Exciton diffusion and charge transfer dynamics in nano phase-separated P3HT/PCBM blend films

Exciton quenching dynamics has been systematically studied in pristine P3HT and nano phase separated P3HT/PCBM blend films under various excitation intensities by femtosecond fluorescence up-conversion technique. The behaviors of excitons in the films can be well described by a three-dimensional diffusion model. The small diffusion length and large charge transfer radius indicate that excitons reach the interface most likely by the delocalization of the excitons in P3HT fibrillar at a range of 4.8-9 nm so that the excitons can quickly delocalize in the P3HT domain to reach the interface (instead of by diffusion).     

Organic Solar Cells: Understanding the Role of F?rster Resonance Energy Transfer

Organic solar cells have the potential to become a low-cost sustainable energy source. Understanding the photoconversion mechanism is key to the design of efficient organic solar cells. In this review, we discuss the processes involved in the photo-electron conversion mechanism, which may be subdivided into exciton harvesting, exciton transport, exciton dissociation, charge transport and extraction stages. In particular, we focus on the role of energy transfer as described by Förster resonance energy transfer (FRET) theory in the photoconversion mechanism. FRET plays a major role in exciton transport, harvesting and dissociation. The spectral absorption range of organic solar cells may be extended using sensitizers that efficiently transfer absorbed energy to the photoactive materials. The limitations of Förster theory to accurately calculate energy transfer rates are discussed. Energy transfer is the first step of an efficient two-step exciton dissociation process and may also be used to preferentially transport excitons to the heterointerface, where efficient exciton dissociation may occur. However, FRET also competes with charge transfer at the heterointerface turning it in a potential loss mechanism. An energy cascade comprising both energy transfer and charge transfer may aid in separating charges and is briefly discussed. Considering the extent to which the photo-electron conversion efficiency is governed by energy transfer, optimisation of this process offers the prospect of improved organic photovoltaic performance and thus aids in realising the potential of organic solar cells.     

Enhancing the light absorbance of polymer solar cells by introducing pulsed laser-deposited CuIn0.8Ga0.2Se2 nanoparticles

Evenly separated crystalline CuIn_0.8Ga_0.2Se₂ (CIGS) nanoparticles are deposited on ITO-glass substrate by pulsed laser deposition. Such CIGS layers are introduced between conjugated polymer layers and ITO-glass substrates for enhancing light absorbance of polymer solar cells. The P3HT:PCBM absorbance between 300 and 650 nm is enhanced obviously due to the introduction of CIGS nanoparticles. The current density-voltage curves of a P3HT:PCBM/CIGS solar cell demonstrate that the short-circuit current density is improved from 0.77 to 1.20 mA/cm². The photoluminescence spectra show that the excitons in the polymer are obviously quenched, suggesting that the charge transfer between the P3HT:PCBM and CIGS occurred. The results reveal that the CIGS nanoparticles may exhibit the localized surface plasmon resonance effect just as metallic nanostructures.

PACS

61.46. + w; 61.41.e; 81.15.Fg; 81.07.b     

Fabrication of metal nanoparticles on highly dispersed pristine carbon nanotubes

A convenient approach to fabricate metal (i.e. gold, platinum, and palladium) nanoparticles on highly dispersed pristine carbon nanotubes (CNTs) was developed using a conjugated block copolymer of poly(3-hexylthiophene)-b-poly(vinylpyrrolidone) (P3HT-b-PVP). P3HT-b-PVP not only provides a stable dispersion of pristine CNTs through the π–π interactions between P3HT block and CNTs, but also introduces PVP groups on CNT surfaces to induce the heterogeneous nucleation of metal nanoparticles and protect them from aggregating. The density of metal nanoparticles on CNT surfaces was controlled by the metal salt/CNT feed ratio. The simple processing procedure, versatility in synthesizing various metal nanoparticles, high metal nanoparticle loading capacity, and excellent dispersibility and processability of the product make this approach a promising method to fabricate metal nanoparticles on CNTs.     

A novel electrochemically and thermally stable polythiophene for photovoltaic application

Conjugated polymers having good electrochemical and thermal stability are highly desired in optoelectronics. We report a new polythiophene consisting of alternating 4,4′‐didodecyl‐2,2′‐bithiophene and terthiophene units (HPL1) synthesized via Stille coupling reaction. The optical band gap of HPL1 (1.92 eV) is similar to that of regioregular poly(3‐hexylthiophene) (rr‐P3HT, 1.89 eV). In comparison to rr‐P3HT, the HPL1 when subjected to the cyclic voltammetry as thin film shows much superior electrochemical stability and a lower highest occupied molecular orbital energy level (?4.87 eV for rr‐P3HT and ?4.95 eV for HPL1). The transient photoluminescence study of HPL1 and rr‐P3HT shows that both materials have two exciton decay processes, and the excitons of rr‐P3HT are quenched more quickly. The onset decomposition, T_d for rr‐P3HT (465°C) is 4°C lower than HPL1 (469°C). Preliminary photovoltaic study disclosed that the polymer solar cell based on HPL1:[6,6]‐phenyl‐C₆₁‐butyric acid methyl ester blend showed a power conversion efficiency of 0.63%, with a V_oc of 0.6 V, and a short circuit current (J_sc) of 2.79 mA cm^?2 under AM 1.5 illumination (100 mW cm^?2). The whole study provided an important example to design new electrochemically and thermally stable polymers with longer exciton life time for application in bulk heterojunction polymer solar cells. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of shell phase composition on the dielectric property and energy density of core-shell structured BaTiO3 particles modified poly(vinylidene fluoride) nanocomposites

Dielectric nanocomposites have attracted much attention due to their wide applications in electronics and electrical industry. Recently, incorporating core-shell nanoparticles into polymer matrix to improve the dielectric properties of nanocomposites has been widely reported. Tailoring the interfacial region between the polymer and the nanoparticles plays a crucial role in achieving the desired dielectric and energy storage properties of nanocomposites. However, the effect of shell structure in the interface region on the dielectric and energy storage properties is rarely studied. Based on this, core-shell BaTiO₃ nanoparticles with two different shell polymers, a “hard-soft” copolymer of methyl methacrylate and butyl acrylate (P[MMA-BA]) and a “hard” homopolymer of methyl methacrylate (PMMA), were prepared in this paper. The effect of core-shell BaTiO₃ nanoparticles with different shell structures on the dielectric and energy storage properties of poly(vinylidene fluoride) (PVDF) was investigated in depth. Due to the formation of a tight interfacial region between P(MMA-BA)@BT and PVDF matrix, P(MMA-BA)@BT/PVDF nanocomposites not only have low dielectric loss but also higher energy efficiency than PMMA@BT/PVDF nanocomposites. This study suggests a potential strategy that fabricating a “hard-soft” copolymer shell on BaTiO₃ surface can obtain desirable energy storage efficiency than the single “hard” shell structure in dielectric nanocomposites.     

Magnetic field dependence of singlet oxygen generation by nanoporous silicon

Energy transfer from photoexcited excitons localized in silicon nanoparticles to adsorbed oxygen molecules excites them to the reactive singlet spin state. This process has been studied experimentally as a function of nanoparticle size and applied external magnetic field as a test of the accepted understanding of this process in terms of the exchange coupling between the nano-Si exciton and the adsorbed O₂ molecules.     

Towards optimization of functionalized single-walled carbon nanotubes adhering with poly(3-hexylthiophene) for highly efficient polymer solar cells

In this paper, we present the optimization of single-walled carbon nanotubes (SWCNTs) by acid-treatment, solution ultrasonication time and dispersion in photoactive layer for efficient organic solar cells. After non-covalently adhering with poly(3-hexylthiophene) (P3HT), pre-functionalized SWCNTs were blended into the composites of P3HT and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) as photoactive layer, and a maximum power conversion efficiency (PCE) of 3.02% with a short-circuit current density of 11.46 mA/cm² was obtained from photovoltaic cell indium-tin oxide (ITO)/poly(ethylene-dioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS)/P3HT:PCBM:SWCNTs/Al with an optimum 0.3 wt% SWCNTs in P3HT:PCBM:SWCNTs nanocomposite, the PCE can be enhanced by more than 10% as compared to the control device ITO/PEDOT:PSS/P3HT:PCBM/Al. The performance improvement by incorporating with functionalized SWCNTs is mainly attributed to the extension of excitons dissociation area and fastening charge carriers transfer across the active layer.     

Effects of Ta doping and irradiation with He+ ions on photoluminescence of MgAl2O4 spinel ceramics

Photoluminescence (PL) properties of pristine and Ta-doped MgAl₂O₄ spinel ceramics prepared via spark plasma sintering technique and irradiated with He⁺ ions were studied. The results indicate strong influence of the grain boundaries on PL spectra. Ta doping promotes the formation of O and Al vacancies at the grain boundaries leading to an increased number density of F⁺ centres. The ionised irradiation forms antisites preferentially at the grain boundaries, which inhibit excitonic PL and exciton energy transfer while do not affect proper PL of lattice defects. A weak PL excitation band at 7.25 ± 0.25 eV may belong to excitons localised near bulk antisites. In the Ta-doped ceramics, the electronic transitions between 5.75 eV and 7.0 eV belong to an intermediate state situated at the grain boundaries and structurally linked to Ta, which readily transfers energy to F and F⁺ centres; it was assigned to the nucleated Mg₄Ta₂O₉ phase.     

Fabrication of TiO2‒Ag nanocomposite thin films via one-step gas-phase deposition

In this work, TiO₂‒Ag nanocomposite thin films were fabricated for the first time via simultaneous plasma-enhanced chemical vapor deposition and physical vapor deposition of TiO₂ and Ag nanoparticles in the gas-phase, respectively. The presence of Ag nanoparticles in the prepared nanocomposites has been confirmed using transmission electron microscopy and energy dispersive X-ray spectrometry techniques. The obtained electron microscopy images showed that the average size of TiO₂‒Ag nanoparticles was larger than that of pristine TiO₂. Moreover, the temperature of the anatase transformation into the rutile phase was decreased due to the presence of Ag nanoparticles in the TiO₂ matrix, while the photocatalytic activity of the produced nanocomposite (estimated by studying the degradation of methylene blue aqueous solution under UV irradiation) was 35% greater than that of pristine TiO₂. Therefore, the addition of Ag nanoparticles into the TiO₂ matrix significantly affected the morphology, phase transformation temperature, and photocatalytic performance of the fabricated material.     

A study on the properties of PMMA/silica nanocomposites prepared via RAFT polymerization

A number of batch polymerizations were performed to study the effect of pristine nanoparticle loading on the properties of PMMA/silica nanocomposites prepared via RAFT polymerization. In order to improve the dispersion of silica nanoparticles in PMMA matrix, the silanol groups of the silica are functionalized with methyl methacrylate groups and modified nanoparticles were used to synthesize PMMA/modified silica nanocomposites via RAFT polymerization. Prepared samples were characterized by thermogravimetric analysis (TGA), dynamic light scattering (DLS), dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC). According to results, introduction of modified nanoparticles results in better thermal and mechanical properties than those of pristine nanoparticles. Also, surface modification and increasing silica nanoparticles result in variation of thermal degradation behavior of nanocomposites. The best improvement of mechanical and thermophysical properties is achieved for nanocomposites containing 7 wt. % silica nanoparticles.     

Modulation of Fluorescence of a Terbium-Complex-Containing Polymer by Gold Nanoparticles through Energy Transfer

A terbium complex-containing polymer (P-Tb) is prepared via free radical polymerization in solution. The copolymer exhibits the characteristic fluorescence bands of Tb³⁺ complex as well as a strong and broad band at near 400 nm. The fluorescence of P-Tb can be modulated by gold nanoparticles, with the gradual addition of gold nanoparticles into the DMF/toluene solution of P-Tb. The intensity of the characteristic emissions steadily decreases whereas the broad band at ca. 400 nm experiences fluorescence enhancement. For the solid films of P-Tb with varied amount of gold nanoparticles, both the characteristic emissions and the broad band suffers fluorescence quenching. The absorption of gold nanoparticle solution exhibits a prominent red-shift upon addition of P-Tb, suggesting there exists strong binding between the Tb/β-diketone complexes and gold nanoparticles. It is thought that the energy transfer is the driving force for the change in fluorescence intensity; and, the difference in polymer chain conformation in solution and in the solid state leads to different fluorescence behaviors for solution and solid samples.     

Strong plasmon-exciton coupling in a hybrid system of gold nanostars and J-aggregates

Hybrid materials formed by plasmonic nanostructures and J-aggregates provide a unique combination of highly localized and enhanced electromagnetic field in metal constituent with large oscillator strength and extremely narrow exciton band of the organic component. The coherent coupling of localized plasmons of the multispiked gold nanoparticles (nanostars) and excitons of JC1 dye J-aggregates results in a Rabi splitting reaching 260 meV. Importantly, broad absorption features of nanostars extending over a visible and near-infrared spectral range allowed us to demonstrate double Rabi splitting resulting from the simultaneous coherent coupling between plasmons of the nanostars and excitons of J-aggregates of two different cyanine dyes.     

Synthesis of polypyrrole/indium tin oxide nanocomposites via miniemulsion polymerization

Polypyrrole/indium tin oxide nanocomposites were synthesized via in situ miniemulsion polymerization of pyrrole monomer in the presence of indium tin oxide nanoparticles. Different nanocomposites were synthesized by different loadings of nano indium tin oxide. The morphology and nanoparticles distribution of the nanocomposites were characterized by electron microscopy. The results of XRD and TEM analysis showed that indium tin oxide nanoparticles were well placed in the polymeric structure of latex. FTIR analysis was used for the characterization of synthesized polypyrrole and its nanocomposites. TGA analysis was performed to investigate the thermal behavior of pristine polypyrrole and its nanocomposites. Conductivities of nanocomposites were measured by 4-point probe method and compared to the neat polymer.     

Upconversion Luminescence in Yb/Ln (Ln = Er,Tm) Doped Oxyhalide Glasses Containing CsPbBr3 Perovskite Nanocrystals

Yb/Ln (Ln=Er, Tm) doped TeO₂-based glasses containing CsPbBr₃ perovskite quantum dots were successfully prepared via in-situ glass crystallization. The nanocomposites yield typical green downshifting luminescence attributing to CsPbBr₃ exciton recombination under UV excitation, and produce Er³⁺ green, Er³⁺ red and Tm³⁺ blue upconversion emissions under 980 nm laser excitation. Impressively, specific Ln³⁺ emissions will be quenched with the precipitation of CsPbBr₃ in glass, enabling to finely tune upconversion emitting color. Spectroscopic characterizations evidence that the luminescence quenching is originated from non-radiative reabsorption effect induced by the precipitation of CsPbBr₃ rather than energy transfers from Ln³⁺ to CsPbBr₃. Finally, these nanocomposites are demonstrated to exhibit superior water resistance due to the effective protecting role of dense structural glass, particularly, about 95% downshifting luminescence of CsPbBr₃ and upconversion luminescence of Er³⁺ related to pristine ones are retained after immersing the products in water up to 30 days.     

In situ doping of PANI nanocomposites by gold nanoparticles for high‐performance electrochemical energy storage

Polyaniline (PANI) in situ doped with gold nanoparticles (Au/PANI) is synthesized by oxidative polymerization as electrode material for supercapacitor. The morphologies and structure of the obtained products are characterized by transmission electron microscopy, scanning electron microscopy, and Fourier transform infrared spectroscopy; and electrochemical behaviors were measured by electrochemical workstation. The results show that the nanocomposites of Au/PANI are fabricated with gold nanoparticles (nano‐Au) dispersed well in PANI bulk; and specific capacitance (SC) and rate ability of Au/PANI are improved compared to the pristine PANI due to the introduction of nano‐Au. With nano‐Au content increasing, SC first increase and then decrease and the maximum SC of Au/PANI nanocomposite is up to 462 F g^?1 with the nano‐Au content of 1.64 wt %. Finally, both asymmetric and symmetric supercapacitor devices are assembled, exhibiting high energy densities of 8.95 and 4.17 Wh kg^?1, respectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45309.     

Effects of particle size on the molecular orientation and birefringence of magnetic nanoparticles/polyimide composites

Size dependency of nanoparticles for birefringence and molecular orientation of nanocomposite films have been studied using a prism coupler and near‐edge X‐ray absorption fine structure spectroscopy (NEXAFS). We synthesized two different sizes of magnetic nanoparticles, Ni_0.6Zn_0.4Fe₂O₄. The smaller ones were 6.1 ± 1.3 nm‐diameter nanoparticles showing superparamagnetism and the larger ones were 20.7 ± 6.1 nm‐diameter nanoparticles showing ferrimagnetism. To make nanocomposites, we incorporated these particles into poly(N,N′‐bis(phenoxyphenyl)pyromellitimide) (PMDA‐ODA PI). From the prism coupler study, pristine PI without nanoparticles had higher out‐of‐plane birefringence, which indicated high in‐plane orientation of polyimide. However, the birefringence of PI nanocomposites decreased with the increase of particle content. The birefringence of PI nanocomposite with small nanoparticles was smaller than that of PI nanocomposite with large nanoparticles. The birefringence of PI nanocomposite with 1 wt % of small nanoparticles was reduced to almost half of that of pristine PI due to the decreased orientation of PI molecules. NEXAFS spectra of N K‐edge were the same as the birefringence results. Imide and phenyl rings of pristine PI aligned more parallel to the in‐plane direction, but those of PI with nanoparticles aligned less parallel to the in‐plane direction. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3433–3440, 2006     

INORGANIC NANOPARTICLES AS OPTICALLY EFFECTIVE ADDITIVES FOR POLYMERS

The transparency of polymer-particle composites can be markedly enhanced when nanoparticles are employed instead of larger particles, due to a reduction in light scattering. In addition, nanoparticles of metals (e.g., gold or silver) or semiconductors (e.g., TiO₂, ZnO, or PbS) can exhibit intrinsic optical properties that may be of interest per se or in combination with the enhanced transparency caused by the nanoparticles. For such reasons, inorganic nanoparticles have found special interest in studies devoted to optical properties in composites that look back to a long history. For instance, the size-dependent color of gold nanoparticles has been used to color glass for centuries. More recently, inorganic nanoparticles were investigated with regard to optical effects in polymeric nanocomposites such as very high or very low refractive index, reversible color switching in elastomers via swelling processes, dichroism in oriented polymers, reversible photochromic behavior, or UV absorption in visually transparent materials.     

Highly visible light active Ag@ZnO nanocomposites synthesized by gel-combustion route

Highly visible light active 1% and 3% Ag@ZnO nanocomposites were synthesized via a gel combustion route using citric acid as a fuel. The formation of the nanocomposites with enhanced properties was confirmed using a range of characterization techniques, photocatalysis and photoelectrochemical studies. Compared to the pristine ZnO nanoparticles, the Ag@ZnO nanocomposites exhibited enhanced visible light photocatalytic activity for the degradation of methylene blue and photoelectrochemical response. A mechanism was proposed to account for the photocatalytic activities of the Ag@ZnO nanocomposite that showed the surface plasmon resonance (SPR) of Ag is an effective way of enhancing the visible light photocatalytic activities.     

Hybrid nanocomposites of semiconductor nanoparticles and conjugated polyelectrolytes and their application as fluorescence biosensors

Weakly emissive silicon nanoparticles with an average diameter of about 5 nm are prepared via pulsed laser ablation of silicon wafers in water. Electrostatic assembly of water-soluble conjugated polyelectrolytes on the surface of the silicon nanoparticles steadily enhances the photoluminescence of these nanocomposites, indicating the possibility of energy transfer between the semiconductor nanoparticles and the conjugated polymer, or silicon nanoparticle-induced elimination of chain aggregates of the conjugated polyelectrolyte. Fluorescence emission of the hybrid silicon-conjugated polymer nanocomposites is steeply quenched by cytochrome c, and the minimum detection concentration for the redox-active protein is found to be 50 nM. The sensitization is realized by ultrafast photoinduced electron transfer between the electron-deficient protein and the conjugated polyelectrolyte binding on the silicon nanoparticle surfaces. The results offer guidelines to explore novel sensors for detecting nanoparticles, and also help develop high-efficiency sensory materials based on electrostatic complexes of conjugated polyelectrolytes and inorganic semiconductor nanoparticles.