Defects in GaN Films Grown on Si（111） Substrates by Metal-Organic Chemical Vapour Deposition

We report the transmission-electron microscopy study of the defects in wurtzitic GaN films grown on Si(111) substrates with AlN buffer layers by the metal-organic chemical vapour deposition method. The In0.1 Ga0.9N/GaN multiple quantum well (MQW) reduced the dislocation density by obstructing the mixed and screw dislocations passing through the MQW. No evident reduction of the edge dislocations density by the MQW was observed. It was found that dislocations with screw component can be located at the boundaries of sub-grains slightly in-plane misoriented.     

Structural evolution of a-Si:H/SiO2 multilayers upon step by step thermal annealing

a-Si:H/SiO_2 multilayers were prepared by alternatively changing plasma enhanced chemical vapour deposition of a-Si:H layers and in situ plasma oxidation process. Subsequently, as-grown samples were annealed at temperatures from 350℃ to 1100℃ in N_2 ambient with an increment of 100℃. The evolution of bonding configurations and structures with annealing treatments was systematically investigated by Fourier-transform infrared spectroscopy. The peak position of Si－O stretching vibration of SiO_2 layers shift to 1087cm^{-1} after annealing at 1100℃, which demonstrates that the SiO_2 films fabricated by plasma oxidation after high temperature annealing can have similar properties to the thermal grown ones. A Si－O vibration from interfacial SiO_x was identified: the value x was found to increase as increasing the annealing temperature, which is ascribed to the cooperation of hydrogen effusion and reordering of the oxygen bond in SiO_x networks. The H-related bonds were observed in the form of H－Si－O_3 and H－Si－Si_{3-n}O_n (n=1－2) configurations, which are supposed to be present in SiO_2 and interfacial SiO_x layers, respectively. The H atoms bonded in different bonding configurations effuse at different temperatures due to their different desorption energies.     

Density functional theory study on the structure and properties of Si3N4 clusters

The hybrid density functional theory B3LYP with basis sets 6-31G＊ has been used to study on the equilibrium geometries and electronic structures of possible isomers of Si3N4 clusters. 24 possible isomers are obtained. The most stable isomer of Si3N4 is a 3D structure with 7 Si-N bonds and 2 N-N bonds that could beformed by 3 quadrangles. The bond properties of the most stable isomer was analyzed by using natural bond orbital method （NBO）, the results suggest that the charges on Si and N atoms in Si-N bonds are quite large, so theinteraction of N-Si atoms in Si3N4 cluster is of strongly electric interaction. The primary IR and Raman vibrational frequency located at 1033.40 cm^-1, 473.63 cm^-1 respectively. The polarizabilities and hyperpolarizabilities of the most stable isomer are also analyzed.     

Pressure-induced phase transition in silicon nitride material

The equilibrium crystal structures,lattice parameters,elastic constants,and elastic moduli of the polymorphs α-,β-,and γ-Si3N4,have been calculated by first-principles method.β-Si3N4 is ductile in nature and has an ionic bonding.γSi3N4 is found to be a brittle material and has covalent chemical bonds,especially at high pressures.The phase boundary of the β→γ transition is obtained and a positive slope is found.This indicates that at higher temperatures it requires higher pressures to synthesize γ-Si3N4.On the other hand,the α→γ phase boundary can be described as P = 14.37198+ 3.27 × 10?3T-7.83911 × 10?7T2-3.13552 × 10?10T3.The phase transition from α-to γ-Si3N4 occurs at 16.1 GPa and 1700 K.Then,the dependencies of bulk modulus,heat capacity,and thermal expansion on the pressure P are obtained in the ranges of 0 GPa-30 GPa and 0 K-2000 K.Significant features in these properties are observed at high temperatures.It turns out that the thermal expansion of γ-Si3N4 is larger than that of α-Si3N4 over wide pressure and temperature ranges.The evolutions of the heat capacity with temperature for the Si3N4 polymorphs are close to each other,which are important for possible applications of Si3N4.     

Mechanical strains in pecvd SiN_x:H films for nanophotonic application

Hydrogenated amorphous silicon nitride films(Si N x:H) are deposited at low temperature by high-frequency plasmaenhanced chemical vapor deposition(HF PECVD). The main effort is to investigate the roles of plasma frequency and plasma power density in determining the film properties particularly in stress. Information about chemical bonds in the films is obtained by Fourier transform infrared spectroscopy(FTIR). The stresses in the Si N x:H film are determined from substrate curvature measurements. It is shown that plasma frequency plays an important role in controlling the stresses in Si N x:H films. For silicon nitride layers grown at plasma frequency 40.68 MHz initial tensile stresses are observed to be in a range of 400 MPa–700 MPa. Measurements of the intrinsic stresses of silicon nitride films show that the stress quantity is sufficient for film applications in strained silicon photonics.     

Chemical structure of grain-boundary layer in SrTiO_3 and its segregation-induced transition: A continuum interface approach

Grain-boundary(GB) structures are commonly imaged as discrete atomic columns, yet the chemical modifications are gradual and extend into the adjacent lattices, notably the space charge, hence the two-dimensional defects may also be treated as continuum changes to extended interfacial structure. This review presents a spatially-resolved analysis by electron energy-loss spectroscopy of the GB chemical structures in a series of SrTiO_3 bicrystals and a ceramic, using analytical electron microscopy of the pre-Cs-correction era. It has identified and separated a transient layer at the model Σ5 grain-boundaries(GBs) with characteristic chemical bonding, extending the continuum interfacial approach to redefine the GB chemical structure. This GB layer has evolved under segregation of iron dopant, starting from subtle changes in local bonds until a clear transition into a distinctive GB chemistry with substantially increased titanium concentration confined within the GB layer in 3-unit cells, heavily strained, and with less strontium. Similar segregated GB layer turns into a titania-based amorphous film in SrTiO_3 ceramic, hence reaching a more stable chemical structure in equilibrium with the intergranular Ti_2O_3 glass also. Space charge was not found by acceptor doping in both the strained Σ5 and amorphous GBs in SrTiO_3 owing to the native transient nature of the GB layer that facilitates the transitions induced by Fe segregation into novel chemical structures subject to local and global equilibria. These GB transitions may add a new dimension into the structure–property relationship of the electronic materials.     

The effect of single A1GaN interlayer on the structural properties of GaN epilayers grown on Si （111） substrates

High-quality and nearly crack-free GaN epitaxial layer was obtained by inserting a single AlGaN interlayer between GaN epilayer and high-temperature AlN buffer layer on Si (111) substrate by metalorganic chemical vapor deposition. This paper investigates the effect of AlGaN interlayer on the structural properties of the resulting GaN epilayer. It confirms from the optical microscopy and Raman scattering spectroscopy that the AlGaN interlayer has a remarkable effect on introducing relative compressive strain to the top GaN layer and preventing the formation of cracks. X-ray diffraction and transmission electron microscopy analysis reveal that a significant reduction in both screw and edge threading dislocations is achieved in GaN epilayer by the insertion of AlGaN interlayer. The process of threading dislocation reduction in both AlGaN interlayer and GaN epilayer is demonstrated.     

Chemical Structure of HfO2/Si Interface with Angle-Resolved Synchrotron Radiation Photoemission Spectroscopy

Interracial chemical structure of HfO2/Si （100） is investigated using angle-resolved synchrotron radiation photoemission spectroscopy （ARPES）. The chemical states of Hf show that the Hf 4f binding energy changes with the probing depth and confirms the existence of Hf-Si-O and Hf Si bonds. The Si 2p spectra are taken to make sure that the interracial structure includes the Hf silicates, Hf silicides and SiOx. The metallic characteristic of the Hf-Si bonds is confirmed by the valence band spectra. The depth distribution model of this interface is established.     

The charge storage of the nc—Si layer

Sandwiched structures (a-SiN_x/a-Si/a-SiN_x) have been fabricated by the plasma enhanced chemical vapour deposition technique. A Si nanocrystal (nc-Si) layer was formed by crystallization of an a-Si layer according to the constrained crystallization principle after quasi-static thermal annealing at 1100℃ for 30 min. Transmission electron microscopy (TEM) and Raman scattering spectroscopy clearly demonstrated that nc-Si grains were formed in the as-deposited a-Si layer after annealing. The density of nc-Si grains is about 10¹¹cm^-2 as shown by TEM photographs. Using capacitance－voltage (C－V) measurements we investigated the electrical characteristics of the sandwiched structures. The charge storage phenomenon of the nc-Si layer was observed from the shift of flat-band voltage (V_FB) in C－V curves at a high frequency (1 MHz). We estimated the density of nc-Si grains to be about 10¹¹cm^-2 from the shift value of V_FB, which is in agreement with the result of TEM photographs. At the same time, we found that the shift of V_FB increased with the increase of the applied constant dc voltage or the thickness of the nc-Si layer.     

First-Principles Calculations of Atomic and Electronic Properties of T1 and In on Si（111）

The atomic and electronic structures of T1 and In on Si（111） surfaces are investigated using the firstprinciples total energy calculations. Total energy optimizations show that the energetically favored structure is 1/3 ML T1 adsorbed at the T4 sites on Si（111） surfaces. The adsorption energy difference of one T1 adatom between （√3 × √3） and （1 × 1） is less than that of each In adatom. The DOS indicates that TI 6p and Si 3p electrons play a very important role in the formation of the surface states. It is concluded that the bonding of TI adatoms on Si（111） surfaces is mainly polar covalent, which is weaker than that of In on Si（111）. So T1 atom is more easy to be migrated than In atom in the same external electric field and the structures of T1 on Si（111） is prone to switch between （√3 × √3） and （1 × 1）.     

Passivation of carbon dimer defects in amorphous SiO_2/4H–SiC(0001) interface:A first-principles study

An amorphous SiO_2/4 H–Si C(0001) interface model with carbon dimer defects is established based on density functional theory of the first-principle plane wave pseudopotential method.The structures of carbon dimer defects after passivation by H_2 and NO molecules are established,and the interface states before and after passivation are calculated by the Heyd–Scuseria–Ernzerhof(HSE06) hybrid functional scheme.Calculation results indicate that H_2 can be adsorbed on the O_2–C = C–O_2 defect and the carbon–carbon double bond is converted into a single bond.However,H_2 cannot be adsorbed on the O_2–(C = C) –O_2 defect.The NO molecules can be bonded by N and C atoms to transform the carbon–carbon double bonds,thereby passivating the two defects.This study shows that the mechanism for the passivation of Si O_2/4 H–SiC(0001) interface carbon dimer defects is to convert the carbon–carbon double bonds into carbon dimers.Moreover,some intermediate structures that can be introduced into the interface state in the band gap should be avoided.     

Growth and fabrication of semi-polar InGaN/GaN multi-quantum well light-emitting diodes on microstructured Si(001) substrates

Semi-polar(1-101) In Ga N/Ga N light-emitting diodes were prepared on standard electronic-grade Si(100) substrates.Micro-stripes of Ga N and In Ga N/Ga N quantum wells on semi-polar facets were grown on intersecting {111} planes of microscale V-grooved Si in metal–organic vapor phase epitaxy, covering over 50% of the wafer surface area. In-situ optical reflectivity and curvature measurements demonstrate that the effect of the thermal expansion coefficient mismatch was greatly reduced. A cross-sectional analysis reveals low threading dislocation density on the top of most surfaces. On such prepared(1-101) Ga N, an In Ga N/Ga N LED was fabricated. Electroluminescence over 5 m A to 60 m A is found with a much lower blue-shift than that on the c-plane device. Such structures therefore could allow higher efficiency light emitters with a weak quantum confined Stark effect throughout the visible spectrum.     

Influence of AlN buffer layer thickness on structural properties of GaN epilayer grown on Si (111) substrate with AlGaN interlayer

We present the growth of GaN epilayer on Si (111) substrate with a single AlGaN interlayer sandwiched between the GaN epilayer and AlN buffer layer by using the metalorganic chemical vapour deposition. The influence of the AlN buffer layer thickness on structural properties of the GaN epilayer has been investigated by scanning electron microscopy, atomic force microscopy, optical microscopy and high-resolution x-ray diffraction. It is found that an AlN buffer layer with the appropriate thickness plays an important role in increasing compressive strain and improving crystal quality during the growth of AlGaN interlayer, which can introduce a more compressive strain into the subsequent grown GaN layer, and reduce the crack density and threading dislocation density in GaN film.     

Comparison of electronic structure between monolayer silicenes on Ag(111)

√√The electronic structures of monolayer silicenes(4 × 4 and■×■R13.9o) grown on Ag(111) surface are studied by scanning tunneling spectroscopy(STS) and density functional theory(DFT) calculations. While both phases have similar electronic structures around the Fermi level, significant differences are observed in the higher energy unoccupied states.The DFT calculations show that the contributions of Si 3pz orbitals to the unoccupied states are different because of their different buckled configurations.     

Optical study of Ba(Mn_xTi_(1-x)O_3) thin films by spectroscopic ellipsometry

Stoichiometric Ba(Mn_xTi_(1-x)O_3) (BMT)thin films with various values of x were deposited on Si(111)substrates by the sol-gel technique.The influence of Mn content on the optical properties was studied by spectroscopic ellipsometry(SE)in the UV–Vis–NIR region.By fitting the measured ellipsometric parameter(Ψand)with a four-phase model(air/BMT+voids/BMT/Si(111)),the key optical constants of the thin films have been obtained.It was found that the refractive index n and the extinction coefficient k increase with increasing Mn content due to the increase in the packing density.Furthermore,a strong dependence of the optical band gap Egon Mn/Ti ratios in the deposited films was observed,and it was inferred that the energy level of conduction bands decreases with increasing Mn content.     

Effect of high-temperature annealing on AlN thin film grown by metalorganic chemical vapor deposition

The effect of high-temperature annealing on AlN thin film grown by metalorganic chemical vapor deposition was investigated using atomic force microscopy, Raman spectroscopy, and deep ultra-violet photoluminescence(PL) with the excitation wavelength as short as ～ 177 nm. Annealing experiments were carried out in either N2 or vacuum atmosphere with the annealing temperature ranging from 1200℃ to 1600℃. It is found that surface roughness reduced and compressive strain increased with the annealing temperature increasing in both annealing atmospheres. As to optical properties,a band-edge emission peak at 6.036 eV and a very broad emission band peaking at about 4.7 eV were observed in the photoluminescence spectrum of the as-grown sample. After annealing, the intensity of the band-edge emission peak varied with the annealing temperature and atmosphere. It is also found that a much stronger emission band ranging from 2.5 eV to 4.2 eV is superimposed on the original spectra by annealing in either N2 or vacuum atmosphere. We attribute these deep-level emission peaks to the VAL–ONcomplex in the AlN material.     

Observation of positive and small electron affinity of Si-doped AlN films grown by metalorganic chemical vapor deposition on n-type 6H–SiC

We have investigated the electron affinity of Si-doped AlN films(N_(Si)= 1.0 × 10~(18)–1.0 × 10_(19)cm~(-3)) with thicknesses of 50, 200, and 400 nm, synthesized by metalorganic chemical vapor deposition(MOCVD) under low pressure on the ntype(001)6H–SiC substrates. The positive and small electron affinity of AlN films was observed through the ultraviolet photoelectron spectroscopy(UPS) analysis, where an increase in electron affinity appears with the thickness of AlN films increasing, i.e., 0.36 eV for the 50-nm-thick one, 0.58 eV for the 200-nm-thick one, and 0.97 e V for the 400-nm-thick one.Accompanying the x-ray photoelectron spectroscopy(XPS) analysis on the surface contaminations, it suggests that the difference of electron affinity between our three samples may result from the discrepancy of surface impurity contaminations.     

Thin film micro-scaled cold cathode structures of undoped and Si-doped AlN grown on SiC substrate with low turn-on voltage

The field emission characteristics of the AlN thin films with micro-scaled cold cathode structures are tested in the high vacuum system. The aluminum nitride(AlN) thin films with a thickness of about 100 nm are prepared on the n-type 6H-SiC(0001) substrate at 1100°C by metal organic chemical vapor deposition(MOCVD) under low pressure. The I–V curves and surface micro-images of undoped and Si-doped AlN films are investigated. From the I–V and Fowler–Nordheim plots,it can be seen that the Si-doped Al N shows better field emission characteristics compared with the undoped AlN sample.The obtained turn-on field is 6.7 V/μm and the maximum emission current density is 154 m A/cm2 at 69.3 V for the Sidoped AlN film cathode after proper surface treatment. It is proposed that the relatively low electric resistivity of Si-doped Al N films is significant for electron migration to the surface region, and their rougher surface morphology is beneficial to a higher local electric field enhancement for the field emission.     

Variation of passivation behavior induced by sputtered energetic particles and thermal annealing for ITO/SiO_x/Si system

The damage on the atomic bonding and electronic state in a SiO_x(1.4-2.3 nm)/c-Si(150 μm) interface has been investigated.This occurred in the process of depositing indium tin oxide(ITO) film onto the silicon substrate by magnetron sputtering.We observe that this damage is caused by energetic particles produced in the plasma(atoms,ions,and UV light).The passivation quality and the variation on interface states of the SiO_x/c-Si system were mainly studied by using effective minority carrier lifetime(τ_(eff)) measurement as a potential evaluation.The results showed that the samples' τ_(eff)was reduced by more than 90%after ITO formation,declined from 107 μs to 5 μs.Following vacuum annealing at 200 ℃,the τ_(eff) can be restored to 30 μs.The components of Si to O bonding states at the SiO_x/c-Si interface were analyzed by x-ray photoelectron spectroscopy(XPS) coupled with depth profiling.The amorphous phase of the SiO_x layer and the "atomistic interleaving structure" at the SiO_x/c-Si interface was observed by a transmission electron microscope(TEM).The chemical configuration of the Si-O fraction within the intermediate region is the main reason for inducing the variation of Si dangling bonds(or interface states) and effective minority carrier lifetime.After an appropriate annealing,the reduction of the Si dangling bonds between SiO_x and near the c-Si surface is helpful to improve the passivation effect.     

Localized electronic states in gaps on hole-net structures of silicon

Hole-net structure silicon is fabricated by laser irradiation and annealing, on which a photoluminescence (PL) band in a the region of 650--750~nm is pinned and its intensity increases obviously after oxidation. It is found that the PL intensity changes with both laser irradiation time and annealing time. Calculations show that some localized states appear in the band gap of the smaller nanocrystal when Si=O bonds or Si--O--Si bonds are passivated on the surface. It is discovered that the density and the number of Si=O bonds or Si--O--Si bonds related to both the irradiation time and the annealing time obviously affect the generation of the localized gap states of hole-net silicon, by which the production of stimulated emission through controlling oxidation time can be explained.