Charge transfer behavior of Poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C61‐butyric acid methyl eser (PCBM) in solutions and in films were examined by photoluminescence (PL) spectroscopy. PL study in solutions indicated that separation distance between P3HT and PCBM affected charge transfer efficiency more seriously than the interface area issue between P3HT and PCBM. P3HT/PCBM film showed very effective photo‐induced charge transfer before post‐thermal annealing on the bi‐layer P3HT/PCBM film. Charge transfer efficiency was gradually diminished by the annealing‐induced phase separation between P3HT and PCBM as revealed by increasing PL emission intensity of P3HT. 相似文献
Optical properties of a blend thin film (1:1 wt) of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) exposed to a stepwise heating and cooling, have been reported and compared with the properties of pure PCBM and P3HT films. The UV–Vis(T) absorption measurements were performed in situ, during annealing and cooling runs, at the precisely defined temperatures, in a range of 20–210 °C. It was demonstrated that this new method allows to observe the changes of absorption coefficient spectra and absorption edge parameters: the energy gap (EG) and the Urbach energy (EU), connected with the length of conjugation and structural disorder of thin film, respectively. Several stages, during annealing/cooling runs, were distinguished for the P3HT:PCBM blend film and related to the following processes, as an increase of P3HT crystallinity in the blend, the orderly stacking of polymer chains, thermally induced structural defects and the phase separation, caused by an aggregation of PCBM in the polymer matrix. These changes were also observed on the P3HT:PCBM film surface, by means to the microscopic studies. 相似文献
Polymer-based organic solar cells are known to offer a poor stability in real use conditions, and the photodegradation of the active organic layer plays an important role in the reduced lifetime of the devices. This paper focuses on the photodegradation of two conjugated polymers used in organic solar cells, namely poly(2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene (MDMO-PPV) and poly(3-hexyylthiophene) (P3HT), and their blends with [60]PCBM (methano-fullerene[6,6]-phenyl C61-butyric acid methyl ester), a fullerene derivative. MDMO-PPV and P3HT thin films were submitted to photoageing (λ > 300 nm) in the presence and in the absence of oxygen. The mechanisms by which these polymers degrade were elucidated. P3HT, pristine and blended with PCBM, was shown to be much more stable under illumination than MDMO-PPV. The results showed that, if deposited on an inert substrate and well protected from oxygen with a convenient encapsulation, P3HT:PCBM based active layer should be intrinsically stable for several years in use conditions. 相似文献
The surface composition of poly(3-hexylthiophene-2,5-diyl) and fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (P3HT/PCBM) blend films could be changed by controlling the film formation process via using mixed solvents with different evaporation rates. The second solvent, with a higher boiling point than that of the first solvent and much better solubility for PCBM than P3HT, is chosen to mix with the first solvent with a lower boiling point and good solubility for both PCBM and P3HT. The slow evaporation rate of the second solvent provides enough time for PCBM to diffuse upwards during the solvent evaporation. Thus, the weight ratio of PCBM and P3HT (mPCBM/mP3HT) at surface of the blend films was varied from ca. 0.1 to ca. 0.72, i.e., it increases about seven times by changing from single solvent to mixed solvents. Meanwhile, the mixed solvents were in favor to form P3HT naonofiber network and enhance phase separation of P3HT/PCBM blend films. As a result, the power conversion efficiency of the device from mixed solvents with slow evaporation process was about 1.5 times of the one from single solvents. 相似文献
In this article, we present the research on the influence of the composition of thin films of a blend of poly (3-hexylthiophene −2,5-diyl) - P3HT with fullerene derivatives [6,6]-phenyl-C71-butyric acid methyl ester – PC70BM and [6,6]-phenyl-C61-butyric acid methyl ester – PC60BM on their thermal transitions. The influence of molar mass (Mw) of P3HT (Mw = 65.2; 54.2 and 34.1 kDa) and PCBM (PC60BM – Mw = 911 g/mol and PC70BM – Mw = 1031 g/mol) is examined in details. The article presents significantly expanded research compared to our previous work on thermal transitions in thin films of blend P3HT (Mw = 65.2 kDa) with PC60BM. For this reason, we also compare current results with previous ones. Here, we present for the first time a phase diagram of thin films of the P3HT(Mw = 65.2 kDa):PC70BM blend using variable-temperature ellipsometry. Our research reveals the presence of characteristic temperatures of pure phases in thin films of P3HT: PCBM blends. It turns out that the cold crystallization temperature of the P3HT phase in P3HT(Mw = 65.2 kDa):PC70BM blend films is lower than corresponding temperature in P3HT(Mw = 65.2 kDa):PC60BM blend films. At the same time, the cold crystallization temperature of the PC70BM phase behaves inversely. We demonstrate also that variable-temperature spectroscopic ellipsometry is a very sensitive technique for studying thermal transitions in these thin films. In addition, we show that the entire phase diagram can be determined based on the raw ellipsometric data analysis, e.g. using a delta angle at wavelength λ = 280 nm. 相似文献
The morphology of bulk-heterojunctions (BHJ) is critically important for conjugated polymer and fullerene blend solar cells. To alter the morphology, high pressure (gas phase) carbon dioxide (CO(2)) treatment is applied to poly(3-hexyl thiophene) (P3HT) and [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) blend films under ambient temperature. This process can achieve vertically phase separated morphology such that PCBM distributes toward the film surface, which is suggested by secondary ion mass spectroscopy (SIMS), contact angle, X-ray photoelectron spectroscopy (XPS) and cross-sectional scanning electron microscope (SEM) studies. While pristine P3HT films do not show a significant change upon CO(2) treatment, pristine PCBM films are plasticized in high pressure CO(2). Thus, PCBM is selectively plasticized by CO(2) in the blend film and is drawn towards the surface due to depressed surface energy, although P3HT tends to distribute around the surface without CO(2). This stratification process can enhance solar cell performance. 55% improvement is achieved in the power conversion efficiency of the CO(2) treated device compared to the untreated one, indicating that CO(2) treatment can be a good candidate for optimizing the morphology and enhancing the performance of BHJ polymer solar cells. 相似文献
Indium tin oxide (ITO) is used as a substrate was covered with 4-[4-(4-methoxy-N-naphthalen-2-ylanilino) phenyl] benzoic acid (MNA) as a self-assembled monolayer (SAM). Poly(3-hexylthiophene) (P3HT) and 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6) C61 (PCBM) were mixed and used as a donor–acceptor in organic solar cell (OSC). The MNA (SAM) layer is used as an interface instead of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS) for hole injection. The HOMO-LUMO energy level of MNA-SAM molecule and the electronic charge distribution were calculated theoretically using Chemissian software. The HOMO-LUMO energy level of the MNA is calculated as EHOMO = ?5.10 eV and ELUMO = ?1.60 eV. The OSC modified with MNA showed an efficient performance in the absence of PEDOT: PSS as hole transport layer. The annealing of the ITO/SAM/P3HT: PCBM films at different temperatures are also investigated to study the effect of reducing defects. The interface structures of the organic semiconductor layer on ITO were characterized by Atomic Force Microcopy (AFM). In addition, Kelvin Probe Microscopy (KPM) is used to understand how the annealing changes the surface potential energy of the ITO/SAM substrate. Using the KPM method, which measures the surface potential energy of the films, the energy bands of the ITO were increased to maximum 5.09 eV. The ITO/SAM/P3HT: PCBM film's surface potential was determined to be 0.18 eV after being annealed at 80 °C. The surface potential of the modified films was discovered to be 0.33 V and 0.39 V when the annealing temperature was raised from 80 °C to 120 °C and 160 °C. The maximum device efficiency was demonstrated by the ITO/SAM/P3HT: PCBM film after an hour of annealing at 160 °C. 相似文献
In this study double linked porphyrin-fullerene and phthalocyanine-fullerene dyads and a single linked phthalocyanine-fullerene dyad were studied as components in inverted organic solar cells (OSCs) equipped with the well known P3HT:PCBM bulk heterojunction as the photoactive layer. The dyad monolayers were deposited onto a surface of P3HT:PCBM by using the Langmuir-Sch?fer method, therefore forming oriented monolayers in which the electron donor (D) and the acceptor (A) exist as a close proximity pair in a 1:1 molar ratio. As a result of this structure short circuit current density (J(sc)), open circuit voltage (V(oc)), and power conversion efficiency (η) increased, while the fill factor (FF) remained the same. The devices which contained dyads with double linkage produced higher efficiencies than the one with a single linked dyad. This result can be explained in terms of molecular orientation. It was also verified that the prepared OSC devices have promising long term air stability. 相似文献
We have developed an improved small-angle X-ray scattering (SAXS) model and analysis methodology to quantitatively evaluate the nanostructures of a blend system. This method has been applied to resolve the various structures of self-organized poly(3-hexylthiophene)/C61-butyric acid methyl ester (P3HT/PCBM) thin active layer in a solar cell from the studies of both grazing-incidence small-angle X-ray scattering (GISAXS) and grazing-incidence X-ray diffraction (GIXRD). Tuning the various length scales of PCBM-related structures by a different annealing process can provide a flexible approach and better understanding to enhance the power conversion of the P3HT/PCBM solar cell. The quantitative structural characterization by this method includes (1) the mean size, volume fraction, and size distribution of aggregated PCBM clusters, (2) the specific interface area between PCBM and P3HT, (3) the local cluster agglomeration, and (4) the correlation length of the PCBM molecular network within the P3HT phase. The above terms are correlated well with the device performance. The various structural evolutions and transformations (growth and dissolution) between PCBM and P3HT with the variation of annealing history are demonstrated here. This work established a useful SAXS approach to present insight into the modeling of the morphology of P3HT/PCBM film. In situ GISAXS measurements were also conducted to provide informative details of thermal behavior and temporal evolution of PCBM-related structures during phase separation. The results of this investigation significantly extend the current knowledge of the relationship of bulk heterojunction morphology to device performance. 相似文献
The nature of main in-plane skeleton Raman modes (C=C and C-C stretch) of poly(3-hexylthiophene) (P3HT) in pristine and its blend thin films with [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) is studied by resonant and nonresonant Raman spectroscopy and Raman simulations. Under resonant conditions, the ordered phase of P3HT with respect to its disordered phase is identified by (a) a large shift in the C=C mode peak position to lower wavenumber (~21 cm(-1) shift), (b) a narrower fwhm of the C=C mode (~9 cm(-1) narrower), (c) a larger intensity of the C-C mode relative to the C=C mode (~56% larger), and (d) a very small Raman dispersion (~5 cm(-1)) of the C=C mode. The behavior of the C=C and C-C modes of the ordered and disordered phases of P3HT can be explained in terms of different molecular conformations. The C=C mode of P3HT in P3HT:PCBM blend films can be reproduced by simple superposition of the two peaks observed in different phases of P3HT (ordered and disordered). We quantify the molecular order of P3HT after blending with PCBM and the subsequent thermal annealing to be 42 ± 5% and 94 ± 5% in terms of the fraction of ordered P3HT phase, respectively. The increased molecular order of P3HT in blends upon annealing correlates well with enhanced device performance (J(SC), -4.79 to -8.72 mA/cm(2) and PCE, 1.07% to 3.39%). We demonstrate that Raman spectroscopy (particularly under resonant conditions) is a simple and powerful technique to study molecular order of conjugated polymers and their blend films. 相似文献
The nanostructure of thermally annealed thin films of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) blends on hydrophobic and hydrophilic substrates was studied to unravel the relationship between the substrate properties and the phase structure of polymer blends in confined geometry. Indeed, the nature of the employed substrates was found to affect the extent of phase separation, the PCBM aggregation state and the texture of the whole system. In particular, annealing below the melting temperature of the polymer yielded the formation of PCBM nanometric crystallites on the hydrophobic substrates, while mostly amorphous microscopic aggregates were formed on the hydrophilic ones. Moreover, while an enhanced in-plane orientation of P3HT lamellae was promoted on hydrophobic substrates, a markedly tilted geometry was produced on the hydrophilic ones. The observed effects were interpreted in terms of a simple model connecting the interface free energy for the blend films to the different polymer chain mobility and diffusion velocity of PCBM molecules on the different substrates. 相似文献
The structure of P3HT in P3HT:PCBM films is examined on a poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) substrate subjected to cryo‐cooling to low temperature (−143 °C) followed by gradual heating to 50 °C. The behavior of these systems is examined in the absence and presence of an Al electrode on top of the P3HT:PCBM film. At temperatures below −10 °C, only the type‐I phase of P3HT is observed. However, the type‐II phase of P3HT starts to form near −10 °C, in both the presence and absence of the Al layer. In the system without an Al layer, the type‐II phase disappears at 30 °C, but this phase persists to 50 °C in the presence of the Al layer. Concomitant with the formation of the type‐II phase, a 1:3 ordered P3HT type‐II (1/3,0,0) superlattice peak emerged. The type‐II domains tend to form near the Al electrode layer and show a higher degree of alignment than the type‐I crystals.
The thermal stability of poly(3-hexylthiophene) (P3HT) in its molten state was investigated in air and nitrogen atmospheres under no illumination conditions, with the aim of testing the feasibility of processing it using polymer melt techniques. A large set of different experimental characterization techniques was used including thermogravimetric analysis (TGA), rotational rheometry, infrared spectroscopy (FTIR-ATR), proton nuclear magnetic resonance spectroscopy (1H-NMR), gel permeation chromatography (GPC), UV-Vis and fluorescence spectroscopy. The results obtained strongly suggest that the processing of P3HT in its molten state is possible, without noticeable degradation, if carried out under nitrogen atmosphere and if the processing (residence) times are relatively short. Conversely, as expected, in a normal air atmosphere P3HT degrades rapidly at temperatures above its melting point. The effect of PCBM on the thermal stability of P3HT:PCBM blends in the molten state was also studied using TGA, and in air atmosphere PCBM is shown to delay oxidation. 相似文献
We have recently reported that dispersion forces can have drastic effects on the structure and charge separation in organic photovoltaics (OPVs) (Martinez et al., J. Phys. Chem. C 121, 20 134 [2017]). Here we investigate dimer complexes formed by the polymer P3HT and the fullerene derivative PCBM. We show how van der Waals (vdW) interactions affect the geometrical structure, which has strong effects on the electronic structure and UV-Vis absorption spectrum. Time-dependent density functional theory calculations demonstrate that the experimentally observed blue-shift of the absorption maximum of P3HT/PCBM OPV cells with respect to pure P3HT results mainly from distortions in P3HT due to vdW interactions between donor and acceptor fragments. Reduced absorption in the red region of the UV-Vis spectrum results from distortions of P3HT and small charge transfer between P3HT and PCBM. These results are in qualitative agreement with experiments and recent theoretical results on the corresponding solid-state films. 相似文献
We report on the ultrafast photoinduced charge separation processes in varying compositions of poly(3-hexylthiophene) (P3HT) blended with the electron acceptor [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Through the use of time-resolved terahertz spectroscopy, the time- and frequency-dependent complex photoconductivity is measured for samples with PCBM weight fractions (WPCBM) of 0, 0.2, 0.5, and 0.8. By analysis of the frequency-dependent complex conductivity, both the charge carrier yield and the average charge carrier mobility have been determined analytically and indicate a short (<0.2 nm) carrier mean free path and a suppressed long-range transport that is characteristic of carrier localization. Studies on pure films of P3HT demonstrate that charge carrier generation is an intrinsic feature of the polymer that occurs on the time scale of the excitation light, and this is attributed to the dissociation of bound polaron pairs that reside on adjacent polymer chains due to interchain charge transfer. Both interchain and interfacial charge transfer contribute to the measured photoconductivity from the blended samples; interfacial charge transfer increases as a function of increasing PCBM. The addition of PCBM to the polymer films surprisingly does not dramatically increase the production of charge carriers within the first 2 ps. However, charge carriers in the 0.2 and 0.5 blended films survive to much longer times than those in the P3HT and 0.8 films. 相似文献