Time-resolved luminescence in conducting polymer/antidot nanocomposites

We report modification of the structure and properties of conjugated polymers through controlled embedding wide-gap nanocrystals (antidots) within the polymer matrix. Investigations were carried out by means of stationary and time-resolved photoluminescence. Antidots strongly modify the luminescence spectrum of poly(p-phenylene vinylene) but have almost no influence on the spectrum of poly(2-(6-cyano-6'-methylheptyloxy)-1, 4-phenylene. We explain this observation with respect to the different chain structure and electron density distribution in these two materials. The temporal evolution of luminescence spectra in polymer/antidot composites contains a series of characteristic times. The shortest of these (0.35-0.6 ns) are independent of antidot material and characterize processes in the polymer matrix. Larger times considerably exceeding 1 ns are composition-sensitive and attributable to carrier capture by nanocrystals. The qualitative character of the modification of luminescence spectra associated with the inclusion of antidots depends strongly on the characteristics of the polymer matrices and more weakly on the antidot material. This suggests that the predominant effect of the nanocrystals relates to the modification of the matrix near the polymer-inorganic interface.     

基于聚乙烯醇的共轭聚合物/二氧化钛复合光催化剂的结构及光催化性能

通过聚乙烯醇（PVA）在酸性条件下的热消除反应制备了具有共轭结构的聚合物（C-PVA）,进一步有机/无机杂化制备出C-PVA/TiO2复合光催化剂。紫外-可见吸收光谱、傅里叶变换红外光谱和热失重结果表明,C-PVA含有共轭双键和羰基;X射线光电子能谱和紫外-可见漫反射光谱分析结果表明,C-PVA/TiO2复合光催化剂表...     

Preparation and photovoltaic properties of near-infrared absorbing manganese(II) phthalocyanine polymer films

2,9,16,23-Tetra-amino manganese(II) phthalocyanine (TAMnPc) was synthesized and characterized by mass spectrometry, infrared (IR) and electronic absorption spectrum. TAMnPc polymer films were prepared by spin-coating. The electronic absorption spectra of TAMnPc and its polymer films both exhibit an intense Q-band beyond 800 nm in the near-infrared region. The current-voltage characteristics of TAMnPc polymer films in the dark and under infrared irradiation were recorded. The electrical conductivity of films under infrared irradiation was obviously higher than that in the dark, indicating that TAMnPc has good photovoltaic response.     

Time-resolved electrostatic force microscopy of polymer solar cells

Blends of conjugated polymers with fullerenes, polymers, or nanocrystals make promising materials for low-cost photovoltaic applications. Different processing conditions affect the efficiencies of these solar cells by creating a variety of nanostructured morphologies, however, the relationship between film structure and device efficiency is not fully understood. We introduce time-resolved electrostatic force microscopy (EFM) as a means to measure photoexcited charge in polymer films with a resolution of 100 nm and 100 micros. These EFM measurements correlate well with the external quantum efficiencies measured for a series of polymer photodiodes, providing a direct link between local morphology, local optoelectronic properties and device performance. The data show that the domain centres account for the majority of the photoinduced charge collected in polyfluorene blend devices. These results underscore the importance of controlling not only the length scale of phase separation, but also the composition of the domains when optimizing nanostructured solar cells.     

Alkyl Passivation and Amphiphilic Polymer Coating of Silicon Nanocrystals for Diagnostic Imaging

A method to produce biocompatible polymer‐coated silicon nanocrystals for medical imaging is shown. Silica‐embedded Si nanocrystals are formed by HSQ thermolysis. The nanocrystals are then liberated from the oxide and terminated with Si–H bonds by HF etching, followed by alkyl monolayer passivation by thermal hydrosilylation. The Si nanocrystals have an average diameter of 2.1 nm ± 0.6 nm and photoluminesce with a peak emission wavelength of 650 nm, which lies within the transmission window of 650–900 nm that is useful for biological imaging. The hydrophobic Si nanocrystals are then coated with an amphiphilic polymer for dispersion in aqueous media with the pH ranging between 7 and 10 and an ionic strength between 30 mM and 2 M , while maintaining a bright and stable photoluminescence and a hydrodynamic radius of only 20 nm. Fluorescence imaging of polymer‐coated Si nanocrystals in biological tissue is demonstrated, showing the potential for in vivo imaging.     

Recent developments of hybrid nanocrystal/polymer bulk heterojunction solar cells

Hybrid nanocrystal/polymer bulk heterojunction (BHJ) solar cells consisting of colloidal inorganic semiconductor nanocrystals as electron acceptors and conjugated polymers as electron donors have been extensively investigated in the past few decades, which take advantage of the strongpoints of the inorganic semiconductor nanocrystals and the conjugated polymers. Currently, power conversion efficiency over 3% for the hybrid nanocrystal/polymer BHJ solar cells has been achieved. Although the development of hybrid nanocrystal/polymer BHJ solar cells lacks behind the international level, great progress in this research field has been made in China. In this article, we first review the general fabrication techniques and general working principles of hybrid nanocrystal/polymer BHJ solar cells. Secondly, we highlight the international and national developments of hybrid nanocrystal/polymer BHJ solar cells based on different types of semiconductor nanocrystals and conjugated polymers. Finally, we give a future outlook for the hybrid nanocrystal/polymer BHJ solar cells in the worldwide.     

UV Raman spectroscopy of group IV nanocrystals embedded in a SiO<Subscript>2</Subscript> matrix

Nanostructures of both Ge nanocrystals formed by thermal oxidation of SiGe layers, and SiGe nanocrystals formed by crystallization of amorphous SiGe nanoparticles deposited by LPCVD have been analyzed by Raman spectroscopy. The nanostructures are formed on a silicon substrate. Raman spectra have been acquired with visible (514.5 nm) and UV (325 nm) excitation lines. When the amount of material is very small, as it has happens in these nanostructures, the visible line is not able to excite the characteristic peaks of the Ge or SiGe in the Raman spectrum; instead the Si second order spectrum of the substrate appears and it can be misinterpreted by attributing it to the Ge–Ge band associated with the nanocrystals. In this work, the use of UV excitation has been demonstrated to enhance the sensitivity respect to the conventional visible excitation, allowing the characteristic peaks of the Ge or SiGe nanocrystals to appear in the spectrum. We attributed this effect to the resonance effects.     

High contrast in vitro and in vivo photoluminescence bioimaging using near infrared to near infrared up-conversion in Tm3+ and Yb3+ doped fluoride nanophosphors

A new approach for photoluminescence imaging in vitro and in vivo has been shown utilizing near infrared to near infrared (NIR-to-NIR) up-conversion in nanophosphors. This NIR-to-NIR up-conversion process provides deeper light penetration into biological specimen and results in high contrast optical imaging due to absence of an autofluorescence background and decreased light scattering. Aqueous dispersible fluoride (NaYF4) nanocrystals (20-30 nm size) co-doped with the rare earth ions, Tm(3+) and Yb(3+), were synthesized and characterized by TEM, XRD, and photoluminescence (PL) spectroscopy. In vitro cellular uptake was shown by the PL microscopy visualizing the characteristic emission of Tm(3+) at approximately 800 nm excited with 975 nm. No apparent cytotoxicity was observed. Subsequent animal imaging studies were performed using Balb-c mice injected intravenously with up-converting nanophosphors, demonstrating the high contrast PL imaging in vivo.     

Effect of PbS nanocrystal concentration on the physical properties of a polymer–nanocrystal composite

Semiconductor nanocrystals doped in stable matrices such as polymers are of interest due to fundamental scientific aspects as well as their scope for technological applications. In the present investigation, PbS nanocrystals are synthesized in polyvinyl alcohol (PVA) matrix using a simple technique based on colloidal chemistry. Various concentrations of nanocrystalline PbS (with an average size of 4.5 nm) are loaded into the polymer to study the effect of PbS concentration on the optical, thermal and electrical properties of the composite. An increase in PbS content results in decrease in thermal stability and an increase in electrical conductivity, presumably resulting from interactions between the nanofiller and polymer. Considerations for designing composites with desired combinations of electrical, thermal, and optical properties to suit specific device operating environments are studied systematically.     

Smart nanoprobes for ultrasensitive detection of breast cancer via magnetic resonance imaging

Antibody-conjugated hydrophilic magnetic nanocrystals for use as smart nanoprobes were developed for ultrasensitive detection of breast cancer via magnetic resonance (MR) imaging. MnFe(2)O(4) nanocrystals (MNCs) for use as MR imaging contrast agents were synthesized by thermal decomposition to take advantage of their MR signal enhancement effect. The MNC surfaces were then modified with amphiphilic tri-block copolymers (dicarboxy poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol)), not only allowing the MNCs to transfer from the organic to the aqueous phase, but also increasing the colloidal stability of the MNCs by masking poly(ethylene glycol). The physicochemical properties of the synthesized hydrophilic magnetic nanocrystals (HMNCs) were fully investigated. Trastuzumab (TZ), a monoclonal antibody against human epidermal growth factor receptor (HER2/neu), was further conjugated on the surface of HMNCs to specifically target HER2/neu over-expressed breast cancer cells. MR imaging analysis of target cells treated with TZ-conjugated HMNCs (TZ-HMNCs) clearly demonstrated their potential as high-performance nanoprobes for selective imaging.     

8.78% Efficient All‐Polymer Solar Cells Enabled by Polymer Acceptors Based on a B←N Embedded Electron‐Deficient Unit

In the field of all‐polymer solar cells (all‐PSCs), all efficient polymer acceptors that exhibit efficiencies beyond 8% are based on either imide or dicyanoethylene. To boost the development of this promising solar cell type, creating novel electron‐deficient units to build high‐performance polymer acceptors is critical. A novel electron‐deficient unit containing B←N bonds, namely, BNIDT, is synthesized. Systematic investigation of BNIDT reveals desirable properties including good coplanarity, favorable single‐crystal structure, narrowed bandgap and downshifted energy levels, and extended absorption profiles. By copolymerizing BNIDT with thiophene and 3,4‐difluorothiophene, two novel conjugated polymers named BN‐T and BN‐2fT are developed, respectively. It is shown that these polymers possess wide absorption spectra covering 350–800 nm, low‐lying energy levels, and ambipolar film‐transistor characteristics. Using PBDB‐T as the donor and BN‐2fT as the acceptor, all‐PSCs afford an encouraging efficiency of 8.78%, which is the highest for all‐PSCs excluding the devices based on imide and dicyanoethylene‐type acceptors. Considering that the structure of BNIDT is totally different from these classical units, this work opens up a new class of electron‐deficient unit for constructing efficient polymer acceptors that can realize efficiencies beyond 8% for the first time.     

Copper selenide nanocrystals for photothermal therapy

Ligand-stabilized copper selenide (Cu(2-x)Se) nanocrystals, approximately 16 nm in diameter, were synthesized by a colloidal hot injection method and coated with amphiphilic polymer. The nanocrystals readily disperse in water and exhibit strong near-infrared (NIR) optical absorption with a high molar extinction coefficient of 7.7 × 10(7) cm(-1) M(-1) at 980 nm. When excited with 800 nm light, the Cu(2-x)Se nanocrystals produce significant photothermal heating with a photothermal transduction efficiency of 22%, comparable to nanorods and nanoshells of gold (Au). In vitro photothermal heating of Cu(2-x)Se nanocrystals in the presence of human colorectal cancer cell (HCT-116) led to cell destruction after 5 min of laser irradiation at 33 W/cm(2), demonstrating the viabilitiy of Cu(2-x)Se nanocrystals for photothermal therapy applications.     

Quantum dot conjugated hydroxylapatite nanoparticles for in vivo imaging

Hydroxylapatite (HA) nanoparticles were conjugated with quantum dots (QDs) for in vivo imaging. The surface structures of HA nanoparticles with conjugated quantum dots (HA-QD) were studied by transmission electron microscopy (TEM) and laser fluorescent spectroscopy. The TEM data showed that the quantum dots were well conjugated on the HA nanoparticle surfaces. The laser fluorescent spectroscopy results indicated that the HA-QD exhibited promising luminescent emission in vitro. The initial in vivo experiments revealed clear images of HA-QD from the hypodermic injected area at the emission of 600?nm. Furthermore, the optimized in vivo images of HA-QD with near-infrared emission at 800?nm were visualized after intravenous injection. These luminescent HA-QD nanoparticles may find important applications as biodegradable substrates for biomarkers and in drug delivery.     

无机纳米晶/共轭聚合物太阳能电池光敏层制备方法及微观形貌调控

相比硅太阳能电池,无机纳米晶/共轭聚合物太阳能电池因其兼备有机/无机杂化的优点,而近年来一直是国内外广泛关注的热点之一.文中对目前该种太阳能电池光敏层的各种微观形貌、制备方法及研究进展进行了综述.详细介绍了无机纳米晶/共轭聚合物光敏层的三种制备方法,即物理共混法、化学键合式共混法和原位法.同时着重关注了无机纳米晶/共轭...     

Cyclodextrin Insulation Prevents Static Quenching of Conjugated Polymer Fluorescence at the Single Molecule Level

Conjugated polymers (CPs) are promising materials for fluorescence imaging application. However, a significant problem in this field is the unexplained abnormally low fluorescence brightness (or number of fluorescence photons detected per one excitation photon) exhibited by most of CP single chains in solid polymer hosts. Here it is shown that this detrimental effect can be fully avoided for short chains of polyfluorene‐bis‐vinylphenylene (PFBV) embedded in a host polymer matrix of PMMA, if the conjugated backbone is insulated by cyclodextrin rings to form a polyrotaxane (PFBV‐Rtx). Fluorescence kinetics and quantum yields are measured for the polymers in liquid solutions, pristine films, and solid PMMA blends. The fluorescence brightness of PFBV‐Rtx single chains dispersed in a solid PMMA is very close to that expected for a chain with 100% fluorescence quantum yield, while the unprotected PFBV chains of the same length possess 4 times lower brightness. Despite this, the fluorescence decay kinetics are the same for both polymers, suggesting the presence of static or ultrafast fluorescence quenching in the unprotected polymer. About 80% of an unprotected PFBV chain is estimated to be completely quenched. The hypothesis is that the cyclodextrin rings prevent the quenching by working as ‘bumpers’ reducing the mechanical forces applied by the host polymer to the conjugated backbone and help retaining its conformational freedom. While providing a recipe for making CP fluorescence bright at the single‐molecule level, these results identify a lack of fundamental understanding in the community of the influence of the environment on excited states in conjugated materials.     

A Supramolecular Nanocomposite as a Near‐Infrared‐Transmitting Optical Filter for Security and Forensic Applications

Visibly opaque but near‐infrared (NIR)‐transparent materials are an essential component for night‐vision photography, security imaging, and forensic applications. Herein, the development of a novel supramolecular black dye from a diketopyrrolopyrrole (DPP)‐based low‐molecular‐weight organogelator is described. In the solution state, the monomer of DPP–Amide exhibits a deep green color with a broad absorption in the visible region due to firm intramolecular charge transfer from the donor to the acceptor unit. Interestingly, due to the synergistic effect of H‐bonding and π‐stacking, DPP–Amide can form a black organogel in toluene with complete spectral coverage from 300 to 800 nm, and transmits beyond 850 nm. In the gel state, complete visible‐spectrum coverage is achieved due to the simultaneous formation of both H‐ and J‐type aggregates, which is confirmed via absorption studies. To create a free‐standing NIR‐transmitting elastomeric black filter, nanoscopic molecular aggregates of DPP–Amide (0.15 wt%) are embedded into a poly(dimethylsiloxane) matrix. This nanocomposite possesses high NIR transparency with good thermal and photostability for practical applications. Finally, the use of the developed material for NIR photography, security, and forensic‐related applications is demonstrated.     

Effect of polymer aggregation on the open circuit voltage in organic photovoltaic cells: aggregation-induced conjugated polymer gel and its application for preventing open circuit voltage drop

To investigate the structure-dependent aggregation behavior of conjugated polymers and the effect of aggregation on the device performance of conjugated polymer photovoltaic cells, new conjugated polymers (PVTT and CN-PVTT) having the same regioregularity but different intermolecular packing were prepared and characterized by means of UV-vis spectroscopy and atomic force microscopy (AFM). Photovoltaic devices were prepared with these polymers under different polymer-aggregate conditions. Polymer aggregation induced by thermal annealing increases the short circuit current but provides no advantage in the overall power conversion efficiency because of a decrease in the open circuit voltage. The device fabricated from a pre-aggregated polymer suspension, acquired from ultrasonic agitation of a conjugated polymer gel, showed enhanced performance because of better phase separation and reduced recombination between polymer/PCBM.     

Conjugated polymer loaded nanospheres with surface functionalization for simultaneous discrimination of different live cancer cells under single wavelength excitation

Two conjugated polymers, poly[9,9-bis(2-(2-(2-methoxyethoxy)ethoxy)ethyl) fluorenyldivinylene] (PFV) and the PFV derivative containing 10 mol % 2,1,3-benzothiadiazole (BT) units (PFVBT), have been synthesized and employed to fabricate conjugated polymer loaded nanospheres for simultaneous discrimination of mixed live cancer cells in one solution. The incorporation of BT units into the PFV backbone leads to PFVBT with a similar absorption maximum but significantly red-shifted emission in film state as compared to those of PFV, due to aggregation enhanced energy transfer from the fluorenevinylene segments to electron-deficient BT units. Both conjugated polymer loaded nanospheres have shown optical features that are similar to their film states, which allow simultaneous multichannel signal collection with negligible interference upon excitation at a single wavelength. After further surface functionalization with antihuman epidermal growth factor receptor 2 (HER2) affibody or arginine-glycine-aspartic acid (RGD) peptide, the distinct fluorescence from PFV or PFVBT loaded nanospheres allows differentiation of SKBR-3 breast cancer cells (HER2 overexpression) from HT-29 colon cancer cells (integrin receptor overexpression) in live cell mixtures. The conjugated polymer loaded nanospheres with high quantum yield, low cytotoxicity, and multiple color emission upon single laser excitation are ideal for simultaneous multiple-target imaging and detection.     

共轭多孔聚合物应用于近红外光热转换材料

近红外光热转换材料在光热治疗、光驱动智能器件等医学和能源领域受到广泛重视.本文以商业化芳香小分子为单体,通过一步简单的交联聚合方法制得了四种共轭多孔聚合物,并首次系统研究了它们的光热转换性能.结果表明,它们均具有灵敏的近红外光热响应性,且材料的光热转换效率与单体结构中共轭苯环数有很大关系,其中两种聚合物的光热转换效率可...     

Ultrasmall Near‐Infrared Non‐cadmium Quantum Dots for in vivo Tumor Imaging

The high tumor uptake of ultrasmall near‐infrared quantum dots (QDs) attributed to the enhanced permeability and retention effect is reported. InAs/InP/ZnSe QDs coated by mercaptopropionic acid (MPA) exhibit an emission wavelength of about 800 nm (QD800‐MPA) with very small hydrodynamic diameter (<10 nm). Using 22B and LS174T tumor xenograft models, in vivo and ex vivo imaging studies show that QD800‐MPA is highly accumulated in the tumor area, which is very promising for tumor detection in living mice. The ex vivo elemental analysis (Indium) using inductively coupled plasma (ICP) spectrometry confirm the tumor uptake of QDs. The ICP data are consistent with the in vivo and ex vivo fluorescence imaging. Human serum albumin (HSA)‐coated QD800‐MPA nanoparticles (QD800‐MPA‐HSA) show reduced localization in mononuclear phagocytic system‐related organs over QD800‐MPA plausibly due to the low uptake of QD800‐MPA‐HSA in macrophage cells. QD800‐MPA‐HSA may have great potential for in vivo fluorescence imaging.