Re-charging the luminescence states in CdSe/ZnS quantum dots at the conjugation to Osteopontin antibodies

The paper presents the original study of photoluminescence (PL) and Raman scattering spectra of core–shell CdSe/ZnS quantum dots (QDs) covered by the amine-derivatized polyethylene glycol (PEG) with luminescence interface states. First commercially available CdSe/ZnS QDs with emission at 640 nm (1.94 eV) covered by PEG polymer have been studied in nonconjugated states. PL spectra of nonconjugated QDs are characterized by a superposition of PL bands related to exciton emission in a CdSe core and to the hot electron–hole recombination via high energy luminescence states. The study of high energy PL bands in QDs at different temperatures has shown that these PL bands are related to luminescence interface states at the CdSe/ZnS or ZnS/polymer interface. Then CdSe/ZnS QDs have been conjugated with biomolecules—the Osteopontin antibodies. It is revealed that the PL spectrum of bioconjugated QDs changed essentially with decreasing hot electron–hole recombination flow via luminescence interface states. It is shown that the QD bioconjugation process to Osteopontin antibodies is complex and includes the covalent and electrostatic interactions between them. The variation of PL spectra due to the bioconjugation is explained on the basis of electrostatic interaction between the QDs and biomolecule dipoles that stimulates re-charging QD interface states. The study of Raman scattering of bioconjugated CdSe/ZnS QDs has confirmed that the antibody molecules have the electric dipoles. It is shown that CdSe/ZnS QDs with luminescence interface states are promising for the study of bioconjugation effects with specific antibodies and can be a powerful technique in biology and medicine.     

[MnHg(SCN)4(H2O)2]·2C4H9NO(MMTWD)晶体的光谱分析

根据商群对称性分析法对MMTWD晶体的振动模作了理论计算.计算结果显示,通过实验可观察到的拉曼散射峰和红外反射带应分别不超过297和148个.运用实验的手段,分别测定晶体的拉曼光谱和红外光谱,给出了MMTWD晶体在50～3 000 cm-1范围内的拉曼光谱图和400～4 000 cm-1范围里的红外光谱图,并对光谱中的谱线作了指认.给出了MMTWD晶体的分子结构示意图,最终确定MMTWD晶体结构为三维网状结构,说明在众多新型光功能材料当中MMTWD晶体是一种更适合生长成较大尺寸且稳定性较好的非线性光学晶体,在光电子领域中具有良好的应用前景.     

Resonant Raman scattering from CdTe/ZnTe self-assembled quantum dot structures

We report resonant Raman scattering results of CdTe/ZnTe self-assembled quantum dot (QD) structures. Photoluminescence spectra reveal that the band gap energies of the CdTe QDs decrease with the increase of CdTe thickness from 2.0 to 3.5 monolayers, which indicates that the size of the QDs increases. When the CdTe/ZnTe QD structures are excited by non-resonant excitation, a longitudinal optical (LO) phonon response from the ZnTe barrier material is observed at 206 cm⁻¹. In contrast, when the CdTe/ZnTe QD structures are resonantly excited near the band gap energy of the QDs, additional phonon modes emerge at 167 and 200 cm⁻¹, while the ZnTe LO phonon response completely disappears. The 167 cm⁻¹ mode corresponds to the LO phonon of the CdTe QDs. A spatially resolved Raman scattering from the cleaved edge of the QD sample reveals that the 200 cm⁻¹ mode is strongly localized at the interface between the CdTe QDs and ZnTe cap layer. This phonon mode is attributed to the interface optical (IO) phonon. The analytically calculated value of the IO phonon energy using a dielectric continuum approach, assuming a spherical dot boundary, agrees well with the experimental value.     

Design issues of 1.55 µm emitting GaInNAs quantum dots

We present a theoretical study of the optical properties of GaInNAs quantum dot (QD) structures, emitting at 1.55 µm wavelength. The theoretical model is based on a 10 × 10 k · p band-anti-crossing Hamiltonian, incorporating valence, conduction and nitrogen-induced bands. We have investigated the influence of the nitrogen to the conduction band mixing, and piezoelectric field on the ground state optical matrix element. For QDs grown on GaAs substrate with a reduced amount of indium and an increased amount of nitrogen in the QD the e _x polarized optical matrix element becomes on the average larger and less sensitive to the variation of both the QD shape and size than is the case of an InNAs QD. For the QD grown on InP substrate the dominant optical dipole matrix element is of the e _z light polarization. Our results identify the specific In and N content in the QDs required for optimal long-wavelength emission on both substrates.     

Phonons in Ge/Si quantum dot structures: influence of growth temperature

In this paper we present the results of a Raman study of Ge/Si quantum dot (QD) superlattices grown with different thicknesses of a Si interlayer and at different substrate temperatures. The built-in strain and atomic intermixing in the QDs are deduced from an analysis of optical phonon frequencies of the QDs obtained from Raman spectra of the structures.     

Influence of the shallow impurity environment on the luminescence of single-quantum dots

The evolution of low-temperature photoluminescence (PL) spectra of single GaAs/AlGaAs quantum dots (QD) is studied as a function of laser excitation power. At very low powers, where multi-exciton occupation of the QD can be excluded, an unexpected and pronounced spectral evolution is observed. In this weak excitation regime, a significant difference in the fine structure of single-QD spectra is observed not only among different, structurally identical QDs of the same sample, but also among spectra taken from the same single QD excited above and below the AlGaAs barrier. A time-resolved, two-color pump and probe PL experiment on a single QD indicates relaxation times between the different spectral shapes in the ms-range. A model, taking into account the influence of the shallow impurities in the environment of each QD, explains the experimental results.     

Synthesis and characterization of binary and ternary III–V quantum dots

Quantum dots of InP, GaP, GaInP₂, and GaAs with diameters ranging from 20–80 Å can be synthesized as well-crystallized nanoparticles with bulk zinc blende structure. The synthesis is achieved by heating appropriate organometallic precursors with stabilizers in high boiling solvents for several days to produce QDs, which can then be dissolved in nonpolar organic solvents to form transparent colloidal QD dispersions. The high sample quality of the InP and Gap QDs results in excitonic features in the absorption spectra; excitonic features could not be observed for GaAs or GaInP₂ QDs. The GaP and GaInP₂ QD colloids exhibit very intense (quantum yields of 15–25%) visible photoluminescence at room temperature. The photoluminescence for InP QDs preparations show two emission bands: one band is in the visible at the band edge of the QD, and a second band appears above 800 nm. The near-IR PL is attributed to deep traps, presumably phosphorus vacancies on the QD surface. This band can be removed after controlled addition of etchant; subsequently, very intense band-edge emission (quantum yield 30%), which is tunable with particle size, is obtained. The QDs were characterized by TEM, SAXS, AFM, powder X-ray diffraction, steady-state optical absorption and photoluminescence spectroscopy, ps to ns transient photoluminescence spectroscopy, and fs to ps pump-probe absorption (i.e., hole-burning) spectroscopy.     

Temperature dependence of optical properties of InAs quantum dots grown on GaAs(113)A and (115)A substrates

We have investigated the temperature dependence of photoluminescence (PL) peak position of InAs self-assembled quantum dots (QDs) grown on GaAs(11N)A (N = 3, 5) substrates. The interband transition energy is calculated by the resolution of the 3D Schrödinger equation for a parallelepipedic InAs QD, with a width of about 8 nm and a height around 3 nm. Experimentally, it was found that the PL spectra quenches at about 160 K. In addition, the full width at half maximum (FWHM) has an abnormal evolution with varying temperature. The latter effect maybe due to the carrier repopulation between QDs. The disorientation of the GaAs substrate and the low width of terraces which was presented in the high index surfaces have an important contribution in the PL spectra. Despite the non-realist chosen shape of QD and the simplest adopted model, theoretical and experimental results revealed a clear agreement.     

Formation of QD-porphyrin molecule complexes in aqueous solutions

The spectral and luminescent manifestations of the electrostatic formation of quantum dot (QD)-porphyrin complexes are studied. The QD luminescence in these complexes is found to be efficiently quenched. The luminescence of molecules complexed with QDs is also partially quenched. The luminescence excitation spectra of porphyrin molecules associated with QDs exhibit a contribution of the QD absorption spectrum, which indicates that energy is transferred from QDs to porphyrin. The efficiency of the nonradiative resonant energy transfer from a QD to a porphyrin molecule is estimated. The observed experimental data agree well with a proposed model of formation of complexes of the QD-organic molecule type.     

Contactless electroreflectance spectroscopy of optical transitions in low dimensional semiconductor structures

The authors present the application of contactless electroreflectance (CER) spectroscopy to study optical transitions in low dimensional semiconductor structures including quantum wells (QWs), step-like QWs, quantum dots (QDs), quantum dashes (QDashes), QDs and QDashes embedded in a QW, and QDashes coupled with a QW. For QWs optical transitions between the ground and excited states as well as optical transitions in QW barriers and step-like barriers have been clearly observed in CER spectra. Energies of these transitions have been compared with theoretical calculations and in this way the band structure has been determined for the investigated QWs. For QD and QDash structures optical transitions in QDs and QDashes as well as optical transitions in the wetting layer have been identified. For QDs and QDashes surrounded by a QW, in addition to energies of QD and QDash transitions, energies of optical transitions in the surrounded QW have been measured and the band structure has been determined for the surrounded QW. Finally some differences, which can be observed in CER and photo-reflectance spectra, have been presented and discussed for selected QW and QD structures.     

异硫氰基-孔雀石绿的拉曼光谱计算及分析

异硫氰基-孔雀石绿(malachite green isothiocyanate,MGITC)是应用于细胞探测,生物组织成分分析和细胞成像等方面的拉曼探针分子.本文首先给出了MGITC分子的结构图,并用密度泛函(DFT)算法对其进行了空间结构优化;然后分别用Hartree-Foek(HF)和MP2两种算法基于STO-3G基组计算了它的拉曼光谱与红外光谱,给出光谱强度图;并对比了两种算法的拉曼光谱图和其实验光谱图,结果显示了很好的一致性;本文还给了MGITC分子中的各个原子键长,键角等空间结构参数;并对MGITC分子在550～4 200cm-1区间的振动谱做了指认.这些工作将促进MGITC作为探针分子在生物学领域的应用.     

六方晶型MgTiO3温致微结构变化及其原位拉曼光谱研究

采用固相烧结法制备了六方晶型结构的MgTiO₃粉体. 经高温原位X射线衍射分析(293-1473 K)进行了表征与确认,获得了晶胞参数及其随温度的变化,测量了高温原位拉曼光谱(273-1623 K),并运用第一性原理理论计算方法对应核实了拉曼谱峰的归属. 结果表明,随着温度升高,MgTiO₃晶面间距和晶格常数增大,从而反映对于拉曼光谱较为敏感的键长和键角的变化;温致拉曼位移可以反映Ti-O,Mg-O等键长以及Ti-O-Ti,Ti-O-Mg与Mg-O-Mg等键角随温度的细微变化,相关关系则独立于温度,有效提升了原位拉曼光谱微探针诊断技术的分析能力;拉曼谱峰随温度升高而展宽,表明原子瞬间运动振幅加剧,弥散性增加,稳定性有所下降,但仍维持六方晶型. 关键词： 3')" href="#">MgTiO₃ 微结构 拉曼光谱 高温     

Nd∶Y_3Al_5O_(12)单晶及纳米粉体的Raman光谱分析

测量了YAG（Y3Al5O12）/Nd∶YAG单晶、Nd∶YAG前驱物及其在不同温度下煅烧获得粉体的拉曼光谱,对谱峰的振动模式进行了指认,对结果进行了分析。Nd∶YAG前驱物在煅烧时,有一个由非晶态向晶态的转化过程;700℃下烧结前驱物获得非晶态产物的结构中含有AlO4四面体结构;随着煅烧温度的升高,拉曼光谱的变化主要表现在两个方面：一是谱峰半高宽（FWHM）减小,谱峰强度增大;二是一些拉曼光谱谱峰发生了频移,这是纳米多晶粉体的界面组元的有序度提高所致。另外,800℃下煅烧获得的Nd∶YAG纳米粉体的晶格振动模式与Nd∶YAG晶体的晶格振动模式存在差异,这是纳米多晶粉体的界面组元的贡献所致。     

农药草甘膦的拉曼光谱计算及分析

草甘膦(glyphosate)是一种高效、低毒、非选择性的芽后除草剂。本文首先给出了草甘膦分子的空间结构图,并用近似方法(Hartree-Fock,HF)对其进行了空间结构优化;然后分别用HF和密度泛函理论(Density Functional Theory,DFT)两种方法基于基组6-31G计算了该分子的振动特性,给出了拉曼光谱和红外光谱强度图,并对比了两种算法的拉曼光谱图和其实验光谱图,结果显示很好的一致性;本文还给出了草甘膦分子的各个键长、键角等空间结构参数,并对草甘膦分子在800cm-1～1600cm-1区间的振动谱做了指认。这些工作将促进针对草甘膦分子的农药残留检测领域的研究。     

Raman study of InAs/GaAs quantum dot solar cells

We report polarized and resonant Raman study of InAs/GaAs quantum dot solar cell (QDSC) structures. Raman spectra obtained from the top surfaces of the samples suggested that the formation of InAs QDs induced tensile strain in the overgrown GaAs layers. Furthermore, a longitudinal optical phonon-plasmon (LPP) coupled modes were observed in the p-type GaAs layers. The tensile strain was increased with an increase in the QD size. The hole concentrations estimated by fitting the individual LPP coupled modes were in the range of 2.4–3.5 × 10¹⁸ cm^?3. Resonant Raman spectra obtained from the cleaved sides, where the QDs were located, showed a 225 cm^?1 mode in parallel polarization configurations. Based on accurate analysis, this mode was identified as the LA(X) phonon of GaAs.     

Influence of annealing temperature on the photoluminescence properties of ZnO quantum dots

The properties of ZnO quantum dots (QDs) synthesized by the sol-gel process are reported. The primary focus is on investigating the origin of the visible emission from ZnO QDs by the annealing process. The X-ray diffraction results show that ZnO QDs have hexagonal wurtzite structure and the QD diameter estimated from Debye-Scherrer formula is 8.9 nm, which has a good agreement with the results from transmission electron microscopy images and the theoretical calculation based on the Potential Morphing Method. The room-temperature photoluminescence spectra reveal that the ultraviolet excitation band has a red shift. Meanwhile, the main band of the visible emission shifts to the green luminescence band from the yellow luminescence one with the increase of the annealing temperature. A lot of oxygen atoms enter into Zn vacancies and form oxygen antisites with increasing temperature. That is probably the reason for the change of the visible emission band.     

基于密度泛函理论的三聚氰胺结构及振动光谱研究

利用密度泛函(DFT)算法,对三聚氰胺分子的空间结构进行了优化;然后分别用MP2/6-31G和DFT/DGTIVP两种算法计算了它的拉曼光谱与红外光谱,给出光谱强度图;对比了两种算法的拉曼光谱图和其实验光谱图,结果显示了很好的一致性;给出了三聚氰胺分子中的各原子间键长,键角等空间结构参数;并对三聚氰胺分子在550～3 800cm-1区间的振动谱做了指认。上述工作将有助于食品中三聚氰胺含量测量技术的研究。     

Folded acoustic phonons in Si/Ge superlattices with Ge quantum dots

The spectra of Raman scattering by folded acoustic phonons in Si/Ge superlattices with pseudomorphic layers of Ge quantum dots (QDs) grown by low-temperature (T = 250°C) molecular beam epitaxy are studied. New features of the folded phonon lines related to the resonant enhancement and unusual intensity ratio of the doublet lines that cannot be explained by the existing theory have been observed. The observed modes are shown to be related to the vibrations localized to the QDs and induced by the folded phonons of the Si spacer layers. The calculations performed in the model of a one-dimensional chain of atoms have allowed the nature of the localization of acoustic phonons attributable to a modification of the phonon spectrum of a thin QD layer to be explained. The observed intensity ratio of the folded phonon doublet lines is caused by asymmetry of the relief of the QD layers.     

Dependence on temperature of homogeneous broadening of InGaAs/InAs/GaAs quantum dot fundamental transitions

We report systematic temperature-dependent measurements of photoluminescence spectra in self-assembled InGaAs/InAs/GaAs quantum dots (QDs). We have studied the rise in temperature of the ground-state homogeneous linewidth.A theoretical model is presented and accounts for the phonon-assisted broadening of this transition in individual QD. We have estimated the homogeneous linewidth of an individual QD from PL spectra of self-organized InAs/GaAs QDs by isolating the PL of each individual QD and fitting the narrow line associated with self-organized QDs through a Lorentzian convoluted by a Gaussian. We have observed a strong exciton–LO–phonon coupling (γ_LO) which becomes the dominating contribution to the linewidth above the temperature of 45 K. We have also derived the activation energy (ΔE) of the exciton–LO–phonon coupling, zero temperature linewidth (Γ₀) and the exciton-LA-phonon coupling parameter (γ_Ac). We report that our values are close to the values found in the literature for single InGaAs QD and InAs QD.