低覆盖度的Au/GaN(0001)界面的同步辐射研究

利用同步辐射光电子能谱研究了低覆盖度Au在GaN(0001)表面的初始生长模式,肖特基势垒高 度以及界面的电子结构.结果表明，Au沉积初始阶段有界面的化学反应,随后呈三维岛状生长 .由光电子能谱实验确定的肖特基势垒高度为14 eV. 通过对界面价带谱和Au 4f芯能级谱 的分析,确定了界面化学反应的存在.利用线性缀加平面波方法计算了GaN(0001)和Au的价带 态密度并分析了化学反应产生的机理,认为在初始阶段界面形成了Au_Ga合金. 关键词： 同步辐射 光电子能谱 Au/GaN欧姆接触 态密度     

Theoretical study of hydrogen adsorption on the GaN(0 0 0 1) surface

Ab initio density functional theory, using the B3LYP hybrid functional with all-electron basis sets, has been applied to the adsorption of H on the (0 0 0 1) surface of wurtzite GaN. For bulk GaN, good agreement is obtained with photoemission and X-ray emission data for the valence band and for the Ga 3d and N 2s shallow core levels. A band gap of E_g = 4.14 eV is computed vs the experimental value (at 0 K) of 3.50 eV. A simple model, consisting of a (2 × 2) structure with 3/4-monolayer (ML) of adsorbed H, is found to yield a density of states in poor agreement with photoemission data for H adsorbed on surfaces prepared by ion bombardment and annealing. A new model, consisting of co-adsorbed Ga (1/4 ML) and H (1/2 ML), is proposed to account for these data.     

Resonant photoemission study of Ti interaction with GaN surface

Ti/GaN interface formation on GaN(0 0 0 1)-(1 × 1) surface has been investigated by means of resonant photoelectron spectroscopy (for photon energies near to Ti 3p → 3d excitation). The sets of photoelectron energy distribution curves were recorded for in situ prepared clean GaN surface and as a function of Ti coverage followed by post-deposition annealing. Manifestations of chemical reactions at the Ti/GaN interface were revealed in the valence band spectra as well as in the Ga 3d core level peak—the discerned contribution of Ti 3d states to the valence band turned out to be similar to that reported in the literature for titanium nitride. The interaction between Ti and N was further enhanced by post-deposition annealing. The study was complemented with SIMS and AFM measurements.     

Band alignment between NiO_x and nonpolar/semipolar GaN planes for selective-area-doped termination structure

Band alignment between NiO_x and nonpolar GaN plane and between NiO_x and semipolar GaN plane are measured by x-ray photoelectron spectroscopy. They demonstrate that the maximum value of the valence band in the unintentional-doped a-plane, m-plane, and r-plane GaN are comparable to each other, which means that all the substrates are of n-type with similar background carrier concentrations. However, the band offset at the NiO_x/GaN interface presents obvious crystalline plane dependency although they are coated with the same NiO_x films. By fitting the Ga 3 d spectrum obtained from the NiO_x/GaN interface, we find that relatively high Ga–O content at the interface corresponds to a small band offset. On the one hand, the high Ga–O content on the GaN surface will change the growth mode of NiO_x. On the other hand, the affinity difference between Ga and O forms a dipole which will introduce an extra energy band bending.     

CuPc molecules adsorbed on Au(1 1 0)-(1 × 2): growth morphology and evolution of valence band states

We present the growth morphology, the long-range ordering, and the evolution of the valence band electronic states of ultrathin films of copper phthalocyanine (CuPc) deposited on the Au(1 1 0)-(1 × 2) reconstructed surface, as a function of the organic molecule coverage. The low energy electron diffraction patterns present a (5 × 3) reconstruction from the early adsorption stages. High-resolution UV photoelectron spectroscopy data show the disappearance of the Au surface states related to the (1 × 2) reconstruction, and the presence of new electronic features related to the molecule-substrate interaction and to the CuPc molecular states. The CuPc highest occupied molecular orbital gradually emerges in the valence band, while the interface electronic states are quenched, upon increasing the coverage.     

Photoemission study of samarium on and CdTe(1 0 0)

Experimental photoemission results on and CdTe(1 0 0) surfaces on a function of samarium adsorbate coverage are presented. Energy distribution curves were recorded at photon energies around the Sm 4d→4f threshold (135–136 eV) to reveal the Sm contribution to the electronic structure and enhance the sensitivity. The evolution of core-level Ga 3d and Cd 4d spectra was also studied. The interaction of Sm with both GaN and CdTe leads to reactive interface formation. In the case of CdTe, it results in creation of an interfacial Sm–CdTe compound, which inhibits further diffusion of Sm into the bulk. The interaction of Sm with GaN leads to the release of Ga atoms on the surface and segregation of Ga clusters.     

Morphological anisotropy during migration enhanced epitaxy of GaAs(0 0 1)

The GaAs(0 0 1) surface morphology and structure during growth by migration enhanced epitaxy (MEE) has been studied by reflection high energy electron diffraction and scanning tunneling microscopy. Changes induced by varying the incident As/Ga flux ratio, growth temperature and the total amount of material deposited in each cycle have been studied and the results compared with GaAs(0 0 1) growth by conventional molecular beam epitaxy (MBE). Comparison of the surface morphology at the end of the Ga and As cycles indicates no clear evidence for any enhancement in the Ga adatom diffusion length during the Ga cycle. However, the morphological anisotropy of the growth front does change significantly and it is proposed that this changing anisotropy during MEE enables Ga adatom diffusion along both azimuths. The surface anisotropy during MEE growth is found to increase with the Ga/As ratio. Although there is a clear correlation between composition and morphology, we have also found that highly ordered and flat surfaces are not necessarily an indication of stoichiometric material. We also attempt to clarify a recent controversy on the structure of the c(4 × 4) reconstruction by studying the surface structure at the end of the As cycle as a function of the As/Ga ratio.     

Structure and electronic properties of gold adsorbed on Ti(0 0 0 1)

The Au/Ti(0 0 0 1) adsorption system was studied by low energy electron diffraction (LEED) and photoemission spectroscopy with synchrotron radiation after step-wise Au evaporation onto the Ti(0 0 0 1) surface. For adsorption of Au at 300 K, no additional superstructures were observed and the (1 × 1) pattern of the clean surface simply became diffuse. Annealing of gold layers more than 1 ML thick resulted in the formation of an ordered Au-Ti surface alloy. Depending on the temperature and annealing time, three surface reconstructions were observed by LEED: (√3 × √3) R30°, (2 × 2) and a one-dimensional incommensurate (√3 × √3) rectangular pattern. The Au 4f core level and valence band photoemission spectra provided evidence of a strong chemical interaction between gold and titanium. The data indicated formation of an intermetallic interface and associated valence orbital hybridization, together with diffusion of gold into the bulk. Au core-level shifts were found to be dependent on the surface alloy stoichiometry.     

GaN nucleation on (0 0 0 1)-sapphire via ion-induced nitridation of gallium

The growth of epitaxial GaN films on (0 0 0 1)-sapphire has been investigated using X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED). In order to investigate the mechanism of the growth in detail, we have focused on the nitridation of pre-deposited Ga layers (droplets) using ion beam-assisted molecular beam epitaxy (IBA-MBE). Comparative analysis of XPS core-level spectra and LEED patterns reveals, that nitride films nucleate as epitaxial GaN islands. The wetting of the surface by GaN proceeds via reactive spreading of metallic Ga, supplied from the droplets. The discussed growth model confirms, that excess of metallic Ga is beneficial for GaN nucleation.     

Wetting and reactive thin film growth

The wetting process of the GaN(0 0 0 1) surface by Ga is studied in situ in real time by low energy electron microscopy and diffraction. The reversibility of the phase transitions in the wetting layer is examined in detail and the consequences for the growth of GaN layers by reaction with ammonia and activated nitrogen are discussed. It is concluded that the growth of smooth (0 0 0 1)-terminated GaN layers may be considered as quasi-liquid phase epitaxy.     

Polarization properties of nonpolar GaN films and (In,Ga)N/GaN multiple quantum wells

We have grown GaN films and (In,Ga)N/GaN multiple quantum wells (MQWs) by plasma-assisted molecular-beam epitaxy on -LiAlO₂(100) substrates. Due to the crystal symmetry of -LiAlO₂(100), GaN films and (In,Ga)N/GaN MQWs can be realized in a nonpolar (M-plane) configuration, i.e., the c axis of the wurtzite unit cell lies in the growth plane. For compressively, anisotropically strained M-plane GaN films, the band structure of the valence band changes in such a way that the optical transmittance becomes 100% linearly polarized for two orthogonal in-plane directions, where one of these directions is parallel to the c axis of the GaN film. The photoluminescence properties of M-plane In_0.1Ga_0.9N/GaN MQWs exhibit a strong in-plane optical anisotropy for linear polarization with an energy-dependent polarization degree of up to 96%, which is presumably also due to a large valence-band splitting induced by the large compressive strain in the QWs. PACS 78.40.Fy; 78.66.Fd; 71.20.Nr     

GaN/LiNbO3 (0 0 0 1) interface formation calculated from first-principles

The stable adsorption sites for both Ga and N ions on the ideal and on the reconstructed LiNbO₃ (0 0 0 1) surface are determined by means of first-principle total energy calculations. A single N layer is found to be more strongly bound to the substrate than a single Ga layer. The adsorption of a GaN monolayer on the polar substrate within different orientations is then modeled. On the basis of our results, we propose a microscopic model for the GaN/LiNbO₃ interface. The GaN and LiNbO₃ (0 0 0 1) planes are parallel, but rotated by 30° each other, with in-plane epitaxial relationship [1 0 0]_GaN‖ [1 1  0]_LiNbO3. In this way the (0 0 0 1) plane lattice mismatch between GaN and LiNbO₃ is minimal and equal to 6.9% of the GaN lattice constant. The adsorbed GaN and the underlying LiNbO₃ substrate have parallel c-axes.     

Effects of KOH etching on the properties of Ga-polar n-GaN surfaces

The effects of a KOH treatment on the properties of n-type GaN surfaces and associated Au/n-GaN contacts have been investigated by X-ray photoelectron spectroscopy, atomic force microscopy, reflection high-energy-electron diffraction, current–voltage and electron-beam-induced current characterization. Ga-polar surfaces grown by molecular beam epitaxy and metal–organic chemical vapour deposition were compared. A decrease in electron barrier height and an increase in non-radiative recombination properties of Au/n-GaN contacts were found with KOH treatment, correlated with an increase of surface Ga vacancies, an increase in surface N–H₂ content and a decrease in surface C contamination. A 0.3-eV shift in the Ga3d peak position towards the valence band and a reduction in the dislocation contrast were observed for the case of molecular-beam-epitaxy-grown GaN only, demonstrating that surface Ga vacancies and threading dislocations play only a limited role in defining the resultant metal/GaN contact properties. Accordingly, the surface atomic content and the resulting surface states, following KOH treatment, should be taken into consideration when appraising the electrical properties of n-GaN surfaces and the performance of associated metallic contacts.     

Valence band studies of the formation of ultrathin pure silicon nitride films on Si(1 0 0)

The growth of ultrathin films of Si₃N₄ directly on Si surfaces is studied with valence band photoemission. The information from these studies about the growth mechanism and the changes of the electronic structure is enhanced by the use of various photon energies with synchrotron radiation. The silicon nitride films are grown isothermally on the Si(1 0 0) and Si(1 1 1) surfaces by reactions with atomic N. The atomic nitrogen is produced by using a remote, microwave excited nitrogen plasma. The growth under these conditions was earlier shown to be self limiting. The details in the valence band spectra are identified and resolved with numerical methods, and followed systematically during the growth. Thus the identification of Si surface states, Si-nitride interface states and bulk nitride states becomes possible. The previously obtained separation between amorphous and crystalline growth occurring around 500 °C is further supported in the present studies.     

Ga-induced superstructures on the Si(1 1 1) 7 × 7 surface

Monolayer Ga adsorption on Si surfaces has been studied with the aim of forming p-delta doped nanostructures. Ga surface phases on Si can be nitrided by N₂⁺ ion bombardment to form GaN nanostructures with exotic electron confinement properties for novel optoelectronic devices. In this study, we report the adsorption of Ga in the submonolayer regime on 7 × 7 reconstructed Si(1 1 1) surface at room temperature, under controlled ultrahigh vacuum conditions. We use in-situ Auger electron spectroscopy, electron energy loss spectroscopy and low energy electron diffraction to monitor the growth and determine the properties. We observe that Ga grows in the Stranski-Krastanov growth mode, where islands begin to form on two flat monolayers. The variation in the dangling bond density is observed during the interface evolution by monitoring the Si (LVV) line shape. The Ga adsorbed system is subjected to thermal annealing and the residual thermal desorption studied. The difference in the adsorption kinetics and desorption dynamics on the surface morphology is explained in terms of strain relaxation routes and bonding configurations. Due to the presence of an energetic hierarchy of residence sites of adatoms, site we also plot a 2D phase diagram consisting of several surface phases. Our EELS results show that the electronic properties of the surface phases are unique to their respective structural arrangement.     

Electronic Structures of Wurtzite GaN with Ga and N Vacancies

The electronic band structures of wurtzite GaN with Ga and N vacancy defects are investigated by means of the first-principles total energy calculations in the neutral charge state. Our results show that the band structures can be significantly modified by the Ga and N vacancies in the GaN samples. Generally, the width of the valence band is reduced and the band gap is enlarged. The defect-induced bands can be introduced in the band gap of GMV due to the Ga and N vacancies. Moreover, the GaN with high density of N vacancies becomes an indirect gap semiconductor. Three defect bands due to Ga vacancy defects are created within the band gap and near the top of the valence band. In contrast, the N vacancies introduce four defect bands within the band gap. One is in the vicinity of the top of the valence band, and the others are near the bottom of the conduction band. The physical origin of the defect bands and modification of the band structures due to the Ga and N vacancies are analysed in depth.     

Growth mode and electronic structure of Au nano-clusters on NiO(0 0 1) and TiO2(1 1 0)

The growth mode and electronic structure of Au nano-clusters grown on NiO and TiO₂ were analyzed by reflection high-energy electron diffraction, a field-emission type scanning electron microscope, medium energy ion scattering and photoelectron spectroscopy. Au was deposited on clean NiO(0 0 1)-1 × 1 and TiO₂(1 1 0)-1 × 1 surfaces at room temperature with a Knudsen cell at a rate of 0.25-0.35 ML/min (1 ML = 1.39 × 10¹⁵ atoms/cm²:Au(1 1 1)). Initially two-dimensional (2D) islands with thickness of one Au-atom layer grow epitaxially on NiO(0 0 1) and then neighboring 2D-islands link each other to form three-dimensional (3D)-islands with the c-axis oriented to the [1 1 1] direction. The critical size to form 3D-islands is estimated to be about 5 nm². The shape of the 3D-islands is well approximated by a partial sphere with a diameter d and height h ranging from 2.0 to 11.8 nm and from 0.95 to 4.2 nm, respectively for Au coverage from 0.13 to 4.6 ML. The valence band spectra show that the Au/NiO and Au/TiO₂ surfaces have metallic characters for Au coverage above 0.9 ML. We observed Au 4f spectra and found no binding energy shift for Au/NiO but significant higher binding energy shifts for Au/TiO₂ due to an electron charge transfer from Au to TiO₂. The work function of Au/NiO(0 0 1) gradually increases with increase in Au coverage from 4.4 eV (NiO(0 0 1)) to 5.36 eV (Au(1 1 1)). In contrast, a small Au deposition(0.15 to 1.5 ML) on TiO₂(1 1 0) leads to reduction of the work function, which is correlated with an electron charge transfer from Au to TiO₂ substrate.     

Electronic properties of Au nano-particles supported on stoichiometric and reduced TiO2(1 1 0) substrates

Growth modes and electronic properties were analyzed for Au nano-particles grown on stoichiometric and reduced TiO₂(1 1 0) substrates by medium energy ion scattering (MEIS) and photoelectron spectroscopy(PES) using synchrotron-radiation-light. Initially, two-dimensional islands (2D) with a height of one and two atomic layers grow and higher coverage increases the islands height to form three-dimensional (3D) islands for the stoichiometric TiO₂(1 1 0) substrate. In contrast, 3D islands start to grow from initial stage with a small Au coverage (?0.1 ML, 1 ML = 1.39 × 10¹⁵  atoms/cm²: Au(1 1 1)) probably due to O-vacancies acting as a nucleation site. Above 0.7 ML, all the islands become 3D ones taking a shape of a partial sphere and the Au clusters change to metal for both substrates. We observed the Au 4f and Ti 3p core level shifts together with the valence band spectra. The Ti 3p peak for the O-deficient surface shifts to higher binding energy by 0.25 ± 0.05 eV compared to that for the stoichiometric surface, indicating downward band bending by an electron charge transfer from an O-vacancy induced surface state band to n-type TiO₂ substrate. Higher binding energy shifts of Au 4f peaks observed for both substrates reveal an electron charge transfer from Au to TiO₂ substrates. The work functions of Au nano-particles supported on the stoichiometric and reduced TiO₂ substrates were also determined as a function of Au coverage and explained clearly by the above surface and interface dipoles.     

The effect of the aminating temperature on the synthesis of gallium nitride nanowires doped with magnesium

GaN nanowires doped with Mg have been synthesized at different temperature through ammoniating the magnetron-sputtered Ga₂O₃/Au layered films deposited on Si substrates. X-ray diffraction (XRD), Scanning electron microscope (SEM), high-resolution TEM (HRTEM) equipped with an energy-dispersive X-ray (EDX) spectrometer and photoluminescence (PL) were used to analyze the structure, morphology, composition and optical properties of the as-synthesized sample. The results show that the ammoniating temperature has a great impact on the properties of GaN. The optimally ammoniating temperature of Ga₂O₃/Au layer is 900 C for the growth of GaN nanowires(NWs). The band gap emission (358 nm) relative to that (370 nm) of undoped GaN NWs has an apparent blueshift, which can be ascribed to the doping of Mg. Finally, the growth mechanism is also briefly discussed.     

Adsorption of Ag on Si(1 0 0) surface

The chemisorption of one monolayer Ag atoms on an ideal Si(1 0 0) surface is studied by using the self-consistent tight-binding linear muffin-tin orbital method. The adsorption energies (E_ad) of different sites are calculated. It is found that the adsorbed Ag atoms are more favorable on C site (fourfold site) than on any other sites on Si(1 0 0) surface, the polar covalent bond is formed between Ag atom and surface Si atom, a Ag and Si mixed layer does not exist and does form an abrupt interface at the Ag–Si(1 0 0) interface. This is in agreement with the experiment results. The layer-projected density of states is calculated and compared with that of the clean surface. The charge transfer is also investigated. Comparing with the Au/Si(1 0 0) system, the interaction is weaker between Ag and Si than between Au and Si.