Synthesis and characterization of a novel fullerene derivative for use in organic solar cells

A novel fullerene derivative with an N-hexylphenothiazine moiety, PTZ-C_60, was synthesized and characterized. The new synthesized fullerene showed good solubility in common organic solvents such as toluene, chlorobenzene and 1, 2 dichlorobenzene. The synthetic product PTZ-C₆₀ was characterized by ¹H and ¹³C NMR, FT-IR and UV-vis spectroscopy. Photovoltaic devices were fabricated using the new fullerene derivative as the electron acceptor and P3HT as the electron donor. The configuration of the device was as follows: ITO/PEDOT:PSS/active layer/LiF/Al. The weight ratios of the electron donor to the acceptor in the active layer were 1:0.5, 1:0.7, and 1:1. The open-circuit voltage (V_oc) of the fabricated devices was found to be higher than that of devices based on C₆₀ because the LUMO energy level of the new fullerene derivative was higher than that of C₆₀. Further, the power conversion efficiency (PCE) of these devices was observed to be high when annealing was carried out at 150 °C for 5 min and the thickness of the active layer was 80 nm. The maximum V_oc, short-circuit current density, and PCE of the best device were 0.608 V, 4.393 mA/cm², and 1.29%, respectively.     

Long-term stability of tandem solar cells containing small organic molecules

In this paper, we discuss long-term stability measurements of tandem solar cells with mixed phthalocyanine: fullerene photoactive layers that exhibit an initial power conversion efficiency of about 4%. These devices are remarkably stable against exposure to halogen light as their power conversion efficiency decreases by less than 3% within more than 1400 h of permanent illumination at an intensity of approximately at . In addition, long-term stability measurements at an elevated temperature of are performed. In comparison to the illumination experiment, the cells show a much faster degradation which is attributed to the low glass transition temperature of the hole transport layer.     

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.     

Degradation of organic solar cells due to air exposure

We present a study of dark air-exposure degradation of organic solar cells based on photoactive blends of the conjugated polymer, poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylene vinylene] (MDMO-PPV) with [6,6]-phenyl C₆₁-butyric acid methyl ester (PCBM). Photovoltaic devices were fabricated on indium tin oxide (ITO) glass with or without a layer of poly (3,4-ethylenedioxythiophene):poly(4-styrene sulfonate) (PEDOT:PSS), and were studied without encapsulation. Photovoltaic performance characteristics were measured as a function of time for different ambient conditions (under white light irradiation and in the dark, and under air, dry oxygen and humid nitrogen atmospheres). It was found that a key cause of degradation under air exposure is light independent and results from water adsorption by the hygroscopic PEDOT:PSS layer. Measurements of the charge mobility and hole injection after air exposure showed that the degradation increases the resistance of the PEDOT:PSS/blend layer interface.     

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.     

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.     

Full day modelling of V-shaped organic solar cell

Folded and planar solar cells are examined with optical simulations, with the finite element method. The maximum photocurrent densities during the full day are compared between cells of different geometries and tilting angles. The change of incident angle and spectrum over time are handled in this analysis. The results show that the light trapping effect of the folded cell makes these cells show higher maximum photocurrent densities than the planar cells during all hours of the day. This is the case for both single and tandem cells. The results also indicate that balancing the currents in the tandem cells by adjusting the active layer thickness may be more cumbersome with the folded tandem cells than the stacked planar cells.     

Improved high temperature stability of organic solar cells using a phosphine oxide type cathode modification layer

The high temperature stability of the organic solar cells (OSCs) was improved using a phosphine oxide based organic cathode modification layer instead of LiF. The OSC modified with the phosphine oxide cathode modification layer showed constant device performances after a thermal treatment at 90 °C, while the LiF based OSC exhibited degraded device performance after the thermal treatment. The use of the phosphine oxide based interlayer was effective to improve the high temperature stability of the OSC.     

Abnormally high photocurrent of a degraded organic solar cell under chopped light

Photocurrent of an organic solar cell under chopped monochromatic light was studied at different stages, i.e. just after fabrication (without degradation) and after serious degradation. A large photocurrent under chopped light was observed for a seriously degraded device, unexpected from intuitionistic reckoning. This work demonstrates that both light bias and chopper frequency affect the photocurrent measurement of an organic solar cell, especially for a degraded device. The influence of light bias and chopper frequency is explained as the result of traps produced during the degradation of an organic solar cell. Thus measuring photocurrent under one sun light bias at low chopper frequency is suggested to more accurately determine the external quantum efficiency.     

Rubrene as an additive in M-phthalocyanine/fullerene organic solar cells

Photovoltaic devices made from metallo-phthalocyanine/fullerene (M-Pc/C₆₀) with 5,6,11,12-tetraphenylnaphthacene (rubrene) as an additive are fabricated and characterized. The effect of rubrene is examined for 4 different M-phthalocyanines – H₂Pc, ZnPc, ClInPc, and VOPc – to represent 4 different valencies of the central moiety of M-Pc. In each case, rubrene has shown a notable increase in the open circuit voltage and in the case of the ClInPc and VOPc results in an increase in the overall power conversion efficiency. Through measurement of external quantum efficiency, it is shown that the increased efficiency is due to increased V_oc and not due to the photocurrent contribution from the complementary absorption profile of rubrene. Finally, the photostability of rubrene-based cells is studied, showing that unencapsulated devices decay rapidly in air as a result of the formation of rubrene peroxide, as evidenced by significant decay of the UV–vis absorption and direct measurement of the cell performance over a time period as short as several minutes.     

Total charge amount as indicator for the degradation of small molecule organic solar cells

We show that the number of extracted charge carriers is a suitable measure to compare lifetime measurements on organic solar cells at different intensities. In detail, we used pin-structures with active layers containing a bulk heterojunction of Zincphthalocyanine (ZnPc) and C₆₀. Extended lifetime measurements under constant monochromatic or white illumination at defined temperatures of 50 °C or 90 °C are done. On the one hand, we show that the number of extracted charge carriers is important to determine the degree of degradation. On the other hand, our results show that the energy of irradiated photons is significant for accelerated measurements. This is an major advantage for the realisation of accelerated lifetime measurements. Additionally, we find that not single charge carriers, but excitons cause the degradation of the observed solar cells.     

Progress in stability of organic solar cells exposed to air

In this paper, the stability of small-molecule organic solar cells based on copper phthalocyanine (CuPc) and fullerene (C₆₀) is investigated. The use of silver instead of aluminum as the metal electrode in these solar cells, with smaller grain size and grain boundaries as well as with more uniform grain size distribution in the film, results in significant improvement in the lifetime of the devices. The substantial role of silver in the protection of the cells against permeation of oxygen and/or water molecules into the organic thin films is confirmed. Substitution of a thin buffer layer (70 Å) of bathophenanthroline (Bphen) for bathocuproine (BCP), sandwiched between C₆₀ and the cathode, makes considerable progress in the lifetime of the device.     

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.     

Stability/degradation of polymer solar cells

Polymer and organic solar cells degrade during illumination and in the dark. This is in contrast to photovoltaics based on inorganic semiconductors such as silicon. Long operational lifetimes of solar cell devices are required in real-life application and the understanding and alleviation of the degradation phenomena are a prerequisite for successful application of this new and promising technology. In this review, the current understanding of stability/degradation in organic and polymer solar cell devices is presented and the methods for studying and elucidating degradation are discussed. Methods for enhancing the stability through the choice of better active materials, encapsulation, application of getter materials and UV-filters are also discussed.     

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.     

Three-layer organic solar cell with high-power conversion efficiency of 3.5%

To prepare organic solar cells with practical level of energy-conversion efficiency, the following strategies were adopted. By using HD as the photosensitizer, which is heterodimer consisting of a weak electron-donating 5, 10, 15, 20-tetra(2, 5-dimethoxyphenyl)porphyrinatozinc and a weak electron-accepting 5, 10, 15-triphenyl-20-(3-pyridyl)porphyrin, intramolecular photoinduced electron transfer is promoted resulting in effective charge separation. To create an energetically well-arranged system, the HD was placed between an electron-acceptor layer of PV (perylene-3, 4, 9, 10-tetracarboxyl-bis-benzimidazole) and strong electron-donor layer of MC (3-carboxymethyl-5-[(3-ethyl-2(3H)-benzothiazolylidine)ethylidene]-2-thioxo-4-thiazolidinone), where photoinduced intermolecular electron transfer from HD to PV and rapid injection of electrons from MC to HD suppress back electron transfer in the charge-separated HD. As a result of this, the three-layer solar cell Al/PV/HD/MC/Au showed fairly good photovoltaic properties, short-circuit photocurrent quantum yield of 49.2%, open-circuit photovoltage of 0.39 V, fill factor of 0.51, and energy conversion yield of 3.51% when irradiated with 445 nm monochromatic light of 12 μW cm⁻² intensity transmitted through the Al/PV interface. Since the photocurrent hardly decreased with age, the photocurrent observed here is really from energy conversion and not from photocorrosion of Al electrode being occasionally responsible for the photocurrent.     

Higher fullerenes as electron acceptors for polymer solar cells: A quantum chemical study

In the present study, we have used quantum chemical methods to study the energy levels of the frontier orbitals of higher fullerene derivatives (from C₇₀ to C₈₄ and having the same addend as in [6,6]-phenyl C₆₁-butyric acid methyl ester) with the aim to understand if they can be used as electron acceptors in bulk heterojunction polymer–fullerene solar cells. Higher fullerenes have a stronger and broader absorption compared to C₆₀ and they can improve the current output of the corresponding devices. The geometries of all the compounds were optimized with the density functional theory at the B3LYP/3-21G* level of calculation. The lowest unoccupied molecular orbital (LUMO) levels of the investigated compounds correlate well with the reduction potentials (obtained by cyclic voltammetry) of the already prepared species. We found that the LUMO level depends not only on the fullerene size (number of carbons of the cage) and constitutional isomer, but also on the position and, in some cases, the addend orientation. This issue should be considered because for a proper device operation, a well-defined LUMO is required. The position of the LUMO level of some higher fullerene derivatives can be suitable for low-bandgap polymers.     

A stabilization effect of [60]fullerene in donor–acceptor organic solar cells

In this paper we compare the behavior of solar cells based on pure regioregular poly(3-hexylthiophene) with those in which the same polymer is blended with a functionalized fullerene, under continuous illumination. We found that the decay of both photocurrent and photovoltage signals with time is substantially reduced when the blend is used.     

Improved the efficiency of small molecule organic solar cell by double anode buffer layers

Small molecule organic solar cell with an optimized hybrid planar-mixed molecular heterojunction (PM-HJ) structure of indium tin oxide (ITO)/ poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT: PSS) doped with 4 wt% sorbitol/ pentacene (2 nm)/ copper phthalocyanine (CuPc) (10 nm)/ CuPc: C₆₀ mixed (20 nm)/ fullerene (C₆₀) (20 nm)/ bathocuproine (BCP) (10 nm)/Al was fabricated. PEDOT: PSS layer doped with 4 wt% sorbitol and pentacene layer were used as interlayers between the ITO anode and CuPc layer to help the hole transport. And then the short-circuit current (J_sc) of solar cell was enhanced by inserting both the PEDOT: PSS (4 wt% sorbitol) and the pentacene, resulting in a 400% enhancement in power conversion efficiency (PCE). The maximum PCE of 3.9% was obtained under 1sun standard AM1.5G solar illumination of 100 mW/cm².     

Solution processable quinacridone based materials as acceptor for organic heterojunction solar cells

Two series of novel quinacridone (QA) based materials that combined a strong absorption over a broad range in visible region with good electrical characteristics, which were used as the new electron-accepting materials for organic solar cells, are explored. Unique cyclic compounds 1-6 are synthesized by incorporating electron withdrawing groups (CN, COOH) at carbonyl position of alkyl substituted quinacridones, which lead to the compounds possessing the characteristics of solution-processed and being suitable for photovoltaic applications. Heterojunction solar cells with simple device configuration using these soluble materials as acceptor and effective donor poly (3-hexyl thiophene) (P3HT) were fabricated. The maximum power conversion efficiency (PCE) achieved in the solar cell based on compound 5 is 0.42% under simulated AM 1.5 solar irradiation with J_sc=1.80 mA cm⁻², V_oc=0.50 V and FF=47%. Although the aimed devices just exhibit moderate PCE, our results clearly suggest that the new-type electron-accepting materials different from fullerene have great potential as acceptor in heterojunction solar cell due to many advantages of the QA derivatives such as relatively inexpensive, good electrochemical stability and could be readily modified.