Computational modeling of forced flow laser chemical vapor deposition

Laser chemical vapor deposition (LCVD) utilizes a laser to localize a CVD reaction. The process involves complex physical interactions within a very small spatial region. Experimental investigations into the dynamics of the LCVD process are limited by spatial and resolution capabilities of instrumentation. Models are developed herein using the computational fluid dynamics (CFD) code, FLUENT, that incorporate heat transfer, fluid flow, and species transport in a single integrated modeling environment. The models are used to study the carbon deposition process. Insight is gained into the relationships among the process parameters and the deposition rates and deposition rate profiles. Phenomena such as thermal diffusion and the relative importance of mass convection and mass diffusion are explored. A designed set of model cases is executed and the results are used to develop a simple polynomial expression for relating experiment conditions to deposit attributes. PACS 81.10.Bk; 81.05.Uw; 81.15.Gh; 47.50.Cd; 81.16.Mk     

Heat and mass-transfer modeling of an angled gas-jet LCVD system

Laser chemical vapor deposition (LCVD) is a new manufacturing process that holds great potential for the production of small and complex metallic, ceramic and composite parts. Since LCVD is a thermally activated process, the most important process variable is temperature. Therefore, a thermal model was developed for a gas-jet LCVD system, accounting for Gaussian-beam laser heating and gas-jet convection cooling. The forced convection cooling imposed by the gas-jet reagent delivery system was significant, accounting for a 15 to 20% change in the substrate temperature. The deposition rate for a given material is not only affected by temperature, but also by the mass transport of reagent gases. An angled gas-jet reagent supply was designed to aid mass transport, but the need and impact of such a system has been debated. Therefore, a two-dimensional mass-transport model was developed to estimate the effects of a gas jet with respect to local reagent concentration variations and reaction rates. Across all deposition regimes, the gas jet was found to be an effective tool for increasing the concentration of reagent gases at the surface of the substrate. The gas jet also generated higher deposition rates and increased deposit resolution for those processes severely limited by diffusion. PACS 05.60.-k; 44.27+g; 44.05+e     

VHF等离子体光发射谱(OES)的在线监测

采用光发射谱(OES)测量技术，对不同制备条件下的甚高频(VHF)等离子体辉光进行了在线监 测.实验表明，VHF等离子体中特征发光峰(Si，SiH,H_α,H^*_β 等)的强度较常规的射 频(RF)等离子体明显增强，并且在制备μc-Si：H的工艺条件下(H稀释度R(H₂/S iH₄)=23 )，随激发频率的增加而增大，这些发光峰的变化趋势与材料沉积速率的变化规律较相似.Si H峰等的强度随气压的变化则因硅烷H稀释度及功率的不同而异：高H稀释(R=23)时，SiH峰强 度在低辉光功率下随反应气压的增大单调下降，在高辉光功率下随气压的变化呈现类高斯规 律；低H稀释(R=5．7)时， SiH峰随气压的变化基本上是单调下降的，下降速率也与功率有 关，这些结果表明，VHF-PECVD制备μc-Si：H和a-Si：H的反应动力学过程存在较大差异.此 外，随着激发功率的增大，Si，SiH峰都先迅速增大然后趋于饱和，并且随着H稀释率的增大 ，将更快呈现饱和现象.通过对OES结果的分析与讨论可知，VHF-PECVD技术沉积硅基薄膜可 以有效提高沉积速率，而且，硅基薄膜的沉积速率的进一步提高需要综合考虑H稀释度、气 压和功率等的匹配与优化. 关键词： 甚高频等离子体化学气相沉积 氢化硅薄膜 光发射谱     

LCVD of tungsten microstructures on quartz

The pyrolytic laser-induced chemical vapor deposition (LCVD) of tungsten microstructures in the form of spots has been investigated. Fused quartz substrates and a mixture of WF₆ and H₂ have been employed in the experiments. Different shapes of spots related to different partial pressures of WF₆ and H₂ have been revealed. The results can qualitatively be described by a combination of surface reactions and gas-phase reactions resulting in tungsten deposition and surface etching.On leave from: Reserch Group on Laser Physics of the Hungarian Academy of Sciences, H-6720 Szeged, Dòm tér 9, Hungary     

Laser grown single crystals of silicon

Single crystal rods of silicon have been grown by laser-induced chemical vapor deposition (LCVD) using visible light. We believe these to be the first reported single crystals of any material grown by LCVD.     

Pulsed laser deposition of Er:BaTiO3 for planar waveguides

Laser radiation is used for the deposition of dielectric erbium doped BaTiO₃ thin films for photonic applications. Pulsed laser deposition with KrF excimer laser radiation (wavelength 248 nm, pulse duration 20 ns) is used to grow dense, transparent, amorphous, poly-crystalline and single crystalline erbium doped BaTiO₃ thin films. Visible emission due to up-conversion luminescence (wavelength 528 nm and 548 nm) under excitation with diode laser radiation at a wavelength of 970–985 nm is investigated as a function of the erbium concentration of 1–20 mol% and structural film properties. PACS 81.15.Fg; 42.55.Wd; 68.55; 78.55.Hx     

Direct writing of carbon nanotube patterns by laser-induced chemical vapor deposition on a transparent substrate

Dot array and line patterns of multi-walled carbon nanotubes (MWCNTs) were successfully grown by laser-induced chemical vapor deposition (LCVD) on a transparent substrate at room temperature. In the proposed technique, a Nd:YVO₄ laser with a wavelength of 532 nm irradiates the backside of multiple catalyst layers (Ni/Al/Cr) through a transparent substrate to induce a local temperature rise, thereby allowing the direct writing of dense dot and line patterns of MWCNTs below 10 μm in size to be produced with uniform density on the controlled positions. In this LCVD method, a multiple-catalyst-layer with a Cr thermal layer is the central component for enabling the growth of dense MWCNTs with good spatial resolution.     

AgAsS2 amorphous chalcogenide films prepared by pulsed laser deposition

A pulsed laser deposition technique has been applied to prepare amorphous ternary Ag–As–S films without an annealing process after the deposition. The films were prepared from AgAsS₂ bulk glass using a KrF excimer laser. Energy-dispersive X-ray analysis and Rutherford backscattering were used to obtain the composition of the studied films. VASE ellipsometry has been used to determine optical properties and homogeneity of the index of refraction. Comparison of two models is presented. PACS 78.66.Jg; 81.15.Fg; 81.40.Wx     

Preparation and characterization of La0.8Sr0.2MnO3 thin films by an excimer laser MOD process for a bolometer

La_0.8Sr_0.2MnO₃ (LSMO) films were prepared on LaAlO₃ substrates by excimer laser metal organic deposition (ELMOD) at 500 °C. The temperature dependence of resistance of the LSMO films was investigated by changing the laser fluence, irradiation time, and film thickness. It was found that the resistance of the LSMO films 80 nm in thickness that were irradiated by an ArF laser at a fluence of 100 mJ/cm² for 60 min showed a metallic temperature dependence, and the maximum temperature coefficient of resistance of the films (defined as 1/R×dR/dT) was 3.4% at 265 K. PACS 81.15.-z; 81.15.Fg; 81.15.Np; 73.61.-r; 71.30.+h     

Gas phase versus surface contributions to photolytic laser chemical vapor deposition rates

The rate of cwphotolytic laser chemical vapor deposition (LCVD) of platinum is measured for 350 nm as a function of the light intensity and the metalorganic vapor pressure. The growth of the metal films is studied in situ and in real time by monitoring their optical transmission. At low intensities the transmitted light decreases monotonically with time, and the LCVD process is photolytic with its rate limiting step in the surface adlayer. At higher intensities we observe two distinct time domains: Relatively slow initial photolytic deposition with its rate limiting step in the gas phase, which is followed by much faster pyrolytic LCVD. An improved method for distinguishing between adlayer and gas-phase limiting processes is demonstrated. These observations are confirmed by studying the photolytic deposition rates while varying the thickness of the adlayer.     

Microstructural investigation of CaxCo4Sb12 films prepared by pulsed laser deposition

Ca_xCo₄Sb₁₂ skutterudite thin films have been synthesized by pulsed laser deposition from a Nd:YAG laser working at 532 or 355 nm. The influence of deposition temperature, laser fluence and working atmosphere on the structure and morphology of the films has been studied. The characterization has been carried out by X-ray diffraction, atomic force microscopy and scanning electron microscopy. Laser wavelength proved to be the most significant parameter to produce the skutterudite phase. PACS 81.15.Fg; 68.55.Jk; 81.05.Bx     

Silicon fibers produced by high-pressure LCVD

Using a unique fiber-growth control mechanism and high-reaction pressures (>1 bar), silicon fibers were grown by laser-assisted chemical vapor deposition (LCVD) from silane near the focal point of a cw Nd:YAG laser beam. Fiber-growth rates ranged from <1 to 500 m/s and fiber tip temperatures from 525 to 1412° C. At low fibertip temperatures (<600° C) silicon fibers yielding glassy fracture were obtained. Some crystallinity was observed by X-ray diffraction. Polycrystalline silicon fibers were formed at intermediate temperatures, single-crystal silicon fibers at high-laser intensities and high-tip temperatures. The single crystal LCVD silicon fibers were formed by a vapor-liquid-solid (VLS) mechanism. Single-crystal VLS-LCVD silicon fibers were also obtained from liquid silicon-metal alloys by initiating fiber growth from the end of thin palladium, gold and platinum wires.     

Bonding configurations in amorphous carbon and nitrogenated carbon films synthesised by femtosecond laser deposition

The effect of nitrogen addition and laser fluence on the atomic structure of amorphous carbon films (a-C) synthesized by femtosecond pulsed laser deposition has been studied. The chemical bonding in the films was investigated by means of X-ray photoelectron (XPS) and Raman spectroscopies. XPS studies revealed a decrease in the sp³ bonded carbon sites and an associated increase in the N-sp²C bonding sites with increasing nitrogen content in the CN_x films. An increase in laser fluence from 0.36 to 1.7 J/cm² led to a rise in sp³C sites. These results were further confirmed by Raman spectroscopy. The I_D/I_G ratio increased monotonically and G line-width decreased with the increase of nitrogen content in the films indicating a rise in either the number or the size of the sp² clusters. Furthermore a visible excitation wavelength dependence study established the resonant Raman process in a-C and CN_x films. PACS 81.05.Uw; 81.15.Fg; 82.80     

Mode-specific effects in resonant infrared ablation and deposition of polystyrene

Low molecular weight polystyrene (∼10 kDa) was ablated with a free-electron laser at 3.31 and 3.43 μm and deposited as thin films on Si(100) substrates. The vibrational bands at 3.31 and 3.43 μm correspond to phenyl-ring CH and backbone CH₂ modes, respectively. Even though the absorption coefficients of these two modes are nearly the same, the ablation yield was approximately 50% higher for the ring-mode excitation compared with the backbone mode. Based on spectral line width, the ring-mode lifetime is approximately triple that of the backbone mode, leading to a higher spatiotemporal density of vibrational excitation that more effectively disrupts the relatively weak Van der Waals bonds between neighboring polymer chains and consequently to higher ablation efficiency of the ring mode. Molecular weight assays of the deposited films showed that relatively little bond scission occurred and that the average molecular weight of the films was similar to that of the starting material. PACS 61.41.+e; 78.30.-j; 81.05.Lg; 81.15.Fg     

Study of the gas-phase parameters affecting the silicon-oxide film deposition induced by an ArF laser

A study of the gas-phase parameters involved in ArF laser induced chemical vapour deposition of silicon-oxide thin films is presented. A complete set of experiments has been performed showing the influence of the concentration of the precursor gases, N₂O and SiH₄, and their influence on total and partial pressures on film growth and properties. In this paper we demonstrate the ability of this LCVD method to deposit silicon oxide films of different compositions and densities by appropriate control of gas composition and total pressure. Moreover, a material specific calibration plot comprising data obtained using different preparation techniques is presented, allowing determination of the stoichiometry of SiO _x films by using FTIR spectroscopy independently of the deposition method. For the range of processing conditions examined, the experimental results suggest that chemical processes governing deposition take place mainly in the gas phase.     

Growth of normally-immiscible materials (NIMs), binary alloys, and metallic fibers by hyperbaric laser chemical vapor deposition

This work demonstrates that two or more elements of negligible solubility (and no known phase diagram) can be co-deposited in fiber form by hyperbaric-pressure laser chemical vapor deposition (HP-LCVD). For the first time, Hg-W alloys were grown as fibers from mixtures of tungsten hexafluoride, mercury vapor, and hydrogen. This new class of materials is termed normally-immiscible materials (NIMs), and includes not only immiscible materials, but also those elemental combinations that have liquid states at exclusive temperatures. This work also demonstrates that a wide variety of other binary and ternary alloys, intermetallics, and mixtures can be grown as fibers, e.g. silicon-tungsten, aluminum-silicon, boron-carbon-silicon, and titanium-carbon-nitride. In addition, pure metallic fibers of aluminum, titanium, and tungsten were deposited, demonstrating that materials of high thermal conductivity can indeed be grown in three-dimensions, provided sufficient vapor pressures are employed. A wide variety of fiber properties and microstructures resulted depending on process conditions; for example, single crystals, fine-grained alloys, and glassy metals could be deposited. PACS 81.15.Fg; 81.05.Bx; 81.05.Je; 81.15.Gh     

Structure and morphology of laser-ablated WO3 thin films

The structure and surface morphology of WO₃ thin films deposited by a laser-ablation technique have been found to be strongly dependent on the deposition conditions and the nature of the substrate. By precisely controlling the substrate temperature and the oxygen partial pressure, amorphous, polycrystalline, nano-crystalline and iso-epitaxial WO₃ thin films were successfully grown. The structure and surface morphological features of the films from X-ray diffraction and atomic force microscopy data are described in relation to the deposition conditions. PACS 81.15.Fg; 68.55.-a; 68.37.Ps     

Nucleation and growth of SnO2 nanocrystallites prepared by pulsed laser deposition

We report in detail the synthesis and microstructural characterization of SnO₂ nanocrystallites produced using a pulsed laser deposition (PLD) method. A detailed observation of the microstructural evolution of the as-prepared SnO₂ nanocrystallites has been carried out, and their grain sizes, shapes, crystallography characteristics, and morphologies have been also determined. The nucleation and growth processes of the SnO₂ nanocrystallites are discussed in more detail in order to examine how the PLD techniques and conditions affect the evolution of grain sizes, shapes, crystallography characteristics and morphologies. PACS 81.15.Fg; 81.07.Bc; 68.37.Lp     

Pulsed laser deposited lead-germanate glass systems

Lead-germanate glasses of composition xPbO–(1-x)GeO₂ (x ranging from 0.1 to 0.4) have been synthesized and used as ablation targets for reactive pulsed laser deposition (PLD) at various oxygen pressures. The bulk glassy materials and the PLD-produced films were investigated by Fourier-transform infrared spectroscopy to reveal the effects of the bulk stoichiometry and of the reactive atmosphere employed for film preparation on the structural characteristics of the studied bulk glasses and thin-film forms. PACS 81.15.Fg; 78.30.-j; 42.70.Ce     

Growth of nanostructured ZnO thin films on sapphire

Growth of ZnO nanostructures on c-plane sapphire has been investigated using three different methods. Pulsed laser deposition (PLD) at low incident pulse energies can yield nanorods, the majority of which are aligned at an angle of ∼50° to the substrate plane. Selected area electron diffraction reveals that the nanorods display two distinct epitaxial relationships with the sapphire substrate. Those inclined to the surface normal exhibit the relationships (112̄4)_ZnO//(0001)_sap; [101̄0]_ZnO//[112̄0]_sap and (0001)_ZnO//(101̄4)_sap; [101̄0]_ZnO//[112̄0]_sap. Members of the second family are aligned along the surface normal, with (0001)_ZnO//(0001)_sap and [101̄0]_ZnO//[112̄0]_sap; the relative yield of this latter class increases at higher incident pulse energies. Hydrothermal synthesis and chemical vapour deposition on sapphire substrates that have been pre-coated (by PLD) with a thin ZnO layer result, respectively, in well-aligned ZnO microrod and nanorod arrays, both of which satisfy the relationships (0001)_ZnO//(0001)_sap; [101̄0]_ZnO//[112̄0]_sap. In contrast, employing these latter methods with a bare sapphire substrate results in, respectively, poorly aligned structures and localized islands of growth. PACS  81.07.-b; 81.10.-h; 81.15.Aa; 81.15-z; 68.65.-k