D−A型有机近红外材料的设计、合成及表征

近年来，随着近红外领域研究的深入，特别是光通讯工业的发展，迫切需要一大批具有良好发光性质的近红外材料。有机材料由于成本低、工艺简单和结构易调控等优点而备受关注。目前，对近红外有机发光材料的研究主要集中在两大类：一是稀土元素配合物；二是有机离子染料。但由于稀土元素的4f-4f跃迁是宇称禁阻的，其分子的激发需通过配体与中心离子的能量转移，发光效率低。同时有机离子染料由于静电相互作用，分子容易因聚集而导致发光萃灭，其器件结构主要采用主客体掺杂技术，存在着较强的主体材料发光和器件发光效率低等缺点。传统有机非离子型材料则不受上述因素的限制，可得到聚集态下高效的发光效率。本论文通过将电子给体与受体共轭连接，设计并合成了系列非离子型的窄带隙有机小分子，研究了它们在近红外电致发光等器件中的应用，主要工作内容和结果如下： (1)在分子内同时引入电子给体和受体，将它们共轭连接，设计并合成了系列D-π-A-π-D型的有机小分子，利用分子内电荷转移，实现近红外区域的吸收和发射。我们选择三苯胺和芴为电子给体，苯并双噻二唑及其衍生物为电子受体，苯、噻吩和吡咯为连接基团，得到的系列化合物的光谱及电化学性质能在很大的范围内进行调节。化合物的吸收光谱可从600nm至1400nm，发射光谱从900nm至1600nm范围内调节。化合物的带宽可从1.19eV减小到0.56eV。由于分子间的强相互作用，化合物在混合溶剂中可自组装成带状结构。同时该系列化合物在隔绝氧气的环境中有良好的光化学稳定性，可应用于电致发光或光伏器件中。 (2)多层器件结构是提高有机电致发光效率的有效方法，但前提是发光材料最好是可真空蒸镀。我们在前部分工作的基础上，合成了系列热稳定的可蒸镀型有机小分子。通过改变受体及给体结构可调节发光波长及效率。利用“掺杂剂/主体材料的思想”制备的电致发光器件，发光波长覆盖700nm到1500nm的范围，最长中心波长为1115nm。发光波长752nm时，器件最高外量子效率为1.12%。基于化合物IV-5制备的非掺杂器件，发光波长为1080nm，外量子效率为0.28%。该效率比基于有机离子染料的器件提高了近10倍。基于化合物IV-7的器件最大发射波长为1220nm，为迄今为止非掺杂有机电致发光器件中的最长发射波长。以上结果证明，该系列分子是良好的近红外电致发光材料。 (3)我们研究了含苯并双噻二唑分子与常见阴离子的相互作用关系，发现其只对CN-离子和F-离子有响应，而对其它阴离子如Cl , Br , I , AcO , H2PO4 , HSO4 , 和NO3 等则没有任何响应。并且通过将其中噻二唑环换成硝基，可实现对CN-离子和F-离子的区分。化合物V-2可高选择性的检测氰离子，其它离子的存在不会干扰检测信号，包括氟离子。检测信号为外观颜色的改变，可作为显色传感器。化合物V-3可定量检测CN-离子，检测极限为1μM。并且检测信号包括近红外发射的萃灭、可见发射的增强和吸收光谱的改变，多重检测信号可增加检测的可靠性。由于响应信号处于近红外区的生物波段，可应用于生物领域

有机近红外电致变色器件

光通讯近年来发展迅速，正在从元件向集成发展，迫切需要利于集成的元件。主要的一些光学元件如激光器、放大器等均采用无机材料，连接和集成存在困难。发展易于集成的有机光学元件是目前该领域研发的一个热点。电致变色是一个古老的题目，一般都在可见区，而光通讯波长主要是1300和1550nm，是近红外区。在近红外区的工作刚刚开始，．用于光衰减器的研究已有报道，但还没有达到实际要求，寻找新型的电致变色材料及其适合这些材料的新的器件构型是目前研究的重点。本文研究了三种新的有机近红外电致变色材料及其器件：PEDOT:PSS、Ru星状化合物和酞警噜。本文通过电化学、吸收光谱、X射线衍射、AFM等实验方法和手段表征了样品的本体性质、近红外电致变色，性质和器件性能。结果如下：本论文首先研究了PEDOT:PSS的近红外电致变色性质。实验结果首次表明通过掺杂如Liclo4的电解质可以提高近红外电致变色器件的性能。通过掺杂，褪色时间从30秒缩短到2.8秒，着色时间从9.2秒缩短到2.7秒，变色效率从105cm2／C提高到3llcm2／C。掺杂后薄膜离子导电率提高是器件性能改善的原因。另外还制备了基于不同厚度的PEDOT：PSS薄膜的器件，发现对于一定掺杂浓度有一个最佳的厚度，在这个厚度下器件有较大的调制能力和较小的透过损失。本论文第二部分研究Ru星状化合物。通过对基于Ru星状化合物溶液的动力学的研究，证明了调制能力与溶液浓度和外加电压的关系。之后研究开发了有新构型的近红外电致变色器件，以Ru（II，II）态化合物溶液代替其交联薄膜和电解质层来形成固液型器件，同时改善了氧化钨的制备方法。将器件对1550nm光的调制能力从文献报道的2dB提高到16dB。本论文还首次报道了酞警噜的近红外电致变色性质，发现它既可以作为阳极电致变色材料也可以作为阴极电致变色材料。酞普噜的溶液和薄膜均可用于制备电致变色器件，器件的响应速度分别为23秒和1秒。但因为中性态酞警噜对1300nm和1550nm的光吸收较小，器件的调制能力也较小（-0.3dB）。 论文的最后部分详细阐述了有机光电器件表征系统的搭建及测量方法，包括电调制光的电致变色器件测试系统、光转换为电的有机光电二极管或太阳能电池等光电器件测试系统和电转换为光的有机电致发光二极管的器件测试系统。本论文的结果证明采用新构型可以提高近红外电致变色器件的性能；通过掺杂可以缩短电致变色器件的响应时间和提高其变色效率；同时还首次报道了酞瞥噜的近红外电致变色性质。

Verification of EL2 electronic absorption effect on charge transfer in semi-insulating GaAs

The electronic absorption of EL2 centers has been clarified to be related to the electron acid hole photoionizations, and the transition from its ground state to metastable state, respectively. Under an illumination with a selected photon energy in the near infrared region, these three processes with different optical cross sections will show different kinetics against the illumination time. It has recently been shown that the photosensitivity (measured under 1.25 eV illumination) of the local vibrational mode absorption induced by some deep defect centers in SI-GaAs is a consequence of the electron and hole photoionizations of EL2. This paper directly measures the kinetics of the electronic transition associated with EL2 under 1.25 eV illumination, which implies the expected charge transfer among different charge states of the EL2 center. A calculation based on a simple rate equation model is in good agreement with the experimental results.

RELATION BETWEEN THE METASTABILITY OF EL2 AND THE PHOTOSENSITIVITY OF LOCAL VIBRATIONAL-MODES IN SEMIINSULATING GAAS

Recent infrared spectroscpic observations of local vibrational mode absorptions have revealed a number of photosensitive centers in semi-insulating GaAs. They include (OVAs) center which has three modes at 730 cm(-1) (A), 715 cm(-1) (B), and 714 cm(-1) (C), respectively, a suggested NH center related to a line at 983 cm(-1) (X(1)), and centers related to hydrogen, such as (H-O) or (H-N) bonds, corresponding to a group of peaks in the region of 2900-3500 cm(-1). The photosensitivity of various local vibration centers was observed to have similar time dependence under near-infrared illumination and was suggested to be due to their charge-state interconversion. Mainly described in this work is the effect of the 1.25-eV illumination. It is confirmed that this photoinduced kinetic process results from both electron capture and hole capture, which are closely related to the photoionization behavior and metastability of the EL2 center.

A New Method to Investigate InGaAsP Single-Photon Avalanche Diodes Using a Digital Sampling Oscilloscope

A near-infrared single-photon detection system is established by using pigtailed InGaAs/InP avalanche photodiodes. With a 50GHz digital sampling oscilloscope, the function and process of gated-mode (Geiger-mode) single-photon detection are intuitionally demonstrated for the first time. The performance of the detector as a gated-mode single-photon counter at wavelengths of 1310 and 1550nm is investigated. At the operation temperature of 203K,a quantum efficiency of 52% with a dark count probability per gate of 2. 4 * 10~(-3), and a gate pulse repetition rate of 50kHz are obtained at 1550nm. The corresponding parameters are 43% , 8. 5 * 10~(-3), and 200kHz at 238K.

Controlled synthesis and diameter-dependent optical properties of Cu nanowire arrays

Using electrochemical deposition, Cu nanowire arrays have been successfully fabricated by home-made polycarbonate ion-track templates. The diameters were well controlled by etching time of templates. The minimum diameter is 15 nm. The morphologies and structures were analyzed by scanning electron microscopy, transmission electron microscopy and X-ray diffraction. The wires prefer [1 1 0] growth direction due to H ions absorption. The optical properties of Cu nanowire arrays are studied by an ultraviolet/visible/near-infrared spectrophotometer. Two extinction peaks were observed in spectra. The optical mechanism is discussed based on surface plasmon resonance

Electrochemical polymerization and characterization of polypyrrole nanowires and nanotubules

Polypyrrole nanostructure arrays, including simultaneously large quantities of nanowires and small quantities of partially filled nanotubules have been electrochemically synthesized in home-made etched ion-track polycarbonate (PC) templates. Diameter of the prepared nanostructures varies from 45 to 320 nm with their lengths up to 30 microns. Morphological studies of these nanostructures were performed by field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM) and Raman spectroscopy. While optical absorption properties were studied by ultraviolet-visible-near infrared spectrophotometry (UV-vis-NIR). It has been observed that the absorption maximum of polypyrrole shifts to the longer wavelength side as the diameter of these nanostructures (nanowires and nanotubules) increases. (C) 2010 Elsevier B.V. All rights reserved.

Spectral response of winter wheat to crop development and various agronomic limitations

For maximizing the effective applications of remote sensing in crop recognition, crop performance assessment and canopy variables estimation at large areas, it is essential to fully understand the spectral response of canopy to crop development and varying growing conditions. In this paper, the spectral properties of winter wheat canopy under different growth stages and different agronomic conditions were investigated at the field level based on reflectance measurements. It was proved that crop growth and development, nitrogen fertilization rates, nutrient deficit (e.g. lacking any kind of nitrogen, phosphorus and kalium fertilizer or lacking all of them), irrigation frequency and plant density had direct influence on canopy reflectance in 400-900 nm which including the visible/near infrared bands, and resulted in great changes of spectral curves. It was suggested that spectral reflectance of crop canopy can well reflect the growth and development of crop and the impacts from various factors, and was feasible to provide vital information for crop monitoring and assessment. ©2010 IEEE.

Layer-by-layer assembly of carbon nanotubes and Prussian blue nanoparticles: A potential tool for biosensing devices

A promising method for assembling carbon nanotubes (CNTs) and poly(diallyldimethylammonium chloride) protected Prussian blue nanoparticles (P-PB) to form three-dimensional (3D) nanostructured films is proposed. The electrostatic interaction, combined with layer-by-layer self-assembly (LBL), between negatively charged CNTs and positively charged P-PB is strong enough to drive the formation of the 3D nanostructured films. Thus, prepared multilayer films were characterized by ultraviolet-visible-near-infrared spectroscopy (UV-vis-NIR), scanning electron microscopy (SEM) and cyclic voltammetry (CV).

Synthesis, Spectroscopic Properties, and Stabilities of Ternary Europium Complex in SBA-15 and Periodic Mesoporous Organosilica: A Comparative Study

Ternary europium complex Eu(tta)(3)phen was covalently bonded with the general mesoporous. material SBA-15 and SBA-15-type of periodic mesoporous organosilica (PMO) material via impregnation of Eu(tta)(3)center dot 2H(2)O into phen-S15 and phen-PMO, respectively, through a ligand exchange reaction. The parent materials of phen-S15 and phen-PMO were synthesized by co-condensation of tetraethylorthosilicate (TEOS) or 1,2-bis(triethoxysilyl)ethane (BTESE) and the functionalized chelate ligand 5-(N,N-bis(3-triethoxysilyl)propyl)ureyl-1,10-phenanthroline (phen-Si) in the presence of Pluronic P123 surfactant as template, which were confirmed by SEM, XRD, FTIR, Si-29 CP-MAS NMR, and N-2 adsorption measurements.

Surface enhanced Raman scattering of brilliant green on ag nanoparticles and applications in living cells as optical probes

In this article, surface enhanced Raman scattering (SERS) of different concentrations of brilliant green (13G) on Ag nanoparticles (AgNPs) has been investigated. The results indicate that only 10(-12) M BG can be detected on AgNPs while as low as 10(-11) M BG can be detected upon the activation of AgNPs by chloride ions. The additional improvement of the detection of BG mainly derives from the increase of the electromagnetic field around AgNPs and partially from the reorientation of BG on AgNPs induced by chloride ions, which was proved by the different spectra feature in the two systems. Adsorption of BG on AgNPs has also been demonstrated in applications of living cells as optical probes based on SERS, indicating that dye-AgNPs can probe the local environment in the living cells. The related cytotoxicity measurements demonstrated that BG-AgNPs produced little cytotoxicity to the cells, which shows great potential in biornedical applications of BG labeled-AgNPs for SERS nanosensors in cells as optical probes. Meanwhile, SERS spectra of BG on AgNPs in the presence chloride ions are expected to be used in living cells as more sensitive optical probes.

High-efficiency and low-cost hybrid nanomaterial as enhancing electrocatalyst: Spongelike AWN core/shell nanomaterial with hollow cavity

A high-efficiency and low-cost spongelike Au/Pt core/shell electrocatalyst with hollow cavity has been facilely obtained via a simple two-step wet chemical process. Hollow gold nanospheres were first synthesized via a modified galvanic replacement reaction between Co nanoparticles in situ produced and HAUCl(4). The as-prepared gold hollow spheres were employed as seeds to further grow spongelike Pt shell. It is found that the surface of this hybrid nanomaterial owns many Pt nanospikes, which form a spongelike nanostructure. All experimental data including scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and UV-vis-near-infrared spectroscopy have been employed to characterize the obtained Au/Pt hybrid nanomaterial. The rapid development of fuel cell has inspired us to investigate the electrocatalytic properties for dioxygen and methanol of this novel hybrid nanomaterial. Spongelike hybrid nanomaterial mentioned here exhibits much higher catalytic activity for dioxygen reduction and methanol oxidation than the common Pt electrode.

A General Route to Construct Diverse Multifunctional Fe3O4/Metal Hybrid Nanostructures

We have developed a simple, efficient, economical, and general approach to construct diverse multifunctional Fe3O4/metal hybrid nanostructures displaying magnetization using 3-aminopropyltrimethoxysilane (APTMS) as a linker. High-density Au nanoparticles (NPs) could be supported on the surface of superparamagnetic Fe3O4 spheres and used as seeds to construct Au shell-coated magnetic spheres displaying near-infrared (NIR) absorption., which may make them promising in biosensor and biomedicine applications. High-density flower-like Au/Pt hybrid NPs could be supported on the surface of Fe3O4 spheres to construct multifunctional hybrid spheres with high catalytic activity towards the electron-transfer reaction between potassium ferricyanide and sodium thiosulfate. High-density Ag or Au/Ag core/shell NPs could also be supported on the surface of Fe3O4 spheres and exhibited pronounced surface-enhanced Raman scattering (SERS), which may possibly be used as an optical probe with magnetic function for application in high-sensitivity bioassays.

Large-scale, rapid synthesis and application in surface-enhanced Raman spectroscopy of sub-micrometer polyhedral gold nanocrystals

Macromolecule-protected sub-micrometer polyhedral gold nanocrystals have been facilely prepared by heating an aqueous solution containing poly (N-vinyl-2-pyrrolidone) (PVP) and HAuCl4 without adding other reducing agents. Scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDX), ultraviolet-visible-near-infrared spectroscopy (UV-vis-NIR), and x-ray diffraction (XRD) were employed to characterize the obtained polyhedral gold nanocrystals. It is found that the 10:1 molar ratio of PVP to gold is a key factor for obtaining quasi-monodisperse polyhedral gold nanocrystals. Furthermore, the application of polyhedral gold nanocrystals in surface-enhanced Raman scattering (SERS) was investigated by using 4-aminothiophenol (4-ATP) as a probe molecule. The results indicated that the sub-micrometer polyhedral gold nanocrystals modified on the ITO substrate exhibited higher SERS activity compared to the traditional gold nanoparticle modified film. The enhancement factor (EF) on polyhedral gold nanocrystals was about six times larger than that obtained on aggregated gold nanoparticles (similar to 25 nm).

Bifunctional Au@Pt hybrid nanorods

The controlled synthesis of bifunctional Au@Pt hybrid nanorods has been realized through a simple wet chemical approach. Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-vis-near infrared spectroscopy (UV-vis-NIR) were employed to characterize the obtained hybrid nanorods. TEM results indicate that the thickness of Pt nanoislands on the surfaces of gold nanorods can be easily tunable via controlling the molar ratio of An nanorods to the H2PtCl6. These Au@Pt hybrid nanorods have dual functions, which can be used not only for surface enhanced Raman spectroscopy (SERS), but also to exhibit good catalytic activity for 02 reduction. It is expected that these hybrid nanorods can be used as new functional building blocks to assemble novel three-dimensional (31)) complex multicomponent nanostructures, which are believed to be useful for electrochemical nanodevices.