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.

Strain and magnetic anisotropy of as-grown and annealed Fe films on c(4x4) reconstructed GaAs (001) surface

Fe films with the different thicknesses were grown on c(4x4) reconstructed GaAs (001) surfaces at low temperature by molecular-beam epitaxy. Well-ordered bcc structural Fe epitaxial films are confirmed by x-ray diffraction patterns and high-resolution cross-sectional transmission electron microscopy images. A large lattice expansion perpendicular to the surface in Fe film is observed. In-plane uniaxial magnetic anisotropy is determined by the difference between magnetizing energy along [110] and [110] directions, and the constant of interfacial uniaxial magnetic anisotropy is calculated to be 1.02x10(-4) J m(-2). We also find that magnetic anisotropy is not obviously influenced after in situ annealing, but in-plane strain is completely changed.

Structural anisotropy and optical properties of InxGa1-xAs quantum dots on GaAs(001)

InAs and InxGa1-xAs (x = 0.2 and 0.5) self-organized quantum dots (QDs) were fabricated on GaAs(0 0 1) by molecular beam epitaxy (MBE) and characterized by atomic force microscopy (AFM), transmission electron microscopy (TEM), acid photoluminescence polarization spectrum (PLP). Both structural and optical properties of InxGa1-xAs QD layer are apparently different from those of InAs QD layer. AFM shows that InxGa1-xAs QDs tend to be aligned along the [1 (1) over bar 0] direction, while InAs QDs are distributed randomly. TEM demonstrates that there is strain modulation along [1 1 0] in the InxGa1-xAs QD layers. PLP shows that In0.5Ga0.5As islands present optical anisotropy along [1 1 0] and [1 (1) over bar 0] due to structural and strain field anisotropy for the islands. (C) 2001 Elsevier Science B.V. All rights reserved.

Etching Behavior of GaN/GaAs(001) Epilayers Grown by MOVPE

Wet etching characteristics of cubic GAN (c-GaN) thin films grown on GaAs(001) by metalorganic vapor phase epitaxy (MOVPE) are investigated. The samples are etched in HCl, H_3PO_4, KOH aqueous solutions, and molten KOH at temperatures in the range of 90～300 ℃. It is found that different solution produces different etch figure on the surfaces of a sample. KOH-based solutions produce rectangular pits rather than square pits. The etch pits elongate in [1(1-bar)0] direction, indicating asymmetric etching behavior in the two orthogonal <110> directions. An explanation based on relative reactivity of the various crystallographic planes is employed to interpret qualitatively the asymmetric etching behavior. In addition, it is found that KOH aqueous solution would be more suitable than molten KOH and the two acids for the evaluation of stacking faults in c-GaN epilayers.

Deposition of hydrocarbon molecules on diamond (001) surfaces : atomic scale modeling

The impact induced chemisorption of hydrocarbon molecules (CH3 and CH2) on H-terminated diamond (001)-(2x1) surface was investigated by molecular dynamics simulation using the many-body Brenner potential. The deposition dynamics of the CH3 radical at impact energies of 0.1-50 eV per molecule was studied and the energy threshold for chemisorption was calculated. The impact-induced decomposition of hydrogen atoms and the dimer opening mechanism on the surface was investigated. Furthermore, the probability for dimer opening event induced by chemisorption of CH, was simulated by randomly varying the impact position as well as the orientation of the molecule relative to the surface. Finally, the energetic hydrocarbons were modeled, slowing down one after the other to simulate the initial fabrication of diamond-like carbon (DLC) films. The structure characteristic in synthesized films with different hydrogen flux was studied. Our results indicate that CH3, CH2 and H are highly reactive and important species in diamond growth. Especially, the fraction of C-atoms in the film having sp(3) hybridization will be enhanced in the presence of H atoms, which is in good agreement with experimental observations. (C) 2002 Elsevier Science B.V. All rights reserved.

Single 2×1 domain orientation on Si(001) surfaces using aperiodic Bi line arrays

Studies of Bi heteroepitaxy on Si(001) have shown that lines grow to lengths of up to 500nm if the substrate is heated to above the Bi desorption temperature (500°C) during or after Bi deposition. Unlike many other nanoline systems, the lines formed by this nonequilibrium growth process have no detectable width dispersion. Although much attention has been given to the atomic geometery of the line, in this paper, we focus on how the lines can be used to create a majority 2×1 domain orientation. It is demonstrated that the Bi lines can be used to produce a single-domain orientation on Si(001) if the lines are grown on Si(001) surfaces with a regular distribution of single height steps. This is a compelling example of how a nanoscale motif can be used to modify mesoscopic surface structure on Si(001).

The equilibrium geometry and electronic structure of Bi nanolines on clean and hydrogenated Si(001) surfaces

The equilibrium geometry, electronic structure and energetic stability of Bi nanolines on clean and hydrogenated Si(001) surfaces have been examined by means of ab initio total energy calculations and scanning tunnelling microscopy. For the Bi nanolines on a clean Si surface the two most plausible structural models, the Miki or M model (Miki et al 1999 Phys. Rev. B 59 14868) and the Haiku or H model (Owen et al 2002 Phys. Rev. Lett. 88 226104), have been examined in detail. The results of the total energy calculations support the stability of the H model over the M model, in agreement with previous theoretical results. For Bi nanolines on the hydrogenated Si(001) surface, we find that an atomic configuration derived from the H model is also more stable than an atomic configuration derived from the M model. However, the energetically less stable (M) model exhibits better agreement with experimental measurements for equilibrium geometry. The electronic structures of the H and M models are very similar. Both models exhibit a semiconducting character, with the highest occupied Bi-derived bands lying at ~0.5 eV below the valence band maximum. Simulated and experimental STM images confirm that at a low negative bias the Bi lines exhibit an 'antiwire' property for both structural models.

Enhancement of uniaxial magnetic anisotropy in Fe thin films grown on GaAs(001) with an MgO underlayer

The understanding and control of anisotropy in Fe films grown on cubic systems such as GaAs and MgO has been of interest from the point of view of applications in devices. We report magnetic anisotropy studies on Fe/GaAs(001) and Fe/MgO/GaAs(001) prepared by pulsed laser deposition. In Fe/GaAs(001), magneto optical Kerr effect (MOKE) measurements revealed a dominant uniaxial anisotropy for Fe thickness less than 20 monolayers (ML) and this was confirmed by ferromagnetic resonance (FMR) studies. Multiple steps in the hysteresis loops were observed for Fe films of thickness 20 and 25 ML. Whereas, in Fe/MgO/GaAs(001), even at 25 ML of Fe, the uniaxial anisotropy remained dominant. The anisotropy constants obtained from FMR spectra have shown that the relative strength of uniaxial anisotropy is higher as compared to the cubic anisotropy constant in the case of Fe/MgO/GaAs(001). (C) 2011 American Institute of Physics. doi:10.1063/1.3556941]

GaN/GaAs(001)薄膜的MOCVD生长与结构特性分析

Submitted by zhangdi (zhangdi@red.semi.ac.cn) on 2009-04-13T11:45:31Z

Co doping enhanced giant magnetocaloric effect in Mn1-xCoxAs films epitaxied on GaAs (001)

A giant magnetocaloric effect was found in series of Mn1-xCoxAs films epitaxied on GaAs (001). The maximum magnetic entropy change caused by a magnetic field of 4 T is as large as 25 J/kg K around room temperature, which is about twice the value of pure MnAs film. The observed small thermal hysteresis is more suitable for practical application. Growing of layered Mn1-xCoxAs films with Co concentration changing gradually may draw layered active magnetic regenerator refrigerators closer to practical application. Our experimental result may provide the possibility for the combination of magnetocaloric effect and microelectronic circuitry.

Magnetic anisotropies of laterally confined structures of epitaxial Fe films on GaAs (001)

We have investigated magnetic properties of laterally confined structures of epitaxial Fe films on GaAs (001). Fe films with different thicknesses were grown by molecular-beam epitaxy and patterned into regular arrays of rectangles with varying aspect ratios. In-plane magnetic anisotropy was observed in all of the patterned Fe films both at 15 and 300 K. We have demonstrated that the coercive fields can be tuned by varying the aspect ratios of the structures. The magnitudes of the corresponding anisotropy constants have been determined and the shape anisotropy constant is found to be enhanced as the aspect ratio is increased.

Investigation of GaSb epilayer grown on vicinal GaAs(001) substrate by high resolution x-ray diffraction

GaSb epilayers grown on GaAs(001) vicinal substrate misoriented towards (111) plane were studied using high-resolution x-ray diffraction (HRXRD). The results show that GaSb epilayers exhibit positive crystallographic tilt and the distribution of 60 degrees misfit dislocations (MDs) is imbalanced. The vicinal substrate also leads to the anisotropy of the mosaic structure, i.e. the lateral coherent lengths in [1 (1) over bar0] directions are larger than those in [110] directions. Furthermore, the full-width at half maximum (FWHM) of the off-axis peaks varies with the inclination angle, which is a result of different dislocation densities in the {111} glide planes.

Distribution of dislocations in GaSb and InSb epilayers grown on GaAs (001) vicinal substrates

GaSb and InSb epilayers grown on GaAs (001) vicinal substrates misoriented toward (111) plane were studied using high resolution x-ray diffraction. The results show that GaSb and InSb epilayers take on positive crystallographic tilt, and the asymmetric distribution of 60 degrees misfit dislocations in {111} glide planes have an effect on the tilt. In addition, the vicinal substrate influences the distribution of the threading dislocations in {111} glide planes, and the density of dislocation in the (111) plane is higher than in the ((1) over bar(1) over bar1) plane. A model was proposed to interpret the distribution of full width at half maximum, which can help us understand the formation and glide process of the dislocations. (C) 2009 American Institute of Physics. [DOI 10.1063/1.3115450]

Shape stability of InAs self-assembled islands on vicinal GaAs(001) substrates

We have grown InAs self-assembled islands on vicinal GaAs( 001) substrates. Atomic force microscopy and photoluminescence studies show that the islands have a clear bimodal size distribution. While most of the small islands whose growth is limited by the width of one multi-atomic step have compact symmetric shapes, a large fraction of the large islands limited by the width of one step plus one terrace have asymmetric shapes which are elongated along the multi-atomic step lines. These results can be attributed to the shape-related energy of the islands at different states of their growth. (C) 2008 Elsevier B. V. All rights reserved.

Effect of the growth mode on the two- to three-dimensional transition of InAs grown on vicinal GaAs(001) substrates

Some differences were observed between conventional molecular-beam epitaxy (MBE) and mobility enhanced epitaxy (MEE) of InAs on a vicinal GaAs(001) substrate in the variation of the number density N of the InAs islands, with additional InAs coverage (theta - theta(c)) after the critical InAs coverage theta(c) during the two- to three-dimensional (2D-3D) transition. For MBE the variation was consistent with the power law N(theta) (theta similar to theta(c))(alpha); while for MEE, the linear relation N(theta) proportional to (theta - theta(c)) was observed. The difference is discussed in terms of the randomness in the nucleation of the InAs islands.