Quantum confined luminescence in Si/SiO2 superlattices

Amorphous Si/SiO₂ superlattices with periodicities between 2 and 5 nm have now been grown on (1 00) Si wafers by several different techniques: molecular beam epitaxy, magnetron sputtering, and plasma enhanced chemical vapor deposition (PECVD). With the first two methods little or no hydrogen is incorporated during growth and visible photo-luminescence (PL) is obtained at wavelengths from 520 to 800 nm. The shift in the PL peak position with Si layer thickness is consistent with quantum confined band-to-band recombination. Annealing the sputtered superlattices at temperatures up to 1100°C results in a very bright red PL that is similar in intensity to that observed in porous Si samples. For large numbers of periods (e.g., 425) the PL is strongly modulated in intensity owing to optical interference within the superlattice. Similar quantum confined, but defect induced, PL is also observed in the PECVD grown superlattices, where the amorphous Si layers are heavily hydrogenated.     

氧化硅稳定的氧化锡量子点薄膜的制备及其光学性能

 用溶胶-凝胶-水热过程制备了氧化硅稳定的氧化锡量子点,然后将其分散到氧化硅溶液中,用旋转涂膜的方法制备光学性能良好的氧化硅稳定的氧化锡量子点薄膜。X射线衍射和高分辨透射电镜表征显示氧化锡量子点具有良好的四方金红石晶型,平均粒径约4.0 nm。室温光致发光显示这种氧化硅稳定的氧化锡量子点薄膜在356 nm和388 nm处分别有很强的激子发光和缺陷态发光。根据透射谱拟合得到了氧化锡量子点薄膜的光学禁带宽度,其值约为3.96 eＶ。     

Investigation on preparation and physical properties of nanocrystalline Si/SiO2 superlattices for Si-based light-emitting devices

Structures containing silicon nanocrystals (nc-Si) are very promising for Si-based light-emitting devices. Using a technology compatible with that of silicon, a broader wavelength range of the emitted photoluminescence (PL) was obtained with nc-Si/SiO₂ multilayer structures. The main characteristic of these structures is that both layers are light emitters. In this study we report results on a series of nc-Si/SiO₂ multilayer periods deposited on 200 nm thermal oxide SiO₂/Si substrate. Each period contains around 10 nm silicon thin films obtained by low-pressure chemical vapour deposition at T=625°C and 100 nmSiO₂ obtained by atmospheric pressure chemical vapour deposition T=400°C. Optical and microstructural properties of the multilayer structures have been studied by spectroscopic ellipsometry (using the Bruggemann effective medium approximation model for multilayer and multicomponent films), FTIR and UV–visible reflectance spectroscopy. IR spectroscopy revealed the presence of SiO_x structural entities in each nc-Si/SiO₂ interface. Investigation of the PL spectra (using continuous wave-CW 325 nm and pulsed 266 nm laser excitation) has shown several peaks at 1.7, 2, 2.3, 2.7, 3.2 and 3.7 eV, associated with the PL centres in SiO₂, nc-Si and Si–SiO₂ interface. Their contribution to the PL spectra depends on the number of layers in the stack.     

Temperature behaviour of optical properties of Si+-implanted SiO2

Silicon nanocrystals were prepared by Si⁺-ion implantation and subsequent annealing of SiO₂ films thermally grown on a c-Si wafer. Different implantation energies (20-150 keV) and doses - cm ^-2 ) were used in order to achieve flat implantation profiles (through the thickness of about 100 nm) with a peak concentration of Si atoms of 5, 7, 10 and 15 atomic%. The presence of Si nanocrystals was verified by transmission electron microscopy. The samples exhibit strong visible/IR photoluminescence (PL) with decay time of the order of tens of μs at room temperature. The changes of PL in the range 70-300 K can be well explained by the exciton singlet-triplet splitting model. We show that all PL characteristics (efficiency, dynamics, temperature dependence, excitation spectra) of our Si⁺-implanted SiO₂ films bear close resemblance to those of a light-emitting porous Si and therefore we suppose similar PL origin in both materials. Received 1st September 1998 and Received in final form 7 September 1999     

Visible photoluminescence from Ge+-implanted SiO2 films thermally grown on crystalline Si

+ -implanted SiO₂ films is studied as a function of different fabricating conditions (implantation dose, annealing temperature and time). The SiO₂ films containing Ge nanocrystals exhibit two photoluminescence (PL) bands peaked at 600 nm and 780 nm. There are two excitation bands in the PL excitation (PLE) spectra. With variation in Ge nanocrystal size, the PL and PLE peak energies show no appreciable shift. The PL and PLE spectral analyses suggest that during the PL process, electron–hole pairs are generated by the E(l) and E(2) direct transitions inside Ge nanocrystals, which then radiatively recombine via luminescent centers in the matrix or at the interface between the nanocrystal/matrix. Received: 27 January 1998/Accepted: 18 March 1998     

Photoluminescence from Zinc Oxide Quantum Dots Embedded in Silicon Dioxide Matrices

ABSTRACT

ZnO quantum dots (QDs) embedded in SiO₂ matrix are fabricated by ion implantation and annealing treatment methods. When the Zn-doping dose is (2, 3, 5, and 7) × 10¹⁶ cm^?2, the size of quantum dots is in the range of ～4–10 nm in diameter according to the XRD and HR-TEM results. Ultraviolet and green light emissions from the specimen are obtained at room temperature. With the increase of the Zn-doping dose, the PL peak in the ultraviolet region red shifts from 3.32 to 3.10 eV. This PL peak is related to the size of ZnO QDs, which is ascribed to the free exciton recombination in QDs. The green light emissions centered at 2.43 and 2.25 eV are independent of the Zn-doping dose and annealing temperature, which are attributed to the deep-level defect and the small peroxy radical (SPR) defect, respectively.     

Luminescent silicon nanocrystal dots fabricated by SiCl4/H2 RF plasma-enhanced chemical vapor deposition

Luminescent nanocrystalline Si dots were fabricated directly on thermally grown SiO₂ at 120°C by conventional RF plasma-enhanced chemical vapor deposition using tetrachlorosilane, SiCl₄ and H₂. As-deposited Si dot exhibits photoluminescence (PL) in the visible region, consisting of two broad bands corresponding to photon energies of 1.38 and 1.48 eV. Storage in air enhances PL and shifts the PL peak energy to higher wavelengths for dots of diameter less than 10 nm. Fourier transform attenuated total reflection absorption spectroscopy (FTIR-ATR) study reveals that the spontaneous oxidation proceeds until saturation after 70 h at dot sizes of 3–5 nm. The relationship between PL intensity, blueshift of PL peak energy, and surface termination species during oxidation indicates that these changes are attributed to the increased density of radiative centers at the Si nanocrystal dot/SiO₂ interface and enhancement of the quantum confinement effect.     

Effects of natural oxidation on the photoluminescence properties of Si nanocrystals prepared by pulsed laser ablation

In this work, Si nanocrystals (Si-NCs) have been prepared by pulsed laser ablation technique in dichloromethane, and the microstructure and photoluminescence (PL) properties of the Si-NCs before and after natural oxidation were investigated. Transmission electron microscopy and Raman results show that the average diameter of the Si-NCs is 2.42 nm in the dichloromethane solution. Blue–violet PL with a lifetime of 4.6 ns is observed at room temperature, and the PL peak shifts toward longer wavelength with the red shift of excitation wavelength. The PL excitation spectrum indicates that the bandgap of the Si-NCs in solution is 2.64 eV, which confirms that the blue–violet PL originates from interband transition of Si-NCs caused by quantum confinement effect. The PL peak red shifts to 607 nm after natural oxidation, and the peak lifetime of which is slow down to 13.1 μs. The fixed PL peak excited by different wavelengths and the slow PL decay time indicate that interface defects become the main PL mechanism after natural oxidation. The results will add new information for understanding the PL mechanism of Si-NCs in different environments.     

Theoretical study of quantum-confined band-edge shifts and radiative lifetimes in oxidized Si(001) quantum films: comparison with experiment for Si/SiO2 quantum wells

The electronic structure and radiative lifetimes of Si(001) quantum films terminated by SiO₄ tetrahedra, which simulate Si/SiO₂ quantum wells (QWs), are calculated by the extended Hückel-type non-orthogonal tight-binding method. It is found that calculated band-gap widenings and radiative lifetimes account for band-edge shifts and photoluminescence (PL) peak shifts and lifetimes measured in amorphous-Si/SiO₂ QWs, suggesting that quantum confinement effects on the extended band-edge states in the amorphous-Si layer are responsible for the observed results. However, it is shown that band-edge shifts and PL energies and lifetimes observed in crystalline-Si/SiO₂ QWs cannot be reproduced properly by the interface model proposed in this study, implying that further studies are needed on the atomic structure of the crystalline-Si/SiO₂ interface.     

Au/SiO2纳米多层薄膜的制备及其性质表征

利用多靶磁控溅射技术制备了Au/SiO₂纳米颗粒分散氧化物多层复合薄膜.研究了在保持Au单层颗粒膜沉积时间一定时薄膜厚度一定、变化SiO₂的沉积时间及SiO₂的沉积时间一定而改变薄膜厚度时，多层薄膜在薄膜厚度方向的微观结构对吸收光谱的影响.研究结果表明：具有纳米层状结构的Au/SiO₂多层薄膜在560 nm波长附近有明显的表面等离子共振吸收峰，吸收峰的强度随Au颗粒的浓度增加而增强，在Au颗粒浓度相同的情况下，复合薄膜 关键词： 2纳米复合薄膜')" href="#">Au/SiO₂纳米复合薄膜 多靶磁控溅射 吸收光谱 有效介质理论     

Photoluminescence from ZnO-SiO2 opals with different sphere diameters and thicknesses

We systematically investigated the photoluminescence (PL) and transmittance characteristics of ZnO-SiO₂ opals with varied positions of the stop-band and film thicknesses. An improved ultraviolet (UV) luminescence was observed from ZnO-SiO₂ composites over pure ZnO nanocrystals under 325 nm He-Cd laser excitation at room temperature. The UV PL of ZnO nanocrystals in SiO₂ opals with stop-bands center of 410 nm is sensitive to the thickness of opal films, and the UV PL intensity increases with the film thickness increasing. The PL spectra of ZnO nanocrystals in SiO₂ opals with stop-bands center of 570 nm show a suppression of the weak visible band. The experimental results are discussed based on the scattering and/or absorbance in opal crystals.     

Poole-Frenkel conduction in Al/ZrO2 /SiO 2 /Si structures

Leakage currents through Al/ZrO₂/SiO₂/n-Si metal-insulator-semiconductor (MIS) capacitors were studied. Thin SiO₂ films were chemically grown on monocrystalline phosphorous doped silicon wafers. Zirconia films with thicknesses of 15 and 50 nm were deposited by radio frequency (rf) magnetron sputtering and, then, annealed in oxygen ambient at 850 ^○C, for 1 h. The dielectric constant of the sputtered and annealed ZrO₂ layer was of about 17.8. The equivalent oxide thickness (EOT) of the stack 15 nm and 50 nm-ZrO₂/SiO₂ structure was estimated to be 3.2 nm and 10.7 nm, respectively. The temperature dependence of the leakage currents was explained by Poole-Frenkel (PF) conduction mechanism. Shallow trap levels in the studied structure of about 0.2 eV and 0.46 eV were calculated. The existence of A and D-defects, due to the sputtering and high temperature annealing in oxygen, was suggested.     

多孔TiO2/Al/SiO2纳米复合结构的紫外光吸收特性研究

在SiO₂玻璃衬底上用脉冲激光沉积(PLD)技术，分别沉积Ti和Ti/Al膜，经电化学阳极氧化成功制备了多孔TiO₂/SiO₂和TiO₂/Al/SiO₂纳米复合结构. 其中TiO₂薄膜上的微孔阵列高度有序，分布均匀. 实验研究了Al过渡层对多孔TiO₂薄膜光吸收特性的影响. 结果表明：无Al过渡层的多孔TiO₂薄膜其紫外吸收峰在27     

多孔TiO2/Al/SiO2纳米复合结构的紫外光吸收特性研究

在SiO₂玻璃衬底上用脉冲激光沉积(PLD)技术,分别沉积Ti和Ti/Al膜,经电化学阳极氧化成功制备了多孔TiO₂/SiO₂和TiO₂/Al/SiO₂纳米复合结构. 其中TiO₂薄膜上的微孔阵列高度有序,分布均匀. 实验研究了Al过渡层对多孔TiO₂薄膜光吸收特性的影响. 结果表明：无Al过渡层的多孔TiO₂薄膜其紫外吸收峰在27 关键词： 2薄膜')" href="#">多孔TiO₂薄膜 阳极氧化 紫外光吸收     

Evidence for fast decay dynamics of the photoluminescence from Ge nanocrystals embedded in SiO2

We have investigated the origin of room temperature photoluminescence from ion-beam synthesized Ge nanocrystals (NCs) embedded in SiO₂ using steady state and time-resolved photoluminescence (PL) measurements. Ge NCs of diameter 4-13 nm were grown embedded in a thermally grown SiO₂ layer by Ge⁺ ion implantation and subsequent annealing. Steady state PL spectra show a peak at ∼2.1 eV originating from Ge NCs and another peak at ∼2.3 eV arising from ion-beam induced defects in the SiO₂ matrix. Time-resolved PL studies reveal double exponential decay dynamics on the nanoseconds time scale. The faster component of the decay with a time constant τ₁∼3.1 ns is attributed to the nonradiative lifetime, since the time constant reduces with increasing defect density. The slower component with time constant τ₂∼10 ns is attributed to radiative recombination at the Ge NCs. Our results are in close agreement with the theoretically predicted radiative lifetime for small Ge NCs.     

Effect of particle size on the photochromic response of PWA/SiO2 nanocomposite

A series of photochromic phosphotungstic acid (PWA)/SiO₂ composites were synthesized using the sol-gel method. Depending on the feeding schedule of PWA during synthesis, the size of the formed PWA/SiO₂ particles varied considerably from as small as 1.2 nm to ca. 10 nm. With decreasing silica particle size, the total contact area/interaction between SiO₂ and PWA increases, as revealed by FT-IR and solid-state ²⁹Si-NMR analyses. Particularly, when the size of PWA/SiO₂ is ~1 nm, crystallization of PWA is inhibited, and PWA presents as amorphous molecular entities distributing uniformly in the SiO₂ host, which is in evidence in the XRD spectroscopy and HR-TEM imaging. In contrast, substantial crystallization of PWA takes place when PWA/SiO₂ particles are as large as 10 nm, in which case less amount of surface free Si-OH is available for PWA to make bonds with. Photochromism occurs activated by ultraviolet light irradiation. The rate of coloration/bleaching is found to depend strongly on the particle size of PWA/SiO₂; specifically, the rate increases twice when the particle size is reduced from 10 nm to 1.2 nm.     

非晶Si/SiO2超晶格的制备及其光谱研究

用磁控溅射方法在玻璃基底上制备了非晶Si/SiO₂超晶格.利用透射电子显微镜 (TEM) 和X射线衍射技术对其结构进行了分析,结果表明,超晶格中Si层大部分区域为非晶相,局域微区呈现有序结构,其厚度由1.8—3.2nm变化,SiO₂层厚度为4.0nm.并采用多种光谱测量技术,如吸收光谱、光致发光光谱和Raman光谱技术,对该结构的光学性质进行了系统研究.结果表明,随纳米Si层厚度的减小,光学吸收边以及光致荧光峰发生明显蓝移,Raman峰发生展宽,即观测到明显的量 关键词：     

Coupling between Ge-nanocrystals and defects in SiO2

Room temperature photoluminescence (PL) at around 600 nm from magnetron-sputtered SiO₂ films co-doped with Ge is reported. The PL signal is observed in pure SiO₂, however, its intensity increases significantly in the presence of Ge-nanocrystals (Ge-nc). The PL intensity has been optimized by varying the temperature of heat treatment, type of gas during heat treatment, concentration of Ge in the SiO₂ films, and gas pressure during deposition. Maximum intensity occurs when Ge-nc of around 3.5 nm are present in large concentration in SiO₂ layers deposited at fairly high gas pressure. Based on time resolved PL, and PL measurements after α-particle irradiation or H passivation, we attribute the origin of the PL to a defect in SiO₂ (probably an O deficiency) that is excited through an energy transfer from Ge-nc. There is no direct PL from the Ge-nc; however, there is a strong coupling between excitons created in the Ge-nc and the SiO₂ defect.     

Fabrication and characterization of Au/SiO2 nanocomposite films

Au/SiO₂ nanocomposite films were prepared by radio frequency sputtering technique and annealing. The above nanocomposite films were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and atomic force microscopy (AFM). The surface of the nanocomposite films was uniform with the particle diameter of 100-300 nm. The size of Au crystallites increased on increasing annealing time. The luminescent behavior of the nanocomposite films was characterized by photoluminescence (PL) with different excitation wavelengths. Two emission peaks at around 525 nm and 560 nm were observed with the excitation wavelength at 325 nm. An intensive emission peak at around 325 nm was observed with the excitation wavelength at 250 nm, which is related to the defective structure of the amorphous SiO₂ layer because of oxygen deficiency, and could be applied to many fields, such as ultraviolet laser and ultraviolet detector.     

Effect of nano-sized SiO2 on the optical properties of YVO4:Eu3+ phosphors

In this paper, YVO₄: 1%Eu³⁺ phosphor was synthesized via solid state method at 1100 °C. Then TEOS was used as the source of silica, to coat the phosphors, using sol–gel approach. HRTEM analysis confirmed the formation of adhered and smooth coating layer with the thickness of 40–50 nm. From the experiments and characterizations, we found that although the amounts of added SiO₂ to the phosphors were not remarkable, but it resulted in enhancement of photoluminescence properties. Interestingly, under the excitation wavelength of 310 nm, the efficiency of the phosphors increased by about 20%. Also, a considerable effect of coating layer on decrease in surface oxygen vacancies was studied using ESR technique. Finally it was found that SiO₂ coating of YVO₄:Eu³⁺ phosphors, improves both chemical stability and thermal quenching, effectively.