of ∼0.2 nm/min at a sample temperature of 60 °C. The more graphite-like carbon layers showed an etch rate that was about 10 times lower at this temperature. An activation energy of 0.45 eV was found for etching of the EUV-induced carbon layer.     

Strong influence of substrate temperature on the growth of nanocrystalline MoO3 thin films

Nanocrystalline MoO₃ thin films are prepared by electron beam evaporation technique. By using the dry MoO₃ pellets, the films are deposited on quartz substrates at substrate temperatures ranging from 100 °C to 400 °C. A phase structure of β-MoO₃ at the substrate temperature 200 °C is characterized by X-ray diffraction, but α-MoO₃ comes forth at 300 °C and 400 °C. The surface morphology, cross section view and plate form nanostructures have been illustrated from the scanning electron microscope images. The absorption spectra of films show that the energy band Eg decreases with the increasing substrate temperature, due to the increase in oxygen vacancy. The resistances of thin films prepared at various substrate temperatures gradually decrease with the increasing environmental temperatures.     

The influence of substrate temperature on the morphology, optical and electrical properties of thermal-evaporated ZnTe Thin Films

The structural, morphological, optical and electrical properties of ZnTe films deposited by evaporation were investigated as a function of substrate temperature (at −123 and 27 °C) and post-deposition annealing temperature (at 200, 300 and 400 °C). It was determined that films deposited at both substrate temperatures were polycrystalline in nature with zinc-blende structure and a strong (1 1 1) texture. A small Te peak was detected in XRD spectra for both substrate temperatures, indicating that as-deposited ZnTe films were slightly rich in Te. Larger grains and a tighter grain size distribution were obtained with increased substrate temperature. Scanning electron microscopy (SEM) studies showed that the microstructures of the as-deposited films agreed well with the expectations from structure zone model. Post-deposition annealing induced further grain growth and tightened the grain size distribution. Annealing at 400 °C resulted in randomization in the texture of films deposited at both substrate temperatures. Optical spectroscopy results of the films indicated that the optical band gap value increased from 2.13 to 2.16 eV with increased substrate temperature. Increasing the annealing temperature sharpened the band-edge. Resistivity measurements showed that the resistivity of films deposited at substrate temperatures of −123 and 27 °C were 32 Ω cm, and 1.0 × 10⁴ Ω cm, respectively with corresponding carrier concentrations of 8.9 × 10¹⁵ cm⁻³ and 1.5 × 10¹⁴ cm⁻³. Annealing caused opposite changes in the film resistivity between the samples prepared at substrate temperatures of −123 and 27 °C.