Phonon confinement effects in Raman spectra of porous silicon at non‐resonant excitation condition

Light emitting porous silicon samples with different porosities, i.e. crystalline sizes, were produced from the low level doped p‐type silicon wafers by the anodization process. The effects of strong phonon confinement, redshift and broadening, were found on the O(Γ) phonon mode of the Raman spectra recorded at non‐resonant excitation condition using a near infrared 1064 nm laser excitation wavelength. Similarly, the blueshift of the photoluminescence peak was observed by reducing the crystalline sizes. Vibrational and optical findings were analysed within the existing models of confinement on the vibrational and electronic states of silicon nanocrystals. Since the energy of the photoluminescence peak of small nanocrystals also depends on the oxygen content on the surface of nanocrystals, the surface oxidation states were examined using infrared and energy dispersive spectroscopy. The partial coverage of the surface of nanocrystals was found due to the sample exposure to air. As a consequence, the photoluminescence energy did not increase as would be expected from the quantum confinement model. These results further indicate that the oxygen passivation along with the quantum confinement determines the electronic states of the silicon nanocrystals in porous silicon. Copyright © 2014 John Wiley & Sons, Ltd.     

Surface states induced by metal atoms at the Si/electrolyte interface

Metal atoms have been chemically deposited on n-Si and p-Si and the obtained deposits have been characterized with Auger electron spectroscopy. The obtained samples have been used as electrodes in acetonitrile electrolyte. The electrochemical studies heve been performed using classical current-voltage, impedance and Schottky-Mott measurements, and also subgap photocurrent spectroscopy of the surface states. It appears that the deposited metal atoms do induce surface states on the silicon surface. These surface states have a weak effect on the flatband potential (i.e. no strong pinning of the Fermi level is observed even for monolayer coverage) but the subgap photoyield is increased by several orders of magnitude. The shape of the quantum yield versus photon energy curve points to surface states widely distributed through the bandgap. These experiments finally confirm the ability of the subgap photocurrent technique to distinguish between the two kinds of optical processes that may occur between the surface states and the semiconductor bands.     

Surface treatment of nanoporous silicon with noble metal ions and characterizations

A very large surface to volume ratio of nanoporous silicon (PS) produces a high density of surface states, which are responsible for uncontrolled oxidation of the PS surface. Hence it disturbs the stability of the material and also creates difficulties in the formation of a reliable electrical contact. To passivate the surface states of the nanoporous silicon, noble metals (Pd, Ru, and Pt) were dispersed on the PS surface by an electroless chemical method. GIXRD (glancing incidence X-ray diffraction) proved the crystallinity of PS and the presence of noble metals on its surface. While FESEM (field emission scanning electron microscopy) showed the morphology, the EDX (energy dispersive X-ray) line scans and digital X-ray image mapping indicated the formation of the noble metal islands on the PS surface. Dynamic SIMS (secondary ion mass spectroscopy) further confirmed the presence of noble metals and other impurities near the surface of the modified PS. The variation of the surface roughness after the noble metal modification was exhibited by AFM (atomic force microscopy). The formation of a thin oxide layer on the modified PS surface was verified by XPS (X-ray photoelectron spectroscopy).     

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.     

Electronic states and shapes of silicon quantum dots

A curviform surface breaks the symmetrical shape of silicon quantum dots on which some bonds can produce localized electronic states in the bandgap. The calculation results show that the bonding energy and electronic states of silicon quantum dots are different on various curved surfaces, for example, a Si-O-Si bridge bond on curved surface provides localized levels in bandgap and its bonding energy is shallower than that on the facet. The red-shifting ofthe photoluminescence spectrum on smaller silicon quantum dots can be explained by the curved surface effect. Experiments demonstrate that silicon quantum dots are activated for emission due to the localized levels provided by the curved surface effect.     

Spectroscopy of electroreflection, the electron band structure, and the mechanism of visible photoluminescence of anisotropically etched silicon

We present the results of studies of electroreflection in the 1.1–4.4 eV spectral range, of electron Auger spectroscopy, and of electron diffraction involving the photoluminescent Si-SiO₂ system prepared via anisotropic chemical etching of the Si(100) surface. These results are explained on the basis of a four-layer model of the band structure and energy transition diagram for a system with a quantum well at the silicon surface, surface electron states at the boundary, and a gradient of the band potential in the transition layer. We find that light-emitting silicon remains an indirect-gap semiconductor and that the visible photoluminescence is due to direct recombinations of the light-excited electrons and holes in the quantum well at the center of the Brillouin zone with the participation of the band of deep localized states, which is due to the presence of oxygen at the silicon surface. Zh. éksp. Teor. Fiz. 116, 1750–1761 (November 1999)     

硅量子点的形状及其弯曲表面效应

硅量子点的弯曲表面引起系统的对称性破缺, 致使某些表面键合在能带的带隙中形成局域电子态.计算结果表明:硅量子点的表面曲率不同形成的表面键合结合能和电子态分布明显不同. 例如, Si–O–Si桥键在曲率较大的表面键合能够在带隙中形成局域能级, 而在硅量子点曲率较小的近平台表面上键合不会形成任何局域态, 但此时的键合结合能较低. 用弯曲表面效应(CS)可以解释较小硅量子点的光致荧光光谱的红移现象. CS效应揭示了纳米物理中又一奇妙的特性. 实验证实, CS效应在带隙中形成的局域能级可以激活硅量子点发光. 关键词： 硅量子点 弯曲表面效应 表面键合 局域能级     

Effect of surface Si-Si dimers on photoluminescence of silicon nanocrystals in the silicon dioxide matrix

The effect of surface states of silicon nanocrystals embedded in silicon dioxide on the photoluminescent properties of the nanocrystals is reported. We have investigated the time-resolved and stationary photoluminescence of silicon nanocrystals in the matrix of silicon dioxide in the visible and infrared spectral ranges at 77 and 300 K. The structures containing silicon nanocrystals were prepared by the high-temperature annealing of multilayer SiO _x /SiO₂ films. The understanding of the experimental results on photoluminescence is underlain by a model of autolocalized states arising on surface Si-Si dimers. The emission of autocatalized excitons is found for the first time, and the energy level of the autolocalized states is determined. The effect of these states on the mechanism of the excitation and the photoluminescence properties of nanocrystals is discussed for a wide range of their dimensions. It is reliably shown that the cause of the known blue boundary of photoluminescence of silicon nanocrystals in the silicon dioxide matrix is the capture of free excitons on autolocalized surface states.     

Theoretical study of sorption and diffusion of lithium atoms on the surface of crystalline silicon and inside it

The energy of the sorption and diffusion of lithium atoms on the reconstructed (4 × 2) (100) silicon surface in the process of their transport into near-surface layers, as well as inside crystalline silicon, at various lithium concentrations have been investigated within the density functional theory. It has been shown that single lithium atoms easily migrate on the (100) surface and gradually fill the surface states (T3 and L) located in channels between silicon dimers. The diffusion of lithium into near-surface silicon layers is hampered because of high potential barriers of the transition (1.22 eV). The dependences of the binding energy, potential barriers, and diffusion coefficient inside silicon on distances to the nearest lithium atoms have also been examined. It has been shown that an increase in the concentration of lithium to the Li_0.5Si composition significantly reduces the transition energy (from 0.90 to 0.36 eV) and strongly increases (by one to three orders of magnitude) the lithium diffusion rate.     

Giant core-exciton effects on Si(111) 7 × 7 surfaces

We present the first direct experimental evidence for a large surface influenced core-exciton effect on silicon. The Si(111) 7 × 7 L_2,3 absorption edge has been studied with core-level electron energy loss (ELS) and X-ray photoemission spectroscopy (XPS). An excitonic shift of ～1–2 eV have been found for transitions from Si(2p) to empty surface states.     

Electronic structure of GaN(0001)‐2 × 2 thin films grown by PAMBE

Gallium nitride thin films were grown on silicon carbide (0001) by plasma‐assisted molecular beam epitaxy (PAMBE). The samples were cooled down in nitrogen plasma and characterized in situ by reflection high energy electron diffraction (RHEED), photoelectron spectroscopy (XPS/UPS), and atomic force microscopy (AFM) revealing stoichiometric and smooth GaN films virtually free of contaminations. We present valence band data obtained by UPS with strong emission from surface states inside the fundamental band gap. These states and the observed 2 × 2 surface reconstruction are highly sensitive towards residual molecules. Once these surface states have disappeared the original state could not be recovered by surface preparation methods underlining the necessity of in situ investigations on as‐grown surfaces. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Transport spectroscopy of a single dopant in a gated silicon nanowire

We report on spectroscopy of a single dopant atom in silicon by resonant tunneling between source and drain of a gated nanowire etched from silicon on insulator. The electronic states of this dopant isolated in the channel appear as resonances in the low temperature conductance at energies below the conduction band edge. We observe the two possible charge states successively occupied by spin-up and spin-down electrons under magnetic field. The first resonance is consistent with the binding energy of the neutral D0 state of an arsenic donor. The second resonance shows a reduced charging energy due to the electrostatic coupling of the charged D- state with electrodes. Excited states and Zeeman splitting under magnetic field present large energies potentially useful to build atomic scale devices.     

表面氧钝化碳化硅纳米团簇电子结构和光学性质的第一性原理研究

基于密度泛函理论(DFT)和广义梯度近似(GGA),对氧钝化条件下4H-SiC纳米团簇的电子结构和光学性质进行了研究。计算了不同直径的4H-SiC纳米球氧钝化后的能带结构、电子态密度和光学性质。团簇的尺度在0.4~0.9 nm之间,构建表面仅存在硅氧双键和表面仅存在碳氧双键的两种模型。研究表明硅氧双键和碳氧双键所引起的缺陷态位于原4H-SiC的价带和导带之间,并且缺陷态与价带顶的能量差随纳米团簇颗粒直径的增大而减小;缺陷态主要是由Si原子外层电子和氧原子外层电子轨道杂化引起的。同时,由于氧的存在,对碳化硅的结构产生一定的影响,这也是缺陷态形成的一个原因。另外,碳氧双键和硅氧双键钝化对4H-SiC纳米团簇的光学性质有着不同的影响。在表面仅存在C=O的情况下,4H-SiC纳米团簇表现出各向同性的性质。在表面仅存在Si=O的情况下,4H-SiC纳米团簇表现出各向异性的性质。     

Growth of thin silver films on silicon oxide pretreated by low temperature argon plasma

In the present study, we investigate the influence of low energy ion bombardment on nucleation and growth of thin silver films on silicon oxide by in situ photoelectron spectroscopy (PES) combined with specific resistivity measurements. Thermally grown thin silicon oxide films were exposed to a low temperature argon plasma for different time intervals resulting in changes in surface chemical composition as monitored by angle-resolved X-ray photoelectron spectroscopy (ARXPS). We demonstrate that irradiation of the oxide surface with low energy ions results in substantially changed nucleation of silver. Furthermore, silver films deposited on plasma treated oxide tend to have lower resistivity which is attributed to the effect of reduced grain boundary and surface roughness.     

Electron irradiation effect on the surface composition of Ar+ ion bombarded Si-nitride and Si-oxinitride

Auger electron spectroscopy (AES) and electron energy loss spectroscopy (ELS) have been used to study the surface composition of the Si-nitride and Si-oxinitride prepared by low pressure chemical vapor deposition. Ion bombardment has been shown to result in appearance of the “free” silicon on the surface. Electron irradiation of the samples preliminary bombarded by Ar⁺ ions has led to disappearance of the “free” silicon. This process is assumed to be connected with electron stimulated desorption of the “free” silicon.     

High resolution Si 2p gas phase photoelectron spectra of model silicon compounds: implications for hydrogen adsorbed on a silicon surface

High resolution Si 2p gas phase photoelectron spectroscopy has been used to measure the vibrational energy spacing in SiH₄ (0.295 eV) and SiD₄ (0.212 eV). These values are compared with those measured for the chemical shift (0.30 eV/hydrogen atom) of model compounds which mimic the effects of zero, one, two and three hydrogen atoms bonded to a silicon atom on a silicon surface. Implications for the interpretation of surface photoelectron spectra are discussed.     

Laser irradiation of chemisorbed oxygen on Si(111): Electronic states and clump formation of SiO2

The laser annealed Si(111) 1×1 surface with chemisorbed oxygen at submonolayer coverages and its irradiation with a ruby laser has been studied with ultraviolet photoelectron spectroscopy and high-resolution electron-energy-loss spectroscopy. The surface oxide which forms directly upon O₂ exposure is found to be similar to that which forms on the Si(111) cleaved 2×1 and the 7×7 reconstructed surfaces. Ruby-laser irradiation converts this surface oxide at submonolayer coverages into clumps of silicon dioxide and regions of clean silicon. Both surface oxides show electronic transitions in the visible and ultraviolet energy region which may be related to known network and point defects in vitreous and crystalline silicon dioxide.     

Electronic properties of cleaved CdTe(110) surfaces

Photoemission yield spectroscopy measurements were performed on a set of n- and p-doped CdTe single crystals. The surfaces were obtained by cleavage in ultrahigh vacuum and characterized by low energy electron diffraction and Auger electron spectroscopy. On clean and properly cleaved surfaces, no band bending was found, neither on n- nor on p-type samples, showing the absence of intrinsic surface states in the gap. The ionization energy is found at 5.80±0.05 eV. Oxygen adsorption removes defect-induced surface states on the valence band side of the gap and develops a band bending on n-type samples which indicates the presence of acceptor surface states in the gap down to 0.70 eV below the conduction band edge. The ionization energy remains constant.     

Lifetime-enhanced transport in silicon due to spin and valley blockade

We report the observation of lifetime-enhanced transport (LET) based on perpendicular valleys in silicon by transport spectroscopy measurements of a two-electron system in a silicon transistor. The LET is manifested as a peculiar current step in the stability diagram due to a forbidden transition between an excited state and any of the lower energy states due to perpendicular valley (and spin) configurations, offering an additional current path. By employing a detailed temperature dependence study in combination with a rate equation model, we estimate the lifetime of this particular state to exceed 48 ns. The two-electron spin-valley configurations of all relevant confined quantum states in our device were obtained by a large-scale atomistic tight-binding simulation. The LET acts as a signature of the complicated valley physics in silicon: a feature that becomes increasingly important in silicon quantum devices.     

Spin-polarized surface states on Fe-deposited Au(111) surface: A theoretical study

We have studied electronic structure of Fe-deposited Au(111) by performing ab initio density functional theory calculations. We find that the magnetic moment on the deposited Fe layer is enhanced as compared to that in bulk iron. We observe a large number of new states on the Fe-deposited surface — one of which is in the majority spin channel having similar dispersion to that on the clean surface, and others in the minority spin channel. The effective mass of electrons in surface states near the Fermi level increases on Fe deposition. The electronic properties are found to be insensitive to the stacking of near-surface layers. We need to use very thick slabs in our calculations to avoid splitting of surface states due to spurious interactions between the two surfaces of the slab. Using the local density of states profiles for different surface states, we conclude that in scanning tunneling microscope experiments one can detect two of the surface states — one in the majority channel below the Fermi level, and another in the minority channel appearing just above the Fermi energy. We compare our results to those from scanning tunneling spectroscopy experiments.