Polythiophene/fullerene bulk heterojunction solar cell fabricated via electrochemical co-deposition

We report a polythiophene/fullerene (C₆₀) bulk heterojunction solar cell fabricated via electrochemical co-deposition of polythiophene (PTh) and fullerene on an indium tin oxide (ITO) glass electrode modified with a thin layer of poly (3,4-ethylenedioxylthiophene) (PEDOT). Although the amount of C₆₀ incorporated into the film was relatively low, the photovoltaic performance of the cell based on the polythiophene/fullerene (PTh/C₆₀) composite film was remarkably improved.     

Long-lived bulk heterojunction solar cells fabricated with photo-oxidation resistant polymer

We report the fabrication of long-lived polymer solar cells using a new donor-acceptor type alternating copolymer, poly(5,5,10,10-tetrakis(2-ethylhexyl)-5,10-dihydroindeno[2,1-α]indene-2,7-diyl)-co-4,7-di-2-thienyl-2,1,3-benzothiadiazole (PININE-DTBT) in bulk heterojunction composites with the fullerene derivative [6,6]-phenyl C₇₀-butyricacidmethyl ester (PC₇₀BM). The PININE-DTBT:PC₇₀BM solar cells exhibit an extended device lifetime (as compared with other polymer systems) with a reasonable power conversion efficiency of ∼2.7% under air mass 1.5 global (AM 1.5 G) irradiation of 100 mW/cm². The long-lived feature of the devices originates from the photo-oxidation resistant backbone unit and the deep HOMO (highest occupied molecular orbital) level of PININE-DTBT.     

Effect of organic salt doping on the performance of single layer bulk heterojunction organic solar cell

The effect of organic salt, tetrabutylammonium hexafluorophosphate (TBAPF₆) doping on the performance of single layer bulk heterojunction organic solar cell with ITO/MEHPPV:PCBM/Al structure was investigated where indium tin oxide (ITO) was used as anode, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEHPPV) as donor, (6,6)-phenyl-C61 butyric acid methyl ester (PCBM) as acceptor and aluminium (Al) as cathode. In contrast to the undoped device, the electric field-treated device doped with TBAPF₆ exhibited better solar cell performance under illumination with a halogen projector lamp at 100 mW/cm². The short circuit current density and the open circuit voltage of the doped device increased from 0.54 μA/cm² to 6.41 μA/cm² and from 0.24 V to 0.50 V, respectively as compared to those of the undoped device. The significant improvement was attributed to the increase of built-in electric field caused by accumulation of ionic species at the active layer/electrode interfaces.     

Thermally stable organic bulk heterojunction photovoltaic cells incorporating an amorphous fullerene derivative as an electron acceptor

A highly soluble amorphous fullerene derivative substituted with dihexylfluorene (DHFCBM) was synthesized and used as an electron acceptor material for P3HT-based bulk heterojunction solar cells. By fitting the experimental J-V curves with space charge limited current equation, the electron mobility of DHFCBM was determined to be 4×10⁻⁴ cm²/Vs, possibly leading to balanced charge transport with P3HT. From structural and morphological analysis using X-ray diffraction, UV-vis absorption, and atomic force microscopy, we found that the amorphous nature of DHFCBM stabilized the nanomorphology of P3HT:DHFCBM blend films under high temperature annealing. By optimizing blend ratios and annealing conditions, P3HT:DHFCBM-based solar cells yielded power conversion efficiencies in excess of 3%. In addition, the fabricated cells maintained their initial performances even after high temperature annealing for long times, as predicted from the stable nanomorphology. We believe that the use of thermally stable amorphous fullerene as an electron acceptor can be a promising strategy for commercialization of organic solar cells.     

Benzoselenadiazole-core asymmetric D-A-A small molecule for solution processed bulk heterojunction organic solar cells

The present work is accounted on the designing of a new and efficient asymmetric organic chromophore, named 4-(3,5-bis [trifluoromethyl] phenyl)-7-(5′-hexyl-[2,2′-bithiophen]-5-yl)-benzo[c [1, 2, 5]selenadiazole, (RT-BSe-F), based on benzoselenadiazole central acceptor building blocks. The acceptor unit of 3,5-bis (trifluoromethyl) benzene and donor unit of alkyl bithiophene attached with benzoselenadiazole central unit showed large impacts on the optical and electrochemical properties. The reasonable optical band gap of ~2.02 eV and HOMO of −5.33 eV were obtained by RT-BSe-F chromophore due to a strong electron accepting nature of fluorine based compound. With 3,5-bis(trifluoromethyl) benzene unit, the absorption of RT-BSe-F chromophore was considerably increased to higher wavelength which might enhance the crystallinity of thin film with high hole mobility. RT-BSe-F chromophore was effectively applied to fabricate the solution-processed bulk-heterojunction organic solar cells (BHJ-OSCs) and attained a high power conversion efficiency (PCE) of ~3.75% accompanying high J_SC of ~12.56 mA cm⁻², FF of ~0.42 and V_OC of ~0.71 V. The obtained high PCE might be associated to a high surface energy of TiO₂ layer as buffer and the use of high mobility organic RT-BSe-F chromophore.     

Efficient bulk heterojunction solar cells using an alternating phenylenevinylene copolymer with dithenyl(thienothiadiazole) segments as donor and PCBM or modified PCBM as acceptor

A novel low band gap alternating phenylenevinylene copolymer, P, with dithenyl (thienothiadiazole) segments was synthesized by Heck coupling. It was soluble in common organic solvents, showed broad absorption curve with long-wavelength absorption maximum at 580–598 nm and optical band gap of 1.74 eV, which is comparable with the electrochemical band gap of about 1.80 eV. P (electron donor) was blended with PCBM or modified PCBM i.e. F (electron acceptor) to fabricate bulk heterojunction (BHJ) solar cells. The power conversion efficiency (PCE) of the devices based on P:PCBM and P:F cast from 1.2-dichlorobenzene (DCB) was found to be 1.40% and 2.32%, respectively. The higher value of PCE for the device with P:F as compared to P:PCBM is attributed to the increase in both short circuit current (J_sc) and open circuit voltage (V_oc). The increase in the J_sc is due to the stronger light absorption of F in visible region as compared to PCBM, i.e. more exciton generation in the blend. On the other hand, the higher difference between the LUMO levels of P and F, as compared to P and PCBM is responsible for the enhancement in the V_oc. A maximum overall PCE of 4.20% was obtained for the BHJ polymer cell based on the active layer (P:F) deposited from mixed solvents 1-chloronapthalene/1,2-dichlorobenzene (CN/DCB) and subsequent thermal annealing at 120 °C. This improvement in the PCE has been attributed to the enhanced crystallinity of the blend and more balanced charge transport in the device due to the thermal treatment.     

Hybrid inverted bulk heterojunction solar cells with nanoimprinted TiO2 nanopores

Photovoltaic devices with highly ordered nanoporous titanium dioxide (titania; TiO₂) were fabricated to improve the photovoltaic performances by increasing TiO₂ interface area. The nanoimprinting lithography technique with polymethyl methacrylate (PMMA) mold was used to form titania nanopores. The solar cell with poly(3-hexylthiophene) (P3HT):[6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) active layer on nanoporous titania showed higher power conversion efficiency (PCE) of 1.49% than on flat titania of 1.18%. The improved efficiency using nanoporous titania is interpreted with the enhanced-charge separation and collection by increasing the interface area between TiO₂ and active layer.     

Synthesis and photovoltaic properties of novel PPV-derivatives tethered with spiro-bifluorene unit for polymer solar cells

New thermally robust photoactive arylenevinylene-based conjugated polymers, poly[3,6-bis(3,7-dimethyloctyloxy)-9,9-spirobifluorenyl-2,7-vinylene] [(OC₁₀)₂-spiro-PFV] and poly[{3,6-bis(3,7-dimethyloctyloxy)-9,9-spirobifluorenyl-2,7-vinylene}-co-2-{methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene}] [(OC₁₀)₂-spiro-PFV-co-MEH-PPV], were synthesized and used to fabricate polymer solar cells. Bulk heterojunction solar cells fabricated by blending the new copolymers, spiro-PFV and (OC₁₀)₂-spiro-PFV-co-MEH-PPV, as an electron donor with the fullerene derivative, [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) as an electron acceptor. The effects of electron donor to acceptor ratio, thickness of photoactive layer, and the cathode structures on the power conversion efficiency (PCE) in polymer solar cells were studied. The copolymer feed ratio was found to have a considerable effect on the PCE. The maximum PCE of 1.30% was achieved with (OC₁₀)₂-spiro-PFV-co-MEH-PPV.     

Plasma treatment of zinc oxide-nanoparticles:polyaniline blend as an active layer for the hybrid bulk heterojunction solar cell applications

In this experimental work, plasma treatment of the active layer in the bulk heterojunction solar cells was studied. The active layers consisting of zinc oxide nanoparticles:polyaniline were spin-coated on indium tin oxide covered glasses then kept in the cold plasma medium for different treatment times. The J-V characteristics were considered under air mass 1.5G standard illumination, and variations of the open-circuit voltages and short circuit currents were studied under different treatment times. The results show that there is an optimum treatment time to improve the properties of the layers. In order to understand the origin of this effect, the Hall coefficient, along with ultraviolet-visible spectra were measured, and for studying the topological impact of plasma on the surface of the layers, atomic force microscopy and Fourier-transform infrared spectroscopy were considered. The measurements confirmed the time dependency of the open-circuit voltages and short circuit currents of the cells on the plasma treatment times. Atomic force microscopy of the layers shows the significant topological effects of the plasma treatments on the surface of the active layers for different treatment times.     

Efficient organic tandem cell combining a solid state dye-sensitized and a vacuum deposited bulk heterojunction solar cell

In this letter, we report on an efficient organic tandem solar cell combining a solid state dye-sensitized with a ZnPc/C₆₀-based, vacuum deposited bulk heterojunction solar cell. Due to an effective serial connection of both subcells and to the complementary absorption of the dyes used, a power conversion efficiency of η_p=(6.0±0.1)% was achieved under simulated AM 1.5 illumination. The device parameters are , and FF=(54±1)%.     

Effects of a perfluorinated compound as an additive on the power conversion efficiencies of polymer solar cells

A perfluorinated compound, 4-amino-2-(trifluoromethyl)benzonitrile (ATMB), 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. The addition of 6 wt% ATMB to a P3HT:PCBM layer led to an increased power conversion efficiency of 5.03% due to the enhanced short circuit current and fill factor when compared with that of the reference cell without an additive. On the other hand, the devices with 4-aminobenzonitrile as an additive, not containing fluorine atoms in the molecule, displayed lower PCEs than that of the reference cell. The UV-visible absorption spectra, X-ray measurements and carrier mobility studies revealed that ATMB facilitated ordering of the P3HT chains, resulting in higher absorbance, larger crystal size of P3HT and enhanced hole mobility. XPS depth profiling measurements also showed that the additive molecules were predominantly positioned in the range of 25 nm under the surface of the P3HT:PCBM film, leading to improved fill factor.     

Photovoltaic properties of poly(benzothiadiazole-thiophene-co-bithiophene) as donor in polymer solar cells

We report the photovoltaic properties of a D-A copolymer, poly(benzothiadiazole-thiophene-co-bithiophene) (PBTTbT), containing the donor (D) unit of oligothiophene with a hexyl side chain and the acceptor (A) unit of 2,1,3-benzothiadiazole (BT) with a methyl side chain. The geometry, electronic and absorption spectroscopic properties of bithiophene-benzothiadiazole-thiophene monomer (M1) of the polymer were investigated theoretically by the density functional theory (DFT) method for deep understanding the relationship of the structure and properties of the polymer. Polymer solar cells (PSCs) were fabricated with PBTTbT as an electron donor blended with [6,6]-phenyl-C71-butyric acid methyl ester (PC₇₀BM) as an electron acceptor. The power conversion efficiency (PCE) of PSC is 0.87% for an optimized PBTTbT:PC₇₀BM weight ratio of 1:3, under the illumination of AM 1.5, 100 mW/cm². With the additive of 1% 1,8-dioctanedithiol and thermal annealing at 130 °C for 15 min, the PCE of the device was improved to 1.98%. The efficiency improvement of the device was ascribed to a better morphology of the PBTTbT:PC₇₀BM active layer with the additive and thermal annealing.     

Bulk and contact resistance in P3HT:PCBM heterojunction solar cells

In this paper, the series resistance of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM) bulk heterojunction (BHJ) organic solar cells (OSC) has been studied. The series resistance of thermal annealed and un-annealed devices with different active layer thicknesses was measured. The series resistance of the organic solar cells consists of the bulk resistance of the active layer itself and the specific contact resistance between the active layer and the electrode. The bulk resistance and contact resistance were extracted from the measured series resistance using the vertical transmission line model (TLM) method. By fabricating solar cell devices with different active layer thicknesses, a relationship of the series resistance with thickness was established from which bulk and contact resistances were derived. We have also found that thermal annealing helps reduce both contact resistance and bulk resistance significantly; the contact resistance dropped by a factor of 2, while the bulk resistance decreased by a factor of 8. Results have shown that for an annealed P3HT:PCBM device that has an active layer thickness of 85 nm (optimum thickness for high efficiency), 17% of the total series resistance was due to the contact resistance, and bulk resistance contributed the rest 83%. The bulk resistance value for thermal annealed organic solar cell device with an active area of 0.1 cm² was found to be 150 Ω, and the measured specific contact resistance was 3.1 Ω cm². The measured bulk and contact resistance values are much higher as compared to the high efficiency silicon solar cells. Bulk resistance and contact resistance need to be further decreased in order to achieve higher organic solar cell efficiency.     

Effect of CsF interlayer on the performance of polymer bulk heterojunction solar cells

We fabricated polymer bulk heterojunction solar cells with blends of poly (2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV) and [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) by using CsF as an interlayer. Under illumination, the device with Al/CsF cathode exhibited a higher energy conversion efficiency compared to the Al/LiF cathode. The performance improvement with the Al/CsF cathode comes from the lower series resistance, which is almost constant (~6 Ω cm²) for all the CsF layer thicknesses included in the present study. The mechanism responsible for this phenomenon is attributed to the dissociation of CsF upon Al deposition to liberate Cs with a low work function, which reduces the interface resistance of the active layer/cathode and enhances the interior electric field for more efficient charge transport in the device.     

Temperature dependence of polymer/fullerene organic solar cells

The temperature dependence of bulk heterojunction organic solar cells fabricated from poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) was studied in detail. Individual materials as well as blends and solar cell devices were examined. Light absorption, photoluminescence, quantum efficiency, total efficiency, and current-voltage characteristics were studied from temperatures −10 to 140 °C. A method and apparatus for testing these parameters at various temperatures is described. Parameters were measured for both unannealed and annealed samples to give insight into the annealing process. It was found that absorption and photoluminescence of devices shift both position and intensity with varying temperatures. Quantum efficiency and total efficiency were monitored as they increased with annealing. Once annealed, device efficiency peaked at temperatures from 10 to 60 °C because of competing temperature dependent effects of the materials. The temperature dependence study provides valuable information on device properties and thermal annealing.     

Comparison of normal and inverse poly(3-hexylthiophene)/fullerene solar cell architectures

Polymer solar cells based on regioregular poly(3-hexylthiophene) (P3HT) and ([6,6]-phenyl-C61-butyric acid methyl ester) (PCBM) were fabricated with two different architectures (normal and inverse). Normal cells using indium tin oxide (ITO) as anode and Al as cathode were fabricated on polyester foils and illuminated from substrate side. Inverse cells using Ti as cathode and ultrathin Au layer as anode were illuminated from the top side covered by a transparent Au contact. Both Au layer and PET/ITO show comparable transmission in the spectral range where P3HT absorbs. Inverse cells showed comparable device parameters to normal cell (open circuit voltage 550 mV, short circuit current 6.25 mA/cm², fill factor 0.33 and white light power conversion efficiency 1.12%).     

New amorphous small molecules—Synthesis, characterization and their application in bulk heterojunction solar cells

We successfully synthesized a series of novel solution processible small molecules (2TAPM, 4TAPM and 2BTAPM) consisting of electron-accepting unit (2-pyran-4-ylidenemalononitrile) (PM) and electron-donating unit (Triphenylamine and different thiophene units). Differential scanning calorimetry (DSC) measurement indicates that these small molecules are amorphous. UV-vis absorption spectra show that the combination of PM with moieties having gradually increased electron-donating ability results in an enhanced intramolecular charge transfer (ICT) transition, leading to an extension of the absorption spectral range and a reduction of the band gap of the molecules. Both cyclic voltammetry measurement and theoretical calculations show that the highest occupied molecular orbital (HOMO) energy levels of the molecules could be fine-tuned by changing the electron-donating ability of the electron-donating moieties. The bulk heterojunction (BHJ) photovoltaic devices with a structure of ITO/PEDOT:PSS/small molecules:PC₇₁BM/LiF/Al were fabricated by using the small molecules as donors and (6,6)-phenyl C₇₁-butyric acid methyl ester (PC₇₁BM) as acceptor. Power conversion efficiencies of 1.76% and 2.47% were achieved for the photovoltaic devices based on 2TAPM:PC₇₁BM and 4TAPM:PC₇₁BM under simulated air mass 1.5 global irradiation (100 mW/cm²), respectively.     

Fe3O4 nanoparticles induced magnetic field effect on efficiency enhancement of P3HT:PCBM bulk heterojunction polymer solar cells

Fe₃O₄ magnetic nanoparticles (mean size of about 10 nm) capped by surfactant oleic acid (OA) were incorporated into P3HT:PCBM BHJ-PSCs by doping in the P3HT:PCBM photoactive layer for the first time. The PCE of the OA-Fe₃O₄:P3HT:PCBM BHJ-PSC device is enhanced by ∼18% at the optimum OA-Fe₃O₄ NPs doping ratio of 1%. The role of the magnetic property of Fe₃O₄ NPs on the PCE of OA-Fe₃O₄:P3HT:PCBM devices was studied, confirming the exclusive contribution of the Fe₃O₄ NPs to the observed enhancement of PCE. The enhancement of the PCE of the OA-Fe₃O₄:P3HT:PCBM BHJ-PSC device is found to be primarily due to the increase of short-circuit current (J_sc) by ∼14%, which is attributed to the magnetic field effect originated from the superparamagnetism of Fe₃O₄ NPs, resulting in the increase of the population of triplet excitons. Finally, the effect of Fe₃O₄ NPs on the enhancement of PCE of OA-Fe₃O₄:P3HT:PCBM device is further investigated by comparing different means of doping in P3HT:PCBM or PEDOT:PSS layer, confirming that such an effect can be achieved only when Fe₃O₄ NPs are doped in the P3HT:PCBM photoactive layer.     

Polymeric solar cells based on P3HT:PCBM: Role of the casting solvent

Polymeric photovoltaic (PV) solar cells have been fabricated using six solvents: chloroform (CHCl₃), toluene (T), chlorobenzene (CB), orthodichlorobenzene (ODCB), 1,2,3,4-tetrahydronaphthalene (THN) and 1,2,4-trichlorobenzene (TCB). The active layers were composed of poly(3-hexyl)thiophene (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM). Special care has been taken to keep all experimental parameters constant (thickness of the active layers, donor/acceptor weight ratio, area of active surface and electrodes) in order to avoid artefacts and truly study the effect of solvents. Studies using atomic force microscopy (AFM) and optical absorption (UV-vis) showed the relationship between the photovoltaic performance and the evaporation rate of solvents. The use of solvents with high boiling point results in a higher degree of organization in the structure of P3HT. A direct comparison with devices processed with thermal treatment has also been performed. As often reported thermal annealing increases photo-conversion efficiency of devices created from common solvents, due to better separation of phase between the two materials of the blend. In the case of solvents with high boiling point such as THN and TCB, neither phase separation nor modification of P3HT crystallization induced by thermal annealing has been observed. However thermal treatment appears to enhance performance, ensuing the evaporation of remaining solvent in the active layers. An overview of the effect of solvent on the electrical properties of films containing pure P3HT and P3HT:PCBM blend reported in the literature has been completed for the discussion.     

The effect of introducing a buffer layer to polymer solar cells on cell efficiency

The effect of poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) as a buffer layer was investigated in polymer solar cells (PSCs). Four different types of PEDOT:PSS were used: PH, PH500 and their DMSO (dimethylsulfoxide)-doped counterparts. The efficiency of PSCs was independent of the electric conductivity of the buffer layer as a bulk property while it was significantly related to interfacial properties between the buffer layer and a bulk-heterojunction (BHJ) layer. The interfacial properties included charge transfer resistance (R_CT), hole mobility (μ_h) and contact angle (θ) of the solution of BHJ on the buffer layer. Lower R_CT, higher μ_h and smaller θ led to the higher fill factor (up to 72%), enabling highly efficient PSCs with efficiency (η)=4.25%.