高分子在化学和物理受限环境中结晶行为的研究

高分子的受限结晶是高分子科学中的一个重要研究方向。本论文以受限高分子为研究对象，系统地研究了高分子在化学交联点间的受限（一维）和超薄膜中的物理空间受限（二维）条件下的结晶熔融行为。 以聚乙二醇的交联网络为研究对象，研究了不同分子量的聚乙二醇在化学交联网络中的结晶熔融行为。结果表明，在聚乙二醇链结构中交联点的存在使聚合物的熔点和结晶度降低。当交联点间的分子量减小到1000时，高分子不能结晶。结果表明在交联网络受限下的结晶所需交联点间的最低分子量应介于1000-1500，低于此分子量高分子不能结晶。 以聚卜己内酷为研究对象，系统地研究了聚ε-已内酯在物理受限空间，即在薄膜、超薄膜中的结晶与熔融行为。结果表明，聚卜己内醋的结晶形态与薄膜的厚度有关。当薄膜的厚度大2Rg（Rg为均方回转半径）时，高分子结晶形态呈现球晶；当厚度介于Rg-2Rg之间时，高分子结晶生成枝蔓或树枝状结构，当厚度小于Rg时，其结晶形态为分形结构。熔融过程并不能完全破坏其形态。这些都可归因于表面效应、基底效应和薄膜受限效应之间的复杂的相互作用。此外，本文还讨论了结晶温度、基底、分子量等对高分子结晶形态的影响。最后对树枝晶的生长进行了原位跟踪。结果表明，高分子在薄膜中的结晶是一个扩散控制的动力学过程，同时也是一种远离平衡态的形态生成过程。

Flying lemurs – The 'flying tree shrews'? Molecular cytogenetic evidence for a Scandentia-Dermoptera sister clade

Background: Flying lemurs or Colugos (order Dermoptera) represent an ancient mammalian lineage that contains only two extant species. Although molecular evidence strongly supports that the orders Dermoptera, Scandentia, Lagomorpha, Rodentia and Primates form a superordinal clade called Supraprimates (or Euarchontoglires), the phylogenetic placement of Dermoptera within Supraprimates remains ambiguous. Results: To search for cytogenetic signatures that could help to clarify the evolutionary affinities within this superordinal group, we have established a genome-wide comparative map between human and the Malayan flying lemur (Galeopterus variegatus) by reciprocal chromosome painting using both human and G. variegatus chromosome-specific probes. The 22 human autosomal paints and the X chromosome paint defined 44 homologous segments in the G. variegatus genome. A putative inversion on GVA 11 was revealed by the hybridization patterns of human chromosome probes 16 and 19. Fifteen associations of human chromosome segments (HSA) were detected in the G. variegatus genome: HSA1/3, 1/10, 2/21, 3/ 21, 4/8, 4/18, 7/15, 7/16, 7/19, 10/16, 12/22 (twice), 14/15, 16/19 (twice). Reverse painting of G. variegatus chromosome-specific paints onto human chromosomes confirmed the above results, and defined the origin of the homologous human chromosomal segments in these associations. In total, G. variegatus paints revealed 49 homologous chromosomal segments in the HSA genome. Conclusion: Comparative analysis of our map with published maps from representative species of other placental orders, including Scandentia, Primates, Lagomorpha and Rodentia, suggests a signature rearrangement (HSA2q/21 association) that links Scandentia and Dermoptera to one sister clade. Our results thus provide new evidence for the hypothesis that Scandentia and Dermoptera have a closer phylogenetic relationship to each other than either of them has to Primates.

InGaAsP-InP Square Microlasers With a Vertex Output Waveguide

InGaAsP-InP square microlasers with a vertex output waveguide are fabricated by planar processes, and the etched sidewalls of the lasers are confined by insulating layer SiO2 and p-electrode TiAu metals. For a square microlaser with a side length of 30 mu m and a 2-mu m-wide output waveguide, a continuous-wave threshold current is 26 mA at room temperature and output power is 0.72 mW at 86 mA. The mode interval of 21 and 7.4 nm is observed for the microlasers with the side length of 10 and 30 mu m, respectively. Finite-difference time-domain (FDTD) simulations indicate that the lasing modes have incident angles of about 45 degrees at the boundaries of the resonator. In addition, square resonators surrounded by air, SiO2-Ti-Au, and SiO2-Au are compared by FDTD simulations.

THEORETICAL CALCULATION FOR SHUBNIKOV-DEHAAS OSCILLATIONS IN DEEP MESA STRUCTURES

We have used the rectangular confinement potential to describe Shubnikov-deHaas oscillations produced by one-dimensional electrons confined in deep mesa structures. The edge distortion of the confinement potential caused by electrostatic image forces is taken into account. The model contains no fitting parameters and relates well with experimental data. The comparison with earlier reported parabolic model is presented,

DETERMINATION OF THE CONDUCTION-BAND OFFSET OF A SINGLE ALGAAS BARRIER LAYER USING DEEP-LEVEL TRANSIENT SPECTROSCOPY

The tunneling from an AlGaAs confined thin layer to a GaAs layer in the GaAs/Al0.33Ga0.67As/GaAs structure during the trapped electron emission from deep level in the AlGaAs to its conduction band has been observed by deep level transient spectroscopy. With the aid of the tunneling effect, the conduction-band offset DELTAE(c) was determined to be 0.260 eV, corresponding to 63% of DELTAE(g). A calculation was also carried out based on this tunneling model by using the experimental value of DELTAE(c) = E2 - E1 = 0. 260 eV, and good agreement between the experimental and calculated curves is obtained.

NEAR-RESONANT RAMAN-SCATTERING FROM GAAS/ALAS SUPERLATTICES

This article presents the results of near-resonant Raman scattering measurements on GaAs/AlAs superlattices at room temperature. A strong enhancement of GaAs LO phonon-even modes resulted owing to a dipole-allowed Frohlich interaction in superlattices. Similar to the previous results, the LO phonon-even modes in a polarized configuration are observed. In contrast to previous work, however, what we observed in depolarized configurations is the LO phonon-odd modes instead of even modes. It is confirmed that the selection rules for near-resonant Raman scattering from LO phonons in this kind of superlattices are the same as those for off-resonant scattering. From the second-order Raman scattering, it is confirmed that polarized second-order Raman scattering spectra consist of overtones and combinations of two even modes, and depolarized second-order Raman scattering spectra consist of combinations of an even mode and an odd mode. Our experimental results coincide with the predictions using the recently developed Huang-Zhu model. A brief discussion on interface modes and their combination with confined modes is also presented.

CONTINUUM-THEORIES OF OPTICAL PHONONS AND POLARITONS IN SUPERLATTICES - A BRIEF CRITIQUE - COMMENT

The so-called hydrodynamic (HD) model on optical-phonon modes in superlattices is critically examined. Contrary to the HD model, a comparison between TM polaritons and the Fuchs-Kliewer-type interface modes has shown that the Fuchs-Kliewer interface modes do possess Frohlich potentials.

CHARACTERISTICS OF THE MAGNETIC DEPOPULATION OF SUBBANDS IN VERY NARROW SYSTEMS

We present a model for electrons confined in narrow conducting channels by a parabolic well under moderate to high magnetic fields which takes into account a cutoff in the filling of the subbands. Such a cutoff gives rise to energy-separated subbands and a two-dimensional (2D) like subband depopulation, resulting in a relation between sublevel index n and inverse magnetic field B-1 such that in the high-field regime it changes over to the well-known 2D form as expected, and in the moderate field regime it shows pronounced deviation from linearity. This agrees well with the experimental results. The linear region of the n-B-1 experimental plot is believed to arise from the two dimensionality of the system. Calculations show that no resolvable 1D sublevel exists in the 0.5-mu-m-wide wire at very small magnetic fields (including zero field), which agrees qualitatively with the experimental results found in other wires that the Hall resistance, R(H), approaches its classical value B/n(e)e in this region and R(H) = 0 at B = 0, where n(e) is the electron concentration. In this model the linear and nonlinear regions in the experimental n-B-1 plot are used to extract the characteristic frequency omega-0, and the effective 2D electron concentration N(e)2D, respectively.

NEAR-RESONANCE RAMAN-SCATTERING OF LONGITUDINAL OPTICAL PHONON MODES AND INTERFACE MODES IN GAAS/ALAS SUPERLATTICES

The near-resonance Raman scattering of GaAs/AlAs superlattices is investigated at room temperature. Owing to the resonance enhancement of Frohlich interaction, the scattering intensity of even LO confined modes with A1 symmetry becomes much stronger than that of odd modes with B2 symmetry. The even modes were observed in the polarized spectra, while the odd modes appear in the depolarized spectra as in the off-resonance case. The second-order Raman spectra show that the polarized spectra are composed of the overtone and combinations of even modes, while the depolarized spectra are composed of the combinations of one odd mode and one even mode. The results agree well with the selection rules predicted by the microscopic theory of Raman scattering in superlattices, developed recently by Huang and co-workers. In addition, the interface modes and the combinations of interface modes and confined modes are also observed in the two configurations.

OPTICAL-PHONON MODES AND FROHLICH POTENTIAL IN ONE-DIMENSIONAL QUANTUM-WELL WIRES

By extending our microscopic model on optical-phonon modes in quantum wells to one-dimensional (1D) quantum-well wires (QWW), the optical displacements and associated electrostatic potentials of optical-phonon modes in 1D QWW are calculated. The modes can be clearly divided into confined LO bulklike, TO bulklike modes, and extended interfacelike modes provided the bulk phonon dispersion is ignored. The character of each type of mode is illustrated with special attention to the interfacelike modes, which are hybrids of longitudinal- and transverse-optical waves from the corresponding bulk materials. Based on the numerical results, approximate analytical formulas for bulklike modes are presented. As in 2D wells, both the optical displacements and Frohlich potentials for the bulklike modes vanish at the interfaces. The finite dispersion of bulk phonons has a more pronounced effect on the 1D phonon modes because interfacelike modes show mixed characteristics of 2D interface and bulklike modes.

RAMAN-SCATTERING BY LO PHONONS IN (GAAS)N1/(ALAS)N2 ULTRATHIN-LAYER SUPERLATTICES

Raman spectra of (GaAs)n1/(AlAs)n2 ultrathin-layer superlattices were measured at room temperature and under off-resonance conditions. The experimental results show that there are two effects in ultrathin-layer superlattices: the confinement effect of LO phonons and the alloy effect. It is found that the relative intensity of the disorder-activated TO mode can give a measure of the alloy effect. The Raman spectra of one-monolayer superlattices measured in various scattering configurations are very similar to those of the Al0.5Ga0.5As alloy, and thus the alloy effect is prominent. However, in the case of monolayer number n greater-than-or-equal-to 4, the confined effect is prominent, while the alloy effect is only shown as an interface effect.

Collective excitations in the coupled quantum wires

The dielectric response of an electron system composed of an array of parallel quantum wires with weak coupling and strong coupling are studied, and the dispersions of the collective excitations and the single particle excitations (SPE) as functions of wave-vectors are given. It is found that for the nearly isolated quantum wires with several subbands occupation, there are a series of intra-subband collective excitations between corresponding intra-subband SPE spectra. There also exist inter-subband collective excitations when q(x) not equal 0 (q(x) is the wave-vector component in the modulation direction), whose energies are close by the corresponding inter-subband SPE spectra. The energy of the intra-subband mode decreases and that of inter-subband mode increases with q(x) increasing. The collective excitation dispersions show obvious anisotropy in the 1D quantum limit. The calculated results agree with the experiment well. The coupling between quantum wires affects markedly both the collective and single-particle excitations spectra. The system changes to a near-two-dimensional electron system gradually with increasing coupling.

Asymmetric stark shifts of exciton in InAs/GaAs pyramidal quantum dots

Within the framework of the single-band effective-mass envelope-function theory, the effect of electric field on the electronic structures of pyramidal quantum dot is investigated. Taking the Coulomb interaction between the heavy holes and electron into account, the quantum confined Stark shift of the exciton as functions of the strength and direction of applied electric field and the size of the quantum dot are obtained. An interesting asymmetry of Stark shifts around the zero field is found. (C) 1997 Elsevier Science Ltd.

Interfacial behaviour of quantum well electrode/electrolyte: effect of redox species on EER spectra of a single quantum well GaAs vertical bar AlxGa1-xAs electrode

The EER spectra of a single quantum well GaAs\AlxGa1-xAs electrode were studied as a function of applied reverse bias in ferrocene, p-methyl nitrobenzene and hydroquinone+benzoquinone non-aqueous solutions. EER spectra were compared for different redox species and showed that a pronounced quantum-confined Stark effect and a Franz-Keldysh oscillation for a single quantum well electrode were obtained in the p-methyl-nitrobenzene- and hydroquinone+benzoquinone-containing solutions. A surface interaction of the single quantum well electrode with ferrocene led to fewer changes in the electric field of the space charge layer for reverse bias; this was suggested to explain the weak quantum-confined Stark effect and Franz-Keldysh oscillation effect observed for the single quantum well electrode in the ferrocene-containing solution. (C) 1997 Elsevier Science S.A.