Hydrogen chemisorption on the 100 (2 × 1) surfaces of Si and Ge

This paper combines a theoretical study of the Si(100) surface having a monolayer of atomic hydrogen chemisorbed to it with an experimental study of the analogous Ge(100) and Ge(110) surfaces. In the theoretical work the underlying (100) silicon surface is taken to be reconstructed according to the Schlier-Farnsworth-Levine pairing model with the hydrogen located on the unfilled tetrahedral bonds of this structure. Self-consistent calculations of the electronic potential, charge density, spectrum, and occupied surface density of states are carried out. The force on the hydrogen atoms is then calculated using the Hellman-Feynman theorem. This force is found to be close to zero, confirming that the hydrogen atoms are indeed at the equilibrium position for the chosen silicon geometry. Features in the calculated photoemission spectrum for the Si(100) 2 × 1 : H surface are discussed in terms of related features in the photoemission spectrum of Si(111) : H, but are found not to agree with the previously measured photoemission spectrum of Si(100) 2 × 1 : H. Measured photoemission and ion-neutralization spectra for Ge(100) 2 × 1 : H agree in their major features with what is calculated for Si(100) 2 × 1 : H, however, suggesting that the Ge(100) 2 × 1 : H surface is reconstricted according to the pairing model. Similarly, measured spectra for clean Ge(100) 2 × 1 agree with calculations for the row dimerized Si(100) surface.     

Quantitative analysis of hydrogen in amorphous silicon using Raman scattering spectroscopy

Hydrogenated amorphous silicon (a‐Si:H) films were studied using infrared and Raman spectroscopy. We have experimentally found that ratios of Raman scattering cross‐sections for Si–H to Si–Si bonds and for Si–H₂ to Si–Si bonds are equal to 0.65 ± 0.07 and 0.25 ± 0.03, respectively. It allows to measure the concentration of hydrogen in a‐Si:H films. The developed approach can be applied for in situ control of hydrogen in a‐Si:H films and also suitable for thin a‐Si:H films on substrates that are opaque in infrared spectral region. Copyright © 2013 John Wiley & Sons, Ltd.     

One-dimensional self-consistent solution of modulation doped nanocrystalline/crystalline Si heterojunctions

A kind of modulation doped structure of n-type nanocrystalline hydrogenated silicon (nc-Si:H) film with intrinsic nc-Si:H layer with p-type bulk Si 100 substrate was proposed. The numerical self-consistent solutions of one-dimensional Schrödinger and Poisson equations along the direction normal to the heterojunction were performed to calculate the distribution of electron density and profiles of conduction-band as a function of ionized donor concentration in doped film, thickness of intrinsic layer, and other device parameters in the junctions. The calculated results are shown to be in agreement with experimental data. The relation of mobility vs sheet density of two-dimensional electron gases under different scattering mechanisms was analyzed. The obtained consequences may be used to evaluate optimum design for the modulation doped nc-Si:H-based devices.     

Si adhesion interlayer effects in hydrogen passivated Si/W soft X-ray multilayer mirrors

The use of hydrogen passivation of the silicon layers in Si/W soft X-ray reflective multilayer mirrors is investigated. Standard passivation, corresponding to Si:H/W structures, led to reduced growth properties of the W layers. The additional use of atomically thin Si adhesion layers, corresponding to Si:H/Si/W, led to improved growth and increased soft X-ray reflectivity. The effects taking place at the interfaces are analysed by bright field planar TEM and in situ X-ray reflectivity, and are described in terms of interface and surface energies, with quantitatively analysis of intermixing, materials density, and geometrical optical effects.     

Protons’ generation by laser irradiation at 5 × 10 W/cm from silicon dielectric targets containing an excess of hydrogen

A study of silicon plasma generated in vacuum by 532 nm Nd:YAG laser at intensities of about 5 × 10⁹ W/cm² from dielectric targets containing a relatively huge quantity of hydrogen was presented.Time-of-flight technique was employed to measure the particles’ energy and the relative yield with respect to other ion species. Plasma-accelerated ions show Coulomb-Boltzmann-shifted distributions depending on their charge state.Mass quadrupole spectrometry allowed the estimation of the relative hydrogen amount inside the different samples considered: silicon (Si), silicon nitride (Si₃N₄) and hydrogenated annealed silicon (Si(H)) as a function of the ablation depth and irradiation time.Depth profiles of the laser craters permit to calculate the ablation yield at the used laser fluence. The plasma temperature and density was evaluated by the experimental data. A special regard is given to the protons’ generation process occurring inside the plasma, due to the possible influence of the hydrogen excess on the treated samples in comparison to the not-hydrogenated silicon ones.     

Role of a‐Si:H bulk in surface passivation of c‐Si wafers

The low thermal stability of hydrogenated amorphous silicon (a‐Si:H) thin films limits their widespread use for surface passivation of c‐Si wafers on the rear side of solar cells. We show that the thermal stability of a‐Si:H surface passivation is increased significantly by a hydrogen rich a‐Si:H bulk, which acts as a hydrogen reservoir for the a‐Si:H/c‐Si interface. Based on this mechanism, an excellent lifetime of 5.1 ms (at injection level of 10¹⁵ cm^–3) is achieved after annealing at 450 °C for 10 min. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

绝缘衬底上高密度均匀纳米硅量子点的形成与表面形貌

利用等离子体增强化学气相淀积技术，在绝缘氮化硅(SiNx)衬底上制备超薄非晶硅(aSi：H)薄膜，通过超短脉冲激光辐照与准静态常规热退火技术处理，制备出高密度、均匀纳米硅(ncSi)量子点.使用原子力显微镜对处理前后样品的表面形貌进行了研究，发现激光辐照能量密度增加的同时，所形成的ncSi尺寸也随之增加.在合适的能量密度范围内，可以得到面密度大于10.11cm^2、尺寸分布标准偏差小于20％的10 nm ncSi量子点薄膜，表明所制备的ncSi量子点具有较好的均匀性及较高的面密度.同时，对ncS i量子点 关键词： 纳米硅 激光诱导 尺寸分布     

Pulsed laser deposition of photosensitive a-Si thin films

Si films have been fabricated by pulsed KrF excimer laser deposition (PLD) through the use of various Si targets and deposition conditions. The deposits consisted of droplets and homogeneous films, which were assigned to be crystalline and amorphous silicon, respectively, by the micro Raman scattering measurements. Not only the crystalline but also the amorphous Si part scarcely (<1 atomic %) contained hydrogen regardless of whether or not the films are prepared in the presence of H₂ gas. Conditions were explored to reduce the droplet formation and to produce photosensitive films. Amorphous Si films with photosensitivity (C_ph/C_d) exceeding 10³ were obtained, and they exhibited high stability against light soaking. Thus, PLD is a promising method to fabricate photosensitive and photostable a-Si films.     

Adsorption of gold on hydrogen terminated Si(0 0 1): Formation of chain structure

Possible formation of stable Au atomic wire on the hydrogen terminated Si(0 0 1): 3×1 surface is investigated under the density functional formalism. The hydrogen terminated Si(0 0 1): 3×1 surface is patterned in two different ways by removing selective hydrogen atoms from the surface. The adsorption of Au on such surfaces is studied at different sub-monolayer coverages. At 4/9 monolayer (ML) coverage, zigzag continuous Au chains are found to be stable on the patterned hydrogen terminated Si(0 0 1): 3×1 surface. The reason for the stability of the wire structures at 4/9 ML coverage is explained. It is to be noted that beyond 4/9 ML coverage, the additional Au atoms may introduce clusters on the surface. The continuous atomic gold chains on the substrate may be useful for the fabrication of atomic scale devices.     

纳米晶硅薄膜中氢含量及键合模式的红外分析

采用传统射频等离子体化学气相沉积技术在100—350℃的衬底温度下高速沉积氢化硅薄膜. 傅里叶变换红外光谱和Raman谱的研究表明,纳米晶硅薄膜中的氢含量和硅氢键合模式与薄膜的晶化特性有密切关系,当薄膜从非晶相向晶相转变时,氢的含量减少了一半以上,硅氢键合模式以SiH₂为主. 随着衬底温度的升高和晶化率的增加,纳米晶硅薄膜中氢的含量以及其结构因子逐渐减少. 关键词： 氢化纳米晶硅薄膜 红外透射谱 氢含量 硅氢键合模式     

Surface recombination probabilities of H on stainless steel, a-Si:H and oxidized silicon determined by threshold ionization mass spectrometry in H2 RF discharges

H atom densities are measured by threshold ionization mass spectrometry in a H₂ parallel-plate RF discharge. Variations of H density near the surface in steady-state discharge conditions reveal different surface loss probabilities γ on stainless steel, hydrogenated amorphous silicon (a-Si:H) and oxidized silicon. Absolute γ values are obtained from time-resolved H density measurements in afterglow. The etching probability of Si per H atom incident on a-Si:H is also derived by monitoring SiH₄ partial pressure and SiH(A²Δ) optical emission.     

Hydrogen evolution during deposition of microcrystalline silicon by chemical transport

We exposed a freshly deposited boron-doped, hydrogenated amorphous silicon (a-Si:H) layer to hydrogen plasma under conditions of chemical transport. In situ spectroscopic ellipsometry measurements revealed that atomic hydrogen impinging on the film surface behaves differently before and after crystallization. First, the plasma exposure increases hydrogen solubility in the a-Si:H network leading to the formation of a hydrogen-rich subsurface layer. Then, once the crystallization process engages, the excess hydrogen starts to leave the sample. We have attributed this unusual evolution of the excess hydrogen to the grown hydrogenated microcrystalline (μc-Si:H) layer, which gradually prevents the atomic hydrogen from the plasma reaching the μc-Si:H/a-Si:H interface. Consequently, hydrogen solubility, initially increased by the hydrogen plasma, recovers the initial value of an untreated a-Si:H material. To support the theory that the outdiffusion is a consequence and not the cause of the μc-Si:H layer growth, we solved the combined diffusion and trapping equations, which govern hydrogen diffusion into the sample, using appropriate approximations and a specific boundary condition explaining the lack of hydrogen injection during μc-Si:H layer growth.     

Nuclear magnetic resonance investigation of H, H2 and dopants in hydrogenated amorphous silicon and related materials

Nuclear magnetic resonance has been successfully applied to the study of the microstructure of hydrogenated amorphous silicon and related materials. It has been used to determine the local bonding and structural environment of the host atoms, the hydrogen, and the dopants. First, we review some of these NMR experimental results on the hydrogen microstructure in hydrogentaed amorphous semiconductors and compare the results on plasma deposited hydrogenated amorphous silicon (a-Si:H), remote hydrogen plasma deposited a-Si:H, thermally annealed a-Si:H, doped a-Si:H, microcrystalline Si and amorphous (Si, Ge):H alloys. A common feature is that these materials exhibit a heterogeneous distribution of hydrogen bonded to the semiconductor lattice in dilute and clustered phases. In addition, the lattice contains voids of varying number and size that contain non-bonded molecular hydrogen whose quantity is altered by deposition conditions and thermal treatment. Second, we review some aspects of the local bonding structure of dopants in a-Si:H. A significant fraction of the dopants are found to be in dopant-hydrogen clusters similar to those proposed to explain hydrogen passivation in crystalline silicon. Implications of the determined local structure on the doping efficiency are discussed.     

Surface passivation of crystalline silicon by sputter deposited hydrogenated amorphous silicon

This letter shows that intrinsic hydrogenated amorphous silicon (a‐Si:H) films deposited by RF magnetron sputtering can provide outstanding passivation of crystalline silicon surfaces, similar to that achieved by plasma enhanced chemical vapour deposition (PECVD). By using a 2% hydrogen and 98% argon gas mixture as the plasma source, 1.5 Ω cm n‐type FZ silicon wafers coated with sputtered a‐Si:H films achieved an effective lifetime of 3.5 ms, comparable to the 3 ms achieved by PECVD (RF and microwave dual‐mode). This is despite the fact that Fourier transform infrared spectroscopy measurements show that sputtering and PECVD deposited films have very different chemical bonding configurations. We have found that film thickness and deposition temperature have a significant impact on the passivation results. Self‐annealing and hydrogen plasma treatment during deposition are likely driving forces for the observed changes in surface passivation. These experimental results open the way for the application of sputtered a‐Si:H to silicon heterojunction solar cells. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

RETRACTED ARTICLE: Hydrogenated nanocrystalline silicon germanium thin films

Hydrogenated nanocrystalline silicon germanium thin films (nc-SiGe:H) is an interesting alternative material to replace hydrogenated nanocrystalline silicon (nc-Si:H) as the narrow bandgap absorber in an a-Si/a-SiGe/nc-SiGe(nc-Si) triple-junction solar cell due to its higher optical absorption in the wavelength range of interest. In this paper, we present results of optical, structural investigations and electrical characterization of nc-SiGe:H thin films made by hot-wire chemical vapor deposition (HW-CVD) with a coil-shaped tungsten filament and with a disilane/germane/hydrogen gas mixture. The optical band gaps of a-SiGe:H and nc-SiGe:H thin-films, which are deposited with the same disilane/germane/hydrogen gas mixture ratio of 3.4 : 1.7 : 7, are about 1.58 eV and 2.1 eV, respectively. The nc-SiGe:H thin film exhibits a larger optical absorption coefficient of about 2–4 in the 600–900 nm range when compared to nc-Si:H thin film. Therefore, a thinner nc-SiGe:H layer of ∼500 nm thickness may be sufficient for the narrow bandgap absorber in an a-Si based multiple-junction solar cell. We enhanced the transport properties as measured by the photoconductivity frequency mixing technique. These improved alloys do not necessarily show an improvement in the degree of structural heterogeneity on the nanometer scale as measured by smallangle X-ray scattering. Decreasing both the filament temperature and substrate temperature produced a film with relatively low structural heterogeneity while photoluminescence showed an order of magnitude increase in defect density for a similar change in the process.      

Coverage- and temperature-dependent vibrational spectra of hydrogen chemisorbed on Si(100)2 × 1

The adsorption of atomic hydrogen at Si(100)2 × 1 has been studied for coverages at and below one monolayer at temperatures between 300 and 1200 K using high-resolution Electron Energy Loss Spectroscopy (EELS) and Low Energy Electron Diffraction (LEED). Measurements of EELS frequencies, linewidths and intensities are discussed for different coverages and temperatures during exposure as well as subsequent annealing. Formation of a monohydride Si(100)2 × 1 : H adsorption phase is observed at room temperature in the sub-monolayer range, at 650 K for all coverages up to the saturation, and during thermal decomposition of the low temperature dihydride Si(100)1 × 1 : : 2H adsorption phase. The latter is formed by saturating Si(100) at 300 K with atomic hydrogen.     

Nanocrystalline silicon films prepared by laser—induced crystallization

The excimer laser-induced crystallization technique has been used to investigate the preparation of nanocrystalline silicon (nc-Si) from amorphous silicon ($\al$-Si) thin films on silicon or glass substrates. The $\al$-Si films without hydrogen grown by pulsed-laser deposition are chosen as precursor to avoid the problem of hydrogen effluence during annealing. Analyses have been performed by scanning electron microscopy, atomic force microscopy, Raman scattering spectroscopy and high-resolution transmission--electron microscopy. Experimental results show that silicon nanocrystals can be formed through laser annealing. The growth characters of nc-Si are strongly dependent on the laser energy density. It is shown that the volume of the molten silicon predominates essentially the grain size of nc-Si, and the surface tension of the crystallized silicon is responsible for the mechanism of nc-Si growth.     

Growth mode and interface structure of Ag on the HF-treated Si(111):H surface

A growth mode and interface structure analysis has been performed for Ag deposited at a high temperature of 300°C on the HF-treated Si(111):H surface by means of medium-energy ion scattering and elastic recoil detection analysis of hydrogen. The measurements show that Ag grows in the Volmer-Weber mode and that the Ag islands on the surface are epitaxial with respect to the substrate. The preferential azimuthal orientation is A-type only when Ag is deposited slowly. The interface does not reconstruct to the √3 × √3-Ag structure, which is normally observed for Ag deposition above 200°C on the Si(111)7 × 7 surface, but retain bulk-like structure. The presence of hydrogen at the interface is demonstrated after deposition of thick (1100 Å) Ag films. However, the amount of hydrogen at the interface is not a full monolayer. This partial desorption of hydrogen from the interface explains why the Schottky barrier heights of Ag/Si(111):H diodes are close to those of Ag/Si(111)7 × 7 and Ag/Si(111)2 × 1.     

Influence of temperature-pressure treatment on heavily hydrogenated silicon surface

Microstructure and related properties of hydrogenated silicon samples, Si:H, treated at high-temperature (HT) up to 1270 K under hydrostatic argon pressure (HP) up to 1.1 GPa are investigated. To prepare Si:H, Czochralski grown 0 0 1 oriented single crystalline Si wafer with 50 nm thick surface SiO₂ layer was heavily implanted with hydrogen using the immersion plasma source of hydrogen ions with energy 24 keV.The surface of HT-HP treated Si:H was characterised by scanning electron microscopy. Reflectivity pattern measurements in the wavelength range of 350-2000 nm have been performed to analyse their surface and bulk properties. The volume averaging method for a model of layer-like structure has been used to simulate the HT-HP treated Si:H. The analysis of Si:H samples suggests the multi-layer structure composed of Si, Si:H, SiO, SiO₂, and of porous Si layers in the sub-surface region. The porous Si:H samples model is in good consistency with experimental data from reflectance measurements.     

Silicon doping effects on optical properties of InAs ultrathin layer embedded in GaAs/AlGaAs:δSi high electron mobility transistors structures

Micro-Raman scattering measurements were used to study the silicon delta-doped layer density variation effect on InAs ultrathin layer embedded in silicon-delta-doped GaAs/AlGaAs high electron mobility transistors (HEMTs) structures properties. These structures were grown by molecular beam epitaxy on GaAs substrates with different silicon (Si) delta-doped layer densities. Two coupled plasmon–longitudinal optical (LO) phonon modes (L− and L+) were observed in the micro-Raman spectra of the Si-delta-doped samples, and both their wave numbers and intensities were dependent on the silicon delta-doped layer density. There is evidence to suggest that the increase of the Si doping level results in the increase of exciton–phonon scattering which is mainly due to the incorporation of Si and the increase of the two-dimensional electron gas (2DEG) in the InAs/GaAs interface. From fitting the temperature-dependence of full width at half maximum (FWHM) of quantum well’s photoluminescence peak (P₁) by the exciton–photon coupling model, it was found that the interaction between exciton and phonon in Si-delta-doped quantum wells was higher than that in the undoped sample. This result was confirmed as resulting from the increase of plasmon–phonon scattering which is attributed to the increase of free carriers donated from implanted Si dopant. The self-consistent Poisson–Schrödinger model calculation results are in good agreement with the experimental results, where the 2DEG densities increase linearly with increasing the Si-delta-doped layer density.