Metastability of amorphous silicon from silicon network rebonding

We propose a network rebonding model for light-induced metastability in amorphous silicon, involving bonding rearrangements of silicon and hydrogen atoms. Nonradiative recombination breaks weak silicon bonds and generates dangling bond-floating bond pairs, with very low activation energies. The transient floating bonds annihilate, generating local hydrogen motion. Charged defects are also found. Support for these processes is found with tight-binding molecular dynamics simulations. The model accounts for major experimental features of the Staebler-Wronski effect including electron-spin resonance data, the t(1/3) kinetics of defect formation, two types of metastable dangling bonds, and hysteretic annealing.     

Semi-empirical calculations of hydrogen defects in silicon

Calculations for hydrogen defect(s) in a monovacancy silicon cluster yield a stable position for this defect which: (a) does not saturate any of the silicon dangling bonds; and (b) contributes defect level(s) in the gap whose implications remain to be understood.     

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.     

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.     

Hydrogen incorporation behaviour and radiation damage in proton bombarded InP single crystals

Abstract

In proton bombarded InP single crystals the incorporation behaviour of different hydrogen isotopes is studied in relation to implantation induced radiation defects. Investigations of the fluence dependence (D = 10¹⁶-10¹⁸ cm^?2), of the depth profile and of the annealing behaviour (T _an = 300–1000 K) of hydrogen incorporation and of damage density indicate that only a small fraction of the implanted hydrogen is chemically bonded to host lattice atoms. These bonded hydrogen atoms saturate dangling bonds at defect sites.     

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.     

Light-induced defect creation in hydrogenated polymorphous silicon during repeated cycles of illumination and annealing

We have examined how the intensity of the ESR signal associated with dangling bonds in hydrogenated polymorphous silicon is affected by repeating light-soaking (LS) and 100°C annealing cycles. It was found that the light-induced degradation efficiency decreases with repeated LS–100°C annealing cycles. This result is accounted for in terms of the termination of dangling bonds by mobile hydrogen, i.e. the termination is enhanced by more mobile hydrogen as a result of modification of the amorphous network by the LS–annealing cycles, and consequently the net light-induced defect creation rate is reduced. This is in contrast with previous models in which the decrease in the light-induced degradation efficiency on repeated LS–annealing cycles is attributed to an increase in the amount of hydrogen being ineffective for light-induced defect creation.     

Luminescence and ESR studies of defects in hydrogenated amorphous silicon

New experimental information on luminescence and light induced ESR (LESR) in hydrogenated amorphous silicon is described. We demonstrate that the two experiments involve identical recombination transitions, and identify two separate processes. One process involves defect states, and from the doping dependence of LESR we deduce that the electronically active defects are dangling bonds with positive electronic correlation energy.     

Hydrogen diffusion and electronic metastability in amorphous silicon

Hydrogen diffusion and its role in the many electronic metastability phenomena in hydrogenated amorphous silicon (a-Si:H) is reviewed. A-Si:H contains about 10 at% hydrogen, most of which is bonded to silicon. The hydrogen diffuses at relatively low temperatures by releasing hydrogen from the Si-H bonds into interstitial sites. The reactions of hydrogen with the silicon dangling bonds and the weak bonds provide a hydrogen-mediated mechanism for electron-structural interactions, which are manifested as electronic metastability. The annealing of light-induced defects, the equilibration of defects and dopants, the stretched exponential relaxation kinetics, and the atomic structure formed during growth, are all attributed to hydrogen diffusion.     

Hydrogen incorporation in diamond: the vacancy-hydrogen complex

We report the identification of the vacancy-hydrogen complex in single crystal diamond synthesized by chemical vapor deposition. The S=1 defect is observed by electron paramagnetic resonance in the negative charge state. The hydrogen atom is bonded to one of the carbon atoms neighboring the vacancy. Unlike the analogous defect in silicon, no symmetry lowering reconstruction occurs between the three remaining carbon dangling orbitals. The very small measured hydrogen hyperfine interaction is explained by dipolar coupling between the hydrogen and the unpaired electron probability density delocalized on the three equivalent carbon neighbors.     

Computational studies of the effect of hydrogen on the thermalized positron state in amorphous silicon

The two-component density functional theory is applied to the study of the thermalized positron state in simulated structures of hydrogenated amorphous silicon. Results show that positron properties in bulk and ad hoc defect structures are sensitive to the defect free-volume. Using the normalized positron density, it is determined that the thermalized positron state is weakly localized at hydrogen-decorated vacancy-like complexes, and not at microscopic open volume defects. These defect complexes form as clusters of hydrogen-passivated dangling bonds. It is also found that hydrogen enhances the delocalization of positron density in the simulated structures. The relevance of the present results to the interpretation of actual positron lifetime spectroscopy in real materials is discussed.     

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.     

热处理CZ-Si中新施主与氧沉淀产物的对应关系

本文利用霍耳测量、红外测量及透射电子显微镜等手段,对热处理CZ-Si中的新施主及氧沉淀进行了研究。常规电子显微镜(TEM)结果表明,经650—750℃热处理的CZ-Si中主要形成点状及杆状缺陷。新施主的形成与点状缺陷关系密切。根据高分辨电子显微镜(HREM)观察,这些点状缺陷相当于晶体结构为β-方石英的片状SiO₂晶态沉淀,它们与硅基体界面上有半数硅原子处于失配状态,失配原子的悬挂键可以成为新施主的来源。新施主的产生受控于β-方石英沉淀物的形核、长大及其结构变化。 关键词：     

Modification of Electrical Activity of Grain Boundaries in EFG Silicon Under Influence of Hydrogen Plasma

We investigated an influence of hydrogen plasma treatment on electrical properties of shaped silicon polycrystals. Hydrogen penetration into polycrystalline silicon is demonstrated to depend on the state of the crystal (as-grown or annealed) and type of grain boundary (general or weakly deviated from special orientations). It is found that interaction of atomic hydrogen with grain boundaries can result not only in decrease of their electrical activity, but also in increase of potential barrier height at relatively high (more than 2 × 10¹⁸ cm^–2) doses of incorporated hydrogen. This phenomenon is explained by a phenomenological model which takes into account passivation of grain boundary dangling bonds and boron atoms in the bulk as two main mechanisms controlling hydrogenation effect.     

The relationship between hydrogen and paramagnetic defects in thin film silicon irradiated with 2 MeV electrons

After irradiation of hydrogenated amorphous and microcrystalline silicon (a-Si:H and μc-Si:H) with 2 MeV electrons at 100 K, we observe satellite-like components close to the dominating electron spin resonance (ESR) signal of these materials. The satellites overlap with the commonly observed dangling bond resonance and are proposed to originate from a hyperfine interaction with the nuclear magnetic moment of hydrogen atoms in a-Si:H and μc-Si:H. Our present study is focused on the verification of this hypothesis. Equivalent hydrogenated and deuterated a-/μc-Si:H/D materials have been investigated with ESR before and after 2 MeV electron bombardment. From the difference between ESR spectra of hydrogenated and deuterated samples we identify the doublet structure in the ESR spectra as a hyperfine pattern of hydrogen-related paramagnetic centers. The observations of H-related paramagnetic centers in a-/μc-Si:H are of particular interest in view of metastability models of a-Si:H, which include H-related complexes as precursors for the stabilization of the metastable Si dangling bonds. The nature of the observed center is discussed in the light of known H-related complexes in crystalline Si and suggested H-related dangling bonds in a-Si:H.     

Photoluminescence in hydrogenated amorphous germanium (a-Ge:H)

The photoluminescence of glow discharge deposited a-Ge:H is studied. The spectra exhibit a two-band structure with an intrinsic band centered at 0.65 eV and a defect induced band near 0.5 eV, which is enhanced by using less favorable deposition conditions (low substrate temperature) and by hydrogen effusion. Even in films of good quality the quantum efficiency is only about 1 % of that of good a-Si:H-films. It is suggested that the non-radiative recombination centers are Ge- dangling bonds and that the low efficiency as compared to a-Si:H-films of similar defect density is due to the larger localization length of the db-states which enhances radiationless tunneling processes.     

Metastable states in Si:H

The results of ab initio LDF calculations applied to large clusters of Si atoms containing H in various positions are described. We find the bond centred (BC) defect to be most stable for neutral and positively charged H. H placed at an antibonding site is also stable with an energy 0.1 eV higher than the BC defect. The stability of H₂ and H^*₂ is also discussed. New results are reported for the conversion of BC defects into Si dangling bonds. It is found that H attached to vacancy-like defects is bi-stable: for Si-H-Si lengths less than ≈3.8 Å, the BC defect is stable, whereas for longer separations, the Si-H ··· Si dangling bond is stable. A discussion of the relevance of this to the Staebler-Wronski effect is given.     

Influence of a weak magnetic field on microplasticity of silicon crystals

The possibility of magnetic ordering at dangling bonds in dislocation cores has been investigated theoretically. It has been experimentally shown that magnetic ordering in dislocations affects the spin-dependent effects occurring in dislocation crystals of silicon. It has been found that preliminary magnetic treatment of silicon crystals in a weak magnetic field leads to the suppression of the electroplastic effect induced in silicon crystals excited by an electric current. It has been assumed that a change in the microplasticity under the combined action of a magnetic field and an electric current is caused by a weakening of spin-dependent recombination at dislocation dangling bonds.     

Comparative properties of systems involving dangling bonds

Abstract

The role of dangling bonds in tetrahedrally coordinated systems is analyzed in a variety of different physical situations: tricoordinated silicon atoms at the Si—SiO₂ interface or in a-Si, vacancies in covalent materials or in compounds, pinning of some impurity levels, dangling bonds at surfaces and interfaces. Emphasis is put on the common features that exist in all these apparently very different situations, resulting in a fairly simple and general understanding of the related physical properties.     

氢化纳米硅薄膜中氢的键合特征及其能带结构分析

对氢化纳米硅薄膜中氢的键合特征和薄膜能带结构之间的关系进行了研究.所用样品采用螺 旋波等离子体化学气相沉积技术制备，利用Raman散射、红外吸收和光学吸收技术对薄膜的 微观结构、氢的键合特征以及能带结构特性进行了分析.Raman结果显示不同衬底温度下所生 长薄膜的微观结构存在显著差异，从非晶硅到纳米晶硅转化的衬底温度阈值为200℃.薄膜中 氢的键合特征与薄膜的能带结构密切相关.氢化非晶硅薄膜具有较高的氢含量，因键合氢引 起的价带化学位移和低衬底温度决定的结构无序性，使薄膜呈现较大的光学带隙和带尾宽度 .升 关键词： 氢化纳米硅 螺旋波等离子体 能带结构