From amorphous to crystalline silicon nanoclusters: structural effects on exciton properties

Synchrotron x-ray absorption spectroscopy (XAS) and electron spin resonance (ESR) experiments were performed to determine, in combination with Raman spectroscopy and x-ray diffraction (XRD) data from previous reports, the structure and paramagnetic defect status of Si-nanoclusters (ncls) at various intermediate formation stages in Si-rich Si oxide films having different Si concentrations (y = 0.36-0.42 in Si(y)O(1-y)), fabricated by electron cyclotron resonance plasma-enhanced chemical vapor deposition and isochronally (2 h) annealed at various temperatures (T(a) = 900-1100 °C) under either Ar or (Ar + 5%H(2)) atmospheres. The corresponding emission properties were studied by stationary and time dependent photoluminescence (PL) spectroscopy in correlation with the structural and defect properties. To explain the experimental data, we propose crystallization by nucleation within already existing amorphous Si-ncls as the mechanism for the formation of the Si nanocrystals in the oxide matrix. The cluster-size dependent partial crystallization of Si-ncls at intermediate T(a) can be qualitatively understood in terms of a 'crystalline core-amorphous shell' Si-ncl model. The amorphous shell, which is invisible in most diffraction and electron microscopy experiments, is found to have an important impact on light emission. As the crystalline core grows at the expense of a thinning amorphous shell with increasing T(a), the PL undergoes a transition from a regime dominated by disorder-induced effects to a situation where quantum confinement of excitons prevails.     

Synthesis and optical properties of flower-like ZnO nanorods by thermal evaporation method

Flower-like ZnO nanorods have been synthesized by heating a mixture of ZnO/graphite powders using the thermal evaporation and vapor transport on Si (1 0 0) substrates without any catalyst. The structures, morphologies and optical properties of the products were characterized in detail by using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) and Raman spectroscopy. The synthesized products consisted of large quantities of flower-like ZnO nanostructures in the form of uniform nanorods. The flower-like ZnO nanorods had high purity and well crystallized wurtzite structure, whose high crystalline quality was proved by Raman spectroscopy. The as-synthesized flower-like ZnO nanorods showed a strong ultraviolet emission at 386 nm and a weak and broad yellow-green emission in visible spectrum in its room temperature photoluminescence (PL) spectrum. In addition, the growth mechanism of the flower-like ZnO nanorods was discussed based on the reaction conditions.     

Effect of precursor concentration on the growth of zinc oxide nanorod arrays on pre-treated substrates

Well aligned zinc oxide nanorod arrays (ZNAs) synthesized by a simple chemical bath deposition method were fabricated on pre-treated Si substrates. By keeping the molar VI/II ratio constant, the effect of precursor concentration on the growth and optical quality of the ZNAs was investigated. The as-synthesized ZNAs were characterized by field emission scanning electron microscopy (FESEM), x-ray diffraction (XRD) and photoluminescence spectroscopy (PL). FESEM images show that both the diameter and aspect ratio of the ZNAs increase dramatically as the precursor concentration increases. The XRD analysis indicates that all the as-grown ZNAs are crystalline and are preferentially oriented along the c-axis. The high intensity ratio of the UV emission to visible emission in the room temperature PL spectra illustrate that high optical quality ZNAs were produced.     

Field emission properties of electrophoretic deposition carbon nanotubes film

The field emission properties of electrophoretic deposition(EPD) carbon nanotubes (CNTs) film have been improved by depositing CNTs onto the titanium (Ti)-coated Si substrate, followed by vacuum annealing at 900 °C for 2 h, and the enhanced emission mechanism has been studied using X-ray diffraction (XRD), scanning electron microscope (SEM) and Raman spectroscopy. Field emission measurements showed that the threshold electric field was decreased and the emission current stability was improved compared to that of EPD CNTs film on bare Si substrate. XRD and Raman spectroscopy investigations revealed that vacuum annealing treatment not only decreased the structural defects of CNTs but made a titanium carbide interfacial layer formed between CNTs and substrate. The field emission enhancement could be attributed to the improved graphitization of CNTs and the improved contact properties between CNTs and substrate including electrical conductivity and adhesive strength due to the formed conductive titanium carbide.     

The structure and photoluminescence properties of Cr-doped SiC films

Cr-doped SiC films are prepared by the RF-magnetron sputtering technique on Si substrates with a composite target of a single-crystalline SiC containing several Cr pieces on the surface. The as-deposited films are annealed in the temperature of 1000 °C under nitrogen ambient. The structure of the samples has been characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), and Raman scattering measurement. The results show that the SiC crystal is formed and that majority of Cr doped in the SiC resulted in the formation of the C clusters. Then the photoluminescence (PL) spectra of the samples are observed in the visible range at room temperature. The optical properties of the samples have also been discussed briefly. We attribute the origin of the 412-nm PL band to a kind of C cluster center.     

Quantitative analysis of the phonon confinement effect in arbitrarily shaped Si nanocrystals decorated on Si nanowires and its correlation with the photoluminescence spectrum

Arrays of single‐crystalline Si nanowires (NWs) decorated with arbitrarily shaped Si nanocrystals (NCs) are grown by a metal‐assisted chemical etching process using silver (Ag) as the noble metal catalyst. The metal‐assisted chemical etching‐grown Si NWs exhibit strong photoluminescence (PL) emission in the visible and near infrared region at room temperature. Quantum confinement of carriers in the Si NCs is believed to be primarily responsible for the observed PL emission. Raman spectra of the Si NCs decorated on Si NWs exhibit a red shift and an asymmetric broadening of first‐order Raman peak as well as the other multi‐phonon modes when compared with that of the bulk Si. Quantitative analysis of confinement of phonons in the Si NCs is shown to account for the measured Raman peak shift and asymmetric broadening. To eliminate the laser heating effect on the phonon modes of the Si NWs/NCs, the Raman measurement was performed at extremely low laser power. Both the PL and Raman spectral analysis show a log‐normal distribution for the Si NCs, and our transmission electron microscopy results are fully consistent with the results of PL and Raman analyses. We calculate the size distribution of these Si NCs in terms of mean diameter (D₀) and skewness (σ) by correlating the PL spectra and Raman spectra of the as‐grown Si NCs decorated on Si NWs. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and characterization of GaN nanowires by a catalyst assisted chemical vapor deposition

GaN nanowires have been fabricated on Si(1 1 1) substrates by chemical vapor deposition (CVD) method with NiCl₂ as catalyst and their compositions, microstructures, morphologies and light emitting properties were characterized by X-ray diffraction (XRD), FT-IR spectrophotometer (FTIR), scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM), Raman spectroscopy and photoluminescence (PL). The results demonstrate that the nanowires are single-crystal GaN with hexagonal wurtzite structure and high crystalline quality, having the size of 20-50 nm in diameter and several tens of microns in length with some nano-droplets on their tips, which reveals that the growth mechanism of GaN nanowires agrees with vapor-liquid-solid (VLS) process. Five first-order Raman active phonon bands move to low shift and A₁(TO), E₁(TO), and E₂ (high) bands are overlapped and broaden, which is caused by uncertainty in the phonon wave vector. Five non-first-order active Raman phonons also appear, which is caused by the small dimension and high surface disorder degree. A blue-shift of the band-gap emission occurs due to quantum confinement effect.     

Effect of the Order and Disorder of BaMoO4 Powders in Photoluminescent Properties

The study of the photoluminescent properties affected by order and disorder of the BaMoO₄ powders is the principal objective in this work. BaMoO₄ compounds were prepared using soft chemical process called Complex Polymerization Method. In this work, different deagglomeration types and different heating rates were used to promote different disorder degrees. Scheelite type phase (BaMoO₄) was determined by X-ray Diffraction (XRD), Fourier Transformed Infra-Red (FTIR) and Raman spectroscopy after heat treating the sample at 400°C. The room temperature luminescence spectra revealed an intense single-emission band in the visible region. Based on XRD and Raman data it was observed that the transition between the completely disordered structure to completely ordered structure is a good condition for photoluminescence (PL) emission. The best PL emission is obtained when the material possesses short range disorder, i.e., is periodically ordered (XRD), but some disorder as measured by Raman spectroscopy. The excellent optical properties observed for disordered BaMoO₄ suggested that this material is a highly promising candidate for optical applications.     

CaAl_2Si_2O_8∶Eu,Ce,Tb单基三元掺杂荧光材料的制备及其光谱学特征研究

采用高温固相法制备了CaAl_2Si_2O_8∶Eu,Ce,Tb单基三元掺杂的荧光材料。使用X射线衍射仪(XRD)、拉曼光谱仪(Raman)和荧光分光光度计(PL)等测试手段对该荧光材料进行表征。采用XRD表征了样品的物相组成,测试结果表明稀土离子Eu~(2+)置换Ca~(2+)并没有引起CaAl_2Si_2O_8基质晶格结构的变化。拉曼光谱分析证实了样品中硅氧四面体和铝氧四面体的存在,表明了Eu~(2+)替代Ca~(2+)的数量与晶体形态畸变程度有关,Eu~(2+)进入基质晶格的数量影响着硅(铝)氧四面体的数量。PL测试结果表明样品在325nm光激发下,其发射峰主要表现为426nm(蓝光区)的强宽带发射峰和541nm(绿光区)的弱发射峰,其中426nm处的宽带发射峰可通过高斯拟合成三个位于393,419和474nm的拟合峰;对比分析荧光性能以及同等合成条件下样品荧光强度的不同,确定了该荧光材料在三掺Eu∶Ce∶Tb的摩尔比为1∶1∶1.5时所发射荧光最强。CIE色度图坐标显示三种掺杂比例下制备的荧光材料均发射蓝色荧光,光显色性好,色温低,是一种适合作为紫外-近紫外激发的LED用蓝色荧光材料。     

Pseudo nanocrystal silicon induced .luminescence enhancement in a-Si/SiO2 multilayers

Enhanced photoluminescence （PL） at room temperature from thermally annealed a-Si：H/SiO2 multilayers is observed through the step-by-step thermal post-treatment. The correlation between the PL and the crystallization process is studied using temperature-dependent PL, Raman, cross section high-resolution transmission electron microscopy （XHRTEM） and x-ray diffraction （XRD） techniques. An intensified PL band around 820 nm is discovered from the sample annealed near the crystallization onset temperature, which is composed of two peaks centred at 773 nm and 863 nm, respectively. It is found that the PL band centred at 863 nm is related to the pseudo nanocrystal （p-nc-Si） silicon, and the PL band centred at 773 nm is attributed to Si = O bonds stabilized in the p-nc-Si surface.     

The comparison between CdS thin films grown on Si(111) substrate and quartz substrate by femtosecond pulsed laser deposition

Two kinds of cadmium sulfate (CdS) thin films have been grown at 600 °C onto Si(111) and quartz substrates using femtosecond pulsed laser deposition (PLD). The influence of substrates on the structural and optical properties of the CdS thin films grown by femtosecond pulsed laser deposition have been studied. The CdS thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), photoluminescence (PL) and Raman spectroscopy. Although CdS thin films deposited both on Si(111) and quartz substrates were polycrystalline and hexagonal as shown by the XRD , SEM and AFM results, the crystalline quality and optical properties were found to be different. The size of the grains for the CdS thin film grown on Si(111) substrate were observed to be larger than that of the CdS thin film grown on quartz substrate, and there is more microcrystalline perpendicularity of c-axis for the film deposited on the quartz substrate than that for the films deposited on the Si substrate. In addition, in the PL spectra, the excitonic peak is more intense and resolved for CdS film deposited on quartz than that for the CdS film deposited on Si(111) substrate. The LO and TO Raman peaks in the CdS films grown on Si(111) substrate and quartz substrate are different, which is due to higher stress and bigger grain size in the CdS film grown on Si(111) substrate, than that of the CdS film grown on the amorphous quartz substrate. All this suggests that the substrates have a significant effect on the structural and optical properties of thin CdS films. PACS 81.15.Fg; 81.05.Ea; 78.20.-e; 78.67.-n; 42.62.-b     

Synthesis of Na-doped ZnO nanowires and their photocatalytic properties

Na-doped ZnO nanowires with an average diameter of ∼40 nm have been fabricated by a thermal decomposition route at temperature around 400 °C. Their properties have been investigated using X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), UV-visible spectroscopy, Raman spectra, and photoluminescence (PL) spectroscopy. Room temperature photoluminescence (RT-PL) showed that the as-synthesized ZnO samples exhibited strong visible emission with a major peak at 420 nm. Furthermore, intensity of the visible emission increased and then decreased with increase in Na concentration. The improvement of visible emission at 420 nm in the Na-doped ZnO samples should be a result of the surface defects increased by doping of Na in zinc oxide. In addition, photocatalytic studies indicated that these nanomaterials showed good photocatalytic performance for organic pollutants in water.     

Evolutions of defects and blue–green emissions in ZnO microwhiskers fabricated by vapor-phase transport

The corresponding evolutions of morphologies, defect-states and the PL properties have been employed to explore the defect-origins of visible emissions and growth mechanisms of microstructured ZnO. ZnO microtube and microrod whiskers were fabricated by non-catalytic vapor-phase transport using ZnO and graphite powders in air. The microstructures of the samples were studied in detail based on scanning electron microscopy (SEM), x-ray diffraction (XRD), energy-dispersive x-ray spectroscopy (EDX), and electron paramagnetic resonance (EPR). The main PL emission bands evolve from blue to green, which corresponds to that the main defect-states change from Zn interstitials (Zn_i) to O vacancies (V_O). The formation of Zn_i under the high temperature zinc-rich vapor environment is crucial both for the blue emission and for the formation of the microtubes.     

Synthesis of flower-shape clustering GaN nanorods by ammoniating Ga2O3 films

Flower-shape clustering GaN nanorods are successfully synthesized on Si（111） substrates through ammoniating Ga2O3/ZnO films at 950℃. The as-grown products are characterized by x-ray diffraction （XRD）, scanning electron microscope （SEM）, field-emission transmission electron microscope （FETEM）, Fourier transform infrared spectrum （FTIR） and fluorescence spectrophotometer. The SEM images demonstrate that the products consist of flower-shape clustering GaN nanorods. The XRD indicates that the reflections of the samples can be indexed to the hexagonal GaN phase and HRTEM shows that the nanorods are of pure hexagonal GaN single crystal. The photoluminescence （PL） spectrum indicates that the GaN nanorods have a good emission property. The growth mechanism is also briefly discussed.     

退火及溅射气氛对氮化硅薄膜光致发光的影响

利用射频磁控反应溅射方法制备富硅的氮化硅薄膜。衬底材料为抛光的硅片,靶材为硅靶,在Ar-N₂气环境下,通过改变两种气体的组分比来改变样品成分,并在高纯N₂气氛下对其进行高温退火处理。用X射线光电子能谱(XPS)和X射线衍射(XRD)对样品进行了表征,并测试了样品的光致发光谱 (PL)。实验结果表明：X射线光电子能谱中出现了Si—N键合结构,同时还有少量的Si—O键生成,通过计算得出Si/N比值约为1.51,制备出了富硅的氮化硅薄膜;薄膜未经退火前,在可见光区域没有观察到明显的光致发光峰,经过高温退火后,XRD中新出现的衍射峰证实了纳米硅团簇的生成,PL图谱中在可见光区域出现了光致发光峰的蓝移现象,结合XRD结果,用纳米晶的量子限域效应对上述现象进行了合理解释。     

The structure and optical properties of SiC film on Si (111) substrate with a ZnO buffer layer by RF-magnetron sputtering technique

We have fabricated a multiply layer SiC/ZnO on Si substrates using the RF-magnetron sputtering technique with the targets of a single crystalline SiC and a polycrystalline ZnO. The as-deposited films were annealed in the temperature range of 600–1000 °C under nitrogen ambient. We have observed a strong ultraviolet (UV) emission (370 nm) from the as-deposited SiC/ZnO film and an intense violet emission (412 nm) from the film annealed at high temperature (1000 °C) under nitrogen ambient. The SiC film quality and the PL intensities are considered to be strongly dependent on the crystalline quality of the ZnO buffer layer. With the increase of the annealing temperature, the crystalline quality of the ZnO buffer layer is improved, resulting in the improvement of the SiC film quality and the increase of the PL intensities. The thin films have been characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) to provide the evidences of photoluminescence (PL). We suggest that the UV emission could be attributed to the nanocrystal silicon particles, that the 395 nm band is related to ZnO buffer layer and has a great relation to the crystalline quality of the ZnO film, and that the violet emission is associated with the emission luminescence from 6H-SiC, which bears on the SiC film quality. The obtained results are expected to have important applications in modern optoelectronic devices.     

Structural, optical and Raman studies of template-free solvothermally synthesized ZnSe/ZnSe:Ce nanoparticles

The present work reports a general, single step and easy solvothermal method to synthesize well crystallized and pure phase Ce³⁺ doped ZnSe nanocrystals for the first time in a unified system. The products were well characterized by powder X-ray diffraction (XRD), UV-vis spectroscopy (UV-vis), photoluminescence spectroscopy (PL), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), energy dispersive X-ray diffraction (EDAX) and Raman spectroscopy. The products were found to show significant finite size effect as characterized by broadened XRD peaks, blue-shifts of the interband optical absorption edge and the asymmetric broadening of Raman spectra. The emission intensity of Ce³⁺ ion doped ZnSe was found to be considerably increased with respect to the pure one. The observed lineshape of LO modes indicates broadening that is due to the nanosized effect. The structure and properties were correlated and detailed growth mechanism is also discussed.     

Structure and photoluminescence properties of Er3+-doped TiO2-SiO2 powders prepared by sol-gel method

Er 3+-doped TiO 2-SiO 2 powders are prepared by the sol-gel method,and they are characterized by high resolution transmission electron microscopy (HR-TEM),X-ray diffraction (XRD) spectra,and Raman spectra of the samples.It is shown that the TiO 2 nanocrystals are surrounded by an SiO 2 glass matrix.The photoluminescence (PL) spectra are recorded at room temperature.A strong green luminescence and less intense red emission are observed in the samples when they are excited at 325 nm.The intensity of the emission,which is related to the defect states,is strongest at the annealing temperature of 800 C.The PL intensity of Er 3+ ions increases with increasing Ti/Si ratio due to energy transfer between nano-TiO 2 particles and Er 3+ ions.     

A study on morphology control and optical properties of ZnO nanorods synthesized by microwave heating

In this study, we present morphology control investigations on zinc oxide (ZnO) nanorods synthesized by microwave heating of a mixture of zinc nitrate hexahydrate and hexamethylenetetramine (HMTA) precursors in deionized water (DI water). To study the morphology and structural variations of the obtained ZnO nanorods in different molar ratio of zinc nitrate hexahydrate to HMTA, X-ray diffraction (XRD), scanning electron microscopy (SEM) images, Raman scattering, and photoluminescence (PL) spectroscopy were measured. XRD and SEM images are utilized to examine the crystalline quality as well as the morphological properties of the ZnO nanorods. It is found that morphology control can be achieved by simply adjusting the reactant concentrations and the molar ratio of zinc nitrate hexahydrate to HMTA. Raman scattering and PL spectroscopy measurements were demonstrated to study the size- and shape-dependent optical response of the ZnO nanorods. The Raman scattering result shows that the intensity of LO mode at around 576 cm^?1 decreases with the increase in the molar ratio of zinc nitrate hexahydrate to HMTA, indicating the reduction of defect concentrations in the synthesized ZnO nanorods. Room temperature PL spectrum of the synthesized ZnO nanorods reveals an ultraviolet (UV) emission peak and a broad visible emission. An enhancement of UV emission appears in the PL spectra as the molar ratio of zinc nitrate hexahydrate to HMTA increases, indicating that the defect concentration of the synthesized ZnO nanorods can be reduced by increasing the molar ratio.     

Preparation and characterization of SiO2 nanowires using a SnO2 catalyst

SiO₂ nanowires have been successfully synthesized on the surface of the silicon substrate via a thermal evaporation method using SnO₂ powders as the catalysts. The final synthesized product was systematically studied by X-ray powder diffraction (XRD), Raman spectroscopy (RS), scanning electron microscopy (SEM), and electron energy dispersive X-ray (EDX), UV-Visible absorption and photoluminescence (PL) spectroscopy. The results reveal that in the reaction and growth process, the real catalytic effect is Sn and SnO_x, and the growth of SiO₂ nanowire is most likely controlled by VLS mechanism. The PL spectral results indicate the obtained products have a stable yellow-green emission range. The products have improved performance and can be used in optoelectronic semiconductor devices.