Laser pyrolysis synthesis and characterization of luminescent silicon nanocrystals

Quantum dots of silicon are very attractive materials due to their photoluminescence (PL) emission that can be very strong at room temperature in the visible range under UV illumination. Weighable batches are demanded for several applications in opto-electronic, photovoltaic, medicine, and so on. Laser pyrolysis of silane in a flow reactor is an efficient method to synthesize silicon nanocrystals, but up to now the production rate for the smallest particles was very low. We present here results of a work aimed to overcome this limitation. Optimization of the laser pyrolysis process has been performed through an elaborate study of the synthesis parameters. Weighable batches of very small silicon particles were obtained in a controlled and reproducible way, with production rate in the 0.1–1 g/h. High-resolution electron microscopy and specific surface measurements show that the particles were true silicon nanocrystals in the 4–9 nm range. We have then studied their PL properties. For this purpose, we have paid a particular attention to the surface passivation, an essential step to obtain efficient PL. Various ways were explored: natural oxidation under air and dispersion in liquids. We show that after natural oxidation, the PL properties are, as expected, in agreement with the quantum confinement model. Strong PL is also obtained by dispersion in solvents, but the interpretation is less straightforward in this case, and as discussed in the paper, needs further investigation.     

Investigations of solvents and various sulfur sources influence on the shape-controlled synthesis of CuInS2 nanocrystals

CuInS₂ (CIS) nanocrystals were successfully synthesized through a hot-injection technique employing a reaction of copper (I) acetate and indium (III) acetate with tert-dodecanethiol as a source of sulfur, and trioctylphosphine oxide and 1-dodecanethiol were used as ligands. The reaction medium was a mixture of two solvents: oleylamine and 1-octadecene. Varying the ratio between both solvents leads to the formation of wurtzite CuInS₂ particles with shapes ranging from triangular to rod-shaped with length up to 50 nm. Oleylamine turned out to influence the reaction condition in two opposite ways: by leading to monomer depletion before the injection of the sulfur precursor, and at the same time increasing the activity of the monomers remaining in solution. By changing the sulfur source from tert-dodecanethiol to sulfur dissolved in oleylamine, triangular particles with zinc blend structure and a smaller size (~5 nm) were synthesized. The final materials were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX), and absorption spectroscopy (UV?CVis).     

Diamond cubic Sn-rich nanocrystals: synthesis, microstructure and optical properties

Diamond cubic Sn-rich nanocrystals were fabricated with radii less than 20 nm by post-growth annealing at T=750 °C of Sn_xGe_1-x alloys grown on Ge(001) by molecular beam epitaxy. The crystal phase of the Sn-rich nanocrystals was determined to be diamond cubic from Fourier transform analysis of high-resolution transmission electron microscopy images. Optical transmittance of these Sn_xGe_1-x/Ge (001) films demonstrated changes in optical absorption that can be attributed to absorption from the nanocrystals. The energy bandgap was measured to be 0.45 eV for nanocrystals arrays in Ge with a mean diameter of 32 nm. PACS 68.37.Lp; 78.67.Hc; 81.07.Ta; 81.16.Dn; 68.65.Hb     

Synthesis of cobalt-doped cadmium sulphide nanocrystals and their optical and magnetic properties

Cobalt-doped cadmium sulphide (CdS) nanocrystals (NCs) were synthesized with three different cobalt concentrations by aqueous chemical coprecipitation method. Dopant incorporation was recognised using X-ray diffraction (XRD) analysis with a shift in the diffraction peaks and compression in the lattice. The size and crystallinity of the cobalt-doped CdS NCs were studied by high resolution transmission electron microscopy (HRTEM). The blue shift in the spectra and the band gap value of Co-doped CdS NCs was estimated using reflectance UV spectrophotometer. Variation in the luminescence properties was studied by fluorescence spectroscopy. The change in the optical properties supports the Co incorporation in the CdS NCs. The BET measurement revealed that the powders had a relatively high specific surface area of 131.30, 106.93 and 102.04 m²/g for 2, 4 and 6% Co:CdS, respectively. Room temperature magnetisation was studied using vibrating sample magnetometer for both 4 and 6% cobalt-doped CdS NCs, which revealed a weak ferromagnetic signal and strong ferromagnetic hysteresis respectively.     

Microemulsion-mediated synthesis of cadmium zinc sulfide nanocrystals with composition-modulated optical properties

Cadmium zinc sulfide nanocrystals were synthesized by a microemulsion-mediated process, which involving two steps: the preparation of CdS (or ZnS) seeds and the succedent hydrothermal growth of ZnS (or CdS) component. The XRD results show that the cadmium zinc sulfide nanocrystals with CdS seeds present a hexagonally homogeneous alloyed structure, while the ones with ZnS seeds mainly take on the characteristic of hexagonal CdS nanocrystals. The intrinsic factors influencing the crystal structures were discussed. The UV-vis and photoluminescence (PL) spectra indicate that the optical properties of the obtained nanocrystals with CdS seeds can be continuously modulated by tuning their compositions, although their sizes and size distributions are not under a strict control. The composition-modulated strategy, along with the hydrothermal microemulsion process, will be an effective route to achieve semiconductor nanocrystals with tunable optical properties under more manageable conditions.     

Electronic structure and optical properties of silicon nanocrystals along their aggregation stages

The structural control of silicon nanocrystals is an important technological problem. Typically, a distribution of nanocrystal sizes and shapes emerges under the uncontrolled aggregation of smaller clusters. The aim of this computational study is to investigate the evolution of the nanocrystal electronic states and their optical properties throughout their aggregation stages. To realistically tackle such systems, an atomistic electronic structure tool is required that can accommodate about tens of thousand nanocrystal and embedding lattice atoms with very irregular shapes. For this purpose, a computationally efficient pseudopotential-based electronic structure tool is developed that can handle realistic nanostructures based on the expansion of the wavefunction of the aggregate in terms of bulk Bloch bands of the constituent semiconductors. With this tool, the evolution of the electronic states as well as the polarization-dependent absorption spectra correlated with the oscillator strengths over their aggregation stages is traced. The low-lying aggregate nanocrystal states develop binding and anti-binding counterparts of the isolated states. Such information may become instrumental with the maturity of the controlled aggregation of these nanocrystals.     

Controlled growth of Cu2S hexagonal microdisks and their optical properties

Chalcocite Cu₂S particles have been prepared hydro- and solvo-thermally from a copper plate in pure water, mixed solvents of water and ethylenediamine (en), and pure en, respectively. Their structural and optical properties have been characterized by a combination of powder X-ray diffraction, scanning and transmission electron microscopy (SEM and TEM), and VIS-NIR diffuse reflectance spectroscopy. Their growth and optical properties were found to be highly dependent on synthesis conditions and in particular the en/water volume ratio. For the first time, Cu₂S particles wish the shape of hexagonal microdisks were synthesized in a mild hydrothermal condition and these crystalline particles were found to exhibit unique optical properties.     

Monodisperse Co,Zn-Ferrite nanocrystals: Controlled synthesis,characterization and magnetic properties

Co_xZn_yFe_3−x−yO₄ ferrite (x=1 to 0; y=0 to1) nanocrystals have been synthesized by reverse microemulsion method. The nanocrystals are then comprehensively characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Field emission transmission electron microscopy (FETEM), and magnetic properties were measured by using Vibrating sample magnetometer. X-ray analysis showed that all the crystals were cubic spinel. The lattice constant increased with the increase in Zn substitution. FETEM reveals that particle size varies in the range from 3 to 6 nm. As the concentration of Zn increases the magnetic behavior varies from ferromagnetic at y=0 and 0.2 to superparamagnetic to paramagnetic at y=1. The Curie temperature decreases with increasing concentration of Zn.     

Optical transient bleaching/absorption of surface-oxidized CuInS2 nanocrystals

2 nanocrystals in a polymer film have been studied with the picosecond pump-probe technique. The oxidized CuInS₂ nanocrystals have an additional absorption band with a peak at 1.03 eV, which is bleached under picosecond excitation. Rapid (∼50 ps) trapping into midgap surface states results in long-lived (≫300 ps) bleaching and induced absorption features. A schematical energy-level diagram for oxidized CuInS₂ nanocrystals is given based on the experimental results. Received: 7 January 1997/Revised version: 16 April 1997     

Hydrothermal synthesis and optical properties of full-color-emission ZnS:Cu, Al nanocrystals

ZnS:Cu, Al nanocrystals were synthesized by a hydrothermal method at 200 degrees C and their optical properties were studied. The analysis of XRD and TEM show that the spherical-like nanocrystals had a grain size of approximately 15 nm and were well dispersed, with a zinc blende structure. The energy dispersive X-ray spectroscopy (EDX) and atomic absorption spectrometry were applied to the analysis of S, Zn and Cu content in the sample. The results proved that a large number of zinc vacancies exist and Cu is incorporated into the sample lattice. The photoluminescence (PL) spectra were investigated. The PL mechanism is discussed. The excitation spectrum is broad. Under 337 nm excitation the sample emits bright green light. Under 370-410 nm excitation the sample emits white light. The broad emission spectra are almost coincident with any excitation wavelength of between 370 and 410 nm making them attractive as conversion phosphors for LED applications and full-color fluorescence display devices. The emitted white light under 375 nm excitation was found to be the result of blue, green, and orange emission bands. For Cu/Zn, Cu/Al and S/Zn molar ratios of 3 x 10(-4), 2 and 3, respectively, the near blue white light can be observed with the naked eye in daylight.     

Plasma synthesis and liquid-phase surface passivation of brightly luminescent Si nanocrystals

While silicon's optical properties are improved at the nanoscale, they also become highly sensitive to the properties of the surfaces and interfaces of silicon nanostructures. For instance, while reported quantum yields for photoluminescence of silicon quantum dots covered by a native oxide are often in the few percent range, quantum yields as high as 30% have been found in quantum dots whose surfaces were passivated by covalently bonded organic molecules. In this paper, we describe an approach that is based on the gas phase synthesis of silicon quantum dots in a nonthermal plasma, and the subsequent organic surface passivation in the liquid phase. Nanocrystals are formed within a few milliseconds with a high mass yield in a nonthermal plasma. Various organic ligands such as octadecene, dodecence, and styrene are grafted onto the nanocrystal surfaces in a reaction known as hydrosilylation. Materials are characterized through transmission electron microscopy, atomic force microscopy, and fluorescence measurements. The particle size distributions are found to be relatively monodisperse and are well controllable through the plasma process parameters. Photoluminescence quantum yields as high as 60-70% have been achieved for particles luminescing in the red range of the visible spectrum.     

Large-scale synthesis of ZnO microhollowspheres and their optical properties

ZnO microhollowspheres (MHs) were synthesized by evaporation of a mixture of zinc, graphite, and zinc oxide powders. The microstructures of the resultant MHs have been characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), selected-area electron diffraction (SAED), X-ray diffraction, and photoluminescence (PL). The PL results indicated that the green emission peak at 510 nm of the MHs was higher and broader than that of the nanocombs, which was due to oxygen vacancies formed in the MHs. In addition, the mechanism of ZnO MHs was discussed in detail.     

Nonlinear optical properties of Cu x S and CuInS2 semiconductor nanoparticles in sol-gel glass

Quartz glasses containing ultradisperse particles (with a mean radius of 5 ± 3 nm) of semiconductor compounds Cu_xS and CuInS₂ were synthesized using the sol-gel technology. The line and differential absorption spectra of such glasses were investigated. In the range 600–700 nm, the samples demonstrate absorption bands that are assigned to the lowest-lying energy transition in quantum-size particles. Excitation by laser pulses with a wavelength of 540 nm causes the effect of induced absorption in the range of 500–950 nm. The induced absorption in the samples containing Cu_xS nanoparticles undergoes relaxation which has a characteristic time of ∼500 psec, and in the samples with CuInS₂ nanoparticles it has a two-exponential form with τ₁ ≈ 30 psec and τ₂>1 nsec. Translated from Zhurnal Prikladnoi Spektroskopii, vol. 67, No. 4, pp. 507–511, July–August, 2000.     

Morphology and optical properties of Mg and Sr doped CaF2 nanocrystals

Magnesium (Mg) and Strontium (Sr) doped Calcium fluoride nanocrystals were synthesized by co-precipitation method. The cubic structure of the samples was confirmed by Powder X-ray diffraction. The average crystallite size of Mg doped samples was found to be ~ 25 nm whereas in Sr doped one it was ~ 35 nm. The morphological features revealed that the nanocrystals were agglomerated, crispy and porous. The as-prepared samples showed the presence of hydroxyl groups. The optical absorption spectrum of as-prepared Mg doped samples showed a strong absorption band peaked at ~ 233 nm whereas the Sr doped one showed a prominent absorption peak at 248 nm. A strong PL emission was observed at ~ 300 nm in Mg doped samples. However, the Sr doped samples showed two prominent emissions at ~ 345 and 615 nm.     

Structural and galvanomagnetic properties of CuInS2 films

Thin copper-indium-disulphide films were prepared by thermal evaporation technique. X-ray diffraction analysis of the compound used for evaporation showed a tetragonal polycrystalline structure. Differential Thermal Analysis (DTA) of this compound showed two exothermic peaks at 585 and 632 °C. Thin films with thicknesses of 0.14 and 0.27 nm have a deposition rate 10 nm/min, while those with thicknesses of 0.54 and 0.56 nm have a deposition rate 48 nm/min. The obtained films have polycrystalline structure as shown from the electron diffraction study. A growth process was detected in the films by transmission electron microscopy as the film thickness increases. The surface topography was revealed by scanning electron microscopy. The variations of Hall mobility and carrier concentration with magnetic induction were studied. The resistivity-temperature relationship was investigated, from which the activation energies before and after annealing were found to be 0.2, 0.3 and 0.055 eV, respectively.     

Synthesis and optical properties of In-doped GaN nanocrystals

Indium-doped GaN nanocrystals with 5% and 10% In have been prepared by a low temperature solvothermal method using hexamethyldisilazane as the nitriding reagent. The nanocrystals show Raman bands at lower frequencies compared to GaN. Photoluminescence spectra of the In-doped GaN nanocrystals exhibit an increase in the FWHM with the decrease in the PL band energy, the band energy itself decreasing with increase in the In content.     

Structural stabilities and optical properties of SixGeyHz nanocrystals

Based on the high-throughput first-principles calculations with structural recognition, we have ystematically investigated the structural stabilities and optical properties of Si_xGe_yH_z nanocrystals(H-SiGeNCs), including various sizes, shapes and compositions. The total energies of H-SiGeNCs can be simply estimated by the bond energy model in high accuracy, where the error of test set is less than 0.5 meV per atom. According to the energy difference of Si/Ge in various bonding environments, we have determined the ground state structures by the geometry analysis, as is confirmed the convex hulls of formation enthalpy from the first-principles calculations. In addition, the energy gaps of H-SiGeNCs are modulated by the atomic distributions, as well as the vibrations of Si-H and Ge-H bonds at room temperature which is revealed by ab initio molecular dynamics simulations.     

太阳能材料CuInS2的晶体结构、电子和光学特性

用全电势线性缀加平面波法加局域轨道方法调查了黄铜矿半导体CuInS2的结构、电子和光学特性。我们计算的带隙0.17 eV是直接的,其它实验和理论也表明这种材料有一个直接带隙。在 In 4d和S 3p轨道之间有相当强的杂化,构成了(InS2)4-阴离子。我们计算的反射率光谱,介电函数的实部和虚部,消光系数和折射率和实验结果取得了很好的一致。     

Electrical properties of cadmium and zinc doped CuInS2

The electrical resistivity and mobility of Cd and Zn doped CuInS₂ single crystals grown by a Bridgman technique have been investigated. Crystals annealed in Cd or Zn vapor at high temperatures (～ 800°C) exhibit degenerate behaviour while those crystals annealed at more moderate temperatures (～650°C) show ionized impurity conduction with a shallow activation energy on the order of 0.004 eV. Resistivities as low as 0.15 Ω-cm and mobilities as high as 90 cm²/v-sec have been observed.