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1.
    
The spectroscopic response of a poly(3‐hexylthiophene)/[6,6]‐phenyl‐C61‐butyric acid methyl ester (P3HT/PCBM)‐based bulk heterojunction solar cell is extended into the near infrared region (NIR) of the spectrum by adding the low bandgap polymer poly[2,6‐(4,4‐bis‐(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b´]‐dithiophene)‐alt‐4,7‐(2,1,3‐benzothiadiazole)] [PCPDTBT] to the blend. The dominant mechanism behind the enhanced photosensitivity of the ternary blend is found to be a two‐step process: first, an ultrafast and efficient photoinduced charge transfer generates positive charges on P3HT and PCPDTBT and a negative charge on PCBM. In a second step, the positive charge on PCPDTBT is transferred to P3HT. Thus, P3HT serves two purposes. On the one hand it is involved in the generation of charge carriers by the photoinduced electron transfer to PCBM, and, on the other hand, it forms the charge transport matrix for the positive carriers transferred from PCPDTBT. Other mechanisms, such as energy transfer or photoinduced charge transfer directly between the two polymers, are found to be absent or negligible.  相似文献   

2.
    
A fundamental limitation of the photocurrent of solar cells based on a blend of poly(2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐p‐phenylene vinylene) (MDMO‐PPV) and [6,6]‐phenyl C61‐butyric acid methyl ester (PCBM) is caused by the mobility of the slowest charge‐carrier species, the holes in the MDMO‐PPV. In order to allow the experimentally observed photocurrents electrostatically, a hole mobility of at least 10–8 m2 V–1 s–1 is required, which exceeds the observed hole mobility in pristine MDMO‐PPV by more than two orders of magnitude. However, from space‐charge‐limited conduction, admittance spectroscopy, and transient electroluminescence measurements, we found a hole mobility of 2 × 10–8 m2 V–1 s–1 for the MDMO‐PPV phase in the blend at room temperature. Consequently, the charge‐carrier transport in a MDMO‐PPV:PCBM‐based solar cell is much more balanced than previously assumed, which is a necessary requirement for the reported high fill factors of above 50 %.  相似文献   

3.
    
New electroactive and photoactive conjugated copolymers consisting of alternating 2,7‐carbazole and oligothiophene moieties linked by vinylene groups have been developed. Different oligothiophene units have been introduced to study the relationship between the polymer structure and the electronic properties. The resulting copolymers are characterized by UV‐vis spectroscopy, size‐exclusion chromatography, and thermal and electrochemical analyses. Bulk heterojunction photovoltaic cells from different copolymers and a soluble fullerene derivative, [6,6]‐phenyl‐C61 butyric acid methyl ester, have been fabricated, and promising preliminary results are obtained. For instance, non‐optimized devices using poly(N‐(4‐octyloxyphenyl)‐2,7‐carbazolenevinylene‐alt‐3″,4″‐dihexyl‐2,2′;5′,2″;5″,2″′;5″′,2″″‐quinquethiophenevinylene 1″,1″‐dioxide) as an absorbing and hole‐carrier semiconductor exhibit power conversion efficiency up to 0.8 % under air mass (AM) 1.5 illumination. These features make 2,7‐carbazolenevinylene‐based and related polymers attractive candidates for solar‐cell applications.  相似文献   

4.
    
The photoconductive properties of a novel low‐bandgap conjugated polymer, poly[2,6‐(4,4‐bis‐(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene)‐alt‐4,7‐(2,1,3‐benzothiadiazole)], PCPDTBT, with an optical energy gap of Eg ~ 1.5 eV, have been studied. The results of photoluminescence and photoconductivity measurements indicate efficient electron transfer from PCPDTBT to PCBM ([6,6]‐phenyl‐C61 butyric acid methyl ester, a fullerene derivative), where PCPDTBT acts as the electron donor and PCBM as the electron acceptor. Electron‐transfer facilitates charge separation and results in prolonged carrier lifetime, as observed by fast (t > 100 ps) transient photoconductivity measurements. The photoresponsivities of PCPDTBT and PCPDTBT:PCBM are comparable to those of poly(3‐hexylthiophene), P3HT, and P3HT:PCBM, respectively. Moreover, the spectral sensitivity of PCPDTBT:PCBM extends significantly deeper into the infrared, to 900 nm, than that of P3HT. The potential of PCPDTBT as a material for high‐efficiency polymer solar cells is discussed.  相似文献   

5.
    
The dependence of the performance of OC1C10‐PPV:PCBM (poly(2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐p‐phenylene vinylene):methanofullerene [6,6]‐phenyl C61‐butyric acid methyl ester)‐based bulk heterojunction solar cells on their composition has been investigated. With regard to charge transport, we demonstrate that the electron mobility gradually increases on increasing the PCBM weight ratio, up to 80 wt.‐%, and subsequently saturates to its bulk value. Surprisingly, the hole mobility in the PPV phase shows an identical behavior and saturates beyond 67 wt.‐% PCBM, a value which is more than two orders of magnitude higher than that of the pure polymer. The experimental electron and hole mobilities were used to study the photocurrent generation of OC1C10‐PPV:PCBM bulk‐heterojunction (BHJ) solar cells. From numerical calculations, it is shown that for PCBM concentrations exceeding 80 wt.‐% reduced light absorption is responsible for the loss of device performance. From 80 to 67 wt.‐%, the decrease in power conversion efficiency is mainly due to a decreased separation efficiency of bound electron–hole (e–h) pairs. Below 67 wt.‐%, the performance loss is governed by a combination of a reduced generation rate of e–h pairs and a strong decrease in hole transport.  相似文献   

6.
The performance of organic bulk heterojunction solar cells is strongly dependent on the donor/acceptor morphology. Morphological parameters, such as the extent and the composition of donor- and acceptor-rich domains, influence both the charge generation and the charge transport throughout the active layer. This work focuses on a polymer:fullerene system based on a small bandgap diketopyrrolopyrrole–quinquethiophene alternating copolymer (PDPP5T) mixed with [6,6]-phenyl-C71-butyric acid methyl ester ([70]PCBM) that is capable of efficiencies higher than 6%. By changing the processing conditions, the morphology can be varied from a coarse separated morphology, with fullerene domains (blobs) embedded in a polymer-rich matrix, to a completely mixed layer.  相似文献   

7.
    
Two new ruthenium complexes [Ru(dcbpy)(L)(NCS)2], where dcbpy is 4,4′‐dicarboxylic acid‐2,2′‐bipyridine and L is 3,8‐bis(4‐octylthiophen‐2‐yl)‐1,10‐phenanthroline (CYC‐P1) or 3,8‐bis(4‐octyl‐5‐(4‐octylthiophen‐2‐yl)thiophen‐2‐yl)‐1,10‐phenanthroline (CYC‐P2), are synthesized, characterized by physicochemical and semiempirical computational methods, and used as photosensitizers in nanocrystalline dye‐sensitized solar cells. It was found that the difference in light‐harvesting ability between CYC‐P1 and CYC‐P2 is associated mainly with the location of the frontier orbitals, in particular the highest occupied molecular orbital (HOMO). Increasing the conjugation length of the ancillary ligand decreases the energy of the metal‐to‐ligand charge transfer (MLCT) transition, but at the same time reduces the molar absorption coefficient, owing to the HOMO located partially on the ancillary ligand of the ruthenium complex. The incident photon‐to‐current conversion efficiency curves of the devices are consistent with the MLCT band of the complexes. Therefore, the overall efficiencies of CYC‐P1 and CYC‐P2 sensitized cells are 6.01 and 3.42 %, respectively, compared to a cis‐di(thiocyanato)‐bis(2,2′‐bipyridyl)‐4,4′‐dicarboxylate ruthenium(II)‐sensitized device, which is 7.70 % using the same device‐fabrication process and measuring parameters.  相似文献   

8.
    
The superior performance of certain polycrystalline (PX) solar cells compared to that of corresponding single‐crystal ones has been an enigma until recently. Conventional knowledge predicted that grain boundaries serve as traps and recombination centers for the photogenerated carriers, which should decrease cell performance. To understand if cell performance is limited by grain bulk, grain surface, and/or grain boundaries (GBs), we performed high‐resolution mapping of electronic properties of single GBs and grain surfaces in PX p‐CdTe/n‐CdS solar cells. Combining results from scanning electron and scanning probe microscopies, viz., capacitance, Kelvin probe, and conductive probe atomic force microscopies, and comparing images taken under varying conditions, allowed elimination of topography‐related artifacts and verification of the measured properties. Our experimental results led to several interesting conclusions: 1) current is depleted near GBs, while photocurrents are enhanced along the GB cores; 2) GB cores are inverted, which explains GB core conduction. Conclusions (1) and (2) imply that the regions around the GBs function as an extension of the carrier‐collection volume, i.e., they participate actively in the photovoltaic conversion process, while conclusion (2) implies minimal recombination at the GB cores; 3) the surface potential is diminished near the GBs; and 4) the photovoltaic and metallurgical junction in the n‐CdS/p‐CdTe devices coincide. These conclusions, taken together with gettering of defects and impurities from the bulk into the GBs, explain the good photovoltaic performance of these PX cells (at the expense of some voltage loss, as is indeed observed). We show that these CdTe GB features are induced by the CdCl2 heat treatment used to optimize these cells in the production process.  相似文献   

9.
    
The control of interfacial charge transfer is central to the design of photovoltaic devices. This charge transfer is strongly dependent upon the local chemical environment at each interface. In this paper we report a methodology for the fabrication of a novel nanostructured multicomponent film, employing a dual‐function supramolecular organic semiconductor to allow molecular‐level control of the local chemical composition at a nanostructured inorganic/organic semiconductor heterojunction. The multicomponent film comprises a lithium ion doped dual‐functional hole‐transporting material (Li+–DFHTM), sandwiched between a dye‐sensitized nanocrystalline TiO2 film and a mono‐functional organic hole‐transporting material (MFHTM). The DFHTM consists of a conjugated organic semiconductor with ion supporting side chains, designed to allow both electronic and ionic charge transport properties. The Li+–DFHTM layers provide a new and versatile way to control the interface electrostatics, and consequently the charge transfer, at a nanostructured dye‐sensitized inorganic/organic semiconductor heterojunction.  相似文献   

10.
    
Solid‐state dye‐sensitized solar cells employing a solid organic hole‐transport material (HTM) are currently under intensive investigation, since they offer a number of practical advantages over liquid‐electrolyte junction devices. Of particular importance to the design of such devices is the control of interfacial charge transfer. In this paper, the factors that determine the yield of hole transfer at the dye/HTM interface and its correlation with solid‐state‐cell performance are identified. To this end, a series of novel triarylamine type oligomers, varying in molecular weight and mobility, are studied. Transient absorption spectroscopy is used to determine hole‐transfer yields and pore‐penetration characteristics. No correlation between hole mobility and cell performance is observed. However, it is found that the photocurrent is directly proportional to the hole‐transfer yield. This hole‐transfer yield depends on the extent of pore penetration in the dye‐sensitized film as well as on the thermodynamic driving force ΔGdye–HTM for interfacial charge transfer. Future design of alternative solid‐state HTMs should focus on the optimization of pore‐filling properties and the control of interfacial energetics rather than on increasing material hole mobilities.  相似文献   

11.
    
A supramolecular complex [Ru(dcb)2(α‐CD‐5‐bpy)]Cl2 ( 1‐α‐CD ) (dcb = 4,4′‐dicarboxyl‐2,2′‐bipyridine, α‐CD‐5‐bpy = 6‐mono[5‐methyl(5′‐methyl‐2,2′‐bipyridyl)]‐permethylated α‐CD) (CD: cyclodextrin) based on a ruthenium tris‐bipyridyl core with an appended α‐CD cavity is designed and synthesised, in order to facilitate dye/redox couple interaction and dye regeneration in nanocrystalline TiO2 solar cells. The luminescent complex is fully characterized and anchored on mesoporous titania electrodes showing increased power‐conversion efficiency in solid‐state dye‐sensitized solar cells using a composite polymer electrolyte. Direct comparison of the properties of the CD complex with an analogous ruthenium complex [Ru(dcb)2(5,5′‐dmbpy)]Cl2 ( 2 ) (5,5′‐dmbpy = 5,5′‐dimethylbipyridine) without the CD cavity reveals that the photovoltaic performance of 1‐α‐CD is enhanced by about 40 % compared to 2 . Independent studies have shown complexation of the iodide redox couple to the CD in 1‐α‐CD . These results indicate that the CD moiety is able to act as a mediator and fine tune the photoelectrode/electrolyte interface.  相似文献   

12.
    
The photo‐induced charge transfer and the dynamics of persistent charge carriers in blends of semiconducting polymers and nanocrystals are investigated. Regioregular poly(3‐hexylthiophene) (P3HT) is used as the electron donor material, while the acceptor moiety is established by CdSe nanocrystals (nc‐CdSe) prepared via colloidal synthesis. As a reference system, organic blends of P3HT and [6,6]‐phenyl C61‐butyric acid methyl ester (PCBM) are studied as well. The light‐induced charge transfer between P3HT and the acceptor materials is studied by photoluminescence (PL), photo‐induced absorption (PIA) and light‐induced electron spin resonance spectroscopy (LESR). Compared to neat P3HT samples, both systems show an intensified formation of polarons in the polymer upon photo‐excitation, pointing out successful separation of photogenerated charge carriers. Additionally, relaxation of the persistent charge carriers is investigated, and significant differences are found between the hybrid composite and the purely organic system. While relaxation, reflected in the transient signal decay of the polaron signal, is fast in the organic system, the hybrid blends exhibit long‐term persistence. The appearance of a second, slow recombination channel indicates the existence of deep trap states in the hybrid system, which leads to the capture of a large fraction of charge carriers. A change of polymer conformation due to the presence of nc‐CdSe is revealed by low temperature LESR measurements and microwave saturation techniques. The impact of the different recombination behavior on the photovoltaic efficiency of both systems is discussed.  相似文献   

13.
The effects of residual catalyst impurities (palladium) on the hole mobility of a fluorene-thiophene-benzothiadiazole copolymer (poly{[4′-(9,9-bis(2-ethylhexyl)fluoren-2-yl)-2′,1′,3′-benzothiadiazole-7,7′-diyl]-co-[2′-(9,9-bis(2-ethylhexyl)fluoren-2-yl)thien-7,5′-diyl]}) (PFB-co-FT), as well as on its photovoltaic and photophysical response when blended with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), are investigated. Two samples of the copolymer, only differing for the Pd content (9 and 3360 ppm), are considered and compared. The transport of positive carriers is characterized by a lower mobility and a higher dispersion in the Pd-rich PFB-co-FT sample. The photovoltaic parameters of PFB-co-FT:PCBM solar cells show a significant dependence on the residual catalyst impurities, attributed to a different concentration of trap states. Variations in charge mobility and trapping induced by impurities was confirmed also by ESR (Electron Spin Resonance) experiments: an increased concentration of trapped charges in the presence of a higher level of metal impurities was revealed by light induced ESR, while the variation of polaron mobility correlates with the lifetime variation of the photogenerated PCBM triplet state detected by time-resolved ESR. All experimental evidences point to a strong effect of Pd impurities on the transport properties of charge carriers.  相似文献   

14.
    
The charge transport mechanism and the macroscopic dielectric constant in polycrystalline device materials commonly exhibit several components such as electrode‐sample interface, grain boundary and bulk contributions. In order to gain precise understanding of the functionality of polycrystalline electroceramic device materials it is essential to deconvolute these contributions. The paradigm of functional NTC thermistor ceramics based on thick film spinel manganates has been studied by temperature dependent alternating current impedance spectroscopy. Three typical relaxation phenomena were detected, which all showed a separated temperature dependence of resistivity consistent with thermally activated charge transport. The dominating grain boundary and the interface contributions exhibited distinctively different capacitance allowing clear identification. The composite nature of the dielectric properties in polycrystalline functional ceramics was emphasized, and impedance spectroscopy was shown to be a powerful tool to account for and model such behavior.  相似文献   

15.
    
Well‐crystallized Nb‐doped anatase TiO2 nanoparticles are prepared by a novel synthetic route and successfully used as the photoanode of dye‐sensitized solar cells (DSSCs). The homogenous distribution of Nb in the TiO2 lattice is confirmed by scanning transmission electron microscopy (STEM) elemental mapping and line‐scanning analyses. After Nb doping, the conductivity of the TiO2 powder increases, and its flat‐band potential (Vfb) has a positive shift. The energy‐conversion efficiency of a cell based on 5.0 mol% Nb‐doped TiO2 is significantly better, by about 18.2%, compared to that of a cell based on undoped TiO2. The as‐prepared Nb‐doped TiO2 material is proven in detail to be a better photoanode material than pure TiO2, and this new synthetic approach using a water‐soluble precursor provides a simple and versatile way to prepare excellent photoanode materials.  相似文献   

16.
    
A study of the photo‐oxidation of films of poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene vinylene] (MDMO‐PPV) blended with [6,6]‐phenyl C61‐butyric acid methyl ester (PCBM), and solar cells based thereon, is presented. Solar‐cell performance is degraded primarily through loss in short‐circuit current density, JSC. The effect of the same photodegradation treatment on the optical‐absorption, charge‐recombination, and charge‐transport properties of the active layer is studied. It is concluded that the loss in JSC is primarily due to a reduction in charge‐carrier mobility, owing to the creation of more deep traps in the polymer during photo‐oxidation. Recombination is slowed down by the degradation and cannot therefore explain the loss in photocurrent. Optical absorption is reduced by photo‐bleaching, but the size of this effect alone is insufficient to explain the loss in device photocurrent.  相似文献   

17.
    
Evidence is presented for the formation of a weak ground‐state charge‐transfer complex in the blend films of poly[9,9‐dioctylfluorene‐coN‐(4‐methoxyphenyl)diphenylamine] polymer (TFMO) and [6,6]‐phenyl‐C61 butyric acid methyl ester (PCBM), using photothermal deflection spectroscopy (PDS) and photoluminescence (PL) spectroscopy. Comparison of this polymer blend with other polyfluorene polymer/PCBM blends shows that the appearance of this ground‐state charge‐transfer complex is correlated to the ionization potential of the polymer, but not to the optical gap of the polymer or the surface morphology of the blend film. Moreover, the polymer/PCBM blend films in which this charge‐transfer complex is observed also exhibit efficient photocurrent generation in photovoltaic devices, suggesting that the charge‐transfer complex may be involved in charge separation. Possible mechanisms for this charge‐transfer state formation are discussed as well as the significance of this finding to the understanding and optimization of polymer blend solar cells.  相似文献   

18.
    
Several recent papers have demonstrated that charge‐carrier mobility in organic field‐effect transistors made of vacuum‐evaporated films may become temperature‐independent at low temperature. To account for this behavior, we developed a model based on the polycrystalline nature of these films, where charge transport is mostly limited by grain boundaries. The free‐carrier density in the intergrain regions is controlled by traps, which leads to the formation of back‐to‐back Schottky barriers at each side of the grain boundaries. The height and width of these barriers is estimated from solving Poisson’s equation using the graded‐channel approximation. It is shown that in most cases the barrier width is negligibly small as compared to the physical size of the grain boundaries. In the high‐temperature regime, the conducting channel can be simply described by grains and grain boundaries connected in series, so that the overall resistance reduces to that of the grain boundaries. At low temperatures, tunneling through the barrier becomes predominant, leading to temperature‐independent mobility. A complete two‐dimensional model for charge tunneling through the barriers is developed. A quantitative check of the model is made by least‐squares fitting of the gate voltage‐dependent current measured on an octithiophene transistor at low temperature, which gives a reasonable determination of the trap density and size of the grain boundaries.  相似文献   

19.
The technique of photo-CELIV (charge extraction by linearly increasing voltage) is one of the more straightforward and popular approaches to measure the faster carrier mobility in measurement geometries that are relevant for operational solar cells and other optoelectronic devices. It has been used to demonstrate a time-dependent photocarrier mobility in pristine polymers, attributed to energetic relaxation within the density of states. Conversely, in solar cell blends, the presence or absence of such energetic relaxation on transport timescales remains under debate. We developed a complete numerical model and performed photo-CELIV experiments on the model high efficiency organic solar cell blend poly[3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-naphthalene] (PDPP-TNT):[6,6]-phenyl-C71-butyric-acid-methyl-ester (PC70BM). In the studied solar cells a constant, time-independent mobility on the scale relevant to charge extraction was observed, where thermalisation of photocarriers occurs on time scales much shorter than the transit time. Therefore, photocarrier relaxation effects are insignificant for charge transport in these efficient photovoltaic devices.  相似文献   

20.
    
The photoconductivity of solution‐cast Zn1–xMgxO (x=0‐0.4) and poly(3‐hexylthiophene) (P3HT) thin films, and Zn1‐xMgxO/P3HT bilayers is investigated using Time‐Resolved Microwave Conductivity (TRMC) with the aim of determining the locus of free charge carrier generation in the bilayer system. The photoconductivity of Zn1–xMgxO thin films, under illumination with 300 nm laser pulses, is limited by the formation of stable excitons and by scattering of the carriers at grain boundaries. The electron mobility in Zn1–xMgxO films decreases exponentially with Mg concentration, up to x=0.4. In agreement with previous work, free carriers are observed in the P3HT film under illumination with 500 nm pulses in the absence of an acceptor. Under illumination with 500 nm pulses, where only the polymer absorbs, the TRMC signal for the Zn1–xMgxO/P3HT bilayers for x≥0.2 is the same as that of pure P3HT, indicating that free carrier generation in these bilayers occurs predominately by exciton dissociation in the polymer bulk, and not at the interface between the polymer and the solution‐cast oxide. At lower Mg concentrations (x<0.2) the TRMC signal increases with decreasing x following the dependence of the electron mobility in the oxide but its light intensity dependence remains consistent with free carrier generation in the polymer bulk. To explain these results and previously published photovoltaic device data (Adv. Funct. Mater. 2007 , 17, 264) we propose that free carrier generation in the bilayers predominantly occurs in the bulk of P3HT, and is followed by electron injection to the oxide to yield photocurrent in photovoltaic cells. The dependence of the TRMC signal of the bilayers on Mg concentration is explained in terms of the yield for free carrier generation in the polymer and the relative contributions of electrons in the oxide and holes in the polymer.  相似文献   

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