Microstructure of highly oriented, hexagonal, boron nitride thin films grown on crystalline silicon by radio frequency plasma-assisted chemical vapor deposition

We present a high‐resolution electron microscopy study of the microstructure of boron nitride thin films grown on silicon (100) by radio‐frequency plasma‐assisted chemical vapor deposition using B2H6 (1% in H2) and NH3 gases. Well‐adhered boron nitride films grown on the grounded electrode show a highly oriented hexagonal structure with the c‐axis parallel to the substrate surface throughout the film, without any interfacial amorphous layer. We ascribed this textured growth to an etching effect of atomic hydrogen present in the gas discharge. In contrast, films grown on the powered electrode, with compressive stress induced by ion bombardment, show a multilayered structure as observed by other authors, composed of an amorphous layer, a hexagonal layer with the c‐axis parallel to the substrate surface and another layer oriented at rando

In situ spectroellipsometric study of the nucleation and growth of amorphous silicon

A detailed in situ spectroellipsometric analysis of the nucleation and growth of hydrogenated amorphous silicon (a:Si:H) is presented. Photoelectronic quality a‐Si:H films are deposited by plasma‐enhanced chemical vapor deposition on smooth metal (NiCr alloy) and crystalline silicon (c‐Si) substrates. The deposition of a‐Si:H is analyzed from the first monolayer up to a final thickness of 1.2 μm. In order to perform an improved analysis, real time ellipsometric trajectories are recorded, using fixed preparation conditions, at various photon energies ranging from 2.2 to 3.6 eV. The advantage of using such a spectroscopic experimental procedure is underlined. New insights into the nucleation and growth mechanisms of a‐Si:H are obtained. The nucleation mechanism on metal and c‐Si substrates is very accurately described assuming a columnar microstructural development during the early stage of the growth. Then, as a consequence of the incomplete coalescence of the initial nuclei, a surface roughness at the 10-15 Å scale is identified during the further growth of a‐Si:H on both substrates. The bulk a‐Si:H grows homogeneously beneath the surface roughness. Finally, an increase of the surface roughness is evidenced during the long term growth of a‐Si:H. However, the nature of the substrate influenced the film growth. In particular, the film thickness involved in the nucleation‐coalescence phase is found lower in the case of c‐Si (67±8 Å) as compared to NiCr (118±22 Å). Likewise films deposited on c‐Si present a smaller surface roughness even if thick samples are considered (>1 μm). More generally, the present study illustrates the capability of in situ spectroellipsometry to precisely analyze fundamental processes in thin‐film growth, but also to monitor the preparation of complex structures on a few monolayers scale

Influence of pressure and radio frequency power on deposition rate and structural properties of hydrogenated amorphous silicon thin films prepared by plasma deposition

The influence of radio frequency (rf) power and pressure on deposition rate and structural properties of hydrogenated amorphous silicon (a-Si:H) thin films, prepared by rf glow discharge decomposition of silane, have been studied by phase modulated ellipsometry and Fourier transform infrared spectroscopy. It has been found two pressure regions separated by a threshold value around 20 Pa where the deposition rate increases suddenly. This behavior is more marked as rf power rises and reflects the transition between two rf discharges regimes. The best quality films have been obtained at low pressure and at low rf power but with deposition rates below 0.2 nm/s. In the high pressure region, the enhancement of deposition rate as rf power increases first gives rise to a reduction of film density and an increase of content of hydrogen bonded in polyhydride form because of plasma polymerization reactions. Further rise of rf power leads to a decrease of polyhydride bonding and the material density remains unchanged, thus allowing the growth of a-Si:H films at deposition rates above 1 nm/s without any important detriment of material quality. This overcoming of deposition rate limitation has been ascribed to the beneficial effects of ion bombardment on the a-Si:H growing surface by enhancing the surface mobility of adsorbed reactive species and by eliminating hydrogen bonded in polyhydride configurations

Effect of a Balanced Concentration of Hydrogen on Graphene CVD Growth

The extraordinary properties of graphene make it one of the most interesting materials for future applications. Chemical vapor deposition (CVD) is the syntheticmethod that permits obtaining large areas ofmonolayer graphene. To achieve this, it is important to find the appropriate conditions for each experimental system. In our CVD reactor working at low pressure, important factors appear to be the pretreatment of the copper substrate, considering both its cleaning and its annealing before the growing process.The carbon precursor/hydrogen flow ratio and its modification during the growth are significant in order to obtain large area graphene crystals with few defects. In this work, we have focused on the study of the methane and the hydrogen flows to control the production of single layer graphene (SLG) and its growth time. In particular, we observe that hydrogen concentration increases during a usual growing process (keeping stable the methane/hydrogen flow ratio) resulting in etched domains. In order to balance this increase, a modification of the hydrogen flow results in the growth of smooth hexagonal SLG domains. This is a result of the etching effect that hydrogen performs on the growing graphene. It is essential, therefore, to study the moderated presence of hydrogen

Anisotropic surface properties of micro/nanostructured a-C:H:F thin films with self-assembly applications

The singular properties of hydrogenated amorphous carbon (a-C:H) thin filmsdeposited by pulsed DC plasma enhanced chemical vapor deposition (PECVD), such as hardness and wear resistance, make it suitable as protective coating with low surface energy for self-assembly applications. In this paper, we designed fluorine-containing a-C:H (a-C:H:F) nanostructured surfaces and we characterized them for self-assembly applications. Sub-micron patterns were generated on silicon through laser lithography while contact angle measurements, nanotribometer, atomic force microscopy (AFM), and scanning electron microscopy (SEM) were used to characterize the surface. a-C:H:F properties on lithographied surfaces such as hydrophobicity and friction were improved with the proper relative quantity of CH4 and CHF3 during deposition, resulting in ultrahydrophobic samples and low friction coefficients. Furthermore, these properties were enhanced along the direction of the lithographypatterns (in-plane anisotropy). Finally, self-assembly properties were tested with silicananoparticles, which were successfully assembled in linear arrays following the generated patterns. Among the main applications, these surfaces could be suitable as particle filter selector and cell colony substrate

Homogeneous Fe2O3 coatings on carbon nanotube structures for supercapacitors

The combination of carbon nanotubes with transition metal oxides can exhibit complementary charge storage properties for use as electrode materials for next generation energy storage devices. One of the biggest challenges so far is to synthesize homogeneous oxide coatings on carbon nanotube structures preserving their integrity. Here we present the formation of conformal coatings of Fe2O3 on vertically aligned carbon nanotubes obtained by atomic layer deposition. We investigate the effect of pristine, nitrogen plasma and water plasma treated carbon nanotube surfaces on the ALD-growth of Fe2O3 using ferrocene and ozone precursors. The surface morphology, coating thickness, microstructure and surface chemistry of iron oxide-carbon nanotube composites and their ultimate influence on the electrochemical behavior of the composites are evaluated. The most effective surface functionalization is that achieved by H2O plasma treatment, whereas untreated carbon nanotubes, despite the lack of active sites in the starting pristine surface, can be coated with an inhomogeneous Fe2O3 film

Ultrafine particles produced by plasma enhanced chemical vapor deposition -from SiH4, CH4, NH3 and B2H6 gas mixtures- for nanostructured ceramics applications

[eng] Ultrafine particles of silicon and related binary and ternary alloys of the Si-B-C-N system produced in our research group from silane, methane, diborane, ammonia and nitrogen precursor gases by plasma enhanced chemical vapor deposition at low pressure and room temperature are reviewed. The in-situ techniques of plasma analysis and surface characterization (quadrupolar mass spectrometry, optical emission spectroscopy and ellipsometry) providing evidence of powder formation and the polymerization reactions based on the SinH2n- negative radicals electrically confined in the plasma sheath are described. The square wave modulation (SQWM) of the rf power is discussed as an efficient method of controlling the powder particle production with low particle-size dispersion. The properties of the powder particles determined by different structural characterization techniques providing their size and distribution, crystalline order and morphology, chemical composition and chemical bond vibrational characteristics, are analyzed and discussed[cat] Hom presenta una revisió sobre les partícules ultrafines de silici i els seus aliatges binaris i ternaris del sistema Si-B-C-N, produïdes en el nostre grup de recerca a partir dels gasos precursors silà, metà, diborà, amoníac i nitrogen, per dipòsit químic en fase vapor (CVD) reforçat per plasma, a baixa pressió i temperatura ambient. És descrita també la utilització de tècniques in situ d'anàlisi per plasma i de caracterització de superfícies (espectroscòpia de masses quadripolar, espectroscòpia òptica d’emissió i el·lipsometria), que donaren l’evidència de formació de partícules de pols i de reaccions de polimerització basades en radicals negatius SinH2n– confinats elèctricament en l’embolcall del plasma. La modulació d’ona quadrada (SQWM) de la font de rf és estudiada com un eficient mètode de control de la producció de partícules amb una petita dispersió de llurs dimensions. Finalment, hom analitza i discuteix les propietats de les partícules produïdes, determinades per diferents tècniques de caracterització, que permeteren obtenir llurs dimensions i distribució, ordre cristal·lí i morfologia, composició química i les característiques vibracionals dels enllaços químic

Laser induced nanostructuration of vertically aligned carbon nanotubes coated with nickel oxide nanoparticles

A facile method is explored to decorate vertically aligned multi-walled carbon nanotubes (VACNTs) with NiO nanostructures. Multi-walled VACNTs are grown by plasma enhanced chemical vapor deposition and coated with NiO nanoparticles (NPs) by drop casting and submitted to pulsed UV laser irradiation. Laser irradiation provokes rapid heating-melting-cooling processes which lead to the recrystallization of NiO NPs on the outer walls of VACNTs'. In this way, and depending on the laser fluence and the number of accumulated pulses, different nano-architectures such as continuous NiO coatings and spiny features are obtained. High resolution scanning and transmission electron microscopies and Raman spectroscopy, corroborated with photothermal simulations, suggest that the grown nanostructures are mainly created by the laser-induced high temperatures and catalytic action of NiO NPs

Nanostructured DLC coatings for self-assembly applications

The singular characteristics of diamond-like carbon (DLC) thin films, concerning tribological and surfaces properties, are suitable for self-assembly applications. Usually, DLC thin films have been developed as protective coatings for sliding surfaces with relative motion. But, DLC coatings deposited on nanostructured surfaces also provide new potential for self-assembly applications. In particular, the addition of fluorine during the deposition of DLC deposited by pulsed DC plasma enhanced chemical vapor deposition (PECVD) has a significant effect on the surface energy and tribological characteristics, which accelerates the mechanisms involved in self-assembly processes. Among the multiple applications of DLC coatings we also found their biocompatibility and antithrombogenicity. Such properties make them candidates for a number of medical applications where wear-resistant coatings, such as prosthesis, or simply biocompatible parts are required

Temperature-modulated synthesis of vertically oriented atomic bilayer graphene nanowalls grown on stainless steel by inductively coupled plasma chemical vapour deposition

It is now clear that growing flat graphene nanostructures from the gas phase on planar substrates is possible. One of the keys to success ¿particularly in producing a very large specific surface in a reduced space¿ is the use of 3D carbon nanostructures (i.e., vertical graphene nanowalls, VGNWs) over a planar substrate as a growth template for the deposition of electrochemically active materials (as, for example, transition metal oxides (TMO)). Vertical graphene nanowalls, also known as petal-like, vertical graphene flakes or vertical graphene, can achieve a very large specific surface area of 1100 m2/g, which is comparable to or greater than that of carbon nanotubes ¿the reference material for its use in high-performance supercapacitors or in other energy-related applications requiring a large active surface area. Vertical graphene nanowalls also exhibit high vertical and in-plane electrical conductivity when grown on metal electrodes, which benefits their use in electrochemical applications. Here, we focus on the growth of VGNWs on flexible stainless-steel substrates (SS310), in principle suitable for applications to electrodes of electrochemical systems (batteries, supercapacitors, catalysts), by inductively coupled plasma chemical vapour deposition (ICP-CVD), from methane as a carbon precursor, in a wide range of temperatures (575 to 900 ◦C). We will discuss the effect of growth temperature on morphological and structural characteristics of VGNWs based on the results of Raman spectroscopy and field emission scanning electron microscopy (FE-SEM) analysis. Because the nanostructures of graphene nanowalls reported to date are, for the most part, based on multi-layered graphene, here we seek to highlight the effect of temperature on the number of atomic layers of VGNW. In the 700-750 ◦C range, and under the plasma conditions explored, vertical graphene nanowalls are bilayer, which is foreseen to directly affect the magnitude of the VGNW specific surface