Multipeak-structured photoluminescence mechanisms of as-prepared and oxidized Si nanoporous pillar arrays

Silicon dominates the electronic industry, but its poor optical properties mean that it is not preferred for photonic applications. Visible photoluminescence (PL) was observed from porous Si at room temperature in 1990, but the origin of these light emissions is still not fully understood. This paper reports that an Si nanocrystal, silicon nanoporous pillar array (Si-NPA) with strong visible PL has been prepared on a Si wafer substrate by the hydrothermal etching method. After annealing in O₂ atmosphere, the hydride coverage of the Si pillar internal surface is replaced by an oxide layer, which comprises of a great quantity of Si nanocrystal (nc-Si) particles and each of them are encapsulated by an Si oxide layer. Meanwhile a transition from efficient triple-peak PL bands from blue to red before annealing to strong double-peak blue PL bands after annealing is observed. Comparison of the structural, absorption and luminescence characteristics of the as-prepared and oxidized samples provides evidence for two competitive transition processes, the band-to-band recombination of the quantum confinement effect of nc-Si and the radiative recombination of excitons from the luminescent centres located at the surface of nc-Si units or in the Si oxide layers that cover the nc-Si units because of the different oxidation degrees. The sizes of nc-Si and the quality of the Si oxide surface are two major factors affecting two competitive processes. The smaller the size of nc-Si is and the stronger the oxidation degree of Si oxide layer is, the more beneficial for the luminescent centre recombination process to surpass the quantum confinement process is. The clarification on the origin of the photons may be important for the Si nanoporous pillar array to control both the PL band positions and the relative intensities according to future device requirements and further fabrication of optoelectronic nanodevices.     

Mechanism for the Correlated Swinging of Photoluminescence Intensity and Peak Energy Shift with Sizes of Nanoscale Si Particles

Based on the quantum confinement-luminescence center model, we focus on the relationship between the photoluminescence (PL) spectra and sizes of nanoscale silicon particles.We find that when there are two kinds of luminescence centers (LC) in the oxide layer surrounding the silicon particles, both the integrated PL intensity and the spectral peak position swing with reducing the sizes of silicon particles, which is different from the monotonous blueshift of peak position predicted by quantum confinement model. By changing the concentrations of LC we find the correlation between the spectral peak position and the integrated PL intensity when the size of silicon particles is reduced. The effects of other parameters such as the half width of size distribution and the position of photon emission levels of LC are also found to be important.     

氢化非晶硅薄膜退火形成的纳米硅及其光致发光

本文报道对氢化非晶硅(a-Si:H)薄膜在600～620℃温度下快速退火10s可以形成纳米晶硅(nc-Si),其Raman散射表明,在所形成的nc-Si在薄膜中的分布是随机的,直径在1.6～15nm范围内,并且在强激光辐照下观察了nc-Si在薄膜中的结晶和生长情况.经退火所形成的nc-Si可见光辐射较弱,不能检测到它们的光致发光(PL),但用氢氟酸腐蚀钝化后则可检测到较强的红PL,并且钝化后的nc-Si在空气中暴露一定的时间后,其辐射光波长产生了蓝移.文中就表面钝化和量子限制对可见光辐射的重要性作了讨论.     

硅衬底生长的InGaN/GaN多层量子阱中δ型硅掺杂n-GaN层对载流子复合过程的调节作用

为了解决在单晶硅衬底上生长的InGaN/GaN多层量子阱发光二极管器件发光效率显著降低的问题,使用周期性δ型Si掺杂的GaN取代Si均匀掺杂的GaN作为n型层释放多层界面间的张应力。采用稳态荧光谱及时间分辨荧光谱测量,提取并分析了使用该方案前后的多层量子阱中辐射/非辐射复合速率随温度（10~300 K）的变化规律。实验结果表明引入δ-Si掺杂的n-GaN层后,非辐射复合平均激活能由（18±3）meV升高到（38±10）meV,对应非辐射复合速率随温度升高而上升的趋势变缓,室温下非辐射复合速率下降,体系中与阱宽涨落有关的浅能级复合中心浓度减小,PL峰位由531 nm左右红移至579 nm左右,样品PL效率随温度的衰减受到抑制。使用周期性δ型Si掺杂的GaN取代Si均匀掺杂的GaN作为生长在Si衬底上的InGaN/GaN多层量子阱LED器件n型层,由于应力释放,降低了多层量子阱与n-GaN界面、InGaN/GaN界面的缺陷密度,使得器件性能得到了改善。     

Excitonic photoluminescence characteristics of amorphous silicon nanoparticles embedded in silicon nitride film

We have investigated the photoluminescence (PL) properties of amorphous silicon nanoparticles (a-Si NPs) embedded in silicon nitride film (Si-in-SiN_x) grown by helicon wave plasma-enhanced chemical vapor deposition (HWP-CVD) technique. The PL spectrum of the film exhibits a broad band constituted of two Gaussian components. From photoluminescence excitation (PLE) measurements, it is elucidated that the two PL bands are associated with the a-Si NPs and the silicon nitride matrix surrounding a-Si NPs, respectively. The existence of Stokes shift between PL and absorption edge indicates that radiative recombination of carriers occurs in the states at the surface of the Si NPs, whereas their generation takes place in the a-Si NPs cores and the silicon nitride matrix, respectively. The visible PL of the film originates from the radiative recombination of excitons trapped in the surface states. At decreasing excitation energy (E_ex), the PL peak energy was found to be redshifted, accompanied by a narrowing of the bandwidth. These results are explained by surface exciton recombination model taking into account there existing a size distribution of a-Si NPs in the silicon nitride matrix.     

Nonlinear Doping,Chemical Passivation and Photoluminescence Mechanism in Water-Soluble Silicon Quantum Dots by Mechanochemical Synthesis

A series of boron-and phosphorus-doped silicon wafers are used to prepare a series of doped silicon nanocrystals(nc-Si) by high-energy ball milling with carboxylic acid-terminated surface. The sizes of the nc-Si samples are demonstrated to be 5 nm. The doping levels of the nc-Si are found to be nonlinearly dependent on the original doping level of the wafers by x-ray photoelectron spectroscopy measurement. It is found that the nonlinear doping process will lead to the nonlinear chemical passivation and photoluminescence(PL) intensity evolution.The doping, chemical passivation and PL mechanisms of the doped nc-Si samples prepared by mechanochemical synthesis are analyzed in detail.     

内电场对纳米硅光致发光谱的影响

从量子限制发光中心模型出发，计算了纳米硅的光致发光（PL）特征与发光中心间的关系. 研究发现，纳米硅与发光中心间的内电场对载流子复合率及峰位振荡有着十分重要的影响. 在2—5 nm的尺寸范围内，纳米硅发光中心上的载流子复合概率远大于内部复合概率，仅需考虑发光中心上的载流子复合发光. 还发现发光中心与纳米硅粒子间的内电场对于纳米硅的发光峰位振荡有着显著的影响.发光中心与纳米硅粒子间的内电场的存在会显著减小纳米硅粒子的内部发光效率以及外部相应发光中心上的发光强度，使得纳米硅PL谱的峰位随纳米晶粒尺寸变化而发生 关键词： 内电场 纳米硅 光致发光 量子限制发光中心     

Quantum emission efficiency of nanocrystalline and amorphous Si quantum dots

The paper presents the comparison of emission efficiencies for crystalline Si quantum dots (QDs) and amorphous Si nanoclusters (QDs) embedded in hydrogenated amorphous (a-Si:H) films grown by the hot wire-CVD method (HW-CVD) at the variation of technological parameters. The correlations between the intensities of different PL bands and the volumes of Si nanocrystals (nc-Si:H) and/or an amorphous (a-Si:H) phase have been revealed using X-ray diffraction (XRD) and photoluminescence (PL) methods. These correlations permit to discuss the PL mechanisms in a-Si:H films with embedded nc-Si QDs. The QD parameters of nc-Si:H and a-Si:H QDs have been estimated from PL results and have been compared (for nc-Si QDs) with the parameters obtained by the XRD method. Using PL and XRD results the relations between quantum emission efficiencies for crystalline (η_cr) and amorphous (η_am) QDs have been estimated and discussed for all studied QD samples. It is revealed that a-Si:H films prepared by HW-CVD with the variation of wire temperatures are characterized by better passivation of nonradiative recombination centers in comparison with the films prepared at the variation of substrate temperatures or oxygen flows.     

生长温度对6H-SiC上SiCGe薄膜发光特性的影响

利用低压化学气相淀积工艺在6H-SiC衬底成功制备了SiCGe薄膜。通过光致发光(PL)谱研究了生长温度对SiCGe薄膜发光特性的影响。结果表明:生长温度为980,1030,1060℃的SiCGe薄膜的室温光致发光峰分别位于2.13,2.18,2.31eV处;通过组分分析和带隙计算,认定该发光峰来自于带间辐射复合,证实了改变生长温度对SiCGe薄膜带隙的调节作用。同时,对SiCGe薄膜进行了变温PL测试,发现当测试温度高于200K时,发光峰呈现出蓝移现象。认为这是不同机制参与发光所造成的。     

发光纳米硅/二氧化硅多层膜的特性与氢气氛退火的影响

利用等离子体增强化学气相沉积法制备了氢化非晶硅/二氧化硅多层膜，通过两步热退火的方法获得了尺寸可控的纳米硅/二氧化硅多层结构，晶粒尺寸约为4nm，在室温下观察到了较强的光致可见发光，其发光峰位于750nm.在此基础上，发现合适的氢气氛退火能有效地提高材料的发光强度.电子顺磁共振实验表明氢气氛退火有效地降低了纳米硅中的非辐射复合中心而导致发光效率的提高.     

Assessing Carrier Recombination Processes in Type‐II SiGe/Si(001) Quantum Dots

In this work, it is shown how different carrier recombination paths significantly broaden the photoluminescence (PL) emission bandwidth observed in type‐II self‐assembled SiGe/Si(001) quantum dots (QDs). QDs grown by molecular beam epitaxy with very homogeneous size distribution, onion‐shaped composition profile, and Si capping layer thicknesses varying from 0 to 1100 nm are utilized to assess the optical carrier‐recombination paths. By using high‐energy photons for PL excitation, electron‐hole pairs can be selectively generated either above or below the QD layer and, thus, clearly access two radiative carrier recombination channels. Fitting the charge carrier capture‐, loss‐ and recombination‐dynamics to PL time‐decay curves measured for different experimental configurations allows to obtain quantitative information of carrier capture‐, excitonic‐emission‐, and Auger‐recombination rates in this type‐II nano‐system.     

Continuous photoluminescence, time resolved photoluminescence and optically detected magnetic resonance measurements of PbI2 nanometer-sized particles, embedded in SiO2 films

The nanometer sized particles of PbI₂ were embedded in SiO₂ films. X-ray diffraction and the TEM pictures showed the preservation of the bulk layered structure and symmetry. The PL spectrum of the nano-particles exhibited a pronounced blue shift of the exciton band due to quantum size effect. The Lead Iodide represents an exceptionally small exciton Bohr radius (a_B = 19 Å) and a special case in which m_e m_h. The prepared samples contained particles with mean radii, a, in the range a_B < a < 3a_B. Within this limit (with m_e m_h), the experimental results suggest that the electron is localized nearly at the center of the particle, enabling the hole to move around it. Thus, the size confinement permits the creation of an acceptor-like exciton. The PL spectrum revealed additional states, associated with stoichiometric defects either at the interior or surface sites of the nano-particles. These defects act either as donor or acceptor states. The dynamics of the various recombination processes has been investigated by measuring the time resolved PL spectra. The results show a multiexponential behavior of the various recombination emission bands, indicating the occurrence of trapping and detrapping processes. Analysis of these results suggests that the existence of surface states give rise to these complex radiative decay processes. The correlation between donor-acceptor recombination emission bands in the aforementioned samples and lattice imperfections was examined, utilizing optically detected magnetic resonance (ODMR) spectroscopy. The results identified the following imperfection sites: an acceptor site associated with an isotropic Lead vacancy defect, [V⁻]_pb²⁺ and a donor site, associated with an anisotropic Iodine vacancy, [V⁰]_Iodine.     

Size-dependent radiative emission of PbS quantum dots embedded in Nafion membrane

PbS quantum dots (QDs) have been incorporated in a Nafion membrane, where the QD sizes were adjusted by changing the reaction time due to the steady growing process. The radiative emissions of the samples were investigated by optical absorption, photoluminescence (PL), and time-resolved PL spectroscopy. Size-tunable emissions are shown by the PL spectrum in a range of 1.84–1.65 eV, and the emission mechanism was investigated based on a four-band envelope-function model. Possible energy transitions for the radiative emission are listed. The PL lifetime depending on the particle size is about one microsecond, and PL decay curves exhibit a trend of decreasing decay time with an increase of the PbS QD size.     

蓝光激光器结构中InGaN/GaN多量子阱界面效应的精细光致发光光谱研究

金属有机化学气相沉积(MOCVD)方法制备InGaN/GaN多量子阱结构时,在GaN势垒层生长的N2载气中引入适量H2,能够有效改善阱/垒界面质量从而提升发光效率.本工作利用光致发光(PL)光谱技术,对蓝光激光器结构中的InGaN/GaN多量子阱的发光性能进行了精细的光谱学测量与表征,研究了通H2生长对量子阱界面的调控...     

纳米硅薄膜的光致发光特性

用等离子体增强化学汽相淀积法系统制备了发光纳米硅(nc-Si∶H)薄膜.讨论了晶粒尺寸和表面结构对光致发光(PL)谱的影响.用量子限制-发光中心模型解释了nc-Si∶H的PL.研究了PL谱的温度特性.温度从10K上升到250K，PL峰值红移了54meV，且PL强度衰减了两个数量级. 关键词：     

SiO_x(x=1.3)薄膜的优化阻变特性与退火温度的关系探究

采用电子束蒸发技术在Si衬底上制备了亚氧化硅SiOx(x=1.3)薄膜,研究了不同温度热退火处理的SiOx薄膜作为阻变层的ITO/SiOx/Si/Al结构的阻变特性.研究发现,在电极尺寸相同的条件下,随着退火温度的增加,该结构的高低阻态比显著提高,最高可达109.X射线光电子能谱和电子顺磁共振能谱的分析表明,不同退火温度下形成的不同价态的硅悬挂键是低阻态下细丝通道的主要来源.椭偏仪的测试结果表明,经过热退火处理的SiOx薄膜折射率的增大是导致高阻态下器件电阻增大的原因.     

Erbium ion luminescence of silicon nanocrystal layers in a silicon dioxide matrix measured under strong optical excitation

The photoluminescence (PL) spectra and kinetics of erbium-doped layers of silicon nanocrystals dispersed in a silicon dioxide matrix (nc-Si/SiO₂) are studied. It was found that optical excitation of nc-Si can be transferred with a high efficiency to Er³⁺ ions present in the surrounding oxide. The efficiency of energy transfer increases with increasing pumping photon energy and intensity. The process of Er³⁺ excitation is shown to compete successfully with nonradiative recombination in the nc-Si/SiO₂ structures. The Er³⁺ PL lifetime was found to decrease under intense optical pumping, which implies the establishment of inverse population in the Er³⁺ system. The results obtained demonstrate the very high potential of erbium-doped nc-Si/SiO₂ structures when used as active media for optical amplifiers and light-emitting devices operating at a wavelength of 1.5 μm.     

Fabrication of nc-Si/SiO2 structure by thermal oxidation method and its luminescence characteristics

Nano-crystalline silicon/silicon oxide （nc-Si/SiO2） structures have been prepared from amorphous silicon films on both silicon and quartz substrates by using electron-beam evaporation approach and annealing at temperatures about 600 ℃ in air. As a thermal oxidation procedure, the annealing treatment is not only a crystallization process but also an oxidation process. Scanning electron microscopy is employed to characterize the surface morphology of the nc-Si/SiO2 layers. Transmission electron microscopy study shows the sizes of nc-Si grains on the two different substrates. The nc-Si/SiO2 structures exhibit visible luminescence at room temperature as confirmed by photoluminescence spectroscopy. Comparing the photoluminescence spectra of different samples, our results agree with the quantum confinement-luminescence center model.     

玻璃中CdSeS纳米晶体的室温光致发光谱

对掺有过饱和的镉、硒和少量硫的玻璃在500～800℃分别退火4h,生长了不同尺寸的CdSe_1-xS_x纳米晶体。测量了纳米晶体的室温吸收光谱和光致发光(PL)光谱,550℃生长的样品在300～800nm的范围没有观察到吸收和发光峰,表明温度低于550℃玻璃中不能形成纳米晶体。生长温度在600～650℃,纳米晶体的PL光谱主要为两个宽的发光带,即带边激子发光带和通过表面态复合的发光带。随着生长温度的升高,带边复合发光的蓝移减小,通过表面态的发光逐渐消失,并出现了叠加于宽发光带上的一系列明显的弱发射峰。不同温度生长的样品中,叠加峰的能量相同。同一样品中叠加峰的能量不随激发光波长的变化而变化。     

Temperature-dependent photoluminescence of size-tunable ZnAgInSe quaternary quantum dots

Colloidal ZnAgInSe (ZAISe) quantum dots (QDs) with different particle sizes were obtained by accommodating the reaction time. In the previous research, photoluminescence (PL) of ZAISe QDs only could be tuned by changing the composition. In this work the size-tunable photoluminescence was observed successfully. The red shift in the photoluminescence spectra was caused by the quantum confinement effect. The time-resolved photoluminescence indicated that the luminescence mechanisms of the ZAISe QDs were contributed by three recombination processes. Furthermore, the temperature-dependent PL spectra were investigated. We verified the regular change of temperature-dependent PL intensity, peak energy, and the emission linewidth of broadening for ZAISe QDs. According to these fitting data, the activation energy (ΔE) of ZAISe QDs with different nanocrystal sizes was obtained and the stability of luminescence was discussed.