Novel hybrid solar cells based on α-copper phthalocyanine–cadmium sulfide planar heterojunction

Cadmium sulfide (CdS) has been employed as an alternative acceptor for planar heterojunction solar cell based on copper phthalocyanine (CuPc). Spin-coated poly-3,4-ethylenedioxythiophene:polystyrenesulfonate (PEDOT:PSS) on indium tin oxide (ITO)-coated glass substrates was used for the vacuum deposition of CuPc and CdS planar heterojunction. In the present study, we have fabricated two different architectures of CuPc/CdS devices: (1) ITO/PEDOT:PSS/CuPc/CdS/Al and (2) ITO/PEDOT:PSS/CuPc/CdS/LiF/Al. Our results indicate that the CdS could effectively facilitate charge transport in the nanostructured network, and be a good acceptor. The fabricated bare CuPc/CdS device shows 0.13 % conversion efficiency while incorporation of LiF layer between CuPc/CdS and Al contact facilitates low-recombination rate results ~43 % enhancement in efficiency. The ITO/PEDOT:PSS/CuPc/CdS/LiF/Al device shows 0.30 % power conversion efficiency.     

Indium tin oxide nanopillar electrodes in polymer/fullerene solar cells

Using high surface area nanostructured electrodes in organic photovoltaic (OPV) devices is a route to enhanced power conversion efficiency. In this paper, indium tin oxide (ITO) and hybrid ITO/SiO(2) nanopillars are employed as three-dimensional high surface area transparent electrodes in OPVs. The nanopillar arrays are fabricated via glancing angle deposition (GLAD) and electrochemically modified with nanofibrous PEDOT:PSS (poly(3,4-ethylenedioxythiophene):poly(p-styrenesulfonate)). The structures are found to have increased surface area as characterized by porosimetry. When applied as anodes in polymer/fullerene OPVs (architecture: commercial ITO/GLAD ITO/PEDOT:PSS/P3HT:PCBM/Al, where P3HT is 2,5-diyl-poly(3-hexylthiophene) and PCBM is [6,6]-phenyl-C(61)-butyric acid methyl ester), the air-processed solar cells incorporating high surface area, PEDOT:PSS-modified ITO nanoelectrode arrays operate with improved performance relative to devices processed identically on unstructured, commercial ITO substrates. The resulting power conversion efficiency is 2.2% which is a third greater than for devices prepared on commercial ITO. To further refine the structure, insulating SiO(2) caps are added above the GLAD ITO nanopillars to produce a hybrid ITO/SiO(2) nanoelectrode. OPV devices based on this system show reduced electrical shorting and series resistance, and as a consequence, a further improved power conversion efficiency of 2.5% is recorded.     

Efficient organic photovoltaic devices by using PEDOT:PSSs with excellent hole extraction ability

We have demonstrated the poly(3-hexyl-thiophene-1,5-diyl) (P3HT):[6,6]-phenyl C61-butyric acid methyl ester (PCBM) bulk heterojunction (BHJ) organic photovoltaic (OPV) devices on various poly(3,4-ethylene-dioxythiophene):poly(styrenesulfonate) (PEDOT:PSSs). The device with PEDOT:PSS of PH 500 adding 1% dimethyl sulfoxide (DMSO) showed the best performances in term of the fill factor and power conversion efficiency (PCE) than others. The hole extraction ability of PEDOT:PSS is very important to balance between holes and electrons mobility because the carrier mobility of PCBM (approximately 10(-4) cm2/Vs) is higher than that of P3HT (approximately 10(-6) cm2/Vs) in P3HT:PCBM BHJ structure. The optimized BHJ OPV with PEDOT:PSS of PH 500 adding 1% DMSO showed a short-circuit current density of 8.92 mA/cm2 and a PCE of 2.97%, which was nearly increased to 2.5 times than that of control device with PEDOT:PSS of P VP Al 4083.     

Effects of a base coating used for electropolymerization of poly(3,4-ethylenedioxythiophene) on indium tin oxide electrode

Electropolymerization of poly(3,4-ethylenedioxythiophene) (PEDOT) films on indium tin oxide (ITO), using a very thin PEDOT:poly(styrene sulfonate) (PEDOT:PSS) film as a base coating, was carried out in a non-aqueous solution containing the monomer, an electrolyte and propylene carbonate by a two-electrode system. For comparison, PEDOT film electrodeposited on bare ITO substrate under the same condition was also presented. The PEDOT films deposited on these two substrates were characterized by scanning electron microscopy, energy disperse X-ray spectroscopy and Raman spectroscopy. The results indicate that the PEDOT film electrodeposited on bare ITO was not uniform, while the PEDOT film electrodeposited on PEDOT:PSS/ITO has better uniformity. The compositions of the different regions of PEDOT film electrodeposited on bare ITO and PEDOT:PSS/ITO were studied and discussed. Electrochromic devices (ECDs) based on PEDOT films electrodeposited on bare ITO and PEDOT:PSS/ITO were fabricated and characterized by UV-Vis-NIR spectrophotometric study. The results show that the display contrast of the ECD based on PEDOT film electrodeposited on PEDOT:PSS/ITO was improved over that on a bare ITO substrate.     

Laser-induced forward transfer of polymer light-emitting diode pixels with increased charge injection

Laser-induced forward transfer (LIFT) has been used to print 0.6 mm × 0.5 mm polymer light-emitting diode (PLED) pixels with poly[2-methoxy, 5-(2-ethylhexyloxy)-1,4-phenylene vinylene] (MEH-PPV) as the light-emitting polymer. The donor substrate used in the LIFT process is covered by a sacrificial triazene polymer (TP) release layer on top of which the aluminium cathode and functional MEH-PPV layers are deposited. To enhance electron injection into the MEH-PPV layer, a thin poly(ethylene oxide) (PEO) layer on the Al cathode or a blend of MEH-PPV and PEO was used. These donor substrates have been transferred onto both plain indium tin oxide (ITO) and bilayer ITO/PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) blend) receiver substrates to create the PLED pixels. For comparison, devices were fabricated in a conventional manner on ITO substrates coated with a PEDOT:PSS hole-transporting layer. Compared to multilayer devices without PEO, devices with ITO/PEDOT:PSS/MEH-PPV:PEO blend/Al architecture show a 100 fold increase of luminous efficiency (LE) reaching a maximum of 0.45 cd/A for the blend at a brightness of 400 cd/m(2). A similar increase is obtained for the polymer light-emitting diode (PLED) pixels deposited by the LIFT process, although the maximum luminous efficiency only reaches 0.05 cd/A for MEH-PPV:PEO blend, which we have attributed to the fact that LIFT transfer was carried out in an ambient atmosphere. For all devices, we confirm a strong increase in device performance and stability when using a PEDOT:PSS film on the ITO anode. For PLEDs produced by LIFT, we show that a 25 nm thick PEDOT:PSS layer on the ITO receiver substrate considerably reduces the laser fluence required for pixel transfer from 250 mJ/cm(2) without the layer to only 80 mJ/cm(2) with the layer.     

Enhanced performance of polymer solar cells with a monolayer of assembled gold nanoparticle films fabricated by Langmuir–Blodgett technique

We reported the enhanced performance of polymer solar cells with the blend of poly (2-methoxy-5(2′-ethylhexyloxy)-1,4-phenylene-vinylene) (MEH-PPV) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) as active layer by incorporation of an assembled gold nanoparticle (Au NP) monolayer. The dense Au NP monolayer has been fabricated by Langmuir–Blodgett (LB) assembly and positioned between the transparent electrode ITO and the anode-modification PEDOT:PSS [poly (3,4-ethylenedioxythiophene):poly(styrene sulfonate)] layer, resulting in the device architecture of ITO/Au/PEDOT:PSS/MEH-PPV:PCBM/Al. We attribute the performance improvement to the localized surface plasmon resonance (LSPR) effect of Au NP films, which could lead to the increased absorption of the active layer. The parameters (nanoparticle size and interparticle distance) that govern this SPR effect have been optimized by selecting various sizes of Au NPs and controlling the LB assembly conditions. We observed ～10–20% enhancement in power conversion efficiency for all the devices with the Au NP monolayer.     

Surface characterization of polythiophene:fullerene blends on different electrodes using near edge X-ray absorption fine structure

We study the top surface composition of blends of the conjugated polymer regioregular poly-3-hexylthiophene (P3HT) with the fullerene (6,6)-phenyl-C(61)-butyric acid methyl ester (PCBM), an important model system for organic photovoltaics (OPVs), using near-edge X-ray absorption fine structure spectroscopy (NEXAFS). We compare the ratio of P3HT to PCBM near the air/film interface that results from preparing blend films on two sets of substrates: (1) poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) coated indium tin oxide (ITO) as is commonly used in conventional OPV structures and (2) ZnO substrates that are either unmodified or modified with a C(60)-like self-assembled monolayer, similar to those that have been recently reported in inverted OPV structures. We find that the top surface (the film/air interface) is enriched in P3HT compared to the bulk, regardless of substrate or annealing conditions, indicating that changes in device performance due to substrate modification treatments should be attributed to the buried substrate/film interface and the bulk of the film rather than the exposed film/air interface.     

Composition depth profile analysis of bulk heterojunction layer by time-of-flight secondary ion mass spectrometry with gradient shaving preparation

Composition depth profile analysis of bulk heterojunction (BHJ) layer was performed by time-of-flight secondary ion mass spectrometry with gradient shaving preparation. The BHJ layer comprised of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61butyric acid methyl ester (PCBM) was formed on the substrate coated with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) followed by annealing. The P3HT component increased toward the top surface in the BHJ layer. In addition, C₈H₇SO₃⁻ was detected inside the BHJ layer, suggesting penetration of PSS. P3HT was uniformly distributed in the BHJ layer without PEDOT:PSS. The P3HT-rich distribution in the top surface may be attributed to PSS penetration.     

Influence of the polymer matrix on the efficiency of hybrid solar cells based on silicon nanowires

Poly (N-vinylcarbazole) (PVK):SiNWs and poly (2-methoxy, 5-(2-ethyl-hexyloxy)-p-phenyl vinylene) (MEH-PPV):SiNWs bulk-heterojunctions (BHJ) have been elaborated from blends of SiNWs and the polymer in solution from a common solvent. Optical properties of these nanocomposites have been investigated by UV-vis absorption and photoluminescence (PL) spectral measurements. We have studied the charge transfer between SiNWs and the two polymers using the photoluminescence quenching of PVK and MEH-PPV which is a convenient signature of the reduced radiative recombination of the generated charge pairs upon exciton dissociation. We found that PVK and SiNWs constitutes the better donor-acceptor system. In order to understand the difference between PVK:SiNWs or MEH-PPV:SiNWs behaviours, photoluminescence responses were correlated with the topography (SEM) of the thin films. The photovoltaic effect of ITO/PEDOT:PSS/SiNWs:PVK/Al and ITO/PEDOT:PSS/SiNWs:MEH-PPV/Al structures was studied by current-voltage (I-V) measurements in dark and under illumination and interpreted on the basis of the charge transfer differences resulting from the morphologies.     

Solution-processed flexible polymer solar cells with silver nanowire electrodes

The conventional anode for organic photovoltaics (OPVs), indium tin oxide (ITO), is expensive and brittle, and thus is not suitable for use in roll-to-roll manufacturing of OPVs. In this study, fully solution-processed polymer bulk heterojunction (BHJ) solar cells with anodes made from silver nanowires (Ag NWs) have been successfully fabricated with a configuration of Ag NWs/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/polymer:phenyl-C(61)-butyric acid methyl ester (PCBM)/Ca/Al. Efficiencies of 2.8 and 2.5% are obtained for devices with Ag NW network on glass and on poly(ethylene terephthalate) (PET), respectively. The efficiency of the devices is limited by the low work function of the Ag NWs/PEDOT:PSS film and the non-ideal ohmic contact between the Ag NW anode and the active layer. Compared with devices based on the ITO anode, the open-circuit voltage (V(oc)) of solar cells based on the Ag NW anode is lower by ~0.3 V. More importantly, highly flexible BHJ solar cells have been firstly fabricated on Ag NWs/PET anode with recoverable efficiency of 2.5% under large deformation up to 120°. This study indicates that, with improved engineering of the nanowires/polymer interface, Ag NW electrodes can serve as a low-cost, flexible alternative to ITO, and thereby improve the economic viability and mechanical stability of OPVs.     

Nanoimprint of dehydrated PEDOT:PSS for organic photovoltaics

We demonstrate the fabrication of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) nanogratings by a dehydration-assisted nanoimprint lithographic technique. Dehydration of PEDOT:PSS increases its cohesion to protect the nanostructures formed by nanoimprinting during demolding, resulting in the formation of high quality nanogratings of 60?nm in height, 70?nm in width and 70?nm in spacing (aspect ratio of 0.86). PEDOT:PSS nanogratings are used as hole transport and an electron blocking layer in blended poly(3-hexylthiophene-2,5-diyl) (P3HT):[6,6]-penyl-C61-butyric-acid-methyl-ester (PCBM) organic photovoltaic devices (OPV), showing enhancement of photocurrent and power efficiency in comparison to OPV devices with non-patterned PEDOT:PSS films.     

Surface modification of poly(3,4-ethylene dioxthiophene):poly(styrene sulfonic acid) (PEDOT:PSS) films by atmospheric-pressure argon plasma for organic thin-film solar cells

Highly-conductive poly(3,4-ethylene dioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS) films obtained by the addition of dimethylsulfoxide (DMSO) and the argon plasma exposure were used as a transparent conductive anode (TCA) for copper-phthalocyanine (CuPc)/C60 organic thin-film solar cells (OSCs). The CuPc/C60 OSCs on as-grown DMSO added PEDOT:PSS layer showed a power efficiency of 0.6%, whereas it was improved markedly to 1.34% after the atmospheric-pressure argon plasma exposure, which was comparable to that formed on indium-tin-oxide layer. Effects of the DMSO addition and the argon plasma exposure in the spin-coated PEDOT:PSS films is demonstrated in terms of the in-depth characterization of optical and electrical properties.     

Efficient bulk heterojunction solar cells based on D–A copolymers as electron donors and PC70BM as electron acceptor

Two low band gap conjugated polymers P1 (alternating phenylenevinylene containing thiophene and pyrrole rings) and P2 (alternating phenylenevinylene with dithenyl (thienothiadiazole) segments) having optical band gap 1.65 eV and 1.74 eV, respectively, were used as electron donor along with the PC₇₀BM as electron acceptor for the fabrication of bulk heterojunction solar cells. The power conversion efficiency (PCE) of BHJ devices based on P1:PC₇₀BM and P2:PC₇₀BM cast from THF solvent is about 2.84% and 2.34%, respectively, which is higher than the BHJ based on PCBM as electron acceptor. We have investigated the effect of mixed (1-chloronaphthalene (CN)/THF) solvent, modification of PEDOT:PSS layer and inserting of TiO₂ layer, on the photovoltaic performance of polymer solar cell. We have achieved power conversion efficiency of 5.07% for the polymer solar cells having structure ITO/PEDOT:PSS (modified)/P1:PC₇₀BM (CN/THF cast)/TiO₂/Al. The effect of solvent used for spin coating, modification of PEDOT:PSS layer and inclusion of TiO₂ layer has been discussed in detail.     

Improvement of organic solar cell efficiency by solution-processed doping of pentacene in PEDOT:PSS layer

In the current research, organic solar cells (OSCs) with various concentrations of pentacene in Poly(ethylenedioxythiopene):Poly(styrenesulfonate) (PEDOT:PSS) interface layer were investigated for better hole extraction. The ITO/Pentacene?+?PEDOT:PSS/P3HT:PCBM/Al-fabricated solar cell fabricated via brush coating provides superior photovoltaic, electrical and optical characteristics when compared with the ITO/PEDOT:PSS/P3HT:PCBM/Al solar cell. The ITO/Pentacene?+?PEDOT:PSS/P3HT:PCBM/Al solar cells deliver a V_OC ~350?mV and 2.57% efficiency. It is observed that the optimized concentration of pentacene doping in PEDOT:PSS layer, along with an active layer of P3HT and PC₆₀BM, doubles the efficiency of the device, when compared with pristine PEDOT:PSS layer. The degradation studies of the fabricated bulk heterojunction OSCs reveal that the degrading abilities of ITO/Pentacene?+?PEDOT:PSS/P3HT:PCBM/Al solar cells are 60% more better than those of ITO/PEDOT:PSS/P3HT:PCBM/Al devices. Thus, this work will ultimately contribute toward fully solution processed painted device, which will provide low-cost manufacturing and improved stability of pentacene-based organic photovoltaics.     

Electrical conduction through self-assembled monolayers in molecular junctions: Au/molecules/Au versus Au/molecule/PEDOT:PSS/Au

We fabricated and characterized a large number of octanedithiol (denoted as DC8) molecular devices as vertical metal–molecule–metal structure with or without using an intermediate conducting polymer layer of poly (3,4-ethylenedioxythiophene) stabilized with poly(4-styenesulfonic acid) (called as PEDOT:PSS). The electronic transport properties of DC8 molecular devices with and without PEDOT:PSS layer were statistically compared in terms of current density and device yield. The yields of the working molecular devices were found to be ~ 1.75% (84 out of 4800 devices) for Au/DC8/Au junctions and ~ 58% (74 out of 128 devices) for Au–DC8/PEDOT:PSS/Au junctions. The tunneling decay constants were obtained with the Simmons tunneling model and a multibarrier tunneling model for two kinds of molecular devices with and without PEDOT:PSS layer.     

Interface modification of ITO thin films: organic photovoltaic cells

In this paper we review our recent studies of the surface characterization of commercially available indium-tin-oxide (ITO) thin films, using photoelectron spectroscopies (XPS and UPS) and electrochemistry of chemisorbed probe molecules such as ferrocene dicarboxylic acid (Fc(COOH)₂). The modification of these ITO films through chemisorption of carboxylic acid-substituted small molecules, such as Fc(COOH)₂, 3-thiophene acetic acid (3-TAA), and the subsequent modification of these interfaces with electrochemically grown conducting polymer (CP) films is also introduced. We report preliminary results of our studies changes in performance of vacuum deposited organic photovoltaic (PV) cells as a result of these ITO substrate modification steps. The surfaces of as-received ITO films, and those cleaned by various solution and plasma-etching processes, are unavoidably hydrolyzed to In(OH)₃-like and InOOH-like surface species, which leaves the ITO surface with at most 40-50% of the electronically active sites available for electron transfer reactions. Modification of the ITO surface with electroactive small molecules such as Fc(COOH)₂ and 3-TAA provides for better wettability of organic layers to the polar ITO surface and enhanced electrical contact (lower series resistance, R_S) between the ITO anode, spin-cast or electrodeposited PEDOT:PSS layers and copper phthalocyanine (CuPc) layers in multilayer (CuPc/C₆₀/BCP) excitonic PV cells. Improvements in PV J/V (current/voltage) responses are noted mainly through increases in short-circuit photocurrent and lowered series resistances (R_S) when electroactive small molecules are chemisorbed to the ITO surface, prior to spin-casting of conducting polymer, PEDOT:PSS, layers.     

Effects of (NH4)2Sx treatment on the electrical and optical properties of indium tin oxide/conducting polymer electrodes

In this study, the effects of (NH₄)₂S_x treatment on the electrical and optical properties of the indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene) doped with poly(4-styrenesulfonate) (PEDOT:PSS) electrodes were researched. The authors found that (NH₄)₂S_x treatment could result in suppressing the hysteresis-type current-voltage characteristics related to the interfacial capacitance variation and a reduction in the equivalent refractive index of the ITO/PEDOT:PSS electrodes, owing to the improvement in the interfacial stability of the ITO/PEDOT:PSS electrodes and a reduction in the interface trap-states related charge store at the ITO/PEDOT:PSS interface. This implies that the ITO/PEDOT:PSS electrodes fabricated using the (NH₄)₂S_x-treated ITO may produce a higher extraction efficiency for ITO/PEDOT:PSS-based optoelectronic devices.     

Graphene as transparent conducting electrodes in organic photovoltaics: studies in graphene morphology, hole transporting layers, and counter electrodes

In this work, organic photovoltaics (OPV) with graphene electrodes are constructed where the effect of graphene morphology, hole transporting layers (HTL), and counter electrodes are presented. Instead of the conventional poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) PEDOT:PSS HTL, an alternative transition metal oxide HTL (molybdenum oxide (MoO(3))) is investigated to address the issue of surface immiscibility between graphene and PEDOT:PSS. Graphene films considered here are synthesized via low-pressure chemical vapor deposition (LPCVD) using a copper catalyst and experimental issues concerning the transfer of synthesized graphene onto the substrates of OPV are discussed. The morphology of the graphene electrode and HTL wettability on the graphene surface are shown to play important roles in the successful integration of graphene films into the OPV devices. The effect of various cathodes on the device performance is also studied. These factors (i.e., suitable HTL, graphene surface morphology and residues, and the choice of well-matching counter electrodes) will provide better understanding in utilizing graphene films as transparent conducting electrodes in future solar cell applications.     

Polymer-Based Flexible Schottky Diode Made With Pentacene–PEDOT:PSS

This paper reports a polymer-based flexible Schottky diode made on a flexible cellulose substrate with poly(3, 4-ethylenedioxythiophene):poly(styrenesulfonate)-pentacene (PEDOT:PSS). Pentacene was dissolved into the N-methylpyrrolidone (NMP) solvent and mixed with PEDOT:PSS. Three-layered Schottky diodes consisting of Al, PEDOT:PSS or pentacene-PEDOT:PSS, and Au were fabricated. The current density of Au/PEDOT:PSS/Al Schottky diode (4.8 muA/cm² at 2.5 V/mum) was drastically improved to 440 muA/cm² at 1.9 V/mum when the pentacene-PEDOT:PSS was used. This enhancement of current density of Schottky diode is promising for flexible electronic devices.     

Ternary System with Controlled Structure: A New Strategy toward Efficient Organic Photovoltaics

Recently, a new type of active layer with a ternary system has been developed to further enhance the performance of binary system organic photovoltaics (OPV). In the ternary OPV, almost all active layers are formed by simple ternary blend in solution, which eventually leads to the disordered bulk heterojunction (BHJ) structure after a spin‐coating process. There are two main restrictions in this disordered BHJ structure to obtain higher performance OPV. One is the isolated second donor or acceptor domains. The other is the invalid metal–semiconductor contact. Herein, the concept and design of donor/acceptor/acceptor ternary OPV with more controlled structure (C‐ternary) is reported. The C‐ternary OPV is fabricated by a sequential solution process, in which the second acceptor and donor/acceptor binary blend are sequentially spin‐coated. After the device optimization, the power conversion efficiencies (PCEs) of all OPV with C‐ternary are enhanced by 14–21% relative to those with the simple ternary blend; the best PCEs are 10.7 and 11.0% for fullerene‐based and fullerene‐free solar cells, respectively. Moreover, the averaged PCE value of 10.4% for fullerene‐free solar cell measured in this study is in great agreement with the certified one of 10.32% obtained from Newport Corporation.