Microstructure and blue photoluminescence enhancement of silicon nanoporous pillar array embedded in ferroelectric barium strontium titanate

A silicon nanoporous pillar array (Si-NPA) with micrometer/nanometer hierarchical structure was fabricated by hydrothermal etching, followed by spin-coating barium strontium titanate (BST) on Si-NPA substrate. The photoluminescence (PL) spectra of the Si-NPA and BST/Si-NPA thin film were investigated. The emission band of freshly prepared Si-NPA located at 630 nm, and a blueshift at 425 nm as well as degradation in intensity after annealing at 600 °C for 1 h was observed, which might be explained by a quantum confinement effect model. BST ferroelectric material provided a static-electric field and induced the excited carriers in Si-NPA to migrate toward the opposite direction and recombine in an interfacial oxide layer. Therefore, BST enhanced blue emission of Si-NPA as well as passivated Si-NPA.     

Blue–violet photoluminescence from colloidal suspension of nanocrystalline silicon in silicon oxide matrix

We report room temperature visible photoluminescence (PL), detectable by the unaided eye, from colloidal suspension of silicon nanocrystals (nc-Si) prepared by mechanical milling followed by chemical oxidation. The PL bands for samples prepared from Si wafer and Si powder peak at 3.11 and 2.93 eV respectively, under UV excitation, and exhibit a very fast (～ns) PL decay. Invasive oxidation during chemical treatment reduces the size of the nc-Si domains distributed within the amorphous SiO₂ matrix. It is proposed that defects at the interface between nc-Si and amorphous SiO₂ act as the potential emission centers. The origin of blue–violet PL is discussed in relation to the oxide related surface states, non-stoichiometric suboxides, surface species and other defect related states.     

Trap states in oxidation layer of nanocrystal Si

The photoluminescence （PL） of nanocrystal present in porous silicon shifts from the near infrared to the ultraviolet depending on the size when the surface is passivated with Si-H bonds. After oxidation, the centre wavelength of PL band is pinned in a region of 700-750 nm and its intensity increases obviously. Calculation shows that trap electronic states appear in the band gap of a smaller nanocrystal when Si = O bonds or Si-O-Si bonds are formed. The changes in PL intensity and wavelength can be explained by both quantum confinement and trap states in an oxidation layer of nanocrystal. In the theoretical model, the most important factor in the enhancement and the pinning effects of PL emission is the relative position between the level of the trap states and the level of the photoexcitation in the silicon nanocrystal.     

Structure transition and photoluminescence of CdS/Si nanoheterostructure array on thermal annealing

CdS/Si heterojunctions have been prepared through growing CdS nanocrystallites (nc-CdS) on the silicon nanoporous pillar array (Si-NPA) by the chemical bath deposition method. Cadmium nanocrystallites (nc-Cd) have been observed and ascribed to the reducibility of Si-NPA. The reason for the appearance of CdO is indistinct and the related work will be done in the future. The blue, green and red emissions are ascribed to the silicon oxide layer, band gap of nc-CdS and the sulphur vacancies, respectively. Redshift and blueshift with the annealing temperature about green emissions are contributed to quantum size effect and the structure transition from nc-Cd to CdO. It is beneficial for investigating the structures and defects to the application of CdS/Si in the optoelectronic field.     

The Role of Silicon Oxide Layers in Luminescence of Ensembles of Silicon Quantum Dots

Based on the quantum confinement-luminesecence center model,to ensembles of spherical silicon nanocrystals (nc-Si)containg two kinds of luminescence centers(LCs) in the SiOx layers surrounding the nc-Si,the relationship between the photolumincescence(PL) and the thickness of the SiOx layer is studied with the excitation energy flux density as a parameter.When there is no SiOx layer surrounding the nc-Si,the electron-heavy hole pair can only recombine inside the nc-Si,then the PL bluehift with reducing particle sizes roughly accords with the rule predicted by the quantum confinement model of Canham.When there presences a SiOx layer,some of the carriers may tunnel into it and recombine outside the nc-Si at the LCs to emit visible light.The thicker the SiOx layer is,the higher the radiative recombination rate occurred outside the nc-Si will be.When the central Scale of the nc-Si is much smaller than the critical scale,the radiative recombination rate outside the nc-Si dominates,and visible PL will be possible for some nc-Si samples with big average radius,greater than 4nm,for example.When there is only one kind of LC in the SIOx layer,the PL peak position does not shift with reducing particle sizes.All these conclusions are in accord with the experimental results.When there are two or more kinds of LCs in the SiOx layer,the PL peak position energy and intensity swing with reducing particle sizes.     

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.     

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.     

Visible photoluminescence of co-sputtered Ge–Si duplex nanocrystals

The photoluminescence (PL) characteristics of co-sputtered Ge–Si duplex nanocrystal films were examined under excitation by a 325-nm HeCd laser, combined with Raman and Fourier-transform infrared reflection spectra analysis. A broad visible PL spectrum from the as-deposited Ge–Si nanocrystal films was observed in the wavelength range 350–700 nm. Basically, the PL spectrum can be considered to consist of two distinct parts originating from different emission mechanisms: (i) the spectrum in the range 350–520 nm, consisting of characteristic double peaks at 410 and 440 nm with PL intensities decreasing after vacuum annealing, probably due to vacancy defects in Si nanocrystals; and (ii) the spectrum in the range 520–700 nm, consisting of a characteristic peak at 550 nm with a PL intensity not affected by vacuum annealing, probably due to Ge-related interfacial defects. No size dependence of PL peak energy expected from quantum confinement effects was observed in the wavelength range investigated. However, with an increase of crystal size, the PL peak intensity in the blue zone decreased. The PL intensity is found to be strongly affected by silicon concentration. A film heated in air has a different PL mechanism from the as-deposited and vacuum-annealed films. PACS 78.67.Bf; 81.05.Cy; 81.15.Cd     

Fabrication and simulation of glass micromachining using CO2 laser processing with PDMS protection

An efficient synthesis route for highly luminescent silicon nanocrystal (Si-nc) films is presented. Si-ncs in the films are synthesized in the gas phase by using an argon-silane radio-frequency dielectric-barrier discharge (RF-DBD) plasma. The size of Si-ncs is well tunable by changing the resident time. The resulting Si-nc films with different oxidation degree exhibit emission across the full visible spectrum. Structural and optical characterization indicates that the red-to-green luminescence from big particles show quantum confinement effect (QCE), while this effect disappears in blue luminescence from small ones. A model is presented to explain this result. In this model, the radiative process in big particles is Band-to-Band recombination, in which surface states have a negligible impact on the QCE, while the blue emission from small Si-ncs is due to the Band-to-Bound recombination, in which surface state plays an important role, resulting in the disappearance of QCE. Additionally, obvious double-exponential decay from midsize particles is observed, in which the two kinds of recombination may coexist.     

The origin of blue photoluminescence from nc-Si/SiO2 multilayers

Intensive blue photoluminescence (PL) was observed at room temperature from the nanocrystalline-Si/SiO$_{2}$ (nc-Si/SiO$_{2})$ multilayers (MLs) obtained by thermal annealing of SiO/SiO$_{2}$\,MLs for the first time. By controlling the size of nc-Si formed in SiO sublayer from 3.5 to 1.5 nm, the PL peak blueshifts from 457 to 411 nm. Combining the analysis of TEM, Raman and absorption measurement, this paper attributes the blue PL to multiple luminescent centres at the interface of nc-Si and SiO$_{2}$.     

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.     

Structural and optical properties of Si/SiO2 multi-quantum wells

Structural and optical properties of Si/SiO₂ multi-quantum wells (MQW) were investigated by means of Raman scattering and photoluminescence (PL) spectroscopy. The MQW structures were fabricated on a quartz substrate by remote plasma enhanced chemical vapour deposition (RPECVD) of alternating amorphous Si and SiO₂ layers. After layer deposition the samples were subjected to heat treatments, i.e. rapid thermal annealing (RTA) and furnace annealing. Distinct PL signatures of confined carriers evidenced formation of Si-nanocrystals (nc-Si) in annealed samples. Analyses of Raman spectra also show presence of nc-Si phase along with amorphous-Si (a-Si) phase in the samples. The strong influence of the annealing parameters on the formation of nc-Si phase suggests broad possibilities in engineering MQW with various optical properties. Interestingly, conversion of the a-Si phase to the nc-Si phase saturates after certain time of furnace annealing. On the other hand, thinner Si layers showed a disproportionately lower crystalline volume fraction. From the obtained results we could assume that an interface strain prevents full crystallization of the Si layers and that the strain is larger for thinner Si layers. The anomalous dependence of nc-Si Raman scattering peak position on deposited layer thickness observed in our experiments also supports the above assumption.     

Synthesis of Light-emitting Silicon Nanoparticles by Intense Pulsed ion-beam Esvaporation

Synthesis of photoluminescent Si nanoparticles has been successfully prepared using an intense pulsed ion-beam evaporation (IBE) technique in vacuum. Si nanoparticles are produced by the IBE method without any post-annealings. Photoluminescence (PL) mainly in blue range with a peak of 455 nm and a shoulder near 510 nm is observed in as-deposited Si nanoparticles at room temperature. The blue light emission is relatively stable with no noticeable change, as the samples have already stored in air more than 4 months. The observed PL does not fit the quantum confinement model, since a majority of particle size is around ~20 nm, estimated by SEM and XRD measurements. Moreover, hydrofluoric acid (HF) corrosion tests on the Si nanoparticles also indicate a correlation between the presence of the surface oxide layers and the PL. Oxide-related luminescence is likely the source of this blue light emission.     

Room temperature visible light emission from Si/SiO2 multilayers: Roles of interface electronic states and silicon phase

We have studied luminescence properties and microstructure of 20 patterns Si/SiO₂ multilayers. The photoluminescence spectra consist of two gaussian bands in the visible-infrared spectral region. It has been demonstrated that the strong PL band is caused by the radiative recombination in the Si/SiO₂ interfaces states, whereas the weaker band originates from radiative recombination in the nanosized Si layers. The peak shift of this latter band shows a discontinuity that corresponds to a crystalline-to-amorphous phase change when the Si layers are thinner than 30 Å. The peak energy as a function of the layer thickness is interpreted using a quantum confinement model in the case of amorphous Si layers.     

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。     

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.     

Si杂质扩散诱导InGaAs/AlGaAs量子阱混杂的研究（英文）

光学灾变损伤(COD)常发生于量子阱半导体激光器的前腔面处,极大地影响了激光器的出光功率及寿命。通过杂质诱导量子阱混杂技术使腔面区波长蓝移来制备非吸收窗口是抑制腔面COD的有效手段,也是一种高效率、低成本方法。本文选择了Si杂质作为量子阱混杂的诱导源,使用金属有机化学气相沉积设备生长了InGaAs/AlGaAs量子阱半导体激光器外延结构、Si杂质扩散层及Si 3 N 4保护层。热退火处理后,Si杂质扩散诱导量子阱区和垒区材料互扩散,量子阱禁带变宽,输出波长发生蓝移。退火会影响外延片的表面形貌,而表面形貌则可能会影响后续封装工艺中电极的制备。结合光学显微镜及光致发光谱的测试结果,得到825℃/2 h退火条件下约93 nm的最大波长蓝移量,也证明退火对表面形貌的改变,不会影响波长蓝移效果及后续电极工艺。     

纳米Si/SiO2多层膜的结构表征及发光特性

采用等离子体化学气相沉积系统生长非晶硅薄膜并用原位等离子体氧化的方法制备出具有不同子层厚度的非晶Si/SiO₂多层膜,然后利用限制性晶化原理使非晶硅层晶化生成纳米硅。利用Raman、TEM等手段对薄膜结构进行了系统表征,在室温下观测到了光致发光信号,其发光峰峰位在750nm附近。进而在样品上下表面蒸镀电极,构建了电致发光原型器件并观测到了室温下的电致发光谱,开启电压约为6V,有两个明显的发光带,分别位于在650nm和520nm处。初步探讨了纳米硅及纳米硅/二氧化硅界面态对发光特性的影响。     

Structural imaging of a Si quantum dot: Towards combined PL and TEM characterization

Individual silicon quantum dots were fabricated by electron-beam lithography, plasma etching and a two-step oxidation process. This enables photoluminescence (PL) from individual dots at various temperatures to be detected and spectrally resolved using a sensitive charge-coupled device camera-imaging system, as reported previously. The regular array-like arrangement of oxidized pillars containing individual nanocrystals, in principle, enables combined transmission electron microscopy (TEM) and low-temperature PL characterization of the same Si quantum dot. To this end, a technique employing focused ion beam was developed for preparation of the pillar/nanocrystal of interest for TEM. It is shown that silicon quantum dots of several nanometers in size can be characterized using such a method.     

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.