ITO-free inverted polymer solar cells using a GZO cathode modified by ZnO

A gallium-doped ZnO (GZO) layer was investigated and compared with a conventional indium-tin-oxide (ITO) layer for use as a cathode in an inverted polymer solar cell based on poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C₆₁ butyric acid methyl ester (PCBM) bulk heterojunctions (BHJ). By modifying the GZO cathode with a ZnO thin layer, a high power conversion efficiency (3.4%) comparable to that of an inverted solar cell employing the same P3HT:PCBM BHJ photoactive layer with a conventional ITO/ZnO cathode was achieved. This result indicates that GZO is a transparent electrode material that can potentially be used to replace high-cost ITO.     

Improving the efficiency of organic solar cell with a novel ambipolar polymer to form ternary cascade structure

This study describes the utilization of a novel conjugated copolymer, namely, poly[2,3-bis(thiophen-2-yl)-acrylonitrile-9,9′-dioctyl-fluorene] (FLC8) for organic solar cell application for the first time. The highest occupied molecular orbital and the lowest unoccupied molecular orbital of FLC8 are −5.68 and −3.55 eV, respectively, which lie between the corresponding values of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methylester (PCBM). In addition, both electron and hole mobilities of FLC8 are in the range of 10⁻⁴ (cm²/V s), making it an excellent ambipolar polymer. Such unique properties make FLC8 a good candidate to form a ternary cascade bulk-heterojunction organic solar cell when blending with P3HT and PCBM. The power conversion efficiency (PCE) of the ternary cascade solar cell can be increased by up to 30% as compared with the reference cell without FLC8. We suspect that this enhancement of PCE is caused by the additional charge separation offered by the cascade structure and the fast charge transfer due to the ambipolarity of FLC8.     

Effects of intrinsic ZnO buffer layer based on P3HT/PCBM organic solar cells with Al-doped ZnO electrode

Organic solar cell devices were fabricated using poly(3-hexylthiophene) (P3HT) and 6,6-phenyl C61-butyric acid methyl ester (PCBM), which play the role of an electron donor and acceptor, respectively. The transparent electrode of organic solar cells, indium tin oxide (ITO), was replaced by Al-doped ZnO (AZO). ZnO has been studied extensively in recent years on account of its high optical transmittance, electrical conduction and low material cost. This paper reports organic solar cells based on Al-doped ZnO as an alternative to ITO. Organic solar cells with intrinsic ZnO inserted between the P3HT/PCBM layer and AZO were also fabricated. The intrinsic ZnO layer prevented the shunt path in the device. The performance of the cells with a layer of intrinsic ZnO was superior to that without the intrinsic ZnO layer.     

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.     

Effect of P3HT:PCBM concentration in solvent on performances of organic solar cells

Focused on phase separation and morphologies of poly(3-hexylthiophene):[6,6]-phenyl C₆₁ butyric acid methyl ester (P3HT:PCBM) active layers, we studied the effect of preparation conditions of the active layer on photovoltaic performance by changing concentration of P3HT:PCBM in the solvent. The performances of the cells varied depending on concentration of P3HT:PCBM (1:1 ratio by weight) in solvent even with the same thickness. The P3HT:PCBM active layer is prepared in cell structure of ITO/PEDOT/P3HT:PCBM/Al by changing spin-coating speed with different concentrations (1, 2 and 3 wt%) in chlorobenzene. Here, it was found that both the P3HT:PCBM concentrations and spin-coating conditions affected the crystalline structure formation, interchain interaction, morphology and phase separation during drying process of solvent and subsequent annealing.     

Light harvesting in organic solar cells

We present a methodology which allows designing photonic crystals slabs (PCs) able to couple incident light into “slow Bloch modes” (SBMs) and dealing with their incorporation in an organic solar cell (OSC). We theoretically study different structures based on the same couple of organic materials (poly-3-hexylthiophène (P3HT) as donor and [6,6]-phenyl-C61-butiryc acid methyl ester (PCBM) as acceptor): a 2D photonic crystal based on a perfectly ordered P3HT/PCBM blend (placed in the air), a 1D photonic crystal based on a nanostructured PEDOT:PSS (Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)) layer embedded in a P3HT:PCBM host matrix (first placed in the air and then inserted in an organic solar cell) and finally a 1D photonic crystal based on a nanostructured P3HT:PCBM layer covered by a metallic electrode and inserted in an OSC ( with and without nanostructuration of the PEDOT:PSS layer). We show that the light coupling into SBMs in an OSC depends on vertical interferences and that optical spacers are needed. We then demonstrate that the P3HT:PCBM active layer nanostructuring covered by a thick metallic electrode exhibits the highest gain (4% in the 400–700 nm spectral range) thanks to a simultaneous optimisation of the optical properties of the photonic crystal (coupling of SBM) and of the stack of the organic solar cell (vertical interferences).     

Well-aligned single-crystalline silicon nanowire hybrid solar cells on glass

Hybrid solar cells are fabricated on the glass substrate using well-aligned single-crystalline Si nanowires (SiNWs) and poly(3-hexylthiophene):[6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PCBM). Their key benefits are discussed. The well-aligned SiNWs are fabricated from Si wafer and transferred onto the glass substrate with the P3HT:PCBM. Such SiNWs provide uninterrupted conduction paths for electron transport, enhance the optical absorption to serve as an interesting candidate of the absorber, and increase the surface area for exciton dissociation. Our investigations show that SiNWs are promising for hybrid organic photovoltaic cells with improved performance by increasing the short-circuit current density from 7.17 to 11.61 mA/cm².     

ITO-free low-cost organic solar cells with highly conductive poly(3,4 ethylenedioxythiophene): p-toluene sulfonate anodes

Indium tin oxide (ITO)-free organic solar cells were fabricated with highly conductive and transparent tosylate-doped poly(3,4-ethylenedioxythiophene: p-toluene sulfonate) (PEDOT:PTS) anodes of various thicknesses that were prepared by the vapor-phase oxidative polymerization of EDOT using Fe(PTS)₃ as an oxidant. Both solution-processable layers - PEDOT:PSS and photoactive P3HT:PCBM - were spin coated. The anodes transmittance and conductivity varied with thickness. Power conversion efficiency was maximized at 1.4%. The ITO-free organic solar cells photovoltaic characteristics are qualitatively compared with those of ITO-based organic solar cells to explore the possibility of replacing costly, vacuum-deposited ITO with highly conductive, patterned polymer films fabricated by inexpensive vapor-phase polymerization.     

Improved power conversion efficiency of bulk heterojunction poly(3-hexylthiophene):PCBM photovoltaic devices using small molecule additive

We report that the power conversion efficiency (PCE) of the bulk heterojunction organic photovoltaic device based on poly(3-hexylthiophene):[6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PCBM) blend was improved by incorporating a small molecule SM having absorption band in the longer wavelength region. SM is a small molecule containing thienothiadiazole central unit with terminal cyanovinylene 4-nitrophenyl at both sides, which were connected to the central unit via a thiophene ring. The combination of SM with P3HT and PCBM allows not only a broad band absorption up to longer wavelength, but also tuning the inter-energy level leading to a higher short circuit current (J_sc) and open circuit voltage (V_oc). The device based on the as cast P3HT:PCBM:SM exhibits a PCE of 3.69%, which is higher than the device based on P3HT:PCBM and SM:PCBM blends. The overall PCE of the device based on thermally annealed blend is further improved up to 4.1%. The improvement of the PCE has been attributed to a better charge transport in the device, due to the increased crystallinity of the blend through thermal annealing.     

Study of field effect mobility in PCBM films and P3HT:PCBM blends

We report on field effect mobility measurements in methanofullerene [6,6]-phenyl C₆₁-butyric acid methyl ester (PCBM) films and in blends of poly(3-hexylthiophene) (P3HT) and PCBM, identical to those used in polymer solar cells. Electron mobilities in the order of were found in the pure PCBM films, and electron mobilities of were found in P3HT:PCBM blends at room temperature. Mobility measurements on the blends yielded electron mobilities of a factor 10 lower than those in the pure films. Temperature dependent measurements were performed to investigate the temperature dependence of the mobility in both films. In order to understand the discrepancy in the electron mobility between pure film and blend, we investigated the parasitic effects of the contacts on the measured value of mobility, but found that losses in the bulk dominate the current.     

Improvement in light harvesting and performance of P3HT:PCBM solar cell by using 9,10-diphenylanthracene

We have studied the effect of 9,10-diphenylanthracene (DPA) as a conjugated dye with different concentrations on light harvesting and performance of solar cell composed from poly (3-hexylthiophene) (P3HT):[6,6]-phenyl-C₆₁butyric acid methyl ester (PCBM) blend films. The dye concentration effect was investigated with optical absorption spectroscopy, photocurrent spectroscopy, and current density-voltage characteristic measurements on devices under AM1.5 white light illumination with intensity of 100 mW/cm². The incorporation of the conjugated DPA inside P3HT:PCBM blend improved the light harvesting, slightly, and conjugation length indicated from the optical absorption and external quantum efficiency spectra. By adding specific amounts of the DPA into P3HT:PCBM blend, the external quantum efficiency and solar cell performance parameters, i.e., short circuit current density, fill factor, and power conversion efficiency improved as a result of improvement in the light harvesting and charge carrier transfer taking place between P3HT and PCBM through the conjugated DPA molecules.     

The effect of porphyrin inclusion on the spectral response of ternary P3HT:porphyrin:PCBM bulk heterojunction solar cells

Cyanoporphyrins have been included into the active layer of bulk heterojunction poly (3-hexylthiophene) (P3HT): [6,6]-phenyl-C₆₁ butyric acid methyl ester (PCBM) solar cells. The amount of porphyrin, P3HT and PCBM were systematically varied and the characteristics of the devices from the corresponding active layers were recorded. The spectral responses of the devices showed that the addition of the porphyrin to the active layer broadened the absorption efficiency of the device and led to a porphyrin contribution to the photocurrent of the solar cell. The porphyrin molecules did not contribute to the photocurrent unless both P3HT and PCBM were present in the active layer. In most cases, the porphyrin was unable to contribute to the photocurrent after the devices had been annealed, suggesting changes to the morphology of the active layer.     

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%).     

Improvement in stability of poly(3-hexylthiophene-2,5-diyl)/[6,6]-phenyl-C61-butyric acid methyl ester bulk heterojunction solar cell by using UV light irradiation

A study of organic solar cells based on photoactive blends of the conjugated regioregular-poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) with different UV-light treatments is presented. As expected, air exposure of an unencapsulated P3HT:PCBM solar cell is observed to result in rapid degradation of device efficiency. In order to ease this degradation, we found that exposing poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) to UV light may reduce the degradation and preserve good performance. Samples with PEDOT:PSS exposed to UV light show better long-run stability than the pristine cells. The active layer exposed to UV light shows the poorest performance and degrades rapidly. From the initial value, the efficiency decreased by 56% and 35% for pristine cells and cells with PEDOT:PSS exposed to UV light, respectively. It has been found that device half-life was 650 and 400 h for the samples with and without UV treatment, respectively. The trend in device performance was explained by observed changes in work function of the PEDOT:PSS layer and decreased absorption intensity of P3HT:PCBM.     

Gravure printed flexible organic photovoltaic modules

In this letter, organic solar cell modules based on poly-3-hexylthiophene (P3HT) and [6.6]-phenyl-C61-butyric acid methyl ester (PCBM) blend films with a module active area of 15.45 cm² prepared by roll-to-roll (R2R) compatible gravure printing method are demonstrated. The gravure printed organic photovoltaic modules consist of eight serially connected solar cells in same substrate. Indium-tin-oxide (ITO) is patterned by screen printable etching paste. Hole injection layer and active layer are prepared by gravure printing method. All processing steps excluding cathode evaporation are performed in air. Electrical measurements are done to modules consisting of 5-8 serially connected solar cells. The photovoltaic modules comprising 5, 7 and 8 serially connected cells exhibit an active area power conversion efficiency of 1.92%, 1.79% and 1.68%, respectively (Oriel Sol3A Class AAA, AM1.5G, 100 mW cm⁻²).     

Enhancing the durability of polymer solar cells using gold nano-dots

The durability of organic photovoltaic devices is improved by (a) replacing thermally labile poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) with gold nano-dots and (b) stabilizing the morphology of photoactive layers through thermally induced reaction. Gold nano-dots (Au-ND) (3–6 nm in diameter and 0.8 nm in height) were thermally deposited on ITO substrates prior to depositing a hole transporting layer (40 nm) of an azide-functionalized poly(3-hexylthiophene), P1, which was insolubilized by heating to 150 °C. A blend of P1 and [6,6]-phenyl C₆₁-butyric acid methyl ester (PCBM) was deposited and heated to 150 °C prior to the deposition of a Ca/Al cathode. The reaction of P1 with PCBM stabilized the bulk heterojunction film as evidenced by the suppression of crystallization of PCBM. Replacement of PEDOT:PSS with Au-ND, in combination with morphological stabilization, greatly improves the durability of PV devices under accelerated lifetime testing at 150 °C. Power conversion efficiencies (PCE) for the P1:PCBM devices stabilized at 1.25% after 28 h of accelerated testing at 150 °C, whereas conventional P3HT:PCBM devices on PEDOT/ITO dropped to 0.58% after only 7 h of accelerated testing. Prospects for similarly enhancing the durability of highly efficient PV devices are discussed.     

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.     

Highly durable inverted-type organic solar cell using amorphous titanium oxide as electron collection electrode inserted between ITO and organic layer

An indium tin oxide/titanium oxide/[6,6]-phenyl C₆₁ butyric acid methyl ester:regioregular poly(3-hexylthiophene)/poly(3,4-ethylenedioxylenethiophene):poly(4-styrene sulfonic acid)/Au type organic solar cell (ITO/TiO_x/PCBM:P3HT/PEDOT:PSS/Au) with 1 cm² active area, which is called “inverted-type solar cell”, was developed using an ITO/amorphous titanium oxide (TiO_x) electrode prepared by a sol-gel technique instead of a low functional electrode such as Al. The power conversion efficiency (η) of 2.47% was obtained by irradiating AM 1.5G-100 mW cm⁻² simulated sunlight. We found that a photoconduction of TiO_x by irradiating UV light containing slightly in the simulated sunlight was required to drive this solar cell. The device durability in an ambient atmosphere was maintained for more than 20 h under continuous light irradiation. Further, when the air-stable device was covered by a glass plate with a water getter sheet which was coated by an epoxy-UV resin as sealing material, the durability was still higher and over 96% of relative efficiency was observed even after continuous light irradiation for 120 h.     

Investigations of efficiency improvements in poly(3-hexylthiophene) based organic solar cells using calcium cathodes

In this study, we investigate the mechanisms leading to the power conversion efficiency improvement in poly(3-hexylthiophene):[6,6]-phenyl C61-butyric acid methyl ester (P3HT:PCBM) based organic solar cells using calcium (Ca) in cathode structures. Ultraviolet and x-ray photoemission spectroscopy (UPS and XPS) indicate that chemical reactions occur at the P3HT/Ca interface. Upon Ca deposition, UPS results illustrate a 0.8 eV-downward shift in energy levels of P3HT, but not in those of PCBM. In addition to forming an ohmic contact at the cathode the presence of Ca widens the energy difference between the HOMO of P3HT and the LUMO of PCBM at the cathode interfaces, which results in the increase of open circuit voltage and the enhancement of device efficiency.     

Enhancement of short current density in polymer solar cells with phthalocyanine tin (IV) dichloride as interfacial layer

The effect of n-type phthalocyanine tin (IV) dichloride (SnCl₂Pc) as cathode interfacial layer on the performance of poly[2-methoxy,5-(2′-ethylhexyloxy)-1,4-phenylene vinylene] (MEH-PPV):[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) bulk heterojunction solar cells (ITO/PEDOT:PSS/MEH-PPV:PCBM/SnCl₂Pc/LiF/Al) is investigated. Our results show that the integration of SnCl₂Pc into the solar cell not only enhances the exciton dissociation efficiency due to the formation of additional MEH-PPV/SnCl₂Pc exciton dissociation junction, but also improves the electron transport and collection due to the step-like electron injection barrier to cathode caused by SnCl₂Pc interlayer. The incorporation of 6 nm thick SnCl₂Pc interlayer leads to 15.7% improvement of the short circuit current density (J_SC), which in turn results in 15.2% improvement of power conversion efficiency (η) up to 2.49%. The results suggest that the employment of an n-type organic semiconductor like SnCl₂Pc as an interlayer is a promising strategy to improve the device performance of polymer solar cells.