Second-harmonic spectroscopy of electronic structure of Si/SiO2 multiple quantum wells

Size effects in the resonant nonlinear optical response of amorphous Si/SiO₂ multiple quantum wells (MQW) are studied by second-harmonic generation (SHG) spectroscopy in a spectral interval of second-harmonic photon energies from 2.5 to 3.4 eV. The sensitivity of SHG spectroscopy to thickness-dependent electronic structure (sub-band energy position and density of states line shape) of MQW is demonstrated. A monotonic red shift of central energies of SHG resonances by 120 m eV upon increase of the well thickness from 2.5 to 10 ? is observed. This is interpreted as a size dependence of the position of singularities in the combined density of states for a 2D gas of electrons moving in an effective potential well. It is shown that, for agreement with experiment, the simplest (rectangular) shape of the well should be modified in order to take into account the lattice-potential distortion at the interfaces. Received: 16 October 2001 / Revised version: 16 April 2002 / Published online: 6 June 2002     

A sensitive detection method for magnetization-induced second-harmonic generation under an externally applied field

We describe the instrumentation related to the first observation of magnetization-induced enhancement of surface second-harmonic generation (SHG) from the paramagnetic Si(111)-7×7 surfaces. A judicious choice of polarization and sample orientation enabled us to isolate the magnetic-field-dependent tensor element of the nonlinear susceptibility. A conductive liquid-nitrogen system, coupled to an ultrahigh-vacuum system that is immune to the high magnetic field of 10 T, cooled the sample to about 120 K. A high extinction that is necessary to detect the magnetization-induced SHG (MSHG) was accomplished by minimizing stray optical effects such as Faraday rotation, photoluminescence and thermal birefringence in all optical components, with extra care taken for the UHV window. Consistent and stable operation of this sensitive measurement system permitted experiments involving MSHG at multiple wavelengths and temperatures. Probing the magnetization-induced optical nonlinearity was validated by quenching the surface states by oxidation of the surface layers. From MSHG measurements at two wavelengths resonant with different surface-state transitions, we were able to suggest that the observed MSHG is proportional to the number of dangling bond states of Si(111)-7×7. Received: 15 January 2002 / Published online: 2 May 2002     

Quasiparticle spectrum and optical excitations of semiconductor surfaces

I investigated the spectra of well-ordered semiconductor surfaces within an ab-initio framework. Both the quasi-particle spectrum of electron and hole states and the optical differential reflectivity spectrum were addressed. As examples, I discuss the spectra of three surfaces: Si(111)-(2×1), hydrogenated H:Si(111)-(1×1), and Si adatom-terminated 6H-SiC(0001)-(×). I studied a number of physical features beyond the single-particle band-structure picture. In the case of Si(111)-(2×1), the dangling-bond surface states give rise to a surface exciton which dominates the differential reflectivity spectrum. In the case of 6H-SiC(0001)-(×), a Mott-Hubbard metal-insulator transition is observed. All calculations were performed within many-body perturbation theory, employing single- and two-particle Green functions. The solutions of the corresponding equations of motion yielded the observable excitations, i.e., single-particle electron and hole excitations, as well as bound and resonant electron-hole pair excitations. Received: 28 April 2000 / Accepted: 19 June 2000 / Published online: 7 March 2001     

Second-harmonic spectroscopy of Ge/Si(001) and Si1-xGex(001)/Si(001)

0.9 Ge_0.1(001)/Si(001) films with SH photon energies 3.1<2hν<3.5 eV near the bulk E₁ critical point of Si(001) or Si_0.9Ge_0.1(001). Ge was deposited on Si(001) by using atomic layer epitaxy cycles with GeH₄ or Ge₂H₆ deposition at 410 K followed by hydrogen desorption. As Ge coverage increased from 0 to 2 monolayers the SH signal increased uniformly by a factor of seven with no detectable shift in the silicon E₁ resonant peak position. SH signals from Si_0.9Ge_0.1(001)/Si(001) were also stronger than those from intrinsic Si(001). Hydrogen termination of the Si_0.9Ge_0.1(001) and Ge/Si(001) surfaces strongly quenched the SH signals, which is similar to the reported trend on H/Si(001). We attribute the stronger signals from Ge-containingsurfaces to the stronger SH polarizability of asymmetric Ge-Si and Ge-Ge dimers compared to Si-Si dimers. Hydrogen termination symmetrizes all dimers, thus quenching the SH polarizability of all of the surfaces investigated. Received: 13 October 1998 / Revised version: 18 January 1999     

Interplay of surface morphology, strain relief, and surface stress during surfactant mediated epitaxy of Ge on Si

Lattice-mismatch-induced surface or film stress has significant influence on the morphology of heteroepitaxial films. This is demonstrated using Sb surfactant-mediated epitaxy of Ge on Si(111). The surfactant forces a two-dimensional growth of a continous Ge film instead of islanding. Two qualitatively different growth regimes are observed. Elastic relaxation: Prior to the generation of strain-relieving defects the Ge film grows pseudomorphically with the Si lattice constant and is under strong compressive stress. The Ge film relieves strain by forming a rough surface on a nm scale which allows partial elastic relaxation towards the Ge bulk lattice constant. The unfavorable increase of surface area is outbalanced by the large decrease of strain energy. The change of film stress and surface morphology is monitored in situ during deposition at elevated temperature with surface stress-induced optical deflection and high-resolution spot profile analysis low-energy electron diffraction. Plastic relaxation: After a critical thickness the generation of dislocations is initiated. The rough phase acts as a nucleation center for dislocations. On Si(111) those misfit dislocations are arranged in a threefold quasi periodic array at the interface that accommodate exactly the different lattice constants of Ge and Si. Received: 1 April 1999 / Accepted: 17 August 1999 / Published online: 6 October 1999     

Theory of adsorption: Ordered monolayers from Na to Cl on Si(001) and Ge(001)

First principles calculations of clean and adsorbate-covered surfaces of Si(001) and Ge(001) are reported. Chemical trends in the adsorption of ordered Na, K, Ge, As, Sb, S, Se and Cl overlayers are discussed. The calculations are based on the local-density approximation and employ non-local, norm-conserving pseudopotentials together with Gaussian orbital basis sets. The semi-infinite geometry of the substrate is properly taken into account by employing our scattering theoretical method. From total-energy minimization calculations we obtain optimal surface reconstructions which show asymmetric dimers for Si(001), Ge(001) and Ge:Si(001). For As:Si(001), Sb:Si(001) and Sb:Ge(001), we find symmetric adatom dimers in the equilibrium geometries. S or Se adlayers are found to be adsorbed in bridge positions forming a (1×1) unit cell with a geometry very close to the configuration of a terminated bulk lattice. Cl atoms adsorb on top of the dangling bonds of symmetric Si dimers residing in the first substrate-surface layer. Our calculations for Na:Si(001) and K:Si(001) confirm valley-bridge site adsorption for half monolayer coverage. For full monolayer alkali-metal coverage, adsorption in pedestal and valley-bridge positions is found to be energetically most favourable. The calculated optimal adsorption configurations are in excellent agreement with a whole body of recent experimental data on surface-structure determination. For these structural models, we obtain electronic surface band structures which agree very good with a wealth of data from angle-resolved photoemission spectroscopy investigations.     

Thin noble metal films on Si (111) investigated by optical second-harmonic generation and photoemission

Thin noble metal films (Ag, Au and Cu) on Si (111) have been investigated by optical second-harmonic generation (SHG) in combination with synchrotron radiation photoemission spectroscopy. The valence band spectra of Ag films show a quantization of the sp-band in the 4-eV energy range from the Fermi level down to the onset of the d-bands. For Cu and Au the corresponding energy range is much narrower and quantization effects are less visible. Quantization effects in SHG are observed as oscillations in the signal as a function of film thickness. The oscillations are strongest for Ag and less pronounced for Cu, in agreement with valence band photoemission spectra. In the case of Au, a reacted layer floating on top of the Au film masks the observation of quantum well levels by photoemission. However, SHG shows a well-developed quantization of levels in the Au film below the reacted layer. For Ag films, the relation between film thickness and photon energy of the SHG resonances indicates different types of resonances, some of which involve both quantum well and substrate states. Received: 16 October 2001 / Revised version: 14 March 2002 / Published online: 29 May 2002     

Self-assembling of Ge quantum dots in the CaF<Subscript>2</Subscript>/Ge/CaF<Subscript>2</Subscript>/Si heteroepitaxial system and the development of tunnel-resonance diode on its basis

A CaF₂/Ge/CaF₂/Si(111) heteroepitaxial structure with Ge quantum dots was grown by molecular-beam epitaxy. A negative differential conductivity and conductivity oscillations caused by resonant hole tunneling were observed at room temperature. The energy spacing between the levels in quantum dots, as determined from the oscillation period, is 40–50 meV depending on the Ge dot size.     

Nonlinear optical investigations of the dynamics of hydrogen interaction with silicon surfaces

Optical second-harmonic generation (SHG) from silicon surfaces may be resonantly enhanced by dangling-bond-derived surface states. The resulting high sensitivity to hydrogen adsorption combined with unique features of SHG as an optical probe has been exploited to study various kinetical and dynamical aspects of the adsorption system H₂/Si. Studies of surface diffusion of H/Si(111)7×7 and recombinative desorption of hydrogen from Si(111)7 × 7 and Si(100)2 × 1 revealed that the covalent nature of hydrogen bonding on silicon surfaces leads to high diffusion barriers and to desorption kinetics that strongly depend on the surface structure. Recently, dissociative adsorption of molecular hydrogen on Si(100)2×1 and Si(111)7×7 could be observed for the first time by heating the surfaces to temperatures between 550 K and 1050 K and monitoring the SH response during exposure to a high flux of H₂ or D₂. The measured initial sticking coefficients for a gas temperature of 300K range from 10^–9 to 10^–5 and strongly increase as a function of surface temperature. These results demonstrate that the lattice degrees of freedom may play a decisive role in the reaction dynamics on semiconductor surfaces.     

Phonons in Ge/Si superlattices with Ge quantum dots

Ge/Si superlattices containing Ge quantum dots were prepared by molecular beam epitaxy and studied by resonant Raman scattering. It is shown that these structures possess vibrational properties of both two-and zero-dimensional objects. The folded acoustic phonons observed in the low-frequency region of the spectrum (up to 15th order) are typical for planar superlattices. The acoustic phonon lines overlap with a broad emission continuum that is due to the violation of the wave-vector conservation law by the quantum dots. An analysis of the Ge and Ge-Si optical phonons indicates that the Ge quantum dots are pseudoamorphous and that mixing of the Ge and Si atoms is insignificant. The longitudinal optical phonons undergo a low-frequency shift upon increasing laser excitation energy (2.54–2.71 eV) because of the confinement effect in small-sized quantum dots, which dominate resonant Raman scattering.     

Disproportionation phenomena on free and strained Sn/Ge(111) and Sn/Si(111) surfaces

Distortions of the sqrt[3]x sqrt[3] Sn/Ge(111) and Sn/Si(111) surfaces are shown to reflect a disproportionation of an integer pseudocharge, Q, related to the surface band occupancy. A novel understanding of the (3 x 3)-1U ("1 up, 2 down") and 2U ("2 up, 1 down") distortions of Sn/Ge(111) is obtained by a theoretical study of the phase diagram under strain. Positive strain keeps the unstrained value Q=3 but removes distortions. Negative strain attracts pseudocharge from the valence band causing first a (3 x 3)-2U distortion (Q=4) on both Sn/Ge and Sn/Si, and eventually a (sqrt[3] x sqrt[3])-3U ("all up") state with Q=6. The possibility of a fluctuating phase in unstrained Sn/Si(111) is discussed.     

Effect of self-assembled Ge nanostructures on Si surface electronic properties

Incorporating self-assembled Ge islands on Si surfaces into electronic devices has been suggested as a means of forming small features without fine-scale litho- graphy. For use in electronic devices, the electrical properties of the deposited Ge and their relation to the underlying Si substrate must be known. This report presents the results of a surface photovoltage investigation of the surface energy barrier as increasing amounts of Ge are added to a Si surface by chemical vapor deposition. The results are interpreted in terms of band discontinuities and surface states. The surface barrier increases as a wetting layer is deposited and continues to increase as defect-free islands form. It saturates as the islands grow. As the amount of Ge continues increasing, defects form, and the surface barrier decreases because of the resulting allowed states at the Ge/Si interface. Qualitatively similar behavior is found for Si(001) and Si(111). Covering the Ge with Si reduces the surface-state density and possibly modifies the wetting layer, decreasing the barrier to one more characteristic of Si. Initial hydrogen termination of the surface decreases the active surface-state density. As the H desorbs, the surface barrier increases until it stabilizes as the surface oxidizes. The behavior is briefly correlated with scanning-tunneling spectroscopy data. Received: 13 November 2000 / Accepted: 14 November 2000 / Published online: 23 May 2001     

Coupling of ferroelectric and antiferromagnetic order parameters in hexagonal RMnO3

Second-harmonic generation (SHG) is used as a probe for the coexisting ferroelectric and antiferromagnetic orders in hexagonal RMnO₃. SH contributions coupling to the electric and/or magnetic order parameters are identified on the basis of their spectral dependence and the symmetries of the corresponding order parameters. The SH signals from the ferroelectric and antiferromagnetic orders were employed to image the electric and magnetic domain structures separately. The transformation properties of electric and magnetic domains are discussed with respect to the transformation properties of the corresponding order parameters. An investigation of the mutual coupling between the coexisting electric and magnetic orders reveals apparently independent domain structures, which contradicts the symmetry and transformation properties of electric-dipole-induced SHG in this ferroelectromagnetic group of compounds. Apart from higher-order multipole contributions to SHG, interface contributions from clamped electric and magnetic domains can solve the contradiction. Received: 16 October 2001 / Published online: 24 April 2002     

Si衬底上分子束外延Ge,Si时的反射式高能电子衍射强度振荡观察

本文观察了在Si(100)和Si(111)衬底上分子束外延Si,Ge时的反射式高能电子衍射(RHEED)强度振荡现象。其振荡特性表明,外延一定厚度的缓冲层可以改善表面的平整性,较慢的生长速率或中断生长一段时间有利于外延膜晶体质量的提高。Si(100)上外延Si或Ge时,沿[100]和[110]方位观测到的振荡特性均为单原子模式,起因于表面存在双畴(2×1)再构;而Si(111)上外延Ge时,[112]方位观测到的振荡为双原子层模式,但在[110]方位观察到不均匀周期的强度振荡行为。两种衬底上保持RHEED     

Third and fourth harmonic generation at Si-SiO2 interfaces and in Si-SiO2-Cr MOS structures

2 and Si(110)-SiO₂ interfaces and DC-electric-field induced TH and FH generation is then observed in Si(111)-SiO₂-Cr and Si(110)-SiO₂-Cr MOS structures for the first time. A systematic phenomenological analysis of azimuthal anisotropy of TH and FH generation intensity is performed for (111) and (110) surfaces of O_h symmetric single crystals. A phenomenological model of electro-induced effects in TH and FH generation is then developed and the surface specificity and sensitivity of TH and FH generation are discussed. Optical interference of surface electro-induced and bulk bias-independent contributions to the effective third-order nonlinear polarization is proposed as the mechanism underlying surface sensitivity of electro-modulated TH probe. Received: 16 October 1998     

Optical oscillation modes of plasmon particles observed in direct space by phase-contrast near-field microscopy

Light distributions near resonant metal nanoparticles are recorded by a scattering-type scanning near-field optical microscope (s-SNOM), for the first time with a sub-particle-size resolution (<10 nm) and with simultaneous amplitude and phase contrast. The images depict the optical oscillation patterns of single plasmon particles. Examples are presented of particles excited in dominantly dipolar and quadrupolar modes, and also of closely spaced particles sustaining a gap mode. The gap mode can provide enhanced optical fields in nanometric spots for non-linear and single-molecule spectroscopy applications. Received: 20 June 2001 / Revised version: 3 August 2001 / Published online: 19 September 2001     

Thermal behavior of the roughened Cu(110) surface

The roughened Cu(110) surface was prepared by annealing the clean surface at various temperatures ranging from 700 to ∼1000 K. A significant drop in intensity of reflection anisotropy spectroscopy (RAS) peak at 2.1 eV photon energy as a function of increasing sample temperature was found for annealing above the roughening transition at 900 K. The observed change of 2.1 eV peak in RAS spectra is because of the surface state Fermi level shift due to temperature change. The RAS result is in good agreement with an unoccupied surface state energy using inverse photoemission spectroscopy (IPES). New IPES results indicate that the unoccupied surface state intensity decreases with increasing annealing temperature. It was also found that the unoccupied surface state was shifted. IPES results provide that the contributions of the surface state to surface optical properties at 2.1 eV are relevant for the RAS technique.     

Double diffraction spots in RHEED patterns from clean Ge(111) and Si(001) surfaces

In RHEED patterns from clean Ge(111) and Si(001) surfaces, extra diffraction spots have been observed with superlattice reflection spots due to Ge(111) 2 × 8 and Si(001) 2 × 1 surface structures. The extra spots have not been found out in many previous LEED and RHEED patterns of clean Ge(111) and Si(001) surfaces. When the Ge(111) and Si(001) samples were rotated about an axis normal to the surfaces so as to vary the incident direction of the primary electron beam, the intensity of the extra spots showed a remarkable dependence upon the incident direction and they became invisible in some incident directions, in spite of the experimental condition that an Ewald sphere intersected reciprocal lattice rods of the extra spots. In this study, the extra spots are understood as forbidden reflection spots resulting from double diffraction of superlattice reflections of the surface structures, and the remarkable dependence of their intensity upon the incident direction is explained in terms of excitation of the surface wave of the superlattice reflections. These results suggest that the intensity of diffraction spots in RHEED patterns may be greatly influenced by the surface wave excitation of fundamental and superlattice reflections.     

Triangular Mott-Hubbard insulator phases of Sn/Si(111) and Sn/Ge(111) surfaces

The ground state of Sn/Si(111) and Sn/Ge(111) surface alpha phases is reexamined theoretically, based on ab initio calculations where correlations are approximately included through the orbital dependence of the Coulomb interaction (in the local density+Hubbard U approximation). The effect of correlations is to destabilize the vertical buckling in Sn/Ge(111) and to make the surface magnetic, with a metal-insulator transition for both systems. This signals the onset of a stable narrow gap Mott-Hubbard insulating state, in agreement with very recent experiments. Antiferromagnetic exchange is proposed to be responsible for the observed Gamma-point photoemission intensity, as well as for the partial metallization observed above 60 K in Sn/Si(111). Extrinsic metallization of Sn/Si(111) by, e.g., alkali doping, could lead to a novel 2D triangular superconducting state of this and similar surfaces.     

Intrinsic stress of ultrathin epitaxial films

The present article focuses on the stress developing during the deposition of ultrathin epitaxial films in the thickness range of a few atomic layers. The studied systems exhibit the three well-known modes of film growth: Stranski–Krastanow mode [Ge/Si(001), Ge/Si(111), Ag/Si(111)], Frank–Van der Merwe mode [Fe/MgO(001)] and Volmer–Weber mode [Ag/mica(001), Cu/mica(001)]. The experimental results demonstrate the important role of the misfit strain as well as the contribution of surface stress effects as mechanisms for the stress in single atomic layers. Received: 26 April 1999 / Accepted: 25 June 1999 / Published online: 6 October 1999