Lattice Boltzmann model for multi-component mass transfer in a solid oxide fuel cell anode with heterogeneous internal reformation and electrochemistry

We have deposited SiC thin films using two different deposition techniques, Pulsed Electron Deposition (PED) and Pulsed Laser Deposition (PLD). The PED technique is a relatively new technique where a pulsed electron flux with high energy directly hits the target surface producing a plasma in a very similar way to PLD, where, instead, a pulsed laser beam is used. These two techniques can give very dense thin films with stoichiometry much closer to the target one’s compared to others physical vapour deposition techniques (sputtering, e-beam). The major drawback of PED is that the thin film surface is affected by the presence of particulate, due to the impact of the high energy electron beam with the target. In the PLD system we used a magnetic field to curve the plasma path in the vacuum and we placed the substrate at 90^○ with respect to the target allowing the deposition of particulate-free samples. The characterization of the films has been made by measuring the optical reflectance vs angle of incidence in the EUV region (from 121.6 nm down to 40.7 nm), taking measurements at different time from deposition. X-ray photoemission measurements have been also carried out to show stoichiometry and the presence of contaminants. Other measurements such as X-ray diffraction, atomic force microscopy and profiling were also carried out to check crystalline domains and surface roughness.     

Zinc oxide nanostructures grown by pulsed laser deposition

We report the use of PLD to grow different ZnO nanostructures. Very different film morphologies have been observed using different laser wavelengths to ablate the target. The influence of substrate temperature and oxygen background pressure on the film morphology has been investigated too. Smooth and rough films, hexagonal pyramids and columns have been obtained by using a KrF excimer laser (248 nm) for the target ablation, while hexagonal hierarchical structures and pencils have been obtained by using ArF (193 nm). Photoluminescence and X-ray diffraction measurements revealed the good quality of the samples, in particular of those deposited using the ArF laser beam.     

Deposition and stoichiometry control of Nd-doped gadolinium gallium garnet thin films by combinatorial pulsed laser deposition using two targets of Nd:Gd<Subscript>3</Subscript>Ga<Subscript>5</Subscript>O<Subscript>12</Subscript> and Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>

We have demonstrated pulsed laser deposition of Nd-doped gadolinium gallium garnet on Y₃Al₅O₁₂ by the simultaneous ablation of two separate targets of Nd:Gd₃Ga₅O₁₂ (GGG) and Ga₂O₃. Such an approach is of interest as a method of achieving stoichiometry control over films whilst the growth parameters are kept constant and optimal for high quality crystal growth. We show here how the stoichiometry and resultant lattice parameter of a film can be controlled by changing the relative deposition rates from the two targets. Films have been grown with enough extra Ga to compensate for the deficiency that commonly occurs when depositing only from a GGG target. We have also grown crystalline GGG films with an enriched Ga concentration, and this unconventional approach to film stoichiometry control may have potential applications in the fabrication of films with advanced compositionally graded structures.     

脉冲激光沉积(PLD)法生长高质量ZnO薄膜及其发光性能

采用脉冲激光沉积(PLD)法在单晶Si(100)衬底上生长ZnO薄膜,以X射线衍射(XRD)、原子力显微镜(AFM)和透射电镜(TEM)等手段分析了所得ZnO薄膜的晶体结构和微观形貌。优化工艺(700℃,20Pa)下生长的ZnO薄膜呈c轴高度择优取向,柱状晶垂直衬底表面生长,结构致密均匀。室温光致发光(PL)谱分析结果表明,随着薄膜生长时O₂分压的增大,近带边紫外发光峰与深能级发光峰之比显著增强,表明薄膜的结晶性能和化学计量比都有了很大的改善。O₂分压为20Pa时所生长的ZnO薄膜具有较理想的化学计量比和较高的光学质量。     

The effect of oxygen rf discharge on pulsed laser deposition of oxide films

In this work final results on TiO₂ film deposition by Plasma Assisted Pulsed Laser Deposition (PAPLD) with an rf biased substrate are presented. In previous work it has been shown that PAPLD is an improvement over conventional PLD for the elimination of particulates in high refractive index thin film deposition. This paper will give a comparison between conventional PLD and PAPLD on the stoichiometry, morphology, and optical properties of deposited TiO₂ films. It will be demonstrated that oxygen rf discharge during the PLD process makes incorporation of oxygen into the depositing films extremely effective. This effect of the rf discharge allows operation of the PLD process at a lower oxygen background pressure while enhancing the deposition rate. Also, the production of a good quality TiO₂ film by PAPLD using a pure metal titanium target will be shown. PACS 79.20.Ds; 52.80.Pi     

Diamond-like-carbon films produced by magnetically guided pulsed laser deposition

We have compared the quality of carbon films deposited with magnetically guided pulsed laser deposition (MGPLD) and conventional pulsed laser deposition (PLD). In MGPLD, a curved magnetic field is used to guide the plasma but not the neutral species to the substrate to deposit the films while, in conventional PLD, the film is deposited with a mixture of ions, neutral species and clusters. A KrF laser pulse (248 nm) was focused to intensities of 10 GW/cm² on a carbon source target and a magnetic field strength of 0.3 T was used to steer the plasma around a curved arc to the deposition substrate. Electron energy loss spectroscopy was used in order to measure the fraction of sp³ bonding in the films produced. It is shown that the sp³ fraction, and hence the diamond-like character of the films, increased when deposited only with the pure ion component by MGPLD compared with films produced by the conventional PLD technique. The dependence of film quality on the laser intensity is also discussed. Received: 7 December 2000 / Accepted: 20 August 2001 / Published online: 2 October 2001     

Mg-Al layered double hydroxides (LDHs) and their derived mixed oxides grown by laser techniques

Layered double hydroxides (LDHs) have been widely studied due to their applications as multifunctional materials, catalysts, host materials, anionic exchangers, adsorbents for environmental contaminants and for the immobilization of biological materials. As thin films, LDHs are good candidates for novel applications as sensors, corrosion resistant coatings or components in electro optical devices. For these applications, lamellar orientation-controlled film has to be fabricated.In this work, the successful deposition of LDH and their derived mixed oxides thin films by laser techniques is reported. Pulsed laser deposition (PLD) and matrix assisted pulsed laser evaporation (MAPLE) were the methods used for thin films deposition. The ability of Mg-Al LDHs as a carrier for metallic particles (Ag) has been considered. Frozen targets containing 10% powder in water were used for MAPLE, while for PLD the targets consisted in dry-pressed pellets.The structure and the surface morphology of the deposited films were examined by X-ray Diffraction, Atomic Force Microscopy, Scanning Electron Microscopy and Secondary Ion Mass Spectrometry.     

籽晶层对喷雾热分解法生长ZnO薄膜结晶质量和光电性能的影响

通过脉冲激光沉积(PLD)方法在Si(100)衬底上沉积一层高质量的ZnO籽晶层,在籽晶层上进一步采用超声喷雾热分解(USP)法生长ZnO薄膜,研究了籽晶层对ZnO薄膜结晶质量和ZnO/Si异质结光电特性的影响。研究结果表明,在籽晶层的诱导作用下,USP法生长ZnO薄膜由多取向结构变为(002)单一取向,结晶性能得到了显著改善;籽晶层上生长的薄膜呈现出垂直于衬底生长的柱状晶结构,微观结构更加致密。通过研究紫外光照前后ZnO/Si异质结的整流特性,发现引入籽晶层后,反向偏压下异质结的光电响应显著增加,并且在开路状态下出现明显的光伏效应。     

Adjusting chemical bonding of hard amorphous CSixNy thin films by N*-plasma-assisted pulsed laser deposition

Hard amorphous carbon silicon nitride thin films have been grown by pulsed laser deposition (PLD) of various carbon silicon nitride targets by using an additional nitrogen RF plasma source on [100] oriented silicon substrates at room temperature. The influence of the number of laser shots per target site on the growth rate and film surface morphology was studied. Up to about 30 at. % nitrogen and up to 20 at. % silicon were found in the films by Rutherford backscattering spectroscopy (RBS) and X-ray photoelectron spectroscopy (XPS). The XPS of the films showed a clear correlation of binding energy to the variation of PLD parameters. The films show a universal hardness value up to 23 GPa (reference value for silicon substrate 14 GPa) in dependence on target composition and PLD parameters. The results emphasise the possibility of variation of chemical bonding and corresponding properties, such as nanohardness, of amorphous CSi_xN_y thin films by the plasma-assisted PLD process.     

TiN growth on Si by hybrid radical beam PLD

High-quality (good crystallinity and stoichiometry) titanium nitride (TiN) thin films were grown on Si(100) substrates by pulsed laser deposition (PLD) using a high-purity titanium target (99.99%) and nitrogen radical beam. The crystallinity, chemical composition, and depth profiles of the grown films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Rutherford backscattering spectroscopy (RBS), respectively. The XRD pattern indicated that the preferred growth of TiN(200) with an orientation parallel to the Si(100) direction was obtained and the nitrogen radical drastically improved crystallinity compared with that grown in ambient nitrogen gas. RBS spectra indicated that the combination of PLD and the nitrogen radical beam suppressed silicidation at the interface between the Si substrate and TiN thin film during growth. The XPS analysis revealed that this method achieved the synthesis of stoichiometric TiN films.     

Chalcogenide-based thin film sensors prepared by pulsed laser deposition technique

One advantage of the pulsed laser deposition (PLD) method is the stoichiometric transfer of multi-component target material to a given substrate. This advantage of the PLD determined the choice to prepare chalco-genide-based thin films with an off-axis geometry PLD. Ag-As-S and Cu-Ag-As-Se-Tetargets were used to deposit thin films on Si substrates for an application as a heavy metal sensing device. The films were characterized by means of Rutherford backscattering spectrometry (RBS), transmission electron microscopy (TEM), and electrochemical measurements. The same stoichiometry of the films and the targets was confirmed by RBS measurements. We observed a good long-term stability of more than 60 days and a nearly Nernstian sensitivity towards Pb and Cu, which is comparable to bulk sensors.     

The effect of substrate material on pulsed laser deposition of HgCdTe films

This paper describes some recent results of the HgCdTe thin film grown directly on different substrates (sapphire, GaAs and Si) by pulsed laser deposition (PLD). The influences of the substrate material on the properties of HgCdTe thin films were investigated by X-ray diffraction (XRD), selected area electron diffraction (SAED), atomic force microscopy (AFM) and energy dispersive X-ray spectroscopy (EDS). It was found that the quality of the HgCdTe film has a strong relation to the structure and properties of the substrate. The experiment results indicate that the HgCdTe epitaxial thin films grown directly on the sapphire substrates have a high quality, and the composition of the films is close to that of the target. While the quality of the HgCdTe films deposited on the Si and GaAs substrates are not very good.     

Mn掺杂ZnO薄膜的结构及光学性能研究

通过脉冲激光沉积(PLD)法在SiO₂基片上制备了不同含量的Mn掺杂ZnO薄膜.X射线衍射、X射线能谱、原子力显微镜与紫外-可见分光光度计测试结果表明：少量的Mn离子的掺杂并没有改变薄膜的结构，薄膜具有(103)面的择优取向；PLD法制备的ZnO薄膜的成分与靶材基本一致，实现了薄膜的同组分沉积；薄膜表面比较平坦，起伏度小于80nm，颗粒尺寸主要集中在25nm附近；但是Mn离子的掺杂改变了ZnO薄膜的禁带宽度，随Mn掺杂含量的增加，ZnO薄膜的禁带宽度增加；当薄膜中Mn含量从6%增加到 关键词： PLD ZnO薄膜 Mn掺杂 吸收谱     

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     

Optical and electrical properties of aluminum-doped ZnO thin films grown by pulsed laser deposition

Transparent aluminum-doped zinc oxide (AZO) thin films were deposited on quartz glass substrates by pulsed laser deposition (PLD) from ablating Zn-Al metallic targets. The structural, electrical and optical properties of these films were characterized as a function of Al concentration (0-8 wt.%) in the target. Films were deposited at a low substrate temperature of 150 °C under 11 Pa of oxygen pressure. It was observed that 2 wt.% of Al in the target (or 1.37 wt.% of Al doped in the AZO film) is the optimum concentration to achieve the minimum film resistivity and strong ultraviolet emission. The presence of Al in the ZnO film changes the carrier concentration and the intrinsic defects.     

Structural and optical properties of layers of pentacene formed by PLD method

Organic films fabrication offers the possibility of producing electronic devices of low weight, mechanical flexibility and low cost. One suitable material for organic film fabrigation which is the subject of the great interest is pentacene, because it is characterized by the large carrier mobility (∼1 cm²/Vs). In this work, the growth of pentacene layers using pulse laser deposition (PLD) on different substrates (glass/ITO, Si) is described and various processing parameters are investigated. Two pulsed YAG:Nd³⁺ laser wavelengths were used for the ablation of the PLD target: the first harmonic at 1064 nm aGn:dNdth3+e second at 532 nm. The structure of the layers formed was examined using SEM and RHEED methods. The results were compared with results of optical spectroscopy studies. It will be shown that layers deposed using second harmonics have a higher quality than those for first harmonic. The other PLD parametersalso have a strong influence on the structure quality of layers.      

Effects of temperature and oxygen pressure on binary oxide growth using aperture-controlled combinatorial pulsed-laser deposition

In pulsed-laser deposition (PLD), there are many processing parameters that influence film properties such as substrate-target distance, background reactive gas pressure, laser energy, substrate temperature and composition in multi-component systems. By introducing a 12.7-mm diameter circular aperture in front of a 76.2-mm silicon wafer and rotating the substrate while changing conditions during the PLD process, these parameters may be studied in a combinatorial fashion, discretely as a function of processing conditions. We demonstrate the use of the aperture technique to systematically study the effects of oxygen partial pressure on the film stoichiometry and growth rate of VO_x, using Rutherford backscattering spectrometry (RBS). In another example, we discuss the effect of growth temperature on TiO₂ films characterized by X-ray diffraction and Fourier transform far-infrared (Terahertz) absorption spectroscopy. We demonstrate that we have considerable combinatorial control of other processing variables besides composition in our combi-PLD system. These may be used to systematically study film growth and properties.     

激光制备类金刚石膜技术研究

现有技术制备的类金刚石(DLC)膜由于含氢、硬度低、内应力大、附着力差等特点,严重限制了其光学工程应用.激光法是近年发展的一种制备DLC膜的新方法,相比其他制备方法具有诸多优点.综合分析了激光制备DLC膜过程中,激光波长、脉宽、功率密度、衬底温度和偏压等因素对薄膜质量的影响规律.采用氧气氛辅助沉积、元素掺杂和双波长激光...     

The influence of lithium excess in the target on the properties and compositions of Li<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>2</Subscript>O<Subscript>4−<Emphasis Type="Italic">δ</Emphasis></Subscript> thin films prepared by PLD

Li–Mn–O thin films were deposited by pulsed laser deposition (PLD) onto stainless steel substrates using targets containing different concentrations of added Li₂O. The influence of the target composition on the stoichiometry of the resulting thin films, the surface morphology and the electrochemical properties was studied. The application of the target with added 7.5 mol% Li₂O results in an almost ideal lithium content, while all films were still oxygen deficient. The thin films were applied as electrodes in Li//Li_1+x Mn₂O_4−δ cells (i.e. model cells for a rechargeable Li-ion battery) and characterized by cyclic voltammetry and galvanostatic charge/discharge experiments. The electrochemical measurements of the thin films confirmed that the thin films can serve as good model systems and that they show a sufficient cyclability.     

Growth and characterization of pulsed laser deposited ZnO thin films

One of the most important and promising materials from metal oxides is ZnO with specific properties for near UV emission and absorption optical devices. The properties of ZnO thin films strongly depend on the deposition method. Among them, pulsed laser deposition (PLD) plays an important role for preparing various kinds of ZnO films, e.g. doped, undoped, monocrystalline, and polycrystalline. Different approaches — ablation of sintered ZnO pellets or pure metallic Zn as target material are described. This contribution is comparing properties of ZnO thin films deposited from pure Zn target in oxygen atmosphere and those deposited from sintered ZnO target. There is a close connection between final thin film properties and PLD conditions. The surface properties of differently grown ZnO thin films are measured by secondary ion mass spectrometry (SIMS), atomic force microscopy (AFM) and scanning electron microscopy (SEM). Furthermore, different approaches — ablation of sintered ZnO pellet or pure metallic Zn as target materials are described. The main results characterize typical properties of ZnO films versus technological parameters are presented. Presented at 5-th International Conference Solid State Surfaces and Interfaces, November 19–24, 2006, Smolenice Castle, Slovakia