EPR investigation of a-Si:H aerosol particles formed under silane thermal decomposition

The dangling bond defects were investigated in a-Si:H particles formed under silane thermal decomposition in flow reactor. EPR together with hydrogen evolution method were used. The experimental results allowed us to conclude that there are two kinds of dangling bond defects in a-Si:H aerosol particles. The defects of the first kind are localized on the surface of interconnected microvoids and microchannels (surface dangling bonds) and those of the second kind are embedded in amorphous silicon network (volume dangling bonds). The thermal equilibration of dangling bonds and temperature dependence of equilibrium dangling bond concentration were investigated. It was found that at temperatures > 400 K the dangling bond concentrationNApplied Magnetic Resonance _s reversibly depends on sample temperature. The volume dangling bond concentration increases with temperature increasing (the effective activation energy of dangling bond formationU > 0), and the surface dangling bond concentration decreases with temperature increasing (U < 0). It has been found that EPR line is considerably asymmetric for samples with high hydrogen content and for low hydrogen content the EPR line is weakly asymmetric. A conclusion was drawn that the asymmetry degree depends on amorphous silicon lattice distortions. This conclusion has been confirmed by EPR spectra simulations.     

E' centers in alpha quartz in the absence of oxygen vacancies: a first-principles molecular-dynamics study

The displacement of an oxygen atom in pure alpha quartz is studied via first-principles molecular dynamics. The simulations show that when an O atom in a Si-O-Si bridge is moved away from its original equilibrium position, a new stable energy minimum can be reached. Depending on the spin state and charge Q of the system, this minimum can give rise to either a threefold oxygen (singlet ground state and Q=+1) or to an unsaturated Si atom carrying a dangling bond (triplet state). In the latter case, the hyperfine parameters associated with the 29Si dangling bond are in rather good agreement with electron paramagnetic resonance/electron nuclear double resonance experiments.     

Hydrogen adsorption on the silicon (001) surface and on a step on the (111) surface

Adsorption of atomic hydrogen on an ideal (001) silicon surface is investigated in the present paper. Saturation of one of the two dangling bonds of a silicon atom on this surface by hydrogen removes the interaction (hybridization) between them, resulting in the appearance of a bonding and an antibonding chemisorption state associated with the attacked dangling bond, and in the shift of the peak of the remaining unsaturated dangling bond to the energy typical of a surface state of the (111) surface. Further saturation leads to the disappearance of this peak from the energy spectrum. An analogous situation occurs for the silicon atom with two dangling bonds on a step on the (111) surface, when hydrogen is chemisorbed. Both examples testify to the local chemical nature of Shockley surface states in silicon.The authors thank A. N. Sorokin for useful discussions.     

Interaction of silicon dangling bonds with insulating surfaces

We use first principles density functional theory calculations to study the interaction of a model dangling bond silicon tip with the surfaces of CaF2, Al2O3, TiO2, and MgO. In each case the strongest interaction is with the highest anions in the surface. We show that this is due to the onset of chemical bonding with the surface anions, which can be controlled by an electric field across the system. Combining our results and previous studies on semiconductor surfaces suggests that using dangling bond Si tips can provide immediate identification of surface species in atomically resolved noncontact atomic force microscopy and facilitate selective measurements of short-range interactions with surface sites.     

表面悬挂键对GaAs纳米线掺杂的影响及其钝化

利用第一性原理计算方法研究了表面悬挂键对GaAs纳米线掺杂的影响及其钝化．计算结果显示,不论是闪锌矿结构还是纤锌矿结构,GaAs纳米线表面Ga原子上带正电荷的表面悬挂键都是一类稳定的缺陷,并且这种稳定性不会随着纳米线直径的变化而变化．这种表面悬挂键会形成载流子陷阱中心从而从p型掺杂的GaAs纳米线俘获空穴,使得纳米线的掺杂效率下降．和NH₃相比,NO₂ 具有足够的电负性来俘获GaAs纳米线表面悬挂键上的未配对电子,从而有效地钝化GaAs纳米线的表面悬挂键,提高纳米线的p型掺杂效率,并且这种钝化特性不会随着纳米线直径的变化而改变．     

Molecular SCF calculations to model (111) surface states and relaxation of diamond

Ab-initio SCF-MO computations in an STO-3G Gaussian basis on a molecular system, designed to model a carbon atom on the (111) surface of diamond, predict that the danglingbond carbon relaxes about 0.10 Å toward the bulk from its position on an extension of the diamond lattice. The dangling bond carbon cation relaxes Inward 0.30 Å, while the anion relaxes outward 0.10 A. Tentative ways to describe the dangling bond in terms of computed quantities are presented.     

Large spin diffusion length in an amorphous organic semiconductor

We directly measured a spin diffusion length (lambdas) of 13.3 nm in amorphous organic semiconductor (OS) rubrene (C42H28) by spin polarized tunneling. In comparison, no spin-conserved transport has been reported in amorphous Si or Ge. Absence of dangling bond defects can explain the spin transport behavior in amorphous OS. Furthermore, when rubrene barriers were grown on a seed layer, the elastic tunneling characteristics were greatly enhanced. Based on our findings, lambdas in single-crystalline rubrene can be expected to reach even millimeters, showing the potential for organic spintronics development.     

Pulsed EPR hole-burning experiment on dangling bond centers in a-Si:H aerosol particles formed by thermal decomposition of silane

Si dangling bond centers in aerosol particles of amorphous hydrogenated silicon formed by thermal decomposition of SiH₄ in Ar were studied by pulsed electron paramagnetic resonance. The hole-burning and inversion-recovery experiments demonstrate that large-scale rapid spectral diffusion takes place in the samples with high spin concentration. Correlation times τ_c of the spectral diffusion and spin-lattice relaxation timesT ₁ were obtained in the temperature range between 77 and 290 K. Above 130 K, τ_c andT ₁ are proportional one to the other. The unusual feature of this spectral diffusion is that the shape of the central part of the spectral hole does not change when the delay time increases. The other paramagnetic centers previously investigated showed a remarkable change of the hole shape which was induced by modulation of dipolar interaction due to spin flips. It is suggested that the observed anomaly in the Si dangling bond centers arises due to cooperative spin flips.     

Chemical trends for localized gap states in amorphous semiconductors

The absence or presence of unpaired spin and of variable range hopping due to the localized gap states (dangling bond states) in various amorphous semiconductors is explained based on the chemical nature of constituent atoms and randomness of the glass structure. The randomness is also correlated with optical absorption data.     

Hydrogen-induced surface metallization of beta-SiC(100)-(3x2) revisited by density functional theory calculations

Recent experiments on the silicon terminated (3 x 2)-SiC(100) surface indicated an unexpected metallic character upon hydrogen adsorption. This effect was attributed to the bonding of hydrogen to a row of Si atoms and to the stabilization of a neighboring dangling bond row. Here, on the basis of density-functional calculations, we show that multiple-layer adsorption of H at the reconstructed surface is compatible with a different geometry: in addition to saturating the topmost Si dangling bonds, H atoms are adsorbed at rather unusual sites, i.e., stable bridge positions above third-layer Si dimers. The results thus suggest an alternative interpretation for the electronic structure of the metallic surface.     

表面悬挂键导致硅纳米线掺杂失效机理的第一性原理研究

利用第一性原理方法, 本文计算了B/N单掺杂SiNWs, 以及含有表面悬挂键的B/N单掺杂硅纳米线的总能和电子结构, 计算结果表明, 悬挂键的出现会导致单原子掺杂失效. 能带结构分析表明, B/N掺杂的H钝化的SiNWs表现出正常的p/n特性, 而表面悬挂键(dangling binding, DB)的存在会导致p型(B原子)或者n型(N原子)掺杂失效; 其失效的原因主要是因为表面悬挂键所引入的缺陷能级俘获了n型杂质(p型杂质)所带来的电子(空穴); 利用小分子(SO₂)吸附饱和悬挂键可以起到激活杂质的作用, 进而实现Si纳米线的有效掺杂.     

Spin dependent trapping at a silicon grain boundary

We have observed, for the first time, spin dependent trapping in a silicon grain boundary. The results are quantitatively explained in terms of paramagnetic “dangling bond” interface traps and a majority carrier thermionic emission model. This is a sensitive and informative probe of defects in grain boundaries.     

Electronic structure of Si(111) surfaces

We report on new angle-resolved photoemission studies of Si(111) 2 × 1 and 7 × 7 surfaces. The emission from the 2 × 1 surface shows much structure. For normal emission the energy positions are insensitive to the photon energy in the range 19–27 eV. The emission has been interpreted as a probe of the surface density of states, SDOS, including both surface states, resonances and bulk-like states. The SDOS was also calculated as a function of parallel momentum k_∥ for a model of the Si(111) 2 × 1 surface obtained from energy minimization considerations. We identify emission from the dangling bond band, which has a positive dispersion of 0.6 eV, and also emission from surface resonances which have some character of the compressed and stretched back bonds. There are also other predicted surface resonances that correspond to experimental peaks which have not been identified in previous work. Except for the dangling bond band, the surface resonances are limited in k_∥ space, so that it is not possible to follow these resonance bands over all angles. Maximum intensity for the normal emission from the dangling bond is obtained at 23 eV, while the emission from the lowest s-like states monotonically increases towards 30 eV photon energy. When annealing the cleaved 2 × 1 surface to the 7 × 7 reconstructed surface, the spectra broaden significantly. The intensity of the dangling bond decreases and we see a very small metallic edge.     

The chemisorption of hydrogen on silicon and silicon carbide (1 0 0) surfaces

The chemisorption of hydrogen onto semiconductor surfaces is examined. The hydrogen bonds to the dangling bond of a surface atom. These dangling bonds also dictate the reconstruction of the crystal surface. The chemisorbed hydrogen therefore modifies the reconstructed surface topology. In this work theoretical calculations of the surface structures of both covalent elemental silicon and polar silicon carbide are presented. The periodic MINDO method is employed to determine the topologies for the 2 × 1 reconstructed (1 0 0) surfaces. These topologies are obtained from the minimisation of the total energy, for silicon and silicon carbide films of 14 layer thickness, with respect to the atomic co-ordinates of the hydrogen adsorbate and the first four layers of the substrate. The results show that the formation of the hydrogen bond to the substrate leads to a general lengthening of the surface dimer bond. In addition, the buckling of the silicon dimer determined for silicon terminated SiC is removed by hydrogen chemisorption.     

Identification of the carbon dangling bond center at the 4H-SiC/SiO(2) interface by an EPR study in oxidized porous SiC

We report the observation of a paramagnetic interface defect in thermally oxidized porous n-type doped 4H-SiC/SiO(2). Based on its axial symmetry and resolved hyperfine interactions it is attributed to an sp(3) carbon dangling bond center situated at the SiC side of the interface. This center is electrically active and pins the Fermi level in the oxidized samples. No silicon related paramagnetic dangling bond centers are observed. The formation of dangling bond centers seems to be related to interstitial oxygen diffusion at the interface during the oxidation process.     

Evidence for a 2D-metallic state of the clean 7 × 7 Si(111) surface

The energy loss spectrum of electrons reflected from a clean (7 × 7) Si(111) surface exhibits an intense inelastic continuum with a Drude-type tail of the elastic line. The continuum disappears when the surface is covered with an adsorbate. The loss spectrum is indicative of a 2D-metallic state of the dangling bond surface states.     

Relaxation of (111) silicon surface atoms from studies of Si4H9 clusters

Self-consistent Hartree-Fock and generalized valence bond calculations have been performed on clusters modeling the (111) silicon surface. We find that the surface state is accurately described as a dangling bond surface orbital with 93% p character. We determined the optimum relaxation of the surface layer to be 0.08 Å toward the second layer. In the positive ion, the surface atom relaxes toward the second layer by an additional 0.30 Å and for the negative ion the surface atom moves toward the vacuum 0.25 Å. The vertical ionization potential was found to be 5.78 eV (experimental values are 5.6 – 5.9 eV) while the calculated adiabatic electron affinity is 3.02 eV.     

Many-body effects in the Si(111)7×7 reconstructed surface

A two-dimensional Hubbard Hamiltonian is introduced in order to analyse the many-body effects associated with a dangling bond Si(111) 7×7 surface state located at the Fermi energy. Our results indicate that many-body effects can offer an explanation of recently reported experimental data.     

Atomic wire oxidation of H-terminated Si(100)-( 2x1): domino reaction via oxidation and H migration

We studied oxidation at a dangling bond (DB) on the H-terminated Si(100) surface by the first-principles calculations. We found that oxidation easily occurs at the exposed DB on the H-terminated Si(100) surface. The dissociated O atoms are chemisorbed at a dimer bond and a back bond, resulting in adjacent H atom migration onto the DB. As a consequence of the alternate oxidation and subsequent H atom migration processes, the atomic wire oxidation is actually found to occur on the H-terminated Si(100) surface at low temperatures without desorbing H atoms, as observed in our scanning tunneling microscopy experiment.     

Relaxation of (111) silicon surface atoms from studies of Si4H9 clusters

Self-consistent Hartree-Fock and generalized valence bond calculations have been performed on clusters modeling the (111) silicon surface. We find that the surface state is accurately described as a dangling bond surface orbital with 93% p character. We determined the optimum relaxation of the surface layer to be 0.08 Å toward the second layer. In the positive ion, the surface atom relaxes toward the second layer by an additional 0.30 Å, and for the negative ion the surface atom moves toward the vacuum 0.25 Å. The vertical ionization potential was found to be 5.78 eV (experimental values are 5.6 – 5.9 eV) while the calculated adiabatic electron affinity is 3.02 eV.