Hydrogen complexes in hydrogenated silicon

Experimental evidence suggests that H bonds to a fully coordinated Si network in pairs. The total energies and vibration frequencies of various possible pair configurations are calculated using a local density pseudopotential method on supercells. The H^*₂configuration, consisting of a bond centered H and a H located at an adjacent antibonding site, is found to be low in energy and more importantly, these H^*₂configurations bind together with as much as 0.4 eV/pair forming Si>{111} platelet structures. Metastability can also be accounted for when the H^*₂dissociates creating two interstitial H atoms which diffuse to form Si dangling bond-like defects at weak bond sites. Annealing occurs when the H atoms reform complexes.     

MoO_3/Si界面区钼掺杂非晶氧化硅层形成的第一性原理研究

采用基于密度泛函理论的第一性原理计算方法,通过模拟MoO_3/Si界面反应,研究了MoO_x薄膜沉积中原子、分子的吸附、扩散和成核过程,从原子尺度阐明了缓冲层钼掺杂非晶氧化硅(a-SiO_x(Mo))物质的形成和机理.结果表明,在1500 K温度下, MoO_3/Si界面区由Mo, O, Si三种原子混合,可形成新的稳定的物相.热蒸发沉积初始时, MoO_3中的两个O原子和Si成键更加稳定,同时伴随着电子从Si到O的转移,钝化了硅表面的悬挂键. MoO_3中氧空位的形成能小于SiO_2中氧空位的形成能,使得O原子容易从MoO_3中迁移至Si衬底一侧,从而形成氧化硅层;替位缺陷中, Si替位MoO_3中的Mo的形成能远远大于Mo替位SiO_2中的Si的形成能,使得Mo容易掺杂进入氧化硅中.因此,在晶硅(100)面上沉积MoO_3薄膜时, MoO_3中的O原子先与Si成键,形成氧化硅层,随后部分Mo原子替位氧化硅中的Si原子,最终形成含有钼掺杂的非晶氧化硅层.     

First-principles calculations of the hole-induced depassivation of SiO2/Si interface defects

The holes induced by ionizing radiation or carrier injection can depassivate saturated interface defects. The depassivation of these defects suggests that the deep levels associated with the defects are reactivated, affecting the performance of devices. This work simulates the depassivation reactions between holes and passivated amorphous-SiO₂/Si interface defects (HP_b+h→ P_b+H⁺). The climbing image nudged elastic band method is used to calculate the reaction curves and the barriers. In addition, the atomic charges of the initial and final structures are analyzed by the Bader charge method. It is shown that more than one hole is trapped by the defects, which is implied by the reduction in the total number of valence electrons on the active atoms. The results indicate that the depassivation of the defects by the holes actually occurs in three steps. In the first step, a hole is captured by the passivated defect, resulting in the stretching of the Si-H bond. In the second step, the defect captures one more hole, which may contribute to the breaking of the Si-H bond. The H atom is released as a proton and the Si atom is three-coordinated and positively charged. In the third step, an electron is captured by the Si atom, and the Si atom becomes neutral. In this step, a P_b-type defect is reactivated.     

Reversible H2 passivation of Si ≡ Si3 interface defects in (1 1 1)Si/SiO2

K-band electron spin resonance (ESR) at 4.3 K has revealed the dipole-dipole (DD) interaction effects between [1 1 1]P_b centers (^*Si ≡ Si₃ defects with unpaired sp³ hybrid [1 1 1]) at the 2 dimensional (1 1 1)Si/SiO₂ interface. This has been enabled by the perfectly reversible H₂ passivation of P_b, which affects the defect's spin state. Sequential hydrogenation at 253–353°C and degassing treatments in high vacuum at 743–835°C allowed to vary the P_b density in the range 5 × 10¹⁰ < [P_b] (1.14 ± 0.06) × 10¹³ cm^-2. With increasing [P_b] fine structure doublets are clearly resolved. It is found that (1 1 1)Si/SiO₂ interfaces, dry thermally grown at ≈920°C, naturally comprise a ^*Si ≡ Si₃ defect density — passivated or not — of 1.14 × 10¹³ cm^-2.     

Defect versus nanocrystal luminescence emitted from room temperature and hot-implanted SiO2 layers

Silicon nanocrystals have been synthesized in SiO₂ matrix using Si ion implantation. Si ions were implanted into 300-nm-thick SiO₂ films grown on crystalline Si at energies of 30–55 keV, and with doses of 5×10¹⁵, 3×10¹⁶, and 1×10¹⁷ cm⁻². Implanted samples were subsequently annealed in an N₂ ambient at 500–1100°C during various periods. Photoluminescence spectra for the sample implanted with 1×10¹⁷ cm⁻² at 55 keV show that red luminescence (750 nm) related to Si-nanocrystals clearly increases with annealing temperature and time in intensity, and that weak orange luminescence (600 nm) is observed after annealing at low temperatures of 500°C and 800°C. The luminescence around 600 nm becomes very intense when a thin SiO₂ sample is implanted at a substrate temperature of 400°C with an energy of 30 keV and a low dose of 5×10¹⁵ cm⁻². It vanishes after annealing at 800°C for 30 min. We conclude that this luminescence observed around 600 nm is caused by some radiative defects formed in Si-implanted SiO₂.     

Low-temperature ESR study of PbO defects residing in the (111) Si/native oxide interface

A K-band electron spin resonance (ESR) study of the (111) Si/native SiO₂ structure has been carried out in the temperature range 2.4 T 30 K. The ESR signal of the interfacial [111] P_bO center was observed, exhibiting in general similar properties to the well-documented [111] P_bO signal observed on firmly thermally-oxidized (TO) Si. However, many details in the P_bO spectrum differ like, e.g., the strain-induced inhomogeneous (g-spread) part (B^G_pp) of the linewidth. For B|[111] (B being the externally applied magnetic field), the ²⁹Si hyperfine structure of the [111] P_bO center has been observed which is characterized by the hyperfine splitting a^hf = 159±2 G and the hf signal width B^hf_pp = 14.8±0.5 G. Both the observed B^G_pp and B^hf_pp reveal the existence of a significantly larger strain-induced g distribution in Si/native SiO₂. Apart from the [111] P_bO center, also the signals of the P_bO defects with their dangling orbital parallel to [11 ], [1 1] or [ 11] have been observed; as yet, these signals have not been observed on TO structures. The saturation behaviour has been examined showing the P_bO Si/native oxide interface center to be much less saturable than the P_bO in TO structures. The observations are related to the particular physico-chemical interface structure.     

DIET in the bulk: evidence for hot electron cleavage of Si---H bonds in SiO2 films

The observed increase in leakage current through SiO₂ films after hot electron exposure is ascribed to dissociation induced by electronic transitions (“DIET”) of bulk Si---H bonds, producing mobile hydrogen. We use ab initio supercell bandstructure calculations at the local density functional level to locate features produced by hydrogen-containing defects in -SiO₂. The edge of the Si---H σ* resonance is found to be about 2.7 eV above the conduction band rise, in good agreement with the observed threshold for hot electron induced damage in amorphous SiO₂ films grown on Si substrates. The O---H σ* resonance is almost 4 eV higher. Removing H from O---H in the supercell does not affect the gap region (---O⁻ forms); however, removing H from Si---H produces a mid-gap state, suggesting leakage current by hopping conductivity between Si dangling bonds. A Morse potential model is used to explore the dynamics of bond scission by short-lived (<1 fs) hot electron σ* capture. Supercell calculations on interstitial atomic hydrogen indicate the energy cost to break an embedded Si---H bond is about 0.6 eV less than in the gas phase. The DIET yield is substantially increased by reducing both ground and electron-attached state binding by this amount. While uncertainty over the displaced equilibrium in the electron-attached excited state remains, the computed DIET cross-section for reasonable parameters is ≈10⁻¹⁸ cm², and is in agreement with the semi-empirically derived value for trap creation. Comparisons are made to surface DIET processes involving Si---H bonds.     

Competing thermal relaxation processes in response to intrinsic defects produced by exposing SiO2 to synchrotron radiation

Irradiation of SiO₂ with soft X-ray photons (hν>100 eV) produces a variety of defects, of which E₁′ centers and neutral Si–Si bonds are mainly responsible for the dielectric response change. The thermal processes that modify the structures around the defect sites have been investigated by in situ spectroscopic ellipsometry. Annealing the irradiated SiO₂ film diminishes the number of defects which are assigned to E₁′ centers by about half. The competing channels for annihilation of E₁′ centers are the recovery of the Si–O–Si bonding configuration and, in the opposite direction, the decomposition of the material into volatile products until the network is completely restructured. The other half of the defects are converted to Si–Si bond units and precipitates as nanocrystalline particles of Si.     

THE INTERACTION OF Au AND THE Si/SiO2 INTERFACE DEFECT Hit(0.494)

The defects at the Si/SiO₂ interface have been studied by the deep-level transient spectroscopy (DLTS) technique in p-type MOS structures with and without gold diffusion. The experimental results show that the interaction of gold and Si/SiO₂ interface defect,H_it(0.494), results in the formation of a new interface de-fect, Au-H_it(0.445). Just like the interface defect, H_it(0.494), the new interface defect possesses a few interesting properties, for example, when the gate voltage applied across the MOS structure reduces the energy interval between Fermi-level and Si valence band of the Si surface to values smaller than the hole ionization Gibbs free energy of the defect, a sharp DLTS peak is still observable; and the hole apparent activation energy increases with the decrease of the Si surface potential barrier height. These properties can be successfully explained with the transition energy band model of the Si/SiO₂ interface.     

Adsorption and dissociation of Si2H6 on Ge(001)2 × 1

Adsorption and thermally-induced dissociation of disilane (Si₂H₆) on clean Ge(001)2 × 1 surfaces have been investigated using a combination of Auger electron spectroscopy (AES), electron energy loss spectroscopy (EELS), reflection high-energy electron diffraction (RHEED), and scanning tunneling microscopy (STM). With initial Si₂H₆ exposure at room temperature, the Si surface coverage increased monotonically, the EELS surface dangling bond peak intensities continuously decreased, and the intensity of half-order RHEED diffraction rods decreased. The low-coverage Si₂H₆ sticking probability at 300 K on Ge(001) was found to be 0.5 while the saturation coverage was 0.5 ML. A new EELS feature, GSH, involving Si-H and Ge-H bond states was observed at Si₂H₆ exposures φ 3.4 × 10¹³ cm⁻². In contrast to Si₂H₆ -saturated Si(001), the saturated Ge(001) surface significant fraction of dimerized bonds. Adsorbed overlayers were highly disordered with the primary species on saturated surfaces being SiH₂, GeH, and undissociated SiH₃· Si₂H₆-saturated Ge(001)2 × 1 substrates were annealed for l min at temperatures T_a between 425 and 825 K. Admolecules were mobile at T_a = 545 K giving rise to significant ordering in one-dimensional chains. By T_a = 605 K, essentially all of the admolecules were captured into coarsened islands. Dangling-bond EELS peaks reappeared by 625 K and the intensities of the half-order RHEED diffraction rods increased. Ge segregation to the surface, which began at T_a 625 K, occurred rapidly at T_a 675 K. All H was desorbed by 725 K.     

Erbium in silicon–germanium quantum wells

Strained Si_1−xGe_x/Si quantum wells have been doped with erbium by implantation. A comparison is made with strained Si_1−xGe_x/Si quantum wells and relaxed Si_1−xGe_x, with x between 10% and 25%, doped with erbium during MBE growth. The erbium concentration was between 1×10¹⁸ and 5×10¹⁸ cm⁻³ throughout the active regions. Transmission electron microscopy, X-ray diffraction, and photoluminescence studies indicate that good regrowth can been achieved after full amorphisation by implantation of the strained quantum wells. The erbium luminescence is more intense in the Si_1−xGe_x/Si layers, but erbium-implanted samples containing Si_1−xGe_x exhibit defect luminescence in the region of 0.9–1.0 eV. These defects are also present when Si_1−xGe_x/Si quantum wells are implanted with an amorphising dose of silicon, and then regrown. They are attributed to small germanium-rich platelets, rather than to erbium-related defects. Electroluminescence is presented from a forward biased erbium-implanted Si_0.87Ge_0.13/Si structure at a drive current density of only 1.8 mA/cm².     

Hydrogen diffusion in crystalline semiconductors

The diffusion of hydrogen in semiconductors is complicated by the existence of several charge states (notably H⁺ in p-type material and H^- or H⁰ in n-type material, at least for Si) and also that hydrogen is present in a number of different forms, namely atomic, molecular or bound to a defect or impurity. Since the probability of formation of these different states is dependent on the defect or impurity type and concentration in the material and on the hydrogen concentration itself, then the apparent hydrogen diffusivity is a function of the sample conductivity and type and of the method of hydrogen insertion. Under conditions of low H⁺ concentration in p-type Si, for example, the diffusivity is of the order of 10^-10 cm² · s^-1 at 300 K and is consistent with the value expected from an extrapolation of the Van Wieringen and Warmoltz expression D_H = 9.4 × 10^-3 exp[-0.48 eV/kT] cm² · s^-1. The characteristics of hydrogen diffusion in n- and p-type Si and GaAs are reviewed in this paper, and the retardation of hydrogen permeation by molecular formation and impurity trapping is discussed. The measurement of several key parameters, including the energy levels for the hydrogen donor and acceptor in Si and the diffusivity of the H⁰ and H^- species, would allow a more quantitative treatment of hydrogen diffusion in semiconductors.     

Highly stable passivation of a Si(1 1 1) surface using bilayer-GaSe

As a stable and ‘epitaxial’ passivation of a Si surface, we propose the bilayer-GaSe termination of a Si(1 1 1) surface. This surface is fabricated by depositing one monolayer of Ga on a clean Si(1 1 1) surface and subsequent annealing in a Se flux at around 520 °C, which results in unreconstructed 1×1 termination of the Si(1 1 1) surface by bilayer-GaSe. We found by scanning tunneling microscopy observation that slow cooling of the clean Si(1 1 1) surface from 850 to 520 °C with simultaneous deposition of a Ga flux results in better termination of the Si(1 1 1) surface. It was also found that this surface is stable against heating around 400 °C in O₂ atmosphere of 3×10⁻³ Pa. By utilizing these properties of the bilayer-GaSe terminated surface, we have succeeded in fabricating ZnO quantum dots on this substrate.     

Structural and Optical Properties of Point Defects in α-SiO2 Cluster

First-principles methods based on the density functional theory (DFT) are used in order to calculate the structural and optical properties of α-SiO₂ cluster with the non-bridging oxygen hole centers (NBOHC) and NBOHC-E' defects. We clarify the stable structure of the NBOHC-E' point defects for the first time using the functional B3LYP, which is also tested to investigate the influence of electronic properties. The calculation is carried out for cluster configurations extracted from supercell. The results of optical absorption peak for Si₂O₇H₆ and Si₅O₁₆H₁₂ with NBOHC-E' defects are found at 2.66 eV, which is higher than the often observed OA peak at 2.0 eV for the NBOHC defect in α-SiO₂. The overall absorption spectra are in qualitative agreement with the experiment.     

Theoretical study of interaction between atoms of Au, Ag, Cu and clean Si(1 1 1) surface

To evaluate the interactions between the atoms of Au, Ag and Cu and clean Si(1 1 1) surface, two types of silicon clusters Si₄H₇ and Si₁₆H₂₀ together with their metal complexes were studied by using hybrid (U)B3LYP density functional theory method. Optimized geometries and energies on different adsorption sites indicate that: (1) the binding energies at different adsorption sites are large (ranging from 1.2 to 2.6 eV depend on the metal atoms and adsorption sites), suggesting a strong interaction between metal atom and silicon surface; (2) the most favorable adsorption site is the on top (T) site. Mulliken population analysis indicated that in the system of on top (T) site, a covalent bond is formed between metal atom and dangling bond of surface Si atom.     

Characterization of high-k gate dielectric/silicon interfaces

We have shown that, for thermally evaporated Ta₂O₅ or ZrO₂ thin films on Si(1 0 0), O₂ annealing at 300–500 °C causes the formation of an interfacial silicon oxide layer as thin as 1–2 nm which can be interpreted in terms of their high permeability to oxygen. And we have demonstrated how useful the energy loss spectra of photoexcited electrons from core levels such as O 1s are to measure the energy bandgaps of very thin insulators. With the combination of measured bandgaps and valence band lineups determined for X-ray photoelectron spectroscopy valence band spectra, we have determined the energy band alignments of Ta₂O₅ and ZrO₂ with Si(1 0 0) before and after the O₂ annealing at 500 °C. In addition, we have demonstrated that total photoelectron yield spectroscopy provides us direct information to quantify the energy distributions of both the defect states in the high-k dielectrics and the dielectric/Si(1 0 0) interface states over nearly entire Si bandgap.     

Structure of the Si(011)-(16 × 2) surface and hydrogen desorption kinetics investigated using temperature-programmed desorption

D₂ temperature-programmed desorption (TPD) was used to probe the structure of the Si(011)-(16 × 2) surface. Deuterium was adsorbed at 200°C to coverages θ_D ranging up to complete saturation (approximately 1.1 ML) and the sample heated at 5°C s⁻¹. TPD spectra exhibited three second-order desorption peaks labelled β₂, β*₁ and β₁ centered at 430, 520 and 550°C. Of the proposed models for the Si(011)-(16 × 2) reconstruction, the present TPD results as a function of θ_D provide support for the adatom/dimer model with the β₂ peak assigned to D₂ desorption from the dihydride phase, while the β*₁ and β₁ peaks arise from adatom and surface-atom monohydride phases.     

Photoluminescence and paramagnetic defects in silicon-implanted silicon dioxide layers

Thermally grown SiO₂ layers on Si substrates implanted with Si⁺ ions with a dose of 6×10¹⁶ cm⁻² were studied by the techniques of photoluminescence, electron paramagnetic resonance (EPR), and low-frequency Raman scattering. Distinct oxygen-vacancy associated defects in SiO₂ and non-bridging oxygen hole centers were identified by EPR. The luminescence intensity in the 620 nm range was found to correlate with the number of these defects. The low-frequency Raman scattering technique was used to estimate the average size of the Si nanocrystallites formed after the implantation and thermal annealing at T>1100°C, which are responsible for the photoluminescence band with a maximum at 740 nm. The intensity of this band can be significantly enhanced by an additional treatment of the samples in a low-temperature RF plasma.     

Passivation and dissociation of Pb-type defects at a-SiO_2/Si interface

It is well known that in the process of thermal oxidation of silicon,there are P_b-type defects at amorphous silicon dioxide/silicon(a-SiO_2/Si) interface due to strain.These defects have a very important impact on the performance and reliability of semiconductor devices.In the process of passivation,hydrogen is usually used to inactivate P_b-type defects by the reaction P_b+H_2→P_bH+H.At the same time,P_bH centers dissociate according to the chemical reaction P_bH→P_b+H.Therefore,it is of great significance to study the balance of the passivation and dissociation.In this work,the reaction mechanisms of passivation and dissociation of the P_b-type defects are investigated by first-principles calculations.The reaction rates of the passivation and dissociation are calculated by the climbing image-nudged elastic band(CI-NEB)method and harmonic transition state theory(HTST).By coupling the rate equations of the passivation and dissociation reactions,the equilibrium density ratio of the saturated interfacial dangling bonds and interfacial defects(P_b,P_(b0),and P_(b1))at different temperatures is calculated.