Structure, chemistry, and energetics of organic and inorganic adsorbates on Ga-rich GaAs and GaP(001) surfaces

The work described in this dissertation includes fundamental investigations into three surface processes, namely inorganic film growth, water-induced oxidation, and organic functionalization/passivation, on the GaP and GaAs(001) surfaces. The techniques used to carry out this work include scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. Atomic structure, electronic structure, reaction mechanisms, and energetics related to these surface processes are discussed at atomic or molecular levels.

First, we investigate epitaxial Zn₃P₂ films grown on the Ga-rich GaAs(001)(6×6) surface. The film growth mechanism, electronic properties, and atomic structure of the Zn₃P₂/GaAs(001) system are discussed based on experimental and theoretical observations. We discover that a P-rich amorphous layer covers the crystalline Zn3P2 film during and after growth. We also propose more accurate picture of the GaP interfacial layer between Zn₃P₂ and GaAs, based on the atomic structure, chemical bonding, band diagram, and P-replacement energetics, than was previously anticipated.

Second, DFT calculations are carried out in order to understand water-induced oxidation mechanisms on the Ga-rich GaP(001)(2×4) surface. Structural and energetic information of every step in the gaseous water-induced GaP oxidation reactions are elucidated at the atomic level in great detail. We explore all reasonable ground states involved in most of the possible adsorption and decomposition pathways. We also investigate structures and energies of the transition states in the first hydrogen dissociation of a water molecule on the (2×4) surface.

Finally, adsorption structures and thermal decomposition reactions of 1-propanethiol on the Ga-rich GaP(001)(2×4) surface are investigated using high resolution STM, XPS, and DFT simulations. We elucidate adsorption locations and their associated atomic structures of a single 1-propanethiol molecule on the (2×4) surface as a function of annealing temperature. DFT calculations are carried out to optimize ground state structures and search transition states. XPS is used to investigate variations of the chemical bonding nature and coverage of the adsorbate species.

离子束溅射法薄膜生长中结瘤微缺陷的生长机理

用离子束溅射法制备了锆单层薄膜．用设计新型夹具和预置种子方法，对薄膜中结瘤微缺陷的生长过程进行了研究．在高分辨率光学显微镜和扫描电子显微镜下观察发现，结瘤在其生长初期呈现出分形的特征．用分子动力学和薄膜生长的扩散限制聚集模型，薄膜中结瘤微缺陷成核时的分形现象得到了很好的解释．

Structural and optical properties of nanostructured TiO2 thin films fabricated by glancing angle deposition

TiO2 films deposited by electron beam evaporation with glancing angle deposition (GLAD) technique were reported. The influence of flux angle on the surface morphology and the microstructure was investigated by scanning electron microscopy. The GLAD TiO2 films are anisotropy with highly orientated nanostructure of the slanted columns. With the increase of flux angle, refractive index and packing density decrease. This is caused by the shadowing effect dominating film growth. The anisotropic structure of TiO2 films results in optical birefringence, which reaches its maximum at the flux angle alpha = 65 degrees. The maximum birefringence of GLAD TiO2 films is higher than that of common bulk materials. It is suggested that glancing angle deposition may offer an effective method to obtain tailorable refractive index and birefringence in a large continuous range. (c) 2006 Elsevier B.V. All rights reserved.

Effect of deposition conditions on the chemical bonding in sputtered carbon nitride films

A balanced planar r.f. powered magnetron sputter source has been used to deposit carbon nitride films from a graphite target under various conditions. Sample temperature, bias voltage and nitrogen content in the gas mixture were varied. The effects of oxygen, methane and ammonia on the film growth were also studied. Special attention was paid to the effects of the deposition parameters on the structure of the films, in particular the hybridisation of the carbon and nitrogen bonding. The chemical bonding of the carbon and nitrogen atoms was studied by electron energy loss spectroscopy (EELS). The chemical composition was evaluated by Rutherford back-scattering. The intensity of transitions to π antibonding orbitals, as revealed by EELS, was found to increase with the nitrogen content in the films. Ion bombardment of the films during growth and the addition of oxygen or hydrogen-rich gases further increased the proportion of π bonds of both the carbon and nitrogen atoms. It is suggested that the increase in the transitions to μ antibond orbitals is to be explained by increased sp2 or possibly sp hybridisation of the carbon and nitrogen. Also, the effect of annealing on the bonding of nitrogen rich films after deposition was tested. The changes caused by nitrogen and deposition conditions are consistent with previous reports on the formation of paracyanogen structures.

Low field electron emission from nanoclustered carbon grown by cathodic arc

Nanocluster carbon films grown using a cathodic arc process at room temperature in the presence of background gases such as helium are found to be good electron emitters. The variation in the surface morphology and the corresponding emission characteristics of the films with change in helium partial pressure (5×10-4 to 50 Torr) during film growth are reported. The effect of helium partial pressure on clustering was studied for films grown at nitrogen partial pressures of 10-4 and 10-3 Torr. The surface morphology of the films varied from smooth through clusters (with sizes 50-200 nm) to fibrous films. The threshold field varied from 1 to 10 V/μm for an emission current density 1 μA/cm2.

Chemical liquid phase deposition of thin aluminum oxide films

Thin aluminum oxide films were deposited by a new and simple physicochemical method called chemical liquid phase deposition (CLD) on semiconductor materials. Aluminum sulfate with crystallized water and sodium bicarbonate were used as precursors for film growth, and the control of the system's pH value played an important role in this experiment. The growth rate is 12 nm/h with the deposition at [Al-2(SO4)(3)]=0.0837 mol.L-1, [NaHCO3]=0.214 mol.L-1, 15 degreesC. Post-growth annealing not only densifies and purifies the films, but results in film crystallization as well. Excellent quality of Al2O3 films in this work is supported by electron dispersion spectroscopy, Fourier transform infrared spectrum, X-ray diffraction spectrum and scanning electron microscopy photograph.

Characterization of free-standing GaN substrate grown through hydride vapor phase epitaxy with a TiN interlayer

Large-scale GaN free-standing substrate was obtained by hydride vapor phase epitaxy directly on sapphire with porous network interlayer. The bottom surface N-face and top surface Ga-face showed great difference in anti-etching and optical properties. The variation of optical and structure characteristics were also microscopically identified using spatially resolved cathodoluminescence and micro-Raman spectroscopy in cross-section of the GaN substrate. Three different regions were separated according to luminescent intensity along the film growth orientation. Some tapered inversion domains with high free carrier concentration of 5 x 10(19) cm(-3) protruded up to the surface forming the hexagonal pits. The dark region of upper layer showed good crystalline quality with narrow donor bound exciton peak and low free carrier concentration. Unlike the exponential dependence of the strain distribution, the free-standing GaN substrate revealed a gradual increase of the strain mainly within the near N-polar side region with a thickness of about 50 mu m, then almost kept constant to the top surface. (c) 2007 Elsevier B.V. All rights reserved.

Transport phenomena in radial flow MOCVD reactor with three concentric vertical inlets

Transport phenomena in radial flow metalorganic chemical vapor deposition (MOCVD) reactor with three concentric vertical inlets are studied by two-dimensional numerical modeling. By varying the parameters such as gas pressure, flow rates combination of multi-inlets, geometric shapes and sizes of reactor and flow distributor, temperatures of susceptor and ceiling, and susceptor rotation, the corresponding velocity, temperature, and concentration fields inside the reactor are obtained; the onset and change of flow recirculation cells under influences of those parameters are determined. It is found that recirculation cells, originated from flow separation near the bend of reactor inlets, are affected mainly by the reactor height and shape, the operating pressure, the flow rates combination of multi-inlets, and the mean temperature between susceptor and ceiling. By increasing the flow rate of mid-inlet and the mean temperature, decreasing the pressure, maintaining the reactor height below certain criteria, and trimming the bends of reactor wall and flow distributor to streamlined shape, the recirculation cells can be minimized so that smooth and rectilinear flow prevails in the susceptor region, which corresponds to smooth and rectilinear isotherms and larger reactant concentration near the susceptor. For the optimized reactor shape, the reactor size can be enlarged to diameter D = 40 cm and height H = 2 cm without flow recirculation. The susceptor rotation over a few hundred rpm around the reactor central axis will induce the recirculation cell near the exit and deflect the streamlines near the susceptor, which is not the case for vertical reactors. (c) 2006 Elsevier B.V. All rights reserved.

Magnetic Properties of FePt Nanoparticles Prepared by a Micellar Method

FePt nanoparticles with average size of 9 nm were synthesized using a diblock polymer micellar method combined with plasma treatment. To prevent from oxidation under ambient conditions, immediately after plasma treatment, the FePt nanoparticle arrays were in situ transferred into the film-growth chamber where they were covered by an SiO2 overlayer. A nearly complete transformation of L1(0) FePt was achieved for samples annealed at temperatures above 700 A degrees C. The well control on the FePt stoichiometry and avoidance from surface oxidation largely enhanced the coercivity, and a value as high as 10 kOe was obtained in this study. An evaluation of magnetic interactions was made using the so-called isothermal remanence (IRM) and dc-demagnetization (DCD) remanence curves and Kelly-Henkel plots (Delta M measurement). The Delta M measurement reveals that the resultant FePt nanoparticles exhibit a rather weak interparticle dipolar coupling, and the absence of interparticle exchange interaction suggests no significant particle agglomeration occurred during the post-annealing. Additionally, a slight parallel magnetic anisotropy was also observed. The results indicate the micellar method has a high potential in preparing FePt nanoparticle arrays used for ultrahigh density recording media.

Study on pulsed laser ablation and deposition of ZnO thin films by L-MBE

ZnO, as a wide-band gap semiconductor, has recently become a new research focus in the field of ultraviolet optoelectronic semiconductors. Laser molecular beam epitaxy (L-MBE) is quite useful for the unit cell layer-by-layer epitaxial growth of zinc oxide thin films from the sintered ceramic target. The ZnO ceramic target with high purity was ablated by KrF laser pulses in an ultra high vacuum to deposit ZnO thin film during the process of L-MBE. It is found that the deposition rate of ZnO thin film by L-MBE is much lower than that by conventional pulsed laser deposition (PLD). Based on the experimental phenomena in the ZnO thin film growth process and the thermal-controlling mechanism of the nanosecond (ns) pulsed laser ablation of ZnO ceramic target, the suggested effective ablating time during the pulse duration can explain the very low deposition rate of the ZnO film by L-MBE. The unique dynamic mechanism for growing ZnO thin film is analyzed. Both the high energy of the deposition species and the low growth rate of the film are really beneficial for the L-MBE growth of the ZnO thin film with high crystallinity at low temperature.

Fracture of colloidal single-crystal films fabricated by controlled vertical drying deposition

Controlled vertical drying deposition method was used to make high-quality single crystal close-packed colloidal films formed of different radii polystyrene latex spheres on glass substrates coming from a low concentration water suspension (0.1% volume fraction). Regardless of the spheres radii the film thickness was about 6.3 microns. However, cracks destroyed the crystalline film structure during the colloidal film growth. The effect of particle radius (85-215 nm range) on film cracking was systematically studied using in situ optical fracture monitoring. Primary parallel cracks run along the vertical growth direction, later followed by secondary branched cracks in-between the primary cracks due to residual water evaporation. Quantitative theoretical relationship between the cracks spacing and particles radius was derived and shows good agreement with experimental observations. Normalized cracks spacing is related to a reciprocal ratio of the dimensionless particle radius.

Vacuum-deposited submonolayer thin films of a three-ring bent-core compound

Submonolayer thin films of a three-ring bent-core (that is, banana-shaped) compound, m-bis(4-n-octyloxystyryl)benzene (m-OSB), were prepared by the vacuum-deposition method, and their morphologies, structures, and phase behavior were investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The films have island shapes ranging from compact elliptic or circular patterns at low temperatures (below 40 degreesC) to branched patterns at high temperatures (above 60 degreesC). This shape evolution is contrary to the prediction based on the traditional diffusion-limited aggregation (DLA) theory. AFM observations revealed that two different mechanisms governed the film growth, in which the compact islands were formed via a dewetting-like behavior, while the branched islands diffusion-mediated. It is suggested m-OSB forms a two-dimensional, liquid crystal at the low-temperature substrate that is responsible for the unusual formation of compact islands. All of the monolayer islands are unstable and apt to transform to slender bilayer crystals at room temperature. This phase transition results from the peculiar molecular shape and packing of the bent-core molecules and is interpreted as escaping from macroscopic net polarization by the formation of an antiferroelectric alignment.

Synthesis and characterization of the nanoporous ultrathin multilayer films based on molybdenum polyoxometalate (Mo-36)(n)

Ultrathin multilayer films of the wheel-shaped molybdenum polyoxometalate cluster (Mo-36)(n) and poly(allylamine hydrochloride) (PAH) have been prepared by the layer-by-layer (LbL) self-assembly method. The ((Mo-36)(n)/PAH)(m) multilayer films have been characterized by Xray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). UV-VIS measurements reveal regular film growth with each (Mo-36)(n) adsorption. The electrochemical behavior of the film at room temperature was investigated.

In(OH)(3) and In2O3 nanorod bundles and spheres: Microemulsion-mediated hydrothermal synthesis and luminescence properties

Indium hydroxide, In(OH)(3), nano-microstructures with two kinds of morphology, nanorod bundles (around 500 nm in length and 200 nm in diameter) and caddice spherelike agglomerates (around 750 - 1000 nm in diameter), were successfully prepared by the cetyltrimethylammonium bromide (CTAB)/water/cyclohexane/n-pentanol microemulsion-mediated hydrothermal process. Calcination of the In(OH)(3) crystals with different morphologies (nanorod bundles and spheres) at 600 degrees C in air yielded In2O3 crystals with the same morphology. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and photoluminescence (PL) spectra as well as kinetic decays were used to characterize the samples. The pH values of microemulsion play an important role in the morphological control of the as-formed In(OH)(3) nano-microstructures from the hydrothermal process. The formation mechanisms for the In( OH) 3 nano- microstructures have been proposed on an aggregation mechanism. In2O3 nanorod bundles and spheres show a similar blue emission peaking around 416 and 439 nm under the 383-nm UV excitation, which is mainly attributed to the oxygen vacancies in the In2O3 nano-microstructures.

Assembly of multilayer films containing iron(III)- substituted Dawson-type heteropolyanions and its electrocatalytic properties: cyclic voltammetry, electrochemical impedance spectroscopy and UV-Vis spectrometry

Ultrathin multilayer films have been prepared by means of alternate adsorption of iron(Ill)-substituted heteropolytungstate anions and a cationic redox polymer on the 4-aminobenzoic acid modified glassy carbon electrode surface based on electrostatic layer-by-layer assembly. Cyclic voltammetry, electrochemical impedance spectroscopy and UV-Vis absorption spectrometry have been used to easily monitor the uniformity of thus-formed multilayer films. Especially, the electrochemical impedance spectroscopy is successfully used to monitor the multilayer deposition processes and is a very useful technique in the characterization of multilayer films because it provides valuable information about the interfacial impedance features. All these results reveal regular film growth with each layer adsorption. The resulting multilayer films can effectively catalyze the reduction of H2O2,NO2- and BrO3-.