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     

Nonlinear optical and electrostatic force microscopy for ferroelectric polarization imaging

Second-harmonic generation (SHG)-based nonlinear optical microscopy is used for spatially resolved imaging of the polarization switching in lead zirconium titanate ferroelectric thin films. The local SHG hysteresis loops reveal a strong dependence on film composition and structure. The SHG microscopy results are in good agreement with the efficiency of electrostatic force microscopy writing and allow us to predict the microscopic dielectric memory efficiency, both in contact and contact-less ways. Received: 15 January 2001 / Revised version: 27 March 2002 / Published online: 6 June 2002     

Stress anisotropy in circular planar magnetron sputter deposited molybdenum films and its annealing effect

As part of the program to develop a free-standing thin-film filter for soft X-ray optics application, stress anisotropy in the molybdenum films deposited by dc circular planar magnetron sputtering were studied by X-ray diffraction (XRD) as a function of sputtering argon gas pressure over a range of 0.8–1.5 Pa. Surface morphology of the films has been investigated by optical microscopy and scanning tunneling microscopy (STM). It is found that, for the film deposited at 0.8 Pa pressure, the stresses are more compressive in the tangential than in the radial direction; the highest compressive stress exists in the center area. The film deposited at 1.5 Pa pressure has the highest stress anisotropy, and the stresses are less tensile in the tangential than in the radial direction. Annealing in vacuum is more effective in reducing tensile stress and stress anisotropy in the tensile stressed film than in the compressively stressed film. Received: 14 September 2001 / Accepted: 21 January 2002 / Published online: 5 July 2002 RID="*" ID="*"Corresponding author. Fax: +86-21/6598-6323, E-mail: ygwu@mail.tongji.edu.cn     

SHG on ferromagnetic Gd films: indication of surface-state effects

The magnetization of 10-nm Gd films on W (110) has been investigated with second-harmonic generation (SHG). We observed a strong second-harmonic (SH) yield, which we attribute to resonance enhancement by the well-known Gd (0001) d-like surface state above the Fermi level. Since this state is spin-polarized it enhances the magnetic SHG contrast. The contrast, the relative phase between odd and even SH fields, and the amplitude ratio of these fields depend strongly on wavelength, which confirms the resonance enhancement. Further proof is provided by the fact that oxidation of the Gd surface reduces the SH yield by an order of magnitude. Received: 16 October 2001 / Revised version: 21 March 2002 / Published online: 11 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     

Second harmonic generation in α-Si:H thin films: Thickness dependence

The second harmonic generation (SHG) technique has been applied to investigate the nonlinear optical properties of thin films of hydrogenated amorphous silicon on a glass substrate. SHG measurements have been performed in two transmission experimental schemes. Modeling of a film as a three-layer structure and considering the interference and absorption at the SH wavelength have been carried out. The dependence of the nonlinear susceptibility on the film thickness was used to separate the bulk electric dipole contribution.     

A generalized Ginzburg-Landau approach to second harmonic generation

We develop a generalized Ginzburg-Landau theory for second harmonic generation (SHG) in magnets by expanding the free energy in terms of the order parameter in the magnetic phase and the susceptibility tensor in the corresponding high-temperature phase. The non-zero components of the SHG susceptibility in the ordered phase are derived from the symmetries of the susceptibility tensor in the high-temperature phase and the symmetry of the order parameter. In this derivation, the dependence of the SHG susceptibility on the order parameter follows naturally, and therefore its nonreciprocal optical properties. We examine this phenomenology for the magnetoelectric compound Cr₂O₃ as well as for the ferroelectromagnet YMnO₃. Received 27 August 1999     

Optical and non-linear optical properties of vanadium oxide phthalocyanine films

The optical and non-linear optical properties of peripheral-substituted vanadium oxide phthalocyanine (VOPc) film and substituted VOPc/polymer composite film were investigated using stationary and transient spectroscopy techniques. The absorption Q band of the VOPc/polymer composite film shows a red shift relative to that of the peripheral-substituted VOPc film, revealing the monomeric characteristics of VOPc molecules. Effective quenching of PL emission was observed for the VOPc/polymer composite film and could be assigned to the efficient VOPc–polymer interaction. From pump-probe and optical Kerr effect (OKE) measurements, two decay components were obtained by fitting the transients for both VOPc films. The fast component, in a femtosecond time domain, originates from the electron–phonon interaction, and the difference in their slow decay is an indication of an efficient ISC process in the VOPc/polymer composite film. The third-order non-linear optical susceptibilities of these films were determined to be in the order of 10^-11 esu. Received: 25 October 2001 / Revised version: 8 January 2002 / Published online: 7 February 2002     

Second order optical susceptibilities in alkali halide crystals due to FA color centers

This paper presents the first calculation of the second order optical nonlinearity of the F_A color center for second harmonic generation (SHG) in KCl:Li crystals. The real and imaginary components of the nonlinear susceptibility evaluated over a wide spectral range enclosing the resonance region of the center show interesting feature. Second harmonics generation and three wave mixing processes are nonlinear optical effects based on the second order susceptibility of materials and are very effective in providing laser radiation over a wide range of wavelengths. The density matrix formalism is employed and the equation of motion is solved by second order perturbation to evaluate the nonlinear susceptibility for SHG. It is found that the system shows large resonance-enhanced second order susceptibilities for color center concentration of 10²³ m⁻³. A scheme of phase matching in terms of anomalous dispersion of the centers is discussed.     

Second-harmonic generation in resonant waveguide gratings incorporating ionic self-assembled monolayer polymer films

Experimental results on resonantly excited second-harmonic generation (SHG) in a periodic ionically self-assembled monolayer (ISAM) film are reported. A double-layer guided-mode resonance filter (GMRF) structure is coated with 40 bilayers of pyrlium-based chi(2) ISAM thin film and excited with the fundamental of a Nd:YAG laser. Enhanced second-harmonic conversion in the ISAM film is achieved because of the local field enhancement associated with the fundamental resonating leaky mode. This method of SHG is particularly promising, as the ISAM films under investigation exhibit anomalous dispersion that may be applied for phase matching to improve nonlinear conversion efficiency.     

Second harmonic generation polarization microscopy with tightly focused linearly and radially polarized beams

Second harmonic generation microscopy was conducted on rat-tail tendons with linearly and radially polarized beams. Transverse and axial field components were generated in the focal region through tight focusing of linearly and radially polarized. It was found that the generated SHG signals could not be qualitatively explained with a scalar approximation to the electric field at the focus. Only by accounting for the interactions of the axial and transverse components of the electric field interacting through the nonlinear susceptibility χ⁽²⁾ tensor could the SHG images be explained. For the case of collagen we find that the SHG signal varies as a function of the analyzer angle with a cos² or sin² dependency for linearly polarized beams. For tightly focused radially polarized beams we find that the output SHG is radially polarized after collimation and is independent of the analyzer angle.     

Elastic modulus-density relationship for amorphous boron suboxide thin films

Boron suboxide thin films have been deposited on Si(100) substrates by reactive RF magnetron sputtering of a sintered B target in an Ar/O₂ atmosphere. Elastic recoil detection analysis was applied to determine the film composition and density. Film structure was studied by X-ray diffraction and transmission electron microscopy. The elastic modulus, measured by nanoindentation, was found to decrease as the film density decreased. The relationship was affected by tuning the negative substrate bias potential and the substrate temperature during film growth. A decrease in film density, by a factor of 1.55, caused an elastic modulus reduction by a factor of 4.5, most likely due to formation of nano-pores containing Ar. It appears evident that the large scattering in the published data on elastic properties of films with identical chemical composition can readily be understood by density variations. These results are important for understanding the elastic properties of boron suboxide, but may also be qualitatively relevant for other B-based material systems. Received: 22 February 2002 / Accepted: 11 April 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +46-13/288-918, E-mail: denmu@ifm.liu.se     

Asymmetric distribution of surface second harmonic generation for thin silver films deposited on Si(111)

The asymmetric distributions of surface optical second harmonic generation (SHG) through azimuthally angular scans of (111) silicon wafers on which thin silver films were deposited, have been detected with different polarizations of output beams. On account of the inversion symmetry of silicon crystals, the SHG for the Ag/Si system is mainly contributed by the silver film and the silicon surface. In this work, we found that the interface strain implies an asymmetric intensity variation of SHG with respect to the surface azimuthal angles as an ultra thin Ag film is deposited on silicon wafers. This asymmetric behavior is prominent as the deposited silver layer is heated so that the continuous film aggregates to become granular nanoparticles. Similar changes of the surface asymmetric SHG are observed for a bare Si wafer imposed upon by an external force.     

Second-harmonic generation in graded metallic films

We study the effective second-harmonic generation (SHG) susceptibility in graded metallic films by invoking the local field effects exactly and further numerically demonstrate that graded metallic films can serve as a novel optical material for producing a broad structure in both the linear and the SHG response and an enhancement in the SHG signal.     

Nonlinear optics for surface phase transitions

A general approach of second-harmonic generation (SHG) studies for surface phase transitions (PTs) is presented, with a thermodynamic classification of surface PTs and their relation to SHG parameters. The symmetry aspects of SHG near a surface PT are discussed, including issues connected with separation of surface and bulk contributions and the role of atomic and mesoscopic inhomogeneities. This approach is illustrated by applying it to two systems revealing a (near-) surface PT: single-crystalline SrTiO₃ near a bulk structural PT and single-crystalline Au in an electrochemical cell revealing an order–disorder and a reconstructive PT. Received: 15 January 2002 / Published online: 11 June 2002     

Switching behaviour of ferroelectric liquid crystals probed by optical second-harmonic generation

Ferroelectric properties of thin (1.5–4 μm planar cells of a ferroelectric liquid crystal (FLC) mixture are studied using electro-optic measurements, second-harmonic generation (SHG) and SHG interferometry. A switching behaviour of the FLC cells in external dc electric fields is observed. It is characterised by rotation of the polarisation plane of the transmitted light and by changes in the SHG intensity, phase and anisotropy dependences, which are attributed to a collective motion of the system as a ferroelectric uniform state with C₂ symmetry. Received: 16 October 2001 / Revised version: 18 March 2002 / Published online: 6 June 2002     

Anisotropy of the optical and magneto-optical response of Au/Co/Au/Cu multilayers grown on vicinal Si (111) surfaces

The optical and magneto-optical second harmonic reflectivity response of Au/Co/Au/Cu multilayers grown on vicinal Si (111) substrates has been studied. These azimuthal optical non-linear experiments check the uniaxial character of the crystallinity of the Au buffer layer and the magnetic behavior of the ultrathin Co films in the metallic multilayer. They clearly show the strong dependence of the growth parameters and the misorientation of the vicinal surface on the SHG reflectivity signals. This uniaxial behavior is also correlated to linear MOKE experiments on the magnetic anisotropy with an easy magnetization axis parallel to the step edges. Received: 16 October 2001 / Published online: 29 May 2002     

Femtosecond dynamics of spin-dependent SHG response from NiO (001)

Based on a parameterized electronic many-body theory we calculate the spectrum of optical second-harmonic generation (SHG) on an antiferromagnetic (AF) surface: NiO (001). The occurrence of AF spectral lines is further exploited for the calculation of ultra-fast spin dynamics. This spin dynamics is observable in SHG. It is characterized by both a sharp drop of the AF signal within a few femtoseconds and a long persistence (up to nanoseconds) of the spin coherence. These two features constitute an ideal system for possible applications in both magnetic recording and quantum computing. Received: 16 October 2001 / Revised version: 21 March 2002 / Published online: 6 June 2002     

Crystal structure, morphology, depth profile of elements and mid-infrared optical constants of ‘mild’ lead telluride film

The characterizations of a so-called ‘mild’ PbTe layer thermal-evaporated from an excess of Te (<1 mol.%) evaporable materials are reported. The results reveal that the film obtained is polycrystalline and has a single-phase NaCl-type PbTe crystal structure. It is also demonstrated that the film has a homogeneous surface morphology and a high degree of homogeneous distribution of Te-rich components along the layer. The study of mid-infrared optical constants of a surface-polished film indicates that the influence of surface scattering on optical properties is very small. Received: 3 July 2002 / Accepted: 7 August 2002 / Published online: 4 December 2002 RID="*" ID="*"Corresponding author. Fax: +86-21/6516-9946, E-mail: lbincome@yahoo.com     

The orientation-selective growth of LaNiO3 films on Si(100) by pulsed laser deposition using a MgO buffer

Highly (100)-oriented, (110)-oriented and polycrystalline LaNiO₃ (LNO) films were successfully prepared on Si(100) using an oriented MgO film as a buffer. It was somewhat surprising to find that that the orientation relation between the LNO film and the corresponding MgO buffer was: LNO(100)\MgO(110), LNO(110)\MgO(111) and LNO(polycrystalline)\MgO(100). The crystalline quality of the LNO films was shown to be sensitive to the preparation conditions of the MgO buffer. The film surface was very smooth, without micrometer-sized droplets being observed. All LNO films were of metallic conductivity, with a room-temperature resistivities of approximately 250, 280 and 420 μΩ cm for the (110)-oriented, (100)-oriented and polycrystalline LNO, respectively. Received: 2 April 2001 / Accepted: 23 October 2001 / Published online: 3 June 2002