Differences between surface and bulk refractive indices of a-InxSe1−x

Thin films of amorphous indium selenide compounds (a-In_xSe_1−x) are important, e.g. for photovoltaics. The feature of merit in such applications is also the real part of refractive index n of this material. The data on n in literature are divergent. In this paper, the results of investigations on n in the bulk as well as in the interface layers of thin films of a-In_xSe_1−x are presented. The measurements had been performed using optical transmittance and reflectance in spectral range from 1.24 to 1.96 eV of linear polarized radiation that hit the samples with angles of incidence from 0° to 80°. Investigations had been done for sample temperatures from 80 to 340 K. It was found that the refractive index for areas at the free surface n_f is bigger than the refractive index n_b at the interface of thin film-substrate. The averaged over thin film thickness value of real part refractive index have the biggest value in all spectral range. Values of these coefficients increase with increasing the temperature.     

Ion synthesis and laser annealing of Cu nanoparticles in Al2O3

Al₂O₃ samples with Cu nanoparticles, synthesised by ion implantation at 40 keV with a dose of 1×10¹⁷ ion/cm² and a current density from 2.5 to 12.5 μA/cm², were annealed using ten pulses from a KrF excimer laser with a single pulse fluence of 0.3 J/cm². The copper depth distribution, formation and modification of metal nanoparticles under the ion implantation and laser treatment were studied by Rutherford backscattering (RBS), energy dispersive X-ray (EDX) analysis, atomic force microscopy (AFM) and optical spectroscopy. It was found that laser annealing leads to a reduction in the nanoparticle size without diffusion of metal atoms into the bulk. The change in particle size and the possibility for oxidation of the copper particles are examined in the framework of Mie theory. Calculations presented show that under excimer laser treatment, Cu nanoparticles are more likely to be reduced in size than to undergo oxidation. Received: 19 April 2001 / Accepted: 7 November 2001 / Published online: 23 January 2002     

Germania/ormosil hybrid materials derived at low temperature for photonic applications

We report on germania/organically modified silane (ormosil) hybrid materials produced by the sol–gel technique for photonic applications. Acid-catalyzed solutions of γ-glycidoxypropyltrimethoxysilane mixed with germanium isopropoxide have been used as precursors for the hybrid materials. Planar waveguide films with a thickness of about 2 μm have been prepared by a single spin-coating process and low-temperature heat treatment from these high germanium content hybrid materials. Atomic force microscopy, thermal gravimetric analysis, UV–visible spectroscopy, and Fourier-transform infrared spectroscopy have been used to investigate the optical and structural properties of the films. The results have indicated that a dense, low absorption, and high transparency (in the visible range) waveguide film could be achieved at a low temperature. A strong UV-absorption region at short wavelengths ∼200 nm, accompanied by a shoulder peaked at ∼240 nm, has been noticed due to the neutral oxygen monovacancy defects. The propagation mode and loss properties of the planar waveguide films have also been investigated by using a prism-coupling technique. Received: 5 November 2002 / Revised version: 27 December 2002 / Published online: 19 March 2003 RID="*" ID="*"Corresponding author. Fax: +65-67909081, E-mail: ewxque@ntu.edu.sg     

Large-scale synthesis of SnO2 nanobelts

Tin dioxide (SnO₂) nanobelts have been successfully synthesized in bulk quantity by a simple and low-cost process based on the thermal evaporation of tin powders at 800 °C. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations reveal that the nanobelts are uniform, with lengths from several-hundred micrometers to a few millimeters, widths of 60 to 250 nm and thicknesses of 10 to 30 nm. X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX) and selected-area electron diffraction analysis (SAED) indicate that the nanobelts are tetragonal rutile structure of SnO₂. The SnO₂ nanobelts grow via a vapor–solid (VS) process. Received: 3 June 2002 / Accepted: 10 June 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +86-551/559-1434, E-mail: gwmeng@mail.issp.ac.cn     

Synthesis and photoluminescence characteristics of doped ZnS nanoparticles

Free-standing powders of doped ZnS nanoparticles have been synthesized by using a chemical co-precipitation of Zn²⁺, Mn²⁺, Cu²⁺ and Cd²⁺ with sulfur ions in aqueous solution. X-ray diffraction analysis shows that the diameter of the particles is ∼2–3 nm. The unique luminescence properties, such as the strength (its intensity is about 12 times that of ZnS nanoparticles) and stability of the visible-light emission, were observed from ZnS nanoparticles co-doped with Cu²⁺ and Mn²⁺. The nanoparticles could be doped with copper and manganese during the synthesis without altering the X-ray diffraction pattern. However, doping shifts the luminescence to 520–540 nm in the case of co-doping with Cu²⁺ and Mn²⁺. Doping also results in a blue shift on the excitation wavelength. In Cd²⁺-doped ZnS nanometer-scale particles, the fluorescence spectra show a red shift in the emission wavelength (ranging from 450 nm to 620 nm). Also a relatively broad emission (ranging from blue to yellow) has been observed. The results strongly suggest that doped ZnS nanocrystals, especially two kinds of transition metal-activated ZnS nanoparticles, form a new class of luminescent materials. Received: 16 October 2000 / Accepted: 17 October 2000 / Published online: 23 May 2001     

Strong green luminescence of Ni2+-doped ZnS nanocrystals

ZnS nanoparticles doped with Ni²⁺ have been obtained by chemical co-precipitation from homogeneous solutions of zinc and nickel salt compounds, with S^2- as precipitating anion, formed by decomposition of thioacetamide (TAA). The average size of particles doped with different mole ratios, estimated from the Debye–Scherrer formula, is about 2–2.5 nm. The nanoparticles could be doped with nickel during synthesis without altering the X-ray diffraction pattern. A Hitachi M-850 fluorescence spectrophotometer reveals the emission spectra of samples. The absorption spectra show that the excitation spectra of Ni-doped ZnS nanocrystallites are almost the same as those of pure ZnS nanocrystallites (λ_ex=308–310 nm). Because a Ni²⁺ luminescent center is formed in ZnS nanocrystallites, the photoluminescence intensity increases with the amount of ZnS nanoparticles doped with Ni²⁺. Stronger and stable green-light emission (520 nm) (its intensity is about two times that of pure ZnS nanoparticles) has been observed from ZnS nanoparticles doped with Ni²⁺. Received: 18 December 2000 / Accepted: 17 March 2001 / Published online: 20 June 2001     

Combinatorial synthesis of Li-doped NiO thin films and their transparent conducting properties

Transparent and conductive oxide (TCO) thin films of Li-doped NiO were prepared by combinatorial pulsed laser deposition technique. Composition spread approach was applied to optimize the Li concentration for achieving high conductivity and transparency in the film. Conductivity of the composition spread film was found to increase almost linearly from nearly insulating to as high as 1.41 Ω⁻¹ cm⁻¹ with increasing Li content along a 9 mm long film. Optical transparency was found to decrease in an equal proportion across the 40 nm thick film with a slight shift in the absorption edge.     

Large-quantity synthesis of ZnO hollow objects by thermal evaporation: Growth mechanism, structural and optical properties

Synthesis of large-quantity uniformly distributed ZnO hollow objects, i.e. cages and spheres have been performed on Si(1 0 0) and steel alloy substrates by the direct heating of metallic zinc powder in the presence of oxygen. Extensive structural observations revealed that the formed products are crystalline ZnO with the wurtzite hexagonal phases. The Raman-active optical phonon E₂ modes, attributed to wurtzite hexagonal phase of ZnO, were observed at 437 cm⁻¹ for the products grown on both the substrates. The room-temperature photoluminescence spectra showed a broad band in the visible region with a suppressed UV emission, indicating the presence of oxygen vacancies and structural defects in the as-grown structures. Additionally, post growth annealing was also carried out to further investigate the photoluminescence properties of the as-grown products. It was observed that the formation of hollow objects consists of several stages which include the formation of Zn clusters, oxidation on the sheath and sublimation/evaporation of the Zn from the interiors, resulted in the formation of hollow objects.     

Effect of size and synthesis route on the magnetic properties of chemically prepared nanosize ZnFe2O4

Magnetization of the ZnFe₂O₄ sample of average size 4 nm measured with SQUID in the temperature range 5–300 K shows anomalous behaviour in field cooled (FC) and zero-field-cooled (ZFC) conditions. The FC and ZFC curves measured in 50 Oe field cross each other a little before the peaks. No such anomaly is observed with samples of 6 nm particle size made with the same procedure. The characteristics of the FC and ZFC curves are very different in ZnFe₂O₄ samples of the same size (6 nm) made via two different chemical routes. The genesis of these differences are suggested to be in cationic configuration and spin disorder. Fe-extended X-ray absorption fine structure (EXAFS) studies show that there is around 80% inversion in case of zinc ferrite (ZnFe₂O₄) with the particle size 4 nm, whereas ZnFe₂O₄ of size 6 nm shows 40% inversion. The samples with an average particle size of 7 nm and more show negligible inversion. Theoretical simulations suggest that the electrostatic energy of the system plays a crucial role in deciding the cationic configuration of spinel ferrites.     

Photoluminescence of Electrospun Poly-Methyl-Methacrylate:Alq3 Composite Fibres

Tris（8-hydroxyquinoline） aluminium doped poly-methyl-methacrylate （PMMA：Alq3） composite nanofibres are fabricated by electrospinning. The morphology of fibres is characterized by scanning electron microscopy. The photoluminescence of a series of the nanofibres with various contents of Alq3 to PMMA is investigated. UVvisible absorption and the PL spectra analysis are employed to analyse the interaction between the polymer and the luminescent molecule.     

Photoluminescence characteristics of ZnS nanocrystallites doped with Ti3+and Ti4+

Direct synthesis of ZnS nanocrystallites doped with Ti³⁺ or Ti⁴⁺ by precipitation has led to novel photoluminescence properties. Detailed X-ray diffraction (XRD), fluorescence spectrophotometry, UV–vis spectrophotometry and X-ray photoelectron spectroscopy (XPS) analysis reveal the crystal lattice structure, average size, emission spectra, absorption spectra and composition. The average crystallite size doped with different mole ratios, estimated from the Debye–Scherrer formula, is about 2.6±0.2 nm. The nanoparticles can be doped with Ti³⁺ and Ti⁴⁺ during the synthesis without the X-ray diffraction pattern being altered. The strong and stable visible-light emission has been observed from ZnS nanocrystallites doped with Ti³⁺ (its maximum fluorescence intensity is about twice that of undoped ZnS nanoparticles). However, the fluorescence intensity of the ZnS nanocrystallites doped with Ti⁴⁺ is almost the same as that of the undoped ZnS nanoparticles. The emission peak of the undoped sample is at 440–450 nm. The emission spectrum of the doped sample consists of two emission peaks, one at 420–430 nm and the other at 510 nm. Received: 27 April 2001 / Accepted: 16 August 2001 / Published online: 17 October 2001     

Synthesis and photoluminescence properties of Bi2S3 nanowires via surfactant micelle-template inducing reaction

Single-crystalline Bi₂S₃ nanowires, with diameters in the range of 80-200 nm and lengths up to tens of micrometers, have been successfully synthesized through surfactant micelle-template inducing reaction at ambient-pressure and low-temperature. The synthetic route is simple, effective and can provide great opportunities for both fundamental and technological applications. The optical properties of the Bi₂S₃ nanowires with different diameters were firstly examined by means of photoluminescence spectroscopy at room temperature. The representative photoluminescence spectrum exhibits a great blue-shift from the band gap of 1.30 eV of bulk Bi₂S₃ to high energy of 1.44 eV, which indicated that these nanostructures showed quantum confinement effects.     

Structural, electrical and optical properties of ZnS films deposited by close-spaced evaporation

ZnS films have been deposited on glass substrates by close-spaced evaporation (CSE) technique. The films were grown at different temperatures in the range, 200-350 °C. The layers have been characterized with X-ray diffractometer (XRD), atomic force microscope (AFM), energy dispersive analysis of X-rays (EDAX) and optical spectrophotometer to evaluate the quality of the layers for photovoltaic applications. The studies showed that the optimum substrate temperature for the growth of ZnS layers was 300 °C. The films grown at these temperatures exhibited cubic structure with nearly stoichiometric composition. The AFM data revealed that the films had nano-sized grains with a grain size of ∼40 nm. The optical studies exhibited direct allowed transition with an energy band gap of 3.61 eV. The other structural and optical parameters such as lattice stress, dislocation density, refractive index and extinction coefficient were also evaluated. The temperature-dependent conductivity measured in the range, 303-523 K showed a change in the conduction mechanism at 120 °C. The activation energy values evaluated using the temperature dependence of electrical conductivity are 7 and 29 meV at low and high temperature regions, respectively.     

Preparation and characterization of nano-sized Ag/PVP composites for optical applications

A modification of the polyol process has enabled the direct synthesis of nm-sized Ag particles with narrow size distribution and controlled average dimension embedded in a polymeric matrix. Dispersion of colloidal silver was obtained by reduction of silver nitrate in ethylene-glycol in the presence of a polymeric protective agent (i.e., poly(N-vinylpyrrolidone)) and ultrasounds. The final particle size was controlled by removing the colloid from the reactive mixture by addition of acetone. The very strong plasmon resonance peak at 410 nm and a feature at 350 nm in the UV-visible spectra are a clear consequence of the nano-size of dilute Ag particles. The proposed process offers the possibility to effectively use these synthesised materials for the production of colour filters for advanced optical devices. Received 10 November 1999     

Reverse saturable absorption of a novel rhodamine-B cation fulleride salt at 532 nm

A novel rhodamine-B cation fulleride salt was synthesized by metathetical reaction. Its tetrahydrofuran solution was prepared and the fluence-dependent transmission was measured with 10-ns 532-nm laser pulses in a collimated optical setup. With increases in the input fluence, its transmittance decreased significantly, which indicated reverse saturable absorption behavior. For comparison, the input fluence-dependent transmittance of fullerene C₆₀ and rhodamine-B solution were also measured. The nonlinear optical limiting effect of the fulleride salt in tetrahydrofuran is slightly lower than that of C₆₀ in toluene and the explanations are provided. Received: 25 August 2000 / Accepted: 6 November 2000 / Published online: 3 April 2001     

The effect of KI on the formation of Tl2E (E=S, Se) nanorods via solvothermal route

Tl₂E (E=S or Se) nanorods were synthesized via solvothermal route with the addition of KI. The products were characterized with X-ray powder diffraction patterns and transmission electron microscope images. Their optical properties were studied by UV-vis transmittance and photoluminescence spectrum. The band gap of direct forbidden transitions was found larger than that of bulk materials, because of the blue shift caused by nanometer-scale crystalline particles due to quantum confinement effects. A possible growth mechanism is proposed.     

Rapid synthesis of novel flowerlike ZnO structures by thermolysis of zinc acetate

Novel flowerlike ZnO structures have been rapidly synthesized on (1 0 0)-Si substrates via thermolysis of zinc acetate in air ambient without any catalyst. The obtained ZnO products exhibit well-defined flowerlike morphologies consisting of multilayer petal crystals with tapering feature. High-resolution transmission electron microscope (HRTEM) and corresponding selected area electron diffraction pattern (SAED) reveal that these petal crystals are single crystal in nature and preferentially oriented in the c-axis direction. Room-temperature photoluminescence (PL) spectra show that all the samples exhibit prominent UV emissions around 376.8 nm and very weak visible emission peaks, which demonstrates that there are few deep-level defects in the single crystal petals of the flowerlike ZnO structures. The growth mechanism of the as-synthesized flowerlike ZnO structures was also discussed.     

Micrometer-sized Si-Sn-O novel structures with SiONWs on their surfaces

Novel micrometer-sized Si-Sn-O structures with SiO₂ nanowires (SiONWs) growing from their surfaces have been achieved at about 980 °C on Si (111) wafer catalyzed by Sn vapor generated from Sn powders. The Si wafer itself served as a silicon source in the reaction. The micrometer-sized structures, with diameters of several micrometers to several tens of micrometers consisted of Sn, Si and O. The amorphous SiONWs growing from the surface of the micrometer-sized structures were smooth, with diameters about 120 nm and with a composition close to that of SiO₂. The growth mechanism of these novel structures is discussed briefly. Received: 30 July 2002 / Accepted: 18 September 2002 / Published online: 4 December 2002 RID="*" ID="*"Corresponding author. Fax: +86-551/5591434, E-mail: shsuncn@hotmail.com     

Synthesis and characterization of hydrophobic silica nanocomposites

Hydrophobically modified silica nanocomposites have been prepared using a low temperature sol-gel process. In this study, an alkyltriethoxysilane derivative, hexdecyltrimethoxysilane (HDTMS), was co-condensed with tetraethoxyorthosilicate (TEOS) with and without a cross-linking agent, 3-glycidoxypropyltrimethoxysilane (GPTMS), to produce the modified composites. The hydrophobic properties were determined using contact angle measurement. FESEM observations revealed a semispherical nanostructure of the composites with grain size of about 50-75 nm in diameter. The chemical modification was studied by FTIR and EDX, whereas the physicothermal properties were analyzed by DSC and TGA. These long-chain alkyl modified silica nanocomposites are promising materials for use in hydrophobic and water-resistant applications.     

Broadening of resonances in yttrium nanoparticle optical spectra

The dielectric function of yttrium in the range between 0.2 μm and 2 μm is composed of a harmonic oscillator contribution due to a discrete interband transition and the contribution of free electrons. Hence, it is possible to discuss surface plasmon polaritons as well as other electronic resonances in the optical extinction spectra of yttrium nanoparticles. For the latter, we discuss the broadening of the resonance caused by the aggregation of particles. When particles are lumped into aggregates, the color of the particle system also changes. Aggregation also affects the surface plasmon resonance in yttrium nanoparticles in a way comparable to silver or gold nanoparticle aggregates. Comparison is made with the first experimental results on yttriumnanoparticles, showing that aggregation is the dominant effect for the broad resonance in the measured extinction spectra. Received: 2 July 2001 / Revised version: 10 September 2001 / Published online: 15 October 2001