Influence of thermal annealing-induced molecular aggregation on film properties and photovoltaic performance of bulk heterojunction solar cells based on a squaraine dye

Squaraine (SQ) dyes have been considered as efficient photoactive materials for organic solar cells. In this work, we purposely controlled the molecular aggregation of an SQ dye, 2,4-bis[4-(N,N-dibutylamino)-2-dihydroxyphenyl] SQ (DBSQ-(OH)₂) in the DBSQ(OH)₂:[6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) blend film by using the thermal annealing method, to study the influence of the molecular aggregation on film properties as well as the photovoltaic performance of DBSQ(OH)₂:PCBM-based bulk heterojunction (BHJ) solar cells. Our results demonstrate that thermal annealing may change the aggregation behavior of DBSQ(OH)₂ in the DBSQ(OH)₂:PCBM film, and thus significantly influence the surface morphology, optical and electrical properties of the blend film, as well as the photovoltaic performance of DBSQ(OH)₂:PCBM BHJ cells.     

Mapping local photocurrents in polymer/fullerene solar cells with photoconductive atomic force microscopy

The performance of organic solar cells is highly dependent on film morphology. However, directly correlating local film structures with device performance remains challenging. We demonstrate that photoconductive atomic force microscopy (pcAFM) can be used to map local photocurrents with 20 nm resolution in donor/acceptor blend solar cells of the conjugated polymer poly[2-methoxy-5-(3',7'-dimethyloctyl-oxy)-1,4-phenylene vinylene] (MDMO-PPV) with the fullerene (6,6)-phenyl-C61-butyric acid methyl ester (PCBM) spin-coated from various solvents. We present photocurrent maps under short-circuit conditions (zero applied bias) as well as under various applied voltages. We find significant variation in the short-circuit current between regions that appear identical in AFM topography. These variations occur from one domain to another as well as on larger length scales incorporating multiple domains. These results suggest that the performance of polymer-fullerene blends can still be improved through better control of morphology.     

Comparative study: the effect of annealing conditions on the properties of P3HT:PCBM blends

This paper presents a detailed study on the role of various annealing treatments on organic poly(3-hexylthiophene) and [6]-phenyl-C₆₁-butyric acid methyl ester blends under different experimental conditions. A combination of analytical tools is used to study the alteration of the phase separation, structure and photovoltaic properties of the P3HT:PCBM blend during the annealing process. Results showed that the thermal annealing yields PCBM “needle-like” crystals and that prolonged heat treatment leads to extensive phase separation, as demonstrated by the growth in the size and quantity of PCBM crystals. The substrate annealing method demonstrated an optimal morphology by eradicating and suppressing the formation of fullerene clusters across the film, resulting in longer P3HT fibrils with smaller diameter. Improved optical constants, PL quenching and a decrease in the P3HT optical bad-gap were demonstrated for the substrate annealed films due to the limited diffusion of the PCBM molecules. An effective strategy for determining an optimized morphology through substrate annealing treatment is therefore revealed for improved device efficiency.     

Preparation and photo-induced charge transfer of the composites based on branched CdS nanocrystals and PCPDTBT

Rich branched CdS nanocrystals were synthesized by a facile hydrothermal treatment from Cd(NO₃)₂, thiourea and hexamethylenetetramine [(CH₂)₆N₄, HMT], where HMT acted as a capping agent. The morphology, structure and phase composition of CdS nanostructures were examined by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), and high-resolution TEM. The composites based on CdS nanocrystals and 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) have been prepared by mixing of the two components in chloroform. The optical properties of the composites are investigated using ultraviolet–visible (UV–Vis) absorption and photoluminescence (PL) spectroscopies. A significant fluorescence quenching of PCPDTBT in the composites is observed at high CdS nanocrystals/PCPDTBT ratios, indicating that the photo-induced charge transfer occurred due to the energy level offset between the donor PCPDTBT and the acceptor CdS nanocrystals.     

Morphology evolution via self-organization and lateral and vertical diffusion in polymer:fullerene solar cell blends

Control of blend morphology at the microscopic scale is critical for optimizing the power conversion efficiency of plastic solar cells based on blends of conjugated polymer with fullerene derivatives. In the case of bulk heterojunctions of regioregular poly(3-hexylthiophene) (P3HT) and a soluble fullerene derivative ([6,6]-phenyl C61-butyric acid methyl ester, PCBM), both blend morphology and photovoltaic device performance are influenced by various treatments, including choice of solvent, rate of drying, thermal annealing and vapour annealing. Although the protocols differ significantly, the maximum power conversion efficiency values reported for the various techniques are comparable (4-5%). In this paper, we demonstrate that these techniques all lead to a common arrangement of the components, which consists of a vertically and laterally phase-separated blend of crystalline P3HT and PCBM. We propose a morphology evolution that consists of an initial crystallization of P3HT chains, followed by diffusion of PCBM molecules to nucleation sites, at which aggregates of PCBM then grow.     

Formation of phenyl-C<Subscript>61</Subscript>-butyric acid methyl ester nanoscale aggregates after supercritical carbon dioxide annealing

In this study, we successfully developed a novel method to create [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) nanoscale aggregates using supercritical carbon dioxide (scCO₂) annealing and fabricated bulk heterojunction (BHJ) solar cells with the nanoscale PCBM to improve device performance. PCBM forms nanoscale aggregates with a size of approximately 70 nm after scCO₂ annealing at 11 MPa and 50 °C for 60 min. However, PCBM remains amorphous after thermal annealing (TA) at 150 °C for 5 min. The morphology, structure, and crystallinity of poly(3-hexylthiophene) (P3HT) in the scCO₂-treated P3HT film are nearly the same as those in the TA-treated P3HT film. In the P3HT/PCBM blend, the formation of PCBM nanoscale aggregates by scCO₂ treatment decreases the disturbance for P3HT crystallization and improves diffusion and regular packing of P3HT molecular chains. This increases the crystallinity of P3HT so that it becomes higher than that in the TA-treated blend film. The nanoscale aggregates of PCBM and the higher crystallinity of P3HT give the scCO₂-treated P3HT/PCBM BHJ solar cells a maximum power conversion efficiency (PCE) of 2.74%, which is much higher than that of the as-cast device (PCE is 1.70%) and a little higher than the highest PCE (2.64%) of thermally annealed devices. These results indicate that scCO₂ is an effective, mild, and environmental method to modulate the nanoscale aggregates of PCBM and to improve the PCE of BHJ solar cells. However, the size of the PCBM aggregates is a little larger than the most suitable size of the exciton diffusion length, leading to limited improvement of the PCE.     

Inverted polymer solar cells with an ultrathin lithium fluoride buffer layer

An ultrathin lithium fluoride (LiF) buffer layer was applied to inverted polymer solar cells with P3HT [poly(3-hexylthiophene)]:PCBM [[6,6]-phenyl C61-butyric acid methyl ester] blend films. By inserting the LiF layer between the transparent electrode and the P3HT:PCBM blend film, all parameters, including the short-circuit current, the open-circuit voltage and the fill factor, were enhanced compared to those of a reference cell without the LiF layer. The power conversion efficiency of the device with the LiF layer was thereby improved by more than 300% relative to the reference cell.     

Study of the microstructure of inkjet-printed P3HT:PCBM blend for photovoltaic applications

Recently, great interest has been devoted to cost-effective alternative energy sources such as organic solar cells because of the mechanical flexibility and the versatility of chemical structure, the low cost of fabrication, and ease of processing. As regards this last point, the possibility to deposit organic materials from solutions at low temperatures makes them employable for fabricating printed solar cells by direct printing methods. In this study, we used the inkjet-printing technology to deposit P3HT blends with various fullerene acceptors ([60]PCBM, [70]PCBM and bis[60]PCBM) dissolved in single solvents, 1,2-dichlorobenzene (DCB) and chlorobenzene (CB), and their mixtures. After optimizing the printing parameters (printhead speed, drop emission frequency, and substrate temperature), the effect of the solvents on the morphology of the photoactive layers was analyzed through Raman spectroscopy and atomic force microscopy. Polymer solar cells with the structure glass/ITO/PEDOT:PSS/blend/Ca/Al were fabricated and characterized by current–voltage (I–V) measurements under 100 mW/cm² AM 1.5G illumination. A comparative study of the performances of the devices was performed based on three different fullerene derivatives, correlating them to the microstructure of the printed blend films. The optimal devices were obtained when the blend films were deposited from a mixture of DCB:CB 4:1 by volume: this was in agreement with the most favorable morphology of these films.     

The role of solvent and morphology on miscibility of methanofullerene and poly(3-hexylthiophene)

A bicontinuous, percolating bulk heterojunction morphology is integral to organic polymer solar cells. Understanding the factors affecting the miscibility of photovoltaic polymers with a fullerene electron acceptor molecule is a key to controlling the morphology. Starting from discreet pure phases - a poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) bilayer film - the evolution of the P3HT-PCBM interface was studied with particular attention to the role of residual solvent in P3HT on PCBM interdiffusion. This investigation shows that in the bilayer geometry PCBM can rapidly diffuse into amorphous P3HT, but phase separation is maintained if the P3HT layer is cast from a very volatile solvent or if it is annealed prior to casting the PCBM overlayer to complete the bilayer geometry.     

Imaging the bulk nanoscale morphology of organic solar cell blends using helium ion microscopy

We use helium ion microscopy (HeIM) to image the nanostructure of poly(3-hexylthiophene)/[6,6]-phenyl-C(61)-butric acid methyl ester (P3HT/PCBM) blend thin-films. Specifically, we study a blend thin-film subject to a thermal anneal at 140 °C and use a plasma-etching technique to gain access to the bulk of the blend thin-films. We observe a domain structure within the bulk of the film that is not apparent at the film-surface and tentatively identify a network of slightly elongated PCBM domains having a spatial periodicity of (20 ± 4) nm a length of (12 ± 8) nm.     

Improvements of fill factor in solar cells based on blends of polyfluorene copolymers as electron donors

The photovoltaic characteristics of solar cells based on alternating polyfluorene copolymers, poly(2,7-(9,9-dioctyl-fluorene)-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)) (APFO-3), and poly(2,7-(9,9-didodecyl-fluorene)-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)) (APFO-4), blended with an electron acceptor fullerene molecule [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM), have been investigated and compared. The two copolymers have the same aromatic backbone structure but differ by the length of their alkyl side chain. The overall photovoltaic performance of the solar cells is comparable irrespective of the copolymer used in the active layer. However, the fill factor (FF) values of the devices are strongly affected by the copolymer type. Higher FF values were realized in solar cells with APFO-4 (with longer alkyl side chain)/PCBM bulk heterojunction active layer. On the other hand, devices with blends of APFO-3/APFO-4/PCBM were found to render fill factor values that are intermediate between the values obtained in solar cells with APFO-3/PCBM and APFO-4/PCBM active film. Upon using APFO-3/APFO-4 blends as electron donors, the cell efficiency can be enhanced by about 16% as compared to cells with either APFO-3 or APFO-4. The transport of holes in each polymer obeys the model of hopping transport in disordered media. However, the degree of energetic barrier against hopping was found to be larger in APFO-3. The tuning of the photovoltaic parameters will be discussed based on studies of hole transport in the pure polymer films, and morphology of blend layers. The effect of bipolar transport in PCBM will also be discussed.     

Organic memory using [6,6]-phenyl-C(61) butyric acid methyl ester: morphology, thickness and concentration dependence studies

We report a simple memory device in which the fullerene-derivative [6,6]-phenyl-C(61) butyric acid methyl ester (PCBM) mixed with inert polystyrene (PS) matrix is sandwiched between two aluminum (Al) electrodes. Transmission electron microscopy (TEM) images of PCBM:PS films showed well controlled morphology without forming any aggregates at low weight percentages (<10?wt%) of PCBM in PS. Energy dispersive x-ray spectroscopy (EDX) analysis of the device cross-sections indicated that the thermal evaporation of the Al electrodes did not lead to the inclusion of Al metal nanoparticles into the active PCBM:PS film. Above a threshold voltage of <3?V, independent of thickness, a consistent negative differential resistance (NDR) is observed in devices in the thickness range from 200 to 350?nm made from solutions with 4-10?wt% of PCBM in PS. We found that the threshold voltage (V(th)) for switching from the high-impedance state to the low-impedance state, the voltage at maximum current density (V(max)) and the voltage at minimum current density (V(min)) in the NDR regime are constant within this thickness range. The current density ratio at V(max) and V(min) is more than or equal to 10, increasing with thickness. Furthermore, the current density is exponentially dependent on the longest tunneling jump between two PCBM molecules, suggesting a tunneling mechanism between individual PCBM molecules. This is further supported with temperature independent NDR down to 240?K.     

Field-effect transistor-based solution-processed colloidal quantum dot photodetector with broad bandwidth into near-infrared region

We demonstrate a solution-processed colloidal quantum dot (CQDs) photodetector with the configuration of a field-effect transistor (FET), in which the drain and source electrodes are fabricated by a shadow mask. By blending PbS CQDs into the hybrid blend, poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C(61)-butyric acid methylester (PCBM), the photosensitive spectrum of the nanocomposite blend is extended into the near-infrared region. A FET-based photodetector ITO/PMMA (180?nm)/P3HT:PCBM:PbS (110?nm)/Al, in which PMMA (polymethylmethacrylate) acts as the dielectric layer and P3HT:PCBM:PbS (in weight ratio of 1:1:1) as the active layer, shows a broad spectral bandwidth, a responsivity of 0.391?mA?W(-1) and a specific detectivity of 1.31?×?10(11) Jones are obtained at V(GS)?=?1?V under 600?nm illumination with an intensity of 30?μW?cm(-2). Therefore, it provides an easy way to fabricate such a FET-based photodetector with a channel length of some hundreds of micrometers by a shadow mask.     

Investigation of aged organic solar cell stacks by cross-sectional transmission electron microscopy coupled with elemental analysis

Polymer solar cells are of great interest as candidates for future low-cost and lightweight energy sources. One of the major reliability problems of these devices is the thermal instability of the blend morphology typically composed of poly(3-hexylthiophene) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT and PCBM, respectively). Phase segregation of the blend has been extensively investigated by transmission electron microscopy (TEM) on free-standing films. In this study, we investigate in cross-section the morphology reorganization of P3HT:PCBM layers confined between poly(3,4-ethylenedioxythiophene)poly-(styrenesulfonate) (PEDOT:PSS) and a metal electrode similar to functional solar cell devices. The strengths of different TEM imaging and compositional analysis modes for the investigation of organic solar cells is illustrated by studying the evolution of the material stack with ageing conditions. Combining TEM imaging of the layer stack with energy-dispersive X-ray and energy loss electron spectroscopy, we not only gain insight into the phase segregation process but also explore the interdiffusion in the layer stack. More than 100 °C annealing leads to the formation of elongated protrusions ranging 100–500 nm. Thinning of the neighboring areas indicates lateral diffusion in the stack. Interestingly, the metal cathode remains still conformal over these large aggregates. The particles protrude through the metal layer only after prolonged (>100 h) annealing at higher temperatures when they reach several micrometer in height and are identified as crystalline PCBM-like material. Hence, almost full phase separation occurs by PCBM agglomeration and diffusion over large distances. Elemental analysis confirms that diffusion of the electrode materials (In, Sn and Yb) into the P3HT:PCBM stack remains below the detection limit.     

Three dimensional analysis of self-structuring organic thin films using time-of-flight secondary ion mass spectrometry

Selective sub-micrometer structuring of phase-separating organic semiconductor materials has recently got into focus for providing the opportunity of further improvements in optoelectronic device applications. Here we present a 3D-time-of-flight secondary ion mass spectrometry (3D-TOF-SIMS) depth profiling investigation on spin-coated blends consisting of [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) and a cationic cyanine dye (1,1′-diethyl-3,3,3′,3′-tetramethylcarbocyanine iodide). TOF-SIMS provides the required lateral and depth resolution to resolve material and molecular inhomogeneities and phase separation in the blend. The data are illustrating the three-dimensional arrangement of the substances involved and confirm results of earlier studies using atomic force microscopy, UV-vis spectroscopy and x-ray photoelectron spectroscopy, and which have shown well distinguishable morphological features. The formation of this domain structure has been found to be dependent on the absolute as well as the individual film thickness, in accordance with models based on thin liquid two-layer films. Honey-comb like primary structures with micrometer dimension were found in samples containing small amounts of dye molecules in the deposition solution. In this case a thin dye deposit on PCBM was detected, which is well separated from the dye layer at the substrate. For this type of sample, we discuss an extended model of film formation based on partial depletion of dye molecules during film solidification, resulting in two individual dye layers.     

Evolution of vertical phase separation in P3HT:PCBM thin films induced by thermal annealing

The achievement of the desirable morphology at the nanometer scale of bulk heterojunctions consisting of a conjugated polymer with fullerene derivatives is a prerequisite in order to optimize the power conversion efficiency of organic solar cells. The various experimental conditions such as the choice of solvent, drying rates and annealing have been found to significantly affect the blend morphology and the final performance of the photovoltaic device. In this work, we focus on the effects of post deposition thermal annealing at 140 °C on the blend morphology, the optical and structural properties of bulk heterojunctions that consist of poly(3-hexylthiophene) (P3HT) and a methanofullerene derivative (PCBM). The post thermal annealing modifies the distribution of the P3HT and the PCBM inside the blend films, as it has been found by Spectroscopic Ellipsometry studies in the visible to far-ultraviolet spectral range. Phase separation was identified by AFM and GIXRD as a result of a slow drying process which took place after the spin coating process. The increase of the annealing time resulted to a significant increase of the P3HT crystallinity at the top regions of the blend films.     

Development of air stable polymer solar cells using an inverted gold on top anode structure

We developed indium-tin-oxide/perylene diimide (or bathocuproine (BCP))/poly(2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene (MEH-PPV) and [6,6]-phenyl C₆₀ butyric acid methyl ester (PCBM) blend/copper phthalocyanine (CuPc)/Au interpenetrated network polymer solar cells in order to improve air stability. The stability properties of the cells were characterized by current-voltage measurements under the influence of light and air. We achieved long lifetime solar cells which work at least 2 weeks under ambient air conditions without encapsulation. Solar energy conversion efficiency of the cells decrease 30% of the first day value at the end of 2 weeks. Photocurrent absorption properties of the devices were also investigated.     

Improvement of photovoltaic properties by addition of a perylene compound in P3HT:PCBM BHJ system

The synthesized n-type perylene derivative, N,N'-bis-(4-bromophenyl)-1,6,7,12-tetrakis(4-n-butoxy-phenoxy)-3,4,9,10-perylene tetracarboxdiimide (PIBr), was applied as an additive to polymer solar cells (PSCs) with P3HT [poly(3-hexylthiophene)]:PCBM [[6,6]-phenyl C61-butyric acid methyl ester] blend films. Without post thermal annealing, a considerable improvement of about 98% in power conversion efficiency was achieved by the addition of 1 wt% PIBr into a P3HT:PCBM layer, when compared with that of reference cell without the additive. The results, in combination with relevant data from UV-Vis. absorption, photoluminescence, X-ray measurements and carrier mobility studies, revealed that the addition of the perylene compound within active layer contributed to more effective charge transfer and enhanced electron mobility.     

Generation of native polythiophene/PCBM composite nanoparticles via the combination of ultrasonic micronization of droplets and thermocleaving from aqueous dispersion

We report the preparation of native polythiophene (n-PT)/[6, 6]-phenyl-C61-butyric acid methyl ester (PCBM) composite nanoparticles from a poly[3-(2-methylhex-2-yl)oxy-carbonyldithiophene] (P3MHOCT)/PCBM aqueous dispersion prepared from an ultrasonically generated emulsion. The subsequent steps involve both ultrasonic generation of microdroplets in argon as a carrier gas and drying followed by thermocleaving of the P3MHOCT component in the gas phase. The chemical transition from P3MHOCT to n-PT was confirmed by Fourier transform infrared (FTIR) spectroscopy. The morphology and size of n-PT/PCBM nanoparticles were determined by atomic force microscopy (AFM), small-angle x-ray scattering (SAXS) and grazing incidence SAXS (GISAXS), giving an average size of ～ 140?nm. The GISAXS results reveal that n-PT/PCBM nanoparticles pack in an ordered structure as opposed to the P3MHOCT/PCBM nanoparticles. The successful vapour-phase preparation of phase-separated n-PT/PCBM nanoparticles provides a new route to all-aqueous processing of conjugated materials relevant to efficient polymer solar cells with long operational stability. The use of ultrasound was involved in both liquid and gas phases demonstrating it as a low-cost processing method.