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1.
The function of organic solar cells is based upon charge photogeneration at donor/acceptor heterojunctions. In this paper, the origin of the improvement in short circuit current of poly(3‐hexylthiophene)/6,6‐phenyl C61‐butyric acid methyl ester (P3HT/PCBM) solar cells with thermal annealing is examined. Transient absorption spectroscopy is employed to demonstrate that thermal annealing results in an approximate two‐fold increase in the yield of dissociated charges. The enhanced charge generation is correlated with a decrease in P3HT's ionization potential upon thermal annealing. These observations are in excellent quantitative agreement with a model in which efficient dissociation of the bound radical pair into free charges is dependent upon the bound radical state being thermally hot when initially generated, enabling it to overcome its coulombic binding energy. These observations provide strong evidence that the lowest unoccupied molecular orbital (LUMO) level offset of annealed P3HT/PCBM blends may be only just sufficient to drive efficient charge generation in polythiophene‐based solar cells. This has important implications for current strategies to optimize organic photovoltaic device performance based upon the development of smaller optical bandgap polymers.  相似文献   

2.
Mixtures of poly(3‐octylthiophene) (P3OT) with graphite nanoparticles have been investigated by scanning force microscopy (SFM) techniques. The morphology as well as the mechanical and electrical properties of the blends has been characterized at the nanoscale level as a function of the carbon nanoparticle content in the blend. An increase in the concentration of carbon nanoparticles results in an increase in the surface roughness of the blend and the appearance of distinct regions with well‐defined electrical and mechanical properties. At intermediate concentrations (5–10 wt % of carbon nanoparticles), the samples show pure P3OT regions, as well as round regions containing a mixture of the polymer and carbon nanoparticles, while at higher concentrations (> 15 wt %), the entire sample is composed of this mixture. The interface between the two regions has been studied by electrostatic scanning force microscopy (ESFM) as a function of the applied tip–sample voltage. ESFM provides evidence for the creation of new electronic states at the heterojunction. The observed results can be qualitatively explained in terms of the electronic properties of the individual molecular components, P3OT, functionalized graphite nanoparticles, and their corresponding heterojunction. The implications of these results for organic polymer solar cells are also discussed.  相似文献   

3.
A series of poly(3‐hexylthiophene)s (P3HTs) and poly(3‐butylthiophene)s (P3BTs) with predetermined molecular weights and varying polydispersities are prepared using a simplified Grignard metathesis chain‐growth polymerization. Techniques were elaborated to prepare extremely high molecular weight P3HT (number‐average molecular weight of around 280 000 g mol–1) with a low polydispersity (< 1.1) without resorting to fractionation. Optimization of the annealing of a series of solar cells based on blends of poly(3‐alkylthiophene)s (P3ATs) and [6,6]‐phenyl C61 butyric acid methyl ester indicates that the polydispersities, molecular weights, and degrees of conjugation of the P3ATs all have an important impact not only on cell characteristics but also on the most effective annealing temperature required. The results indicate that each cell requires annealing treatments specific to the type of polymer and its molecular weight distribution.  相似文献   

4.
We describe a systematic study on the influence of different experimental conditions on the Kelvin probe force microscopy (KPFM) quantitative determination of the local surface potential (SP) of organic semiconducting nanostructures of perylene‐bis‐dicarboximide (PDI) self‐assembled at surfaces. We focus on the effect of the amplitude, frequency, and phase of the oscillating voltage on the absolute surface potential value of a given PDI nanostructure at a surface. Moreover, we investigate the role played by the KPFM measuring mode employed and the tip–sample distance in the surface potential mapping by lift‐mode KPFM. We define the ideal general conditions to obtain a reproducible quantitative estimation of the SP and we find that by decreasing the tip–sample distance, the area of substrate contributing to the recorded SP in a given location of the surface becomes smaller. This leads to an improvement of the lateral resolution, although a more predominant effect of polarization is observed. Thus, quantitative SP measurements of these nanostructures become less reliable and the SP signal is more unstable. We have also devised a semi‐quantitative theoretical model to simulate the KPFM image by taking into account the interplay of the different work functions of tip and nanostructure as well as the nanostructure polarizability. The good agreement between the model and experimental results demonstrates that it is possible to simulate both the change in local SP at increasing tip–sample distances and the 2D potential images obtained on PDI/highly oriented pyrolytic graphite samples. These results are important as they make it possible to gain a quantitative determination of the local surface potential of π‐conjugated nanostructures; thus, they pave the way towards the optimization of the electronic properties of electroactive nanometer‐scale architectures for organic (nano)electronic applications.  相似文献   

5.
Scanning force microscopy (SFM) is used to study the surface morphology of spin‐coated thin films of the ion‐transport polymer poly(ethylene oxide) (PEO) blended with either cyclodextrin (CD)‐threaded conjugated polyrotaxanes based on poly(4,4′‐diphenylene‐vinylene) (PDV), β‐CD–PDV, or their uninsulated PDV analogues. Both the polyrotaxanes and their blends with PEO are of interest as active materials in light‐emitting devices. The SFM analysis of the blended films supported on mica and on indium tin oxide (ITO) reveals in both cases a morphology that reflects the substrate topography on the (sub‐)micrometer scale and is characterized by an absence of the surface structure that is usually associated with phase segregation. This observation confirms a good miscibility of the two hydrophilic components, when deposited by using spin‐coating, as suggested by the luminescence data on devices and thin films. Clear evidence of phase segregation is instead found when blending PEO with a new organic‐soluble conjugated polymer such as a silylated poly(fluorene)‐alt‐poly(para‐phenylene) based polyrotaxane (THS–β‐CD–PF–PPP). The results obtained are relevant to the understanding of the factors influencing the interfacial and the intermolecular interactions with a view to optimizing the performance of light‐emitting diodes, and light‐emitting electrochemical cells based on supramolecularly engineered organic polymers.  相似文献   

6.
Space resolved Stark spectroscopy is introduced as a non invasive optical technique for imaging electric field distribution in organic semiconductors. Stark spectroscopy relies on the electric field induced change in the absorption/reflection. It is shown that local monitoring of Stark shift with confocal spatial resolution provides quantitative information on the strength of the local field as well as charge distribution within the transport channel.  相似文献   

7.
A new method for the preparation of active layers of polymeric solar cells without the need for thermal post‐treatment to obtain optimal performance is presented. Poly(3‐hexylthiophene) (P3HT) nanofibers are obtained in highly concentrated solutions, which enables the fabrication of nanostructured films on various substrates. Here, the preparation of these fibers along with their characterization in solution and in the solid state is detailed. By mixing these nanofibers with a molecular acceptor such as [6,6]‐phenyl C61‐butyric acid methyl ester (PCBM) in solution, it is possible to obtain in a simple process a highly efficient active layer for organic solar cells with a demonstrated power conversion efficiency (PCE) of up to 3.6 %. The compatibility of the room‐temperature process developed herein with commonly used plastic substrates may lead to applications such as the development of large‐area flexible solar cells.  相似文献   

8.
Kelvin probe force microscopy provides quantitative insight into the electronic properties of thin molecular layers, as shown by the results of P. Samorì and co‐workers on p. 1407. In the cartoon shown in the inside front cover, a scanning charged tip probes the local surface potential of a self‐assembled layer, inducing charge polarization into a nanoscale “effective area”. These measurements make it possible to unravel the interplay between structural and electronic properties of molecule‐based materials and devices. We describe a systematic study on the influence of different experimental conditions on the Kelvin probe force microscopy (KPFM) quantitative determination of the local surface potential (SP) of organic semiconducting nanostructures of perylene‐bis‐dicarboximide (PDI) self‐assembled at surfaces. We focus on the effect of the amplitude, frequency, and phase of the oscillating voltage on the absolute surface potential value of a given PDI nanostructure at a surface. Moreover, we investigate the role played by the KPFM measuring mode employed and the tip–sample distance in the surface potential mapping by lift‐mode KPFM. We define the ideal general conditions to obtain a reproducible quantitative estimation of the SP and we find that by decreasing the tip–sample distance, the area of substrate contributing to the recorded SP in a given location of the surface becomes smaller. This leads to an improvement of the lateral resolution, although a more predominant effect of polarization is observed. Thus, quantitative SP measurements of these nanostructures become less reliable and the SP signal is more unstable. We have also devised a semi‐quantitative theoretical model to simulate the KPFM image by taking into account the interplay of the different work functions of tip and nanostructure as well as the nanostructure polarizability. The good agreement between the model and experimental results demonstrates that it is possible to simulate both the change in local SP at increasing tip–sample distances and the 2D potential images obtained on PDI/highly oriented pyrolytic graphite samples. These results are important as they make it possible to gain a quantitative determination of the local surface potential of π‐conjugated nanostructures; thus, they pave the way towards the optimization of the electronic properties of electroactive nanometer‐scale architectures for organic (nano)electronic applications.  相似文献   

9.
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   

10.
11.
The effects of anode/active layer interface modification in bulk‐heterojunction organic photovoltaic (OPV) cells is investigated using poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) and/or a hole‐transporting/electron‐blocking blend of 4,4′‐bis[(p‐trichlorosilylpropylphenyl)‐phenylamino]biphenyl (TPDSi2) and poly[9,9‐dioctylfluorene‐coN‐[4‐(3‐methylpropyl)]‐diphenylamine] (TFB) as interfacial layers (IFLs). Current–voltage data in the dark and AM1.5G light show that the TPDSi2:TFB IFL yields MDMO‐PPV:PCBM OPVs with substantially increased open‐circuit voltage (Voc), power conversion efficiency, and thermal stability versus devices having no IFL or PEDOT:PSS. Using PEDOT:PSS and TPDSi2:TFB together in the same cell greatly reduces dark current and produces the highest Voc (0.91 V) by combining the electron‐blocking effects of both layers. ITO anode pre‐treatment was investigated by X‐ray photoelectron spectroscopy to understand why oxygen plasma, UV ozone, and solvent cleaning markedly affect cell response in combination with each IFL. O2 plasma and UV ozone treatment most effectively clean the ITO surface and are found most effective in preparing the surface for PEDOT:PSS deposition; UV ozone produces optimum solar cells with the TPDSi2:TFB IFL. Solvent cleaning leaves significant residual carbon contamination on the ITO and is best followed by O2 plasma or UV ozone treatment.  相似文献   

12.
The self‐organization of the polymer in solar cells based on regioregular poly(3‐hexylthiophene) (RR‐P3HT):[6,6]‐phenyl C61‐butyric acid methyl ester (PCBM) is studied systematically as a function of the spin‐coating time ts (varied from 20–80 s), which controls the solvent annealing time ta, the time taken by the solvent to dry after the spin‐coating process. These blend films are characterized by photoluminescence spectroscopy, UV‐vis absorption spectroscopy, atomic force microscopy, and grazing incidence X‐ray diffraction (GIXRD) measurements. The results indicate that the π‐conjugated structure of RR‐P3HT in the films is optimally developed when ta is greater than 1 min (ts ~ 50 s). For t s < 50 s, both the short‐circuit current (JSC) and the power conversion efficiency (PCE) of the corresponding polymer solar cells show a plateau region, whereas for 50 < ts < 55 s, the JSC and PCE values are significantly decreased, suggesting that there is a major change in the ordering of the polymer in this time window. The PCE decreases from 3.6 % for a film with a highly ordered π‐conjugated structure of RR‐P3HT to 1.2 % for a less‐ordered film. GIXRD results confirm the change in the ordering of the polymer. In particular, the incident photon‐to‐electron conversion efficiency spectrum of the less‐ordered solar cell shows a clear loss in both the overall magnitude and the long‐wavelength response. The solvent annealing effect is also studied for devices with different concentrations of PCBM (PCBM concentrations ranging from 25 to 67 wt %). Under “solvent annealing” conditions, the polymer is seen to be ordered even at 67 wt % PCBM loading. The open‐circuit voltage (VOC) is also affected by the ordering of the polymer and the PCBM loading in the active layer.  相似文献   

13.
In this work, an aqueous acidic thin‐layer‐based strategy for fabricating nanostructures on silicon by using atomic force microscopy (AFM) nanolithography is presented. The approach involves the formation of microscale droplets via dilute hydrofluoride (DHF) etching, the conversion of the droplets to acidic thin layers by AFM‐probe scanning, and subsequent lithographic operations using a biased probe in the aqueous layers. By varying the concentration of the acidic DHF layers, the thin layers can facilitate the creation of both positive and negative patterns, such as oxide dots and Si pores, through anodic oxidation and dissolution. In particular, the anodic oxidation in the acidic media is associated with the field‐enhanced nonequilibrium dissociation of the weak electrolyte. The Si pore structure formation is related to the field‐assisted dissolution of anodic oxides and the Si substrate. The acidic‐layer‐based technique allows switching between different lithographic modes by changing the acidity of the DHF layers, and is complementary to bulk solution‐based and local meniscus‐based approaches in AFM nanolithography. In principle, this method can also be extended to other materials that have similar reactions with DHF.  相似文献   

14.
Ultra‐thin films of subphthalocyanine (SubPc) were grown onto Si/SiO2 substrates by organic molecular beam deposition and the complex refractive index has been characterized by spectroscopic ellipsometry. The peak maximum in the extinction coefficient is determined to be 1.6 at 590 nm and the dielectric constant equals 3.9 in the limit of long wavelength. These values are extraordinary high when compared to the well‐known metal‐phthalocyanines and will be beneficial for the performance in a photovoltaic cell. The amorphous SubPc structure on top of indium‐tin‐oxide (ITO) as well as quartz glass is imaged by atomic force microscopy and scanning electron microscopy and we have characterized the nearly flat surface topology. Next, subphthalocyanine films in combination with buckminsterfullerene (C60) have been studied in a planar bilayer donor/acceptor heterojunction by current density‐voltage characterization under AM 1.5 simulated illumination at various light intensities. A power conversion efficiency of 3.0 % under 1 sun was measured. Finally, the external and internal quantum efficiencies demonstrated peak maxima at 590 nm of 46 % and 55 %, respectively. Considering the abrupt junction at the donor/acceptor interface, the electron transfer from SubPc to the acceptor material is thus determined to be highly efficient.  相似文献   

15.
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   

16.
The influence of the solvent on the morphology and performance of polymer solar cells is investigated in devices based on blends of the polyfluorene copolymer, poly(2,7‐(9,9‐dioctyl‐fluorene)‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole)), and [6,6]‐phenyl‐C61‐butyric acid methyl ester. The blends are spin‐coated from chloroform or from chloroform mixed with small amounts of xylene, toluene, or chlorobenzene. The devices are characterized under monochromatic light and solar illumination AM1.5 (AM: air mass). An enhancement of the photocurrent density is observed in diodes made from chloroform mixed with chlorobenzene, and reduced photocurrent density is observed in diodes made from chloroform mixed with xylene or toluene, compared to diodes made from neat chloroform. The open‐circuit voltages are almost the same in all diodes. The surfaces of the active layers are imaged using atomic force microscopy. Height images indicate that a finer and more uniform distribution of domains corresponds to the diodes with enhanced photocurrent that are made from chloroform mixed with chlorobenzene, while a structure with larger domains is associated with the lower photocurrents in the diodes made from chloroform mixed with xylene or toluene. The influence of the morphology on the excited‐state dynamics and charge generation is investigated using time‐resolved spectroscopy. Fast formation of bound charge pairs followed by their conversion into free charge carriers is resolved, and excitation‐intensity‐dependent non‐geminate recombination of free charges is observed. A significant enhancement in free‐charge‐carrier generation is observed on introducing chlorobenzene into chloroform. Imaging photocurrent generation from the solar cells with a light‐pulse technique shows an inhomogeneous photocurrent distribution, which is related to the undulations in the thickness of the active layer. Thicker parts of the diodes yield higher photocurrent values.  相似文献   

17.
Potential characterization of deflected piezoelectric nanowires (NWs) is of great interest for current development of electromechanical nanogenerators that harvest ambient mechanical energy. In this paper, a Kelvin probe microscopy (KPM) technique hybridizing scanning KPM (SKPM) with atomic force microscope (AFM) surface‐approach spectroscopy methods for characterizing in‐plane piezoelectric potential of ZnO microwires (MWs) is presented. This technique decouples the scanning motion of the AFM tip from sample topography, and thus effectively eliminates artifacts induced by high topographical variations along the edges of MWs/NWs which make characterization by conventional SKPM inappropriate or impossible. By virtue of the topography/tip motion decoupling approach, the electrical potential can also be mapped in a three‐dimensional (3D) spatial volume above the sample surface. Therefore, this technique is named 3DKPM. Through 3DKPM mapping, the piezopotential generated by a laterally deflected ZnO MW was determined by extracting the potential asymmetry from opposite sides of the MW. The measurement results agree well with theoretical predictions. Integrating an external bias to the MW sample allowed direct observation of piezopotential and carrier concentration coupling phenomenon in ZnO, opening a door toward quantitative microscopic investigation of the piezotronic effect. With further positioning refinements, 3DKPM could become a powerful technique for the characterization of piezoelectric potential and related effects in micro/nanostructures of high topographical variations, as well as development of MW/NW‐based piezoelectric nanodevices.  相似文献   

18.
The power conversion efficiency of organic and hybrid solar cells is commonly reduced by a low open‐circuit voltage (VOC). In these cases, the VOC is significantly less than the energy of the lowest energy absorbed photon, divided by the elementary charge q. The low photovoltage originates from characteristically large band offsets between the electron donor and acceptor species. Here a simple method is reported to systematically tune the band offset in a π‐conjugated polymer–metal oxide hybrid donor–acceptor system in order to maximize the VOC. It is demonstrated that substitution of magnesium into a zinc oxide acceptor (ZnMgO) reduces the band offset and results in a substantial increase in the VOC of poly(3‐hexylthiophene) (P3HT)–ZnMgO planar devices. The VOC is seen to increase from 500 mV at x = 0 up to values in excess of 900 mV for x = 0.35. A concomitant increase in overall device efficiency is seen as x is increased from 0 to 0.25, with a maximum power‐conversion efficiency of 0.5 % obtained at x = 0.25, beyond which the efficiency decreases because of increased series resistance in the device. This work provides a new tool for understanding the role of the donor–acceptor band offset in hybrid photovoltaics and for maximizing the photovoltage and power‐conversion efficiency in such devices.  相似文献   

19.
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   

20.
Polymer‐based photovoltaic devices have been fabricated by blending the conjugated polymer, poly(2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene) (MEH‐PPV) with the buckminsterfullerene, C60. The photo‐induced current and the open‐circuit voltage show a strong dependence on the polymer processing conditions. It was found that the photovoltaic devices fabricated with tetrahydrofuran or chloroform (non‐aromatic solvents) have smaller photocurrents under same reverse bias as well as higher open circuit voltages than the devices fabricated with xylene, dichlorobenzene, or chlorobenzene (aromatic solvents). The device performance dependence on the processing solvent is attributed to the different solvation‐induced polymer morphology.  相似文献   

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