Nanosecond UV laser graphitization and delamination of thin tetrahedral amorphous carbon films with different sp/sp content

We have produced hydrogen-free tetrahedral amorphous carbon films with different densities and Young's modulus by coating silicon with a filtered vacuum arc under different angles. The films were modified with a pulsed laser (wavelength 355 nm) into sp² rich amorphous carbon and nano crystalline carbon films. The graphitization threshold of the films depends on the film thickness as well as on the carbon density. Simulations of the optical absorption of the different carbon films permitted to confirm the experimental results. On the other side, the delamination threshold of carbon films increases with the film thickness and was found to be controlled by thermal properties of the film. The thin film graphitization and delamination is investigated by optical microscopy, atomic force microscopy, scanning electron microscopy and Raman spectroscopy.     

Improvement of adhesion of DLC coating on nitinol substrate by hybrid ion beam deposition technique

Diamond-like carbon (DLC) films were prepared for a protective coating on nitinol substrate by hybrid ion beam deposition technique with an acetelene as a source of hydrocarbon ions. An amorphous silicon (a-Si) interlayer was deposited on the substrates to ensure better adhesion of the DLC films followed by Ar ion beam treatment. The film thickness increased with increase in ion gun anode voltage. The residual stresses in the DLC films decreased with increase in ion gun anode voltage and film thickness, while the stress values were independent of the radio frequency (RF) bias voltage. The adhesion of the DLC film was improved by surface treatment with argon ion beam for longer time and by increasing the thickness of a-Si interlayer.     

Homogeneous nanocrystalline cubic silicon carbide films prepared by inductively coupled plasma chemical vapor deposition

Silicon carbide films with different carbon concentrations x(C) have been synthesized by inductively coupled plasma chemical vapor deposition from a SiH(4)/CH(4)/H(2) gas mixture at a low substrate temperature of 500?°C. The characteristics of the films were studied by x-ray photoelectron spectroscopy, x-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, Fourier transform infrared absorption spectroscopy, and Raman spectroscopy. Our experimental results show that, at x(C) = 49?at.%, the film is made up of homogeneous nanocrystalline cubic silicon carbide without any phase of silicon, graphite, or diamond crystallites/clusters. The average size of SiC crystallites is approximately 6?nm. At a lower value of x(C), polycrystalline silicon and amorphous silicon carbide coexist in the films. At a higher value of x(C), amorphous carbon and silicon carbide coexist in the films.     

Nanoindentation and AFM studies of PECVD DLC and reactively sputtered Ti containing carbon films

Amorphous carbon film, bdalso known as DLC film, bdis a promising material for tribological application. It is noted that properties relevant to tribological application change significantly depending on the method of preparation of these films. These properties are also altered by the composition of the films. In view of this, bdthe objective of the present work is to compare the nanoindentation and atomic force microscopy (AFM) study of diamond like carbon (DLC) film obtained by plasma enhanced chemical vapour deposition (bdPECVD with the Ti containing amorphous carbon (Ti/a- C : H) film obtained by unbalanced magnetron sputter deposition (UMSD). Towards that purpose, DLC and Ti/a- C : H films are deposited on silicon substrate by PECVD and UMSD processes, respectively. The microstructural features and the mechanical properties of these films are evaluated by scanning electron microscopy (SEM), bdtransmission electron microscopy (TEM), nanoindentation and by AFM. The results show that the PECVD DLC film has a higher elastic modulus, hardness and roughness than the UMSD Ti/a- C : H film. It also has a lower pull off force than Ti containing amorphous carbon film.     

用PECVD工艺制备功能装饰氧化硅薄膜的性能

用PECVD技术制备氧化硅薄膜,研究了生成样品的位置对薄膜成分、结构和性能的影响,探讨了制备兼具高透光性和耐刮擦性的功能装饰氧化硅薄膜的方法。结果表明,在阳极位置生成的薄膜具有Si(CH3)nO有机氧化硅结构,在380~780 nm波长范围内透光率高达90%~98%,但是薄膜的结构疏松,硬度仅为2 GPa。提高制备温度可使薄膜硬度提高至6 GPa,但是透光率略有降低;在阴极位置生成的薄膜具有无机氧化硅复合非晶碳结构,薄膜结构致密,硬度可达15 GPa,但是在380~780 nm波长范围内透光性差;增加O2反应气体可促使碳与氧反应生成二氧化碳,非晶碳结构消失,薄膜透光率提高到99%,但是硬度降低到9 GPa。     

Synthesis of carbon nanofiber films and nanofiber composite coatings by laser-assisted catalytic chemical vapor deposition

Uniform carbon nanofiber films and nanofiber composite coatings were synthesized from ethylene on nickel coated alumina substrates by laser-assisted catalytic chemical vapor deposition. Laser annealing of a 50 nm thick nickel film produced the catalytic nanoparticles. Thermal decomposition of ethylene over nickel nanoparticles was initiated and maintained by an argon ion laser operated at 488 nm. The films were examined by scanning electron microscopy and by transmission electron microscopy. Overall film uniformity and structure were assessed using micro-Raman spectroscopy. Film quality was related to the experimental parameters such as incident laser power density and irradiation time. For long irradiation times, carbon can be deposited by a thermal process rather than by a catalytic reaction directly over the nanofiber films to form carbon nanocomposite coatings. The process parameters leading to high quality nanofiber films free of amorphous carbon by-products as well as those leading to nanofiber composite coatings are presented.     

Ag掺杂非晶碳膜结构、力学与电学行为研究

采用反应磁控溅射技术, 通过改变溅射靶电流实现了不同Ag掺杂含量0.7at%~41.4at%非晶碳膜(a-C:Ag)的可控制备, 并系统研究了Ag含量对薄膜组分、结构、机械特性的影响规律, 以及薄膜的电学特性。结果表明: 当Ag含量在0.7at%~1.2at%时, Ag原子固溶于非晶碳基质; 当Ag含量在13.0at%~41.4at%范围, 薄膜中出现尺寸约为6 nm的Ag纳米晶。随着Ag含量增加, 碳网络结构的sp ²团簇尺寸增大, 结构无序度降低。应力测试表明, 在低Ag含量范围, Ag原子固溶于碳膜网络结构中, 起到枢纽作用, 促进碳网络结构键长、键角畸变弛豫, 从而降低薄膜应力。随着Ag含量增加, 部分Ag原子将形成Ag纳米晶粒, 薄膜通过Ag纳米晶与非晶碳界面处的滑移以及扩散作用释放过高的畸变能降低应力。Ag含量为37.8at%时, 在11.6 K附近, 薄膜出现金属-半导体特性转变。而Ag含量为41.4at%的薄膜, 在2~400 K测试温度范围内, 均表现为半导体特性, 其中在164~400 K范围内, 薄膜表现出典型的热激活导电机制。     

Structural and biocompatible characterization of TiC/a:C nanocomposite thin films

In this work, sputtered TiC/amorphous C thin films have been developed in order to be applied as potential barrier coating for interfering of Ti ions from pure Ti or Ti alloy implants. Our experiments were based on magnetron sputtering method, because the vacuum deposition provides great flexibility for manipulating material chemistry and structure, leading to films and coatings with special properties. The films have been deposited on silicon (001) substrates with 300 nm thick oxidized silicon sublayer at 200 °C deposition temperature as model substrate. Transmission electron microscopy has been used for structural investigations. Thin films consisted of ~ 20 nm TiC columnar crystals embedded by 5 nm thin amorphous carbon matrix. MG63 osteoblast cells have been applied for in vitro study of TiC nanocomposites. The cell culture tests give strong evidence of thin films biocompatibility.     

Carbon nanotube arrays for optical design of amorphous silicon solar cells

Effective light trapping is essential for the conversion efficiency increase in thin film solar cells. Vertically aligned multiwalled carbon nanotubes (MWNTs) arrays with proper spacing form an ideal light trapping structure. In this work, we have demonstrated feasibility of the incorporation of MWNTs as back contact into amorphous silicon solar cells. Intrinsic amorphous silicon films were uniformly deposited onto vertically aligned MWNTs arrays. Scanning Electron Microscopy (SEM) was used to investigate the surface morphology of our films. The film surface area exposed to light was found to be increased dramatically due to the high-aspect ratio of MWNTs. Our findings open up a new way of managing light in thin film silicon solar cells by controlling the nano-geometry of MWNTs on substrates.     

Deposition of unhydrogenated amorphous carbon films by sublimation of C60 fullerene in electron beam excited plasma

C₆₀ fullerene clusters are used as a carbon source to deposit unhydrogenated amorphous carbon films. C₆₀ clusters are sublimated by heating up to 850 °C. The sublimated fullerene powders are injected to an electron beam excited argon plasma and dissociated to be active species. Consequently, the carbon species condense as a thin film on the negatively biased substrates that are immersed in the plasma. Deposition rates of approximately 1.0 µm/h and the average surface roughness of 0.2 nm are achieved. X-ray diffraction pattern reveals that the microstructure of the film is amorphous while fullerene film deposited without the plasma shows crystal structure. Raman spectroscopic analysis shows that the films are one of the types of diamond-like carbon films. The nano-indentation technique is used for hardness measurement of the films and results in hardness up to about 20 GPa.     

Synthesis and characterization of carbon/silica superhydrophobic multi-layer films

C/SiO₂ multi-layer films (3-layer films and 5-layer films) were obtained by sol-gel method and physical deposition on glass plates, and then heated at 500 °C for 1 h under a nitrogen atmosphere. The mechanical adhesive force with the substrate of the multi-layer films was sharply enhanced compared to the as-deposited amorphous carbon film. An absorption layer was formed on heat treated C/SiO₂ multi-layer films by modification of the surface with trimethylchlorosilane, and the wettability of the films changed from hydrophilic to super-hydrophobic. The structures of the physically deposited carbon and the multi-layer films were analyzed by X-ray diffraction, transmission electron microscopy and scanning electron microscopy. The experimental results showed that the 5-layer films had a concentric ring structure that caused the film to be superhydrophobic.     

The evolution of well-aligned amorphous carbon nanotubes and porous ZnO/C core-shell nanorod arrays for photosensor applications

Well-aligned amorphous carbon nanotube (a-CNT) and porous ZnO/C core-shell nanorod (NR) arrays were fabricated for the first time by a proposed deposition-etching-evaporation (DEE) route. The arrays were prepared by deposition of carbon on the surface of well-aligned ZnO NR arrays by thermal decomposition of acetone followed by spontaneous etching and evaporation of core-ZnO. By utilizing the decomposition of acetone as well as distinct degrees of interaction between intermediate products and ZnO, well-aligned nonporous ZnO/C core-shell NR, porous ZnO/C core-shell NR, and a-CNT arrays were separately prepared by varying the working temperature from 400 to 700?°C. Scanning electron microscopy and high-resolution transmission electron microscopy show that the thickness of carbon shells increases from 3 to 10 nm with the increase in working temperature. Raman spectra demonstrate slight sp(2) bonds of carbon, indicating small graphite regions embedded in amorphous carbon nanoshells. The E(2) peaks of ZnO reduce with the increase in substrate temperature. Photoresponse measurements of ZnO/C NR arrays shows enhancement of both photoresponsivity and response velocity, and the interference of humidity with regard to photosensing is effectively reduced by the capping of carbon nanoshells. The work not only provides an effective route to improve the photosensing of semiconductor nanomaterials for practical applications, but also sheds light on preparing various hollow carbon and porous ZnO/C core-shell nanostructures with distinct morphologies by employing the routes presented in the paper on diverse ZnO nanostructures for optoelectrochemical applications.     

Thin film deposition on plastic substrates using silicon nanoparticles and laser nanoforming

Reduced melting temperature of nanoparticles is utilized to deposit thin polycrystalline silicon (c-Si) films on plastic substrates by using a laser beam without damaging the substrate. An aqueous dispersion of 5 nm silicon nanoparticles was used as precursor. A Nd:YAG (1064 nm wavelength) laser operating in continuous wave (CW) mode was used for thin film formation. Polycrystalline Si films were deposited on flexible as well as rigid plastic substrates in both air and argon ambients. The films were analyzed by optical microscopy for film formation, scanning electron microscopy (SEM) for microstructural features, energy dispersive spectroscopy (EDS) for impurities, X-ray photoelectron spectroscopy (XPS) for composition and bond information of the recrystallized film and Raman spectroscopy for estimating shift from amorphous to more crystalline phase. Raman spectroscopy showed a shift from amorphous to more crystalline phases with increasing both the laser power and irradiation time during laser recrystallization step.     

Fullerene C60 coated silicon nanowires as anode materials for lithium secondary batteries

A Fullerene C60 film was introduced as a coating layer for silicon nanowires (Si NWs) by a plasma assisted thermal evaporation technique. The morphology and structural characteristics of the materials were studied by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). SEM observations showed that the shape of the nanowire structure was maintained after the C60 coating and the XPS analysis confirmed the presence of the carbon coating layer. The electrochemical characteristics of C60 coated Si NWs as anode materials were examined by charge-discharge tests and electrochemical impedance measurements. With the C60 film coating, Si NW electrodes exhibited a higher initial coulombic efficiency of 77% and a higher specific capacity of 2020 mA h g(-1) after the 30th cycle at a current density of 100 microA cm(-2) with cut-off voltage between 0-1.5 V. These improved electrochemical characteristics are attributed to the presence of the C60 coating layer which suppresses side reaction with the electrolyte and maintains the structural integrity of the Si NW electrodes during cycle tests.     

Formation mechanism of nano-diamond films from energetic species: From experiment to theory

In this paper, a particular class of nano-diamond films deposited by energetic species is described. Deposition is carried out using the direct-current glow-discharge (DC GD) deposition technique from a methane/hydrogen mixture. In this method, film growth occurs from energetic species being accelerated and incorporated into the film surface. The growth of the nano-diamond film occurs on top of a preferentially oriented graphitic precursor with its basal planes perpendicular to the substrate surface. The nano-diamond films consist of an agglomerate of diamond particles with particle sizes in the 3-5 nm range with amorphous grain boundaries. The hydrogen concentration in the graphitic precursor is only a few percent; however, it increases to ∼15-20 at.% in the nano-diamond film.From a microscopic perspective nano-diamond film and growth from energetic species is explained as a sub-surface process in terms of a four-step cyclic process. The DC GD-deposited nano-diamond films were comprehensively explored by a number of complementary techniques. The hydrogen content and its role in nano-diamond film formation were assessed. The experimental methods used in our studies comprise near-edge X-ray adsorption fine structure (NEXAFS) to prove the short-range coordination of the carbon films and indirectly their phase composition. The surface and grain boundary phase composition were investigated by a combination of electron energy loss spectroscopy (EELS) measured as a function of incident electron energy and hydrogen etching experiments. By transmission electron microscopy (TEM), the micro-structural evolution and their visualization were achieved. The density evolution of the films was determined by X-ray reflectivity (XRR). The hydrogen content and its distribution in the films were studied by secondary ion microscopy spectroscopy (SIMS) and elastic recoil detection (ERD). The hydrogen bonding was investigated by high-resolution electron energy loss spectroscopy (HREELS).Most likely, hydrogen is bonded within the amorphous grain boundaries and saturates the nano-diamond particles. The surface of the films is amorphous in nature.     

Synthesis of TaZnO thin films using combinatorial magnetron sputtering and its electrical, structural and optical properties

The structural, electrical, and optical properties of tantalium zinc oxide (TaZnO) thin films grown using combinatorial magnetron sputtering system were investigated. To explore the effects of film thickness and post annealing treatment on the properties of the films, we have fabricated TaZnO sample libraries having different thicknesses and carried out post annealing treatment. Sample libraries fabricated at room temperature showed the resistivity ranged 2.1 to approximately 7.1 x 10(-3) Omega cm, while the films post annealed at 200 degrees C under 1 mTorr exhibited the resistivity as low as 1.2 x 10(-3) Omega cm. XRD measurements revealed that the film structure was strongly depended on the film thickness, showing that the structure was changed from amorphous to polycrystalline with increasing the film thickness. Furthermore, it was found that figure of merit (0TC), which was determined by T% and Rs of the TaZnO films, showed maximum value as the films with a thickness of 230 nm was post-annealed at 200 degrees C under vacuum of 1 mTorr.     

Morphology and texture evolution of nanostructured CaF2 films on amorphous substrates under oblique incidence flux

The morphology and biaxial texture of vacuum evaporated CaF(2) films on amorphous substrates as a function of vapour incident angle, substrate temperature and film thickness were investigated by scanning electron microscopy, x-ray pole figure and reflection high energy electron diffraction surface pole figure analyses. Results show that an anomalous [220] out-of-plane texture was preferred in CaF(2) films deposited on Si substrates at < 200?°C with normal vapour incidence. With an increase of the vapour incident angle, the out-of-plane orientation changed from [220] to [111] at a substrate temperature of 100?°C. In films deposited with normal vapour incidence, the out-of-plane orientation changed from [220] at 100?°C to [111] at 400?°C. In films deposited with an oblique vapour incidence at 100?°C, the texture changed from random at small thickness (5 nm) to biaxial at larger thickness (20 nm or more). Using first principles density functional theory calculation, it was shown that [220] texture formation is a consequence of energetically favourable adsorption of CaF(2) molecules onto the CaF(2)(110) facet.     

Influence of annealing temperature on the structural, mechanical and wetting property of TiO2 films deposited by RF magnetron sputtering

TiO₂ films have been deposited on silicon substrates by radio frequency magnetron sputtering of a pure Ti target in Ar/O₂ plasma. The TiO₂ films deposited at room temperature were annealed for 1 h at different temperatures ranging from 400 °C to 800 °C. The structural, morphological, mechanical properties and the wetting behavior of the as deposited and annealed films were obtained using Raman spectroscopy, atomic force microscopy, transmission electron microscopy, nanoindentation and water contact angle (CA) measurements. The as deposited films were amorphous, and the Raman results showed that anatase phase crystallization was initiated at annealing temperature close to 400 °C. The film annealed at 400 °C showed higher hardness than the film annealed at 600 °C. In addition, the wettability of film surface was enhanced with an increase in annealing temperature from 400 °C to 800 °C, as revealed by a decrease in water CA from 87° to 50°. Moreover, the water CA of the films obtained before and after UV light irradiation revealed that the annealed films remained more hydrophilic than the as deposited film after irradiation.     

Thermal stability of magnetron sputtering amorphous carbon nitride films

Magnetron sputtered amorphous carbon nitride films were annealed at different temperatures (450-900°C) and time (30-120 min). Compositional, bonding structural and surface morphological modifications of the films were characterized by Fourier transformation infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy. The as-deposited film was found to have nitrogen content of 30 at%, and the carbon atoms were bonded to nitrogen atoms in the chemical structure state of CN, CN and CN bonds. The FTIR and XPS results showed that the films were thermally stable without an obvious change in the films as annealing temperature was lower than 600°C. The relative intensity ratio of CN over CN bonds reached a maximum at annealing temperature of 750°C, and then decreased gradually at annealing temperature up to 900°C. The CN bonds in the films decreased with the increase of annealing temperature and eliminated completely at annealing temperature of 900°C. These results revealed that annealing caused a substantial decrease in the number of weak bonds between carbon and nitride atoms. The CN bonds have higher thermal stability than CN bonds and CN bonds in the films. Simultaneously annealing also led to the formation of a large fraction graphitic-like carbon in the films while nitrogen escaped from the film. Besides, the surface roughness of the films increased with annealing temperature. However, when annealing time was increased from 30 to 120 min at annealing temperature of 750°C, only a slight effect of the annealing time on composition, bonding structure and the surface roughness of the films was observed.     

Optical transmission through hexagonal arrays of subwavelength holes in thin metal films

We have studied the light transmission through hexagonal arrays of subwavelength holes in thin gold and aluminum films, varying the film thickness between 20 and 120 nm while the hole diameter as well as the interhole distance have been kept constant at approximately 300 and approximately 500 nm, respectively. The films were characterized by means of UV-vis spectroscopy and scanning near-field optical microscopy (SNOM).