Aging effect on blue luminescent silicon nanocrystals prepared by pulsed laser ablation of silicon wafer in de-ionized water

Blue luminescent colloidal silicon nanocrystals (Si-ncs) were synthesized at room temperature by nanosecond pulsed laser ablation of a single-crystal silicon target in de-ionized water. Irregular Si-nc fragments obtained by laser ablation are stabilized into regularly shaped, spherical, and well-separated aggregates during the aging process in water. Aging in de-ionized water for several weeks improved the photoluminescence (PL) intensity. At least two weeks of aging are necessary for observation of broad blue room temperature PL with a maximum centered at 420 nm. Detailed structural analysis revealed that agglomerates after aging for several months contain Si-ncs with irregular shape smaller than the quantum confinement limit (<5 nm). These blue luminescent Si-ncs dispersed in de-ionized water exhibited a PL decay time of 6 ns, which is much faster than that of Si-ncs prepared in traditional ways (usually on the order of microseconds). The oxidized Si-ncs with quantum confinement effects are responsible for a PL band around 400 nm visible to the naked eye at room temperature.     

Luminescent-wavelength tailoring silicon-rich silicon nitride LED

Wavelength tunable photoluminescence （PL） of Si-rich silicon nitride （SRSN） film with buried Si nanocrystals （Si-ncs） grown by plasma enhanced chemical vapor deposition （PECVD） under Sill4 and NH3 environment is investigated. Intense broadband visible emissions tunable from blue to red can be obtained from the as-deposited SiNs thin films with increasing NH3 flow rate from 150 to 250 sccm and detuning the SiH4/NH3 flow ratio during deposition. To date, the normalized PL wavelength of SiNx films after anneal- ing could be detuned over the range of 385-675 nm by decreasing the NH3 flow rate, corresponding to an enlargement on Si-nc size from 1.5-2 to 4-5 nm. The PL linewidth is decreased with increasing ammonia flow rate due to the improved uniformity of Si-ncs under high NH3 flow rate condition. In addition, the PL intensity is monotonically increasing with the blue shift of PL wavelength due to the increasing density of small-size Si-ncs. The ITO/SiNx/p-Si/Al diode reveals highly resistive property with the turn-on voltage and power-voltage slope of only 20 V and 0.18 nW/V, respectively. The turn-on voltage can further reduce from 20 to 3.8 V by improving the carrier injection efficiency with p-type Si nano-rods.     

Maximum fraction of Er ions optically pumped through Si nanoclusters

By quantifying the amount of excited Er ions and considering the interaction distance between Si nanoclusters (Si-ncs) and the nearby Er ions, we were able to determine the maximum excitable Er concentration, when indirectly pumped through the Si-ncs. Our study was carried out on silica layers codoped with Si clusters and Er ions, grown by reactive magnetron sputtering. Si-rich silica layers were formed with different amounts of Si excess and doped to a wide range of Er concentrations. Thermal treatments were performed at 900  °C for different durations to maximize the Er emission at 1540 nm. The saturation limit of Er ions optically excitable through the Si-ncs was found about 3% of the total concentration. Simulations were carried out in order to explain this low value. The modelization takes into account the spatial distribution of the Er population, the measured size and density of Si clusters and the short-range character of the interaction between Er and Si-ncs. The small excitable fraction thus obtained appears as the ultimate intrinsic limitation to attain very high optical efficiency in such structures.     

Green and red up-conversion emissions of Er–Yb Co-doped TiO2 nanocrystals prepared by sol–gel method

In this paper, green and red up-conversion emissions of Er³⁺–Yb³⁺ co-doped TiO₂ nanocrystals were reported. The phase structure, particle size and optical properties of Er³⁺–Yb³⁺ co-doped TiO₂ nanocrystals samples were characterized by using X-ray diffraction (XRD), transmission electron microscopy (TEM), UV–vis–NIR absorption spectra and photoluminescence (PL) spectra. Green and red up-conversion emissions in the range of 520–570 nm (²H_11/2, ⁴S_3/2→⁴I_15/2) and 640–690 nm (⁴F_9/2→⁴I_15/2) were observed for the Er³⁺–Yb³⁺ co-doped TiO₂ nanocrystals. The visible up-conversion mechanism and temperature dependence of up-conversion emission for Er³⁺ in TiO₂ nanocrystals were discussed in detail.     

Interrelation between microstructure and optical properties of erbium-doped nanocrystalline thin films

Nanocrystalline silicon thin films codoped with erbium, oxygen and hydrogen have been deposited by co-sputtering of Er and Si. Films with different crystallinity, crystallite size and oxygen content have been obtained in order to investigate the effect of the microstructure on the photoluminescence properties. The correlation between the optical properties and microstructural parameters of the films is investigated by spectroscopic ellipsometry. PL response of the discussed structures covers both the visible wavelength range (a crystallite size-dependent photoluminescence detected for 5–6 nm sized nanocrystals embedded in a SiO matrix) and near IR range at 1.54 μm (Er-related PL dominating in the films with 1–3 nm sized Si nanocrystals embedded in a-Si:H). It is demonstrated that the different PL properties can be also discriminated on the basis of ellipsometric spectra.     

硅基硒纳米颗粒的发光特性研究

由于尺寸缩小引起的量子效应, 硒(Se) 材料的低维纳米结构具有更高的光响应和低的阈值激射等特性, 因此成为纳米电子与纳米光电子器件领域一个重要的研究方向. 本文通过对非晶硒薄膜的快速热退火来制备硒纳米颗粒, 退火温度在100–180℃之间时, 结晶后的硒纳米颗粒均为三角晶体结构, 其颗粒尺寸随退火温度的增加而线性增大. 光致发光谱测试发现三个发光峰, 分别位于1.4eV, 1.7eV和1.83eV. 研究发现位于1.4eV处的发光峰来源于非晶硒缺陷发光, 位于1.83eV处的发光峰来源于晶体硒的带带跃迁发光; 而位于1.7eV处的发光峰强度随激发功率增强而指数增大, 且向短波长移动, 该发光峰应该来源于非晶硒与硒纳米颗粒界面处的施主-受主对复合发光. 关键词： 硅基 硒纳米颗粒 光致发光 施主-受主对     

Ce3+注入对不同尺寸的nc-Si/SiO2 超晶格发光特性的影响

通过电子束蒸发方法以及高温退火处理,得到nc-Si/SiO₂超晶格。将样品分别注入剂量为2.0×10¹⁴ cm^-2和2.0×10¹⁵ cm^-2的Ce³⁺,再对其进行二次退火处理,获得多组样品。通过对样品光致发光光谱的分析发现,样品发光强度的变化不仅受到Ce³⁺注入剂量的影响,而且也受到nc-Si颗粒大小的影响。在相同注入计量和相同的二次退火处理温度下,nc-Si颗粒较大的样品经Ce³⁺注入后其发光强度增强较为明显。     

Luminescent CdSe and CdSe/CdS core-shell nanocrystals synthesized via a combination of solvothermal and two-phase thermal routes

A new solvothermal route has been developed for synthesizing the size-controlled CdSe nanocrystals with relatively narrow size distribution, and the photoluminescence (PL) quantum yields (QYs) of the nanocrystals can reach 5-10%. Then the obtained CdSe nanocrystals served as cores to prepare the core/shell CdSe/CdS nanocrystals via a two-phase thermal approach, which exhibited much higher PL QYs (up to 18-40%) than the CdSe core nanocrystals. The nanocrystal samples were characterized by ultraviolet-visible (UV-vis) absorption spectra, PL spectra, wide-angle X-ray diffraction (WAXD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM).     

高浓度Er/Yb共掺ZnO薄膜的结构及室温光致发光特性

采用射频磁控溅射方法制备了Er/Yb共掺ZnO薄膜,研究了退火处理对高浓度Er/Yb共掺ZnO薄膜的结构演化和光致发光(PL)特性的影响。X射线衍射分析结果表明:Er/Yb掺杂导致ZnO薄膜的晶粒细化及择优取向性消失,ZnO晶粒随退火温度的增加而逐渐长大。900℃退火时,出现Er3 、Yb3 偏析,退火温度高于1000℃时,薄膜与基体间发生了界面反应,1200℃时,ZnO完全转变为Zn2SiO4相。光致发光测量结果表明:高于900℃退火处理后,Er/Yb共掺ZnO薄膜在1540 nm附近具有明显的光致发光,发光强度在退火温度为1050℃时达到最大值;光致发光光谱呈现典型的晶体基质中Er3 离子发光光谱所具有的明锐多峰结构特征。此外,探讨了薄膜结构演化及其对光致发光光谱的影响。     

Size control of Si nanocrystals by two-step rapid thermal annealing of sputtered Si-rich oxide/SiO2 superlattice

Controllable size of silicon (Si) nanocrystals can be achieved by a two-step rapid thermal annealing technique consisting of rapid annealing at 1000°C in nitrogen ambient and rapid oxidation at 600–800°C of a radio frequency magnetron co-sputtered Si-rich oxide/SiO₂ superlattice structure. The photoluminescence (PL) spectra related to Si nanocrystals were observed in the visible range (600–900 nm). After rapid oxidation, the size of the nanocrystals was reduced and the quality of the Si nanocrystal/SiO₂ interface was improved, resulting in a blue shift and an increase of the PL peak intensity. Finally, annealing in air increases the PL intensity further.     

Temperature-dependent photoluminescence of arsenic-doped Si nanocrystals

The characteristics of temperature-dependent photoluminescence (PL) from Si nanocrystals and effects of arsenic-doping (As-doping) were investigated. The Si nanocrystals on a p-type Si substrate were prepared by low pressure chemical vapor deposition and post-deposition thermal oxidation. The As-doping process was carried out using the gas-phase-doping technique. Temperature-dependent PL from Si nanocrystals exhibited considerable differences between samples with/without As-doping. Phase transition between electron-hole liquid and free exciton was observed in the undoped Si nanocrystals, leading to the increase in PL intensity with temperature less than 50 K. Electron emission from As-doped Si nanocrystals to the p-Si substrate was responsible for the significant increase in PL intensity with temperature greater than 50 K. Characteristics of light emission from Si nanocrystals will facilitate the development of silicon-based nanoscaled light-emitting devices.     

Influence of preparation and storage conditions on photoluminescence of porous silicon powder with embedded Si nanocrystals

The time changes of photoluminescence (PL) characteristics of porous silicon (porSi) powder during storing in different ambients have been reported. A porous silicon material with embedded Si nanocrystals of size of few nanometers was prepared by an electrochemical method from 10 to 20 Ωcm p-type Si wafers, and both constant and pulse current anodization regimes were used. A powder with a submicron average particle size was obtained by simple mechanical lift-off of the porous layer followed by additional manual milling. The air, hexane, and water as storage media were used, and modification by a nonionic surfactant (undecylenic acid) of the porSi surface was applied in the latter case. Dependence of PL characteristics on preparation and storage conditions was then studied. A remarkable blue shift of a position of PL maximum was observed in time for porSi powders in each storage media. In water suspension a many-fold build-up (10–30) of PL intensity in a time scale of few days was accompanied by an observed blue shift. Photoluminescence time behavior of porSi powders was described by a known mechanism of the change of porSi PL from free exciton emission of Si nanocrystals to luminescence of localized oxidized states on the Si nanocrystal surface.     

Absorption cross-sections and lifetimes as a function of size in Si nanocrystals embedded in SiO2

The photoluminescence (PL) emission yield of Si nanocrystals embedded in SiO₂ depends on their size and on Si–SiO₂ interface passivation. In this work we aim at clarifying the relative importance of both contributions by studying lifetimes and absorption cross-sections as a function of size, for samples with and without passivation in forming gas. We find that while the PL lifetime increases steadily (quasi-linear dependence), the radiative lifetime increases exponentially with the nanocrystal size. Thus, as expected, radiative oscillator strengths are much smaller for large nanocrystals, but this reduction is partially compensated by a less effective quenching at interfacial non-radiative states. The absorption cross-section per nanocrystal rises as the nanocrystal size decreases, for all excitation wavelengths, implying that the variation of oscillator strength dominates over the reduction of the density of states. Passivation processes do not affect the emission mechanism and increase the emission yield while reducing the density of non-radiative recombination centers at the Si–SiO₂ interface (P_b centers).     

Emission of Si nanoclusters of different phases in amorphous hydrogenated silicon

This paper presents the results of PL spectrum studies for Si nano-clusters in an amorphous silicon matrix. The four amorphous Si layers were prepared by the hot-wire CVD method on glass substrates at a temperature of 250 ^°C and different filament temperatures in the range of 1650–1950 ^°C. The joint analysis of PL and X ray diffraction results dependant on technological conditions has been done. PL bands deal with Si nanocrystals and amorphous Si nanoclusters are discussed as well.     

Optical studies of Cd and Mn Co-doped ZnS nanocrystals

We report the structural and optical properties of co-doped ZnS nanocrystals synthesized by chemical co-precipitation method using Methacrylic Acid (MAA) as a capping agent. XRD patterns confirm the zinc blend structure of the samples. As calculated by the Debye-Scherrer formula and TEM image, the mean nanocluster diameter of the sample is ranging between 4-8 nm. EDAX analysis of co-doped sample confirms the presence of Mn²⁺ and Cd²⁺ ions in addition to the sulfur deficiencies. Optical characterizations of both doped and co-doped samples are carried out by UV-vis and Photoluminescence (PL) spectroscopy. We observed the coexistence of two metal ions and their effect on the luminescence properties (i.e. red emission) of the host material. The mechanism of energy transfer for the emissions are tried to discuss.     

Excitonic photoluminescence properties of nanocrystalline GaSb and Ga0.62In0.38Sb embedded in silica films

The GaSb and Ga_0.62In_0.38Sb nanocrystals were embedded in the SiO₂ films by radio-frequency magnetron co-sputtering and were grown on GaSb and Si substrates at different temperatures. We present results on the 10 K excitonic photoluminescence (PL) properties of nanocrystalline GaSb and Ga_0.62In_0.38Sb as a function of their size. The measurements show that the PL of the GaSb and Ga_0.62In_0.38Sb nanocrystallites follows the quantum confinement model very closely. By using deconvolution of PL spectra, origins of structures in PL were identified.     

用巯基乙酸作稳定剂制备CdSe纳米晶的光学性质

以巯基乙酸为稳定剂制备了CdSe纳米晶，通过尺寸选择沉淀得到2nm到3nm之间不同尺寸的纳米晶，利用室温光吸收，光致发光（PL）和光致发光激发（PLE）谱来研究了CdSe纳米团簇的光学性质。紫外－可见吸收谱给了具有清晰激光特征的尖锐吸收边，这表明样品的尺寸分布很窄。光致发光研究表明，样品有两个发射带，一个具有较高能量位于吸收边，来自电子－空穴对从最低激发态能级弛豫后的辐射复合，另一个低能发射带归属于基质与纳米晶界面存在的俘获中心。PLE谱中有2个吸收带，分别是S－S和P－P跃迁。最后还给出了不同激发能量下的发光特性。     

Electronic and optical properties of Si and Ge nanocrystals: An ab initio study

First-principles calculations within density functional theory and many-body perturbation theory have been carried out in order to investigate the structural, electronic and optical properties of undoped and doped silicon nanostructures. We consider Si nanoclusters co-doped with B and P. We find that the electronic band gap is reduced with respect to that of the undoped crystals, suggesting the possibility of impurity based engineering of electronic and optical properties of Si nanocrystals. Finally, motivated by recent suggestions concerning the chance of exploiting Ge dots for photovoltaic nanodevices, we present calculations of the electronic and optical properties of a Ge₃₅H₃₆ nanocrystal, and compare the results with those for the corresponding Si₃₅H₃₆ nanocrystals and the co-doped Si₃₃BPH₃₆.     

Syntheses of optically efficient (La1−x−yCexTby)F3 nanocrystals via a hydrothermal method

Optically efficient cerium and terbium doped lanthanide fluoride (La_1−x−yCe_xTb_y)F₃ nanocrystals with different doping concentrations have been synthesized by a hydrothermal route in the presence of ethylenediamine tetraacetic acid disodium salt (EDTA). The results showed that the formation of nanocrystals with different morphologies depends on terbium ion Tb³⁺ doping concentration, but independent of cerium ion Ce³⁺ doping concentration. With increase in Tb³⁺ doping concentration, the morphologies of nanocrystals evolved from a spherical shape to a plated-like one. In addition, both the photoluminescence quantum yield (PL QY) and the fluorescence lifetime of nanocrystals increased with the increase in Ce³⁺ doping concentration in cerium and terbium co-doped system. The PL QY reached up to 55%, and the lifetime up to 7.3 ms. Transmission electron microscopy (TEM), X-ray diffraction (XRD), selected area electron diffraction (SAED), X-ray fluorescence (XRF), energy dispersive spectroscopy (EDS), ultraviolet-visible (UV-vis) absorption, photoluminescence (PL) and infrared (IR) spectroscopies were employed to characterize the properties of nanocrystals. The growth mechanism of nanocrystals with different morphologies and optical properties of nanocrystals with different doping concentrations were investigated.     

Study on phase separation in a-SiOx for Si nanocrystal formation through the correlation of photoluminescence with structural and optical properties

The phase separation in amorphous silicon suboxide (a-SiO_x) films upon thermal annealing for the formation of light emitting silicon nanocrystals (Si-NCs) was studied through the correlation of photoluminescence (PL) and photoluminescence excitation (PLE) with structural and optical properties. The PL and PLE features and the structural and optical properties show a strong dependence on the annealing process and reveal that the precipitation of the excess Si in a-SiO_x and the formation of Si-NCs from the precipitated Si are two separate processes which should be distinguished in the phase separation in a-SiO_x. They proceed at different temperatures and the formation of Si-NCs is a slow process compared with the precipitation of the excess Si. The nanocrystal size and size distribution evolve with annealing time at the initial stages and are mainly dependent on annealing temperature for a certain O content in the initial a-SiO_x with the density of the formed Si-NCs increasing with longer annealing duration.