Relative enhancement of photoluminescence intensity of passivated silicon nanocrystals in a silicon dioxide matrix

Photoluminescence (PL) intensity of passivated silicon nanocrystals (Si NCs) embedded in a SiO 2 matrix is compared with that of unpassivated Si NCs. We investigate the relative enhancement of PL intensity (I R ) as a function of annealing temperature and implanted Si ion dose. The I R increases simultaneously with the annealing temperature. This demonstrates an increase in the number of dangling bonds (DBs) with the degree of Si crystallization varying via the annealing temperature. The increase in I R with implanted Si ion dose is also observed. We believe that the near-field interaction between DBs and neighboring Si NCs is an additional factor that reduces the PL efficiency of unpassivated Si NCs.     

第一性原理研究厚度和空位缺陷对Si/SiO2界面电子结构与光学性质的影响

采用基于密度泛函理论的平面波超软赝势方法,在局域密度近似（LDA）下研究了Si纳米层厚度和O空位缺陷对Si/SiO2界面电子结构及光学性质的影响．电子结构计算结果表明：在0.815~2.580nm的Si层厚度范围内,Si/SiO2界面结构的能隙随着厚度减小而逐渐增大,表现出明显的量子尺寸效应,这与实验以及其他理论计算结果一致;三种不同的O空位缺陷的存在均使得Si/SiO2界面能隙中出现了缺陷态,费米能级向高能量方向移动,且带隙有微弱增加．光学性质计算结果表明：随着Si纳米层厚度的减小,Si/SiO2界面吸收系数产生了蓝移;O空位缺陷引入后,界面光学性质的变化主要集中在低能区,即低能区的吸收系数和光电导率显著增加．可见,改变厚度和引入缺陷能够有效地调控Si/SiO2界面体系的电子和光学性质,上述研究结果为Si/SiO2界面材料的设计与应用提供了一定的理论依据．     

第一性原理研究厚度和空位缺陷对Si/SiO2界面电子结构与光学性质的影响

采用基于密度泛函理论的平面波超软赝势方法,在局域密度近似（ LDA）下研究了Si纳米层厚度和O空位缺陷对Si／SiO2界面电子结构及光学性质的影响．电子结构计算结果表明：在0.815～2.580nm的Si层厚度范围内, Si／SiO2界面结构的能隙随着厚度减小而逐渐增大,表现出明显的量子尺寸效应,这与实验以及其他理论计算结果一致;三种不同的O空位缺陷的存在均使得Si／SiO2界面能隙中出现了缺陷态,费米能级向高能量方向移动,且带隙有微弱增加．光学性质计算结果表明：随着Si纳米层厚度的减小, Si／SiO2界面吸收系数产生了蓝移; O空位缺陷引入后,界面光学性质的变化主要集中在低能区,即低能区的吸收系数和光电导率显著增加．可见,改变厚度和引入缺陷能够有效地调控Si／SiO2界面体系的电子和光学性质,上述研究结果为Si／SiO2界面材料的设计与应用提供了一定的理论依据．     

Investigation of Auger recombination in Ge and Si nanocrystals embedded in SiO2 matrix

We study theoretically the optical properties of embedded Ge and Si nanocrystals (NCs) in wide band-gap matrix and compared the obtained results for both NCs embedded in SiO₂ matrix. We calculate the ground and excited electron and hole levels in both Ge and Si nanocrystals (quantum dots) in a multiband effective mass approximation. We use the envelope function approximation taking into account the elliptic symmetry of the bottom of the conduction band and the complex structure of the top of the valence band in both Si and Ge (NCs). The Auger recombination (AR) in both nanocrystals is thoroughly investigated. The excited electron (EE), excited hole (EH) and biexciton AR types are considered. The Auger recombination (AR) lifetime in both NCs has been estimated and compared.     

Enhancement of optical switching parameter and third-order optical nonlinearities in embedded Si nanocrystals: A theoretical assessment

Third-order bound-charge electronic nonlinearities of Si nanocrystals (NCs) embedded in a wide band-gap matrix representing silica are theoretically studied using an atomistic pseudopotential approach. Nonlinear refractive index, two-photon absorption and optical switching parameter are examined from small clusters to NCs up to a size of 3 nm. Compared to bulk values, Si NCs show higher third-order optical nonlinearities and much wider two-photon absorption-free energy gap which gives rise to enhancement in the optical switching parameter.     

Phosphine-free synthesis of FeTe_2 nanoparticles and self-assembly into tree-like nanoarchitectures

Manipulating the self-assembly of transition metal telluride nanocrystals(NCs) creates opportunities for exploring new properties and device applications. Iron ditelluride(FeTe_2) has recently emerged as a new class of magnetic semiconductor with three-dimensional(3D) magnetic ordering and narrow band gap structure, yet the self-assembly of FeTe_2 NCs has not been achieved. Herein, the tree-like FeTe_2 nanoarchitectures with orthorhombic crystal structure have been successfully synthesized by hot-injection solvent thermal approach using phosphine-free Te precursor. The morphology, size, and crystal structure have been investigated using transmission electron microscopy(TEM), high-resolution TEM(HRTEM),and powder x-ray diffraction(XRD). We study the formation process of tree-like FeTe_2 NCs according to trace the change of the sample morphology with the reaction time. It was found that the FeTe_2 nanoparticles show oriented aggregation and self-assembly behavior with the increase of reaction time, which is attributed to size-dependent magnetism properties of the samples. The magnetic interaction is thought to be the driving force of nanoparticle self-organization.     

Computational modeling of quantum-confined impact ionization in Si nanocrystals embedded in SiO2

Injected carriers from the contacts to delocalized bulk states of the oxide matrix via Fowler–Nordheim tunneling can give rise to quantum-confined impact ionization (QCII) of the nanocrystal (NC) valence electrons. This process is responsible for the creation of confined excitons in NCs, which is a key luminescence mechanism. For a realistic modeling of QCII in Si NCs, a number of tools are combined: ensemble Monte Carlo (EMC) charge transport, ab initio modeling for oxide matrix, pseudopotential NC electronic states together with the closed-form analytical expression for the Coulomb matrix element of the QCII. To characterize the transport properties of the embedding amorphous SiO₂, ab initio band structure and density of states of the α-quartz phase of SiO₂ are employed. The confined states of the Si NC are obtained by solving the atomistic pseudopotential Hamiltonian. With these ingredients, realistic modeling of the QCII process involving a SiO₂ bulk state hot carrier and the NC valence electrons is provided.     

Nanosecond dynamics of the near-infrared photoluminescence of Er-doped SiO2 sensitized with Si nanocrystals

We report on an observation of a fast 1.5 microm photoluminescence band from Er3+ ions embedded in an SiO2 matrix doped with Si nanocrystals, which appears and decays within the first microsecond after the laser excitation pulse. We argue that the fast excitation and quenching are facilitated by Auger processes related to transitions of confined electrons or holes between the space-quantized levels of Si nanocrystals dispersed in SiO2. We show that a great part--about 50%--of all Er dopants is involved in these fast processes and contributes to the submicrosecond emission.     

一维电介质-金属光子晶体的光学特性研究

利用传输矩阵方法,研究了一维电介质-金属光子晶体的光学特性,该光子晶体通过在Si/SiO₂组成的电介质型光子晶体中插入一定厚度Al层形成。计算结果表明,金属层的引入可以有效提高反射效率,[Si(46 nm)/SiO₂(60 nm)/Al(10 nm)/SiO₂(60 nm)]5结构的单位周期传输衰减从[Si(46 nm)/SiO₂(120 nm)]5的7.2 dB增大到了20 dB;可以得到更宽频率范围的全方向反射带隙,例如[Si(46 nm)/SiO₂(60 nm)/Al(30 nm)/SiO₂(60 nm)]5结构即可提供550 nm带宽的全方向反射;同时讨论了金属吸收、金属层厚度及插入位置对其光学特性的影响。这种电介质-金属光子晶体有望作为性能优异的光学反射镜得到应用。     

色散SiO2/TiO2薄膜组成的Fibonacci序列一维光子晶体在可见光波段的传输特性

用特征矩阵法研究了由正常色散SiO₂/TiO₂薄膜组成的Fibonacci序列一维光子晶体在可见光波段的传输特性,并与无色散时的传输特性做了对比。结果表明,随序列项数的增加,相应的前一序列的透射谱中透射率较低的凹带逐渐变成禁带,禁带数增加;初始介质是低折射率的SiO₂薄膜时比高折射率的TiO₂薄膜时各序列的透射谱中的禁带数多,各禁带的宽度和中心波长基本相同;在总厚度一定的条件下,随SiO₂薄膜的厚度增大（TiO₂薄膜的厚度减小）,禁带的宽度减小,禁带的中心波长基本不变;随入射角增大,禁带的中心波长向短波方向移动,禁带宽度变小。在其它相同条件下,无色散时的最宽禁带和最宽禁带的中心波长比有色散时的最宽禁带和最宽禁带的中心波长都有增加。     

Modulation effect of microstructures in silicon-rich oxide matrix on photoluminescence from silicon nanoclusters prepared by different fabrication techniques

The modulation effect of microstructures on photoluminescence (PL) properties of silicon nanoclusters (Si NCs) in silicon-rich oxide (SRO) matrix prepared by electron-beam evaporation (EBE) and magnetron sputtering (MS) is investigated. A loose and porous microstructure is obtained from the SRO film prepared by EBE, while compact microstructure is acquired from that prepared by MS. The Si NCs with high density and good quality are formed in the SRO film prepared by EBE, and preferable PL performance of Si NCs is achieved in the EBE film with loose and porous microstructure. In contrast, the density and quality of Si NCs in the compact SRO film are suppressed and the PL properties are deteriorated due to the volumetric mismatching during the precipitation procedure of Si NCs. Optimization of the microstructures in SRO films should be made to reduce the volumetric mismatching and improve the PL properties of Si NCs.     

ZnO/SiO2 复合薄膜的光学性能

采用溶胶-凝胶法在玻璃衬底上制备ZnO/SiO₂复合薄膜,分别用XRD、TEM、SEM对样品的结构和形貌进行表征,并研究了不同ZnO含量对复合薄膜透过率及荧光特性的影响。结果表明,样品经500 ℃退火处理生成了SiO₂和ZnO,其晶粒尺寸为18.7 nm,薄膜具有双层结构。复合薄膜的透过率随着其中ZnO含量的增加而降低,禁带宽度减小,光学吸收边红移。样品在355 nm波长激发下产生了384 nm的紫外发射峰和440 nm的蓝光发射带,并随ZnO含量的增加而增强,它们分别来自ZnO的电子-空穴复合发光和缺陷发光,及ZnO/SiO₂复合薄膜双层结构的缺陷发光。     

Relative enhancement of photoluminescence intensity of passivated silicon nanocrystals in silicon dioxide matrix

Photoluminescence (PL) intensity of passivated silicon nanocrystals (Si NCs) embeded in an SiO₂ matrix is compared with that of unpassivated ones. We investigate the relative enhancement of PL intensity (I_R) as a function of annealing temperature and implanted Si ion dose. The I_R increases simultaneously with the annealing temperature. This demonstrates an increase in the number of dangling bonds (DBs) with the degree of Si crystallization via varying the annealing temperature. The increase in I_R with implanted Si ion dose is also observed. We believe that the near-field interaction between DBs and neighboring Si NCs is an additional factor that reduces the PL efficiency of unpassivated Si NCs.     

Interface effect on structural and electronic properties of graphdiyne adsorbed on SiO_2 and h-BN substrates:A first-principles study

We use the first-principles calculation method to study the interface effect on the structure and electronic properties of graphdiyne adsorbed on the conventional substrates of rough SiO2 and flat h-BN. For the SiO2 substrate, we consider all possible surface terminations, including Si termination with dangling bond, Si terminations with full and partial hydrogenation, and oxygen terminations with dimerization and hydrogenation. We find that graphdiyne can maintain a flat geometry when absorbed on both h-BN and SiO2 substrates except for the Si termination with partial hydrogenation(Si-H) SiO2 substrate. A lack of surface corrugation in graphdiyne on the substrates, which may help maintain its electronic band character, is due to the weak Van der Waals interaction between graphdiyne and the substrate. Si-H SiO2 should be avoided in applications since a covalent type bonding between graphdiyne and SiO2 will totally vary the band structure of graphdiyne.Interestingly, the oxygen termination with dimerization SiO2 substrate has spontaneous p-type doping on graphdiyne via interlayer charge transfer even in the absence of extrinsic impurities in the substrate. Our result may provide a stimulus for future experiments to unveil its potential in electronic device applications.     

Structural and photoluminescence properties of silicon nanocrystals embedded in SiC matrix prepared by magnetron sputtering

Si nanocrystals (NCs) embedded in an SiC matrix were prepared by the deposition of Si-rich Si_1?xC_x/SiC nanomultilayer films using magnetron sputtering, subsequently followed by thermal annealing in the range of 800～1200 °C. As the annealing temperature increases to 1000 °C, Si NCs begin to form and SiC NCs also start to emerge at the annealing temperature of 1200 °C. With the increase of annealing temperature, two photoluminescence (PL) peaks have an obvious redshift. The intensity of the low-energy PL peak around 669～742 nm gradually lowers, however the intensity of high-energy PL peak around 601～632 nm enhances. The low-energy PL peak might attribute to dangling bonds in amorphous Si (a-Si) sublayers, and the redshift of this peak might be related to the passivation of Si dangling bonds. Whereas the origin of the high-energy PL peak may be the emergence of Si NCs, the redshift of this peak correlates with the change in the size of Si NCs.     

Si quantum dot structures and their applications

This paper presents briefly the history of emission study in Si quantum dots (QDs) in the last two decades. Stable light emission of Si QDs and NCs was observed in the spectral ranges: blue, green, orange, red and infrared. These PL bands were attributed to the exciton recombination in Si QDs, to the carrier recombination through defects inside of Si NCs or via oxide related defects at the Si/SiOx interface. The analysis of recombination transitions and the different ways of the emission stimulation in Si QD structures, related to the element variation for the passivation of surface dangling bonds, as well as the plasmon induced emission and rare earth impurity activation, have been presented.The different applications of Si QD structures in quantum electronics, such as: Si QD light emitting diodes, Si QD single union and tandem solar cells, Si QD memory structures, Si QD based one electron devices and double QD structures for spintronics, have been discussed as well. Note the significant worldwide interest directed toward the silicon-based light emission for integrated optoelectronics is related to the complementary metal-oxide semiconductor compatibility and the possibility to be monolithically integrated with very large scale integrated (VLSI) circuits. The different features of poly-, micro- and nanocrystalline silicon for solar cells, that is a mixture of both amorphous and crystalline phases, such as the silicon NCs or QDs embedded in a α-Si:H matrix, as well as the thin film 2-cell or 3-cell tandem solar cells based on Si QD structures have been discussed as well. Silicon NC based structures for non-volatile memory purposes, the recent studies of Si QD base single electron devices and the single electron occupation of QDs as an important component to the measurement and manipulation of spins in quantum information processing have been analyzed as well.     

Gibbs free energy and equilibrium states in the Si/Si oxide systems

In this paper, the equilibrium states in the Si/Si oxide systems formed as a result of the phase separation of nonstoichiometric silicon oxide films are studied. The expressions for the Gibbs free energy of Si oxide and Si/Si oxide systems are derived thermodynamically. The transformations of the Gibbs free energy in the amorphous Si/Si oxide and the crystalline Si/Si oxide systems with the change in the amount of separated silicon and the composition of the silicon oxide phase are analyzed. By minimizing the Gibbs free energy of these systems, the equilibrium stoichiometry indices of silicon oxide are calculated as functions of its initial stoichiometry and the temperature. The solubility limits of Si in SiO(2) in equilibrium with amorphous and crystalline Si are determined. The obtained results form the basis for the development of a complete thermodynamic theory of phase separation in nonstoichiometric silicon oxide films with the formation of Si nanoinclusions in the silicon oxide matrix.     

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.     

SiO2纳米线中拉曼光谱的理论研究

运用密度泛函理论,在6-31G(d)基组水平上,对二元环组成的SiO2单链、双链纳米线进行几何优化,并对其拉曼振动频率进行计算。结果发现,在两种链状结构的拉曼光谱中,拉曼频移和强度随尺寸的增加单调变化,存在纳米体系中的尺寸效应与各向异性现象。双链两端Si=O的伸缩振动尺寸效应的依赖性大于单链。     

Synthesis and characterization of polypyrrole/Sn-doped TiO2 nanocomposites (NCs) as a protective pigment

We have chemically polymerized pyrrole in the presence of Sn-doped TiO₂ nanoparticles (NPs) and TiO₂ (NPs) which act as a protective pigment. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) results show a core-shell structure of pigments in which TiO₂ and Sn-doped TiO₂ NPs have a nucleus effect and caused a homogenous PPy core-shell type morphology leading to coverage of the TiO₂ and Sn-doped TiO₂ NPs by PPy deposit. The XRD results indicate that the crystalline size of polypyrrole/TiO₂ NCs and polypyrrole/Sn-doped TiO₂ NCs were approximately 93.46 ± 0.06 and 23.36 ± 0.06 nm respectively. The electrochemical impedance spectroscopy (EIS) results show that the performance of polypyrrole/Sn-doped TiO₂ NCs is better than polypyrrole/TiO₂ NCs. The results indicate that increasing the area of synthesized polypyrrole in the presence of Sn-doped TiO₂ NPs can increase its ability to interact with the ions liberated during the corrosion reaction of steel in the presence of NaCl. The UV-vis results show that the band gap of TiO₂ NPs increases with doped of Sn in lattice of TiO₂. The increase of the band gap of TiO₂ with doping of Sn can decrease the charge transfer through the coating.