Effect of finely dispersed platinum on the structure of luminescence spectra of the adsorbates of magnesium phthalocyanine on silicon dioxide

The luminescence and excitation spectra and kinetic characteristics of the luminescence of the adsorbates of magnesium phthalocyanine (MgPhc) on SiO₂ and the effect on them of surface hydration and finely dispersed platinum are studied. It is found that a structure that improves hydration of the adsorbent surface appears on the platinized surface in the luminescence and excitation spectra. It is assumed that the spectral structure is due to the complexes of MgPhc formed with water molecules, the hydroxyl cover of the surface, and the surface centers of SiO₂ modified by a Pt-catalyst. Reported at the VIIIth International Conference on Spectroscopy of Porphyrins and Their Analogs, Minsk, September 22–26, 1998. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 4, pp. 552–555, July–August, 1999.     

X-ray luminescence of disperse SiO2 and porous silicon

We carry out a comparison between the luminescence spectra (photo-and x-ray luminescence) of porous silicon and disperse SiO₂, which by its physical characteristics is most similar to oxide films on porous silicon. The photoluminescence of porous silicon was also investigated using fluorescence (excitation by a nitrogen laser) and metallographic microscopes. We found that the natures of the luminescence centers of porous silicon and disperse SiO₂ are identical. A porous layer on single-crystal silicon ensures the creation of a highly branched surface of oxide film. Luminescence centers are located on its inner (as viewed from the porous silicon) surface. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 2, pp. 247–251, March–April, 1998.     

Role of masking oxide on the silicon surface on defect formation in SIMOX structures

The properties of Si/SiO₂ structures produced by oxygen implantation into silicon (SIMOX technology) are investigated by the high-frequency C-V method and by the electroluminescence (EL) method. The existence of electrically active and luminescence centers in the oxide layer near the interface is established. The effect of a SiO₂ masking layer on the silicon surface on defect formation in the SIMOX structure is elucidated. The dependence of the concentration of the electrically active and luminescence centers on the thickness of the masking layer is found.     

The effect of packing density on luminescence of amorphous SiO<Subscript>2</Subscript> nanoparticles

Photoluminescence of amorphous SiO₂ nanoparticles compressed in the form of tablets is studied under exposure to UV radiation. The observed luminescence spectrum is a broad band extending from the excitation wavelength to 700 nm and with a maximum at ~470 nm. The spectrum can be decomposed into two Gaussian components with maxima at ~460 and ~530 nm. As the pressure applied for sample preparation increases, the integrated intensities of these bands change in opposite directions—the intensity of the short-wavelength band increases, while that of the long-wavelength band decreases. It is concluded that these bands are due to different luminescence centers of silicon dioxide located on the surface and in the bulk of SiO₂ nanoparticles.     

Silicon based polytetrafluoroethylene electrets: Preparation and corona charging characteristics

In this paper, silicon based planar technology and high performance fluorocarbon polymer polytetrafluoroethylene (PTFE) are combined to achieve PTFE thin film electrets on wafer. The PTFE film is fabricated onto SiO₂ substrates and Pt substrates using spin coating and annealing processes, and its electret effect is demonstrated using negative corona charging method. PTFE electrets with different surface morphology exhibit different charge storage capability. Maximally, surface potential of ?396 V is achieved on Pt substrates and ?361 V is achieved on SiO₂ substrates. The average retain rate of surface potential over 240 h is 90.6% for Pt substrates and 76.3% for SiO₂ substrates. The proposed method presents the primary step toward integrated electrostatic devices.     

Radical-Recombination Luminescence of the Uranyl Nitrate Complex in the Adsorbed State

We have investigated the luminescence of uranyl nitrate molecules on the surface of powdery SiO₂ upon excitation by UV light (PhL) and hydrogen atoms (radical-recombination luminescence (RRL)). It has been found that the PhL and RRL spectra have a clearly defined vibrational structure. The luminescence peaks of the adsorbed UO₂ ^2– ion are characterized by a systematic longwave shift from the same peaks of crystalline uranyl nitrate (by 230–430 cm^–1 at 130 K). Moreover, in the adsorption centers the vibration frequencies of UO₂ ^2– are 20–80 cm smaller than in crystalline salt and the RRL bands are 150–350 cm^–1 (130 K) wider than the corresponding PhL bands.     

Luminescent defects in nanostructured silica

The spectral and kinetic properties of excited states of luminescent defects (oxygen-deficient centers) in SiO₂ ceramics are studied using pulsed cathodoluminescence and time-resolved photoluminescence. It is found that, in nanostructured samples prepared by thermal decomposition of polysilazane in air, there can exist modifications of oxygen-deficient centers in the form of surface analogs of either neutral oxygen monovacancies ≡Si-Si≡ (≡Ge-Ge≡) or twofold-coordinated silicon atoms =Si: (=Ge:). Photoluminescence of these centers is efficiently excited in the optical absorption bands of E′_s surface centers and silicon clusters ≡SiSiSi≡ and can be associated with the intercenter energy transfer in the course of their nonradiative relaxation. The photoluminescence and excitation spectra indicate thermally induced conversion of different types of oxygen-deficient centers. The specific features of the thermally induced changes in the luminescence characteristics of the defects due to the transformation of the structure of the silica samples from amorphous to partially crystalline are revealed from analyzing the spectral composition and decay kinetics of pulsed cathodoluminescence.     

Luminescence and structure of nanosized inclusions formed in SiO2 layers under double implantation of silicon and carbon ions

Luminescent and structural characteristics of SiO₂ layers exposed to double implantation by Si⁺ and C⁺ ions in order to synthesize nanosized silicon carbide inclusions have been investigated by the photoluminescence, electron spin resonance, transmission electron microscopy, and electron spectroscopy methods. It is shown that the irradiation of SiO₂ layers containing preliminary synthesized silicon nanocrystals by carbon ions is accompanied by quenching the nanocrystal-related photoluminescence at 700–750 nm and by the enhancement of light emission from oxygen-deficient centers in oxide in the range of 350–700 nm. Subsequent annealing at 1000 or 1100°C results in the healing of defects and, correspondingly, in the weakening of the related photoluminescence peaks and also recovers in part the photoluminescence of silicon nanocrystals if the carbon dose is less than the silicon dose and results in the intensive white luminescence if the carbon and silicon doses are equal. This luminescence is characterized by three bands at ～400, ～500, and ～625 nm, which are related to the SiC, C, and Si phase inclusions, respectively. The presence of these phases has been confirmed by electron spectroscopy, the carbon precipitates have the sp ³ bond hybridization. The nanosized amorphous inclusions in the Si⁺ + C⁺ implanted and annealed SiO₂ layer have been revealed by high-resolution transmission electron microscopy.     

Localized electronic excitations in crystalline phenacite Be2SiO4

The results of coordinated spectroscopic studies of the nature and properties of electronic excitations localized at regular and defect sites of the Be₂SiO₄ lattice are presented. The methods employed are electron-beam-excited pulsed absorption spectroscopy, pulsed cathodoluminescence, and low-temperature VUV spectroscopy with selective excitation by synchrotron radiation. The bands in luminescence spectra of Be₂SiO₄ at 2.70 and 3.15 eV are assigned to [AlO₄]^5? and [SiO₄]^4? centers formed both in direct relaxation of electronic excitations at defect levels and through the formation of exciton-defect complexes. Disruptions of beryllium-oxygen bonds (short-lived defects in the form of beryllium vacancies V _Be ^? ) are considered as initiating the formation of optically active centers with characteristic absorption bands in the range 1.5–4.0 eV. The intrinsic luminescence of the Be₂SiO₄ crystal at 3.6 and 4.1 eV is attributed to radiative decay of self-trapped excitons of two types. A mechanism of exciton self-trapping at the [SiO₄] and [BeO₄] tetrahedral groups is proposed, which involves excitation transfer from a threefold-coordinated oxygen atom to neighboring silicon or beryllium atoms.     

Orientation-dependent ionization potential of CuPc and energy level alignment at C60/CuPc interface

The electronic structure evolution of interfaces of fullerene (C₆₀) with copper phthalocyanine (CuPc) on highly oriented pyrolytic graphite (HOPG) and on native silicon oxide has been investigated with ultraviolet photoemission spectroscopy and inverse photoemission spectroscopy. The LUMO edge of C₆₀ was found to be pinned at the interface with CuPc on SiO₂. A substantial difference in the electron affinity of CuPc on the two substrates was observed as the orientation of CuPc is lying flat on HOPG and standing up on SiO₂. The ionization potential and electron affinity of C₆₀ were not affected by the orientation of CuPc due to the spherical symmetry of C₆₀ molecules. We observed band bending in C₆₀ on the standing-up orientation of CuPc molecules, while the energy levels of C₆₀ on the flat-lying orientation of CuPc molecules were observed to be flat. The observation points to a dependence of photoexcited charge transfer on the relative molecular orientation at the interface.     

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.     

Experimental analysis of the stability of electrostatic bits for assisted nano-assembly

Scanning probe microscopy(SPM)-based nanolithography with injected charges into layered electrets, such as silicon dioxide (SiO₂) and silicon nitride, is a promising tool with far-reaching applications, such as controlled nano-assembly of macro-molecules and data storage. Despite its potential, some practical limitations exist. This paper describes an experimental investigation of the process of charging and charge dissipation in SiO₂ using an AFM probe tip and surface potential (Kelvin probe) microscopy. The stability of charge bits on hexamethyl disilazane(HMDS)-treated SiO₂ under low dielectric constant liquids, fluorocarbon, and benzene has been demonstrated. Results from a numerical simulation of a theoretical charging model, in which the charge traps are assumed to be localized on the silicon/SiO₂ interface, are also presented. The charge transport mechanism considered is modified Fowler–Nordheim tunneling.     

Interaction of nitrogen dioxide molecules with the surface of silicon nanocrystals in porous silicon layers

The methods of infrared absorption spectroscopy and electron paramagnetic resonance are used for studying the effect of adsorption of NO₂ molecules, which are strong acceptors of electrons, on the electronic and optical properties of silicon nanocrystals in mesoporous silicon layers. It is found that the concentration of free charge carriers (holes) in silicon nanocrystals, which exhibits a nonmonotonic dependence on the NO₂ pressure, sharply increases in the presence of these molecules. At the same time, a monotonic increase in the concentration of dangling silicon bonds (P_b1 centers) is observed. A microscopic model proposed for explaining this effect presumes the formation of donor-acceptor pairs P ₊ ^b1 -(NO₂)^? on the surface of nanocrystals, which ensure an increase in the hole concentration in nanocrystals, as well as P_b1 centers, which are hole-trapping centers. The proposed model successfully explains a substantial increase in photoconductivity (by two or three orders of magnitude) in the layers of porous silicon in the presence of NO₂ molecules; the increment in the concentration of free charge carriers is detected within an order of magnitude of this quantity. The results can be used in designing electronic and luminescence devices based on silicon nanocrystals.     

Microdetermination of silicon dioxide on the surface by sensors based on perfluorinated proton-conducting membranes

A microdetermination method of silicon dioxide on the silicon surface is studied. In this method, a thin SiO₂ layer is dissolved in an aqueous solution of hydrofluoric acid and then the resulting solution is analyzed with sensors based on perfluorinated proton-conducting membranes. Quantitative determination of silicon dioxide remaining on the silicon surface in a quantity as low as 1 × 10^?6 mol is demonstrated to be feasible.     

Influence of the ion synthesis and ion doping regimes on the effect of sensitization of erbium emission by silicon nanoclusters in silicon dioxide films

The photoluminescence spectra of erbium centers in SiO₂ films with ion-synthesized silicon nanoclusters under nonresonant excitation were investigated. Erbium was introduced into thermal SiO₂ films by ion implantation. The dependences of photoluminescence intensity on the dose, the order of ion implantation of Si and Er, the annealing temperature, and additional Ar⁺ and P⁺ ion irradiation regimes, i.e., factors determining the influence of radiation damage and doping on sensitization of erbium luminescence by silicon nanoclusters, were determined. It was found that the sensitization effect and its amplification due to doping with phosphorus are most pronounced under the conditions where nanoclusters are amorphous. The quenching of photoluminescence due to radiation damage in this case manifests itself to a lesser extent than for crystalline nanoclusters. The role of various factors in the observed regularities was discussed in the framework of the existing concepts of the mechanisms of light emission and energy exchange in the system of silicon nanoclusters and erbium centers.     

Structure, morphology and optical properties of SiO2−x thin films prepared by plasma-assisted pulsed laser deposition

The amorphous silicon oxide SiO_2−x thin films were prepared by the plasma-assisted pulsed laser deposition (PLD) method. X-ray diffraction spectrometry (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), UV-VIS-NIR scanning spectrophotometry and ellipsometry were used to characterize the crystallinity, microscopic morphology and optical properties of obtained thin films. The influences of substrate temperatures, oxygen partial pressures and oxygen plasma assistance on the compositions of silicon oxide (SiO_2−x) thin films were investigated. Results show that the deposited thin films are amorphous and have high surface quality. Stoichiometric silicon dioxide (SiO₂) thin film can be obtained at elevated temperature of 200 °C in an oxygen plasma-assisted atmosphere. Using normal incidence transmittance, a novel and simple method has been proposed to evaluate the value of x in transparent SiO_2−x thin films on a non-absorbing flat substrate.     

Nanostructuring Si surface and Si/SiO2 interface using porous-alumina-on-Si template technology. Electrical characterization of Si/SiO2 interface

In this work, anodic porous alumina thin films with pores in the nanometer range are grown on silicon by electrochemistry and are used as masking material for the nanopatterning of the silicon substrate. The pore diameter and density are controlled by the electrochemical process. Through the pores of the alumina film chemical oxidation of the silicon substrate is performed, leading to the formation of regular arrays of well-separated stoichiometric silicon dioxide nanodots on silicon, with a density following the alumina pores density and a diameter adjustable by adjusting the chemical oxidation time. The alumina film is dissolved chemically after the SiO₂ nanodots growth, revealing the arrays of silicon dioxide dots on silicon. In a next step, the nanodots are also removed, leaving a nanopatterned bare silicon surface with regular arrays of nanopits at the footprint of each nanodot. This silicon surface structuring finds interesting applications in nanoelectronics. One such application is in silicon nanocrystals memories, where the structuring of the oxidized silicon surface leads to the growth of discrete silicon nanocrystals of uniform size. In this work, we examine the electrical quality of the Si/SiO₂ interface of a nanostructured oxidized silicon surface fabricated as above and we find that it is appropriate for electronic applications (an interface trap density below 1–3×10¹⁰ eV⁻¹ cm⁻² is obtained, indicative of the high quality of the thermal silicon oxide).     

Photoelectron spectroscopy of E′ centers in crystalline and glassy silicon dioxide

Radiation-induced E′ centers in SiO₂ were studied to test the possibility of applying optically stimulated electron emission (OSEE) to the spectroscopy of excited states of point defects in dielectrics. The spectral responses of the OSEE of crystalline α quartz and silica glass irradiated by 10-MeV electrons were measured and studied. It was established that volume E′ centers in the crystalline and glassy SiO₂ modifications are dominant emission-active defects. Surface E’_s (1) centers were also detected in glassy SiO₂. A model of the energy structure of E′ centers accounting for the absence of luminescence and taking into account the presence of two nonradiative (intracenter and ionization) relaxation channels is proposed. This model was used to explain the mechanism of photothermal decay of the E′ centers and to determine the ionization activation barriers and quantum yields of these centers. The emission, spectral, and kinetic parameters of the volume and surface E′ centers in glassy SiO₂ were obtained, showing the excited states of these defects to have identical atomic configurations.     

Influence of self-assembly monolayers on the characteristics of copper phthalacyanine thin film transistor

Self-assembly monolayers (SAMs) of octadecyltrichlorosilane (OTS) on a silicon dioxide substrate were formed in solution, or by vacuum vapor methods, and characterized by Fourier transform infrared (FTIR) spectroscopy. We found that the OTS SAMs on SiO₂ substrates greatly affect the order and connectivity of evaporated copper phthalocyanine (CuPc) thin films, as confirmed by an atomic force microscopy (AFM) and X-ray diffraction analysis. The performance of the organic CuPc thin film transistor comprising OTS SAMs interposed between a gate dielectric and an organic semiconductor layer could be effectively enhanced as a result of improvements in the quality both of the organic/dielectric interface and the evaporated CuPc thin films. The deposition of an OTS SAM leads to a mobility of 1.48×10^-3 cm²/Vs, 1–2 orders higher than that of bare silicon dioxide. PACS 73.61.Ph; 85.30.Tv; 78.66.Tr     

Photoluminescence properties of core-shell SiO2/Lu2O3: Eu monodisperse heteronanoparticles

Core-shell monodisperse heteroparticles of the composition SiO₂/Lu_1.86Eu_0.14O₃ have been synthesized using the developed technique for preparing spherical colloidal silicon dioxide particles with the size dispersion in the range 2.0–2.5% and the procedure for producing nanocoatings on the surface of spheres by codeposition. The structure of heteroparticles has been investigated, their excitation and photoluminescence spectra have been analyzed, and the lifetime of the ⁵ D ₀ excited state of Eu³⁺ ions has been examined. It has been revealed that the luminescence decay time for heteroparticles increases by a factor of approximately two compared to that for a powdered luminophor Lu₂O₃: Eu (7 at %) prepared and treated under the same temperature conditions as the SiO₂/Lu₂O₃: Eu (7 at %) heteroparticles. This effect has been attributed to the change in the effective refractive index and the local density of photon states in luminophor nanolayers of heteroparticles.