Compositional dependence of the open-circuit voltage in ternary blend bulk heterojunction solar cells based on two donor polymers

Ternary blend bulk heterojunction (BHJ) solar cells containing as donor polymers two P3HT analogues, high-band-gap poly(3-hexylthiophene-co-3-(2-ethylhexyl)thiophene) (P3HT(75)-co-EHT(25)) and low-band-gap poly(3-hexylthiophene-thiophene-diketopyrrolopyrrole) (P3HTT-DPP-10%), with phenyl-C(61)-butyric acid methyl ester (PC(61)BM) as an acceptor were studied. When the ratio of the three components was varied, the open-circuit voltage (V(oc)) increased as the amount of P3HT(75)-co-EHT(25) increased. The dependence of V(oc) on the polymer composition for the ternary blend regime was linear when the overall polymer:fullerene ratio was optimized for each polymer:polymer ratio. Also, the short-circuit current densities (J(sc)) for the ternary blends were bettter than those of the binary blends because of complementary polymer absorption, as verified using external quantum efficiency measurements. High fill factors (FF) (>0.59) were achieved in all cases and are attributed to high charge-carrier mobilities in the ternary blends. As a result of the intermediate V(oc), increased J(sc) and high FF, the ternary blend BHJ solar cells showed power conversion efficiencies of up to 5.51%, exceeding those of the corresponding binary blends (3.16 and 5.07%). Importantly, this work shows that upon optimization of the overall polymer:fullerene ratio at each polymer:polymer ratio, high FF, regular variations in V(oc), and enhanced J(sc) are possible throughout the ternary blend composition regime. This adds to the growing evidence that the use of ternary blends is a general and effective strategy for producing efficient organic photovoltaics manufactured in a single active-layer processing step.     

Significance of miscibility in multidonor bulk heterojunction solar cells

Ternary organic blends have potential in realizing efficient bulk heterojunction (BHJ) organic solar cells by harvesting a larger portion of the solar spectrum than binary blends. Several challenging requirements, based on the electronic structure of the components of the ternary blend and their nanoscale morphology, need to be met in order to achieve high power conversion efficiency in ternary BHJs. The properties of a model ternary system comprising two donor polymers, poly(3-hexylthiophene) (P3HT) and a furan-containing, diketopyrrolopyrrole-thiophene low-bandgap polymer (PDPP2FT), with a fullerene acceptor, PC₆₁BM, were examined. The relative miscibility of PC₆₁BM with P3HT and PDPP2FT was examined using diffusion with dynamic secondary ion mass spectrometry (dynamic SIMS) measurements. Grazing incidence small and wide angle X-ray scattering analysis (GISAXS and GIWAXS) were used to study the morphology of the ternary blends. These measurements, along with optoelectronic characterization of ternary blend solar cells, indicate that the miscibility of the fullerene acceptor and donor polymers is a critical factor in the performance in a ternary cell. A guideline that the miscibility of the fullerene in the two polymers should be matched is proposed and further substantiated by examination of known well-performing ternary blends. The ternary blending of semiconducting components can improve the power conversion efficiency of bulk heterojunction organic photovoltaics. The blending of P3HT and PDPP2FT with PC₆₁BM leads to good absorptive coverage of the incident solar spectrum and cascading transport energy levels. The performance of this ternary blend reveals the impact of the miscibility of PC₆₁BM in each polymer as a function of composition, highlighting an important factor for optimization of ternary BHJs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 237–246     

Effect of side chain conjugation lengths on photovoltaic performance of two‐dimensional conjugated copolymers that contain diketopyrrolopyrrole and thiophene with side chains

Two new two‐dimensional conjugated copolymers that contain diketopyrrolopyrrole and thiophene with different π conjugation lengths as side chains, called PDPPMTD and PDPPBTD , were designed and synthesized for use in polymer solar cells (PSCs). The resulting copolymers in the thin film state displayed broad absorption in the visible range with an absorption edge at over 1000 nm, and both had relatively low‐lying HOMO levels, at ?5.20 and ?5.18 eV for PDPPMTD and PDPPBTD , respectively. The power conversion efficiency (PCE) of the PSC that was based on PDPPBTD /PC61BM (w/w = 1:2) reached 4.10 % with a Jsc of 14.5 mA/cm2, a Voc of 0.59 V and an FF of 48%, while PDPPMTD /PC61BM (w/w = 1:2) had a PCE of 2.96% with a Jsc of 12.6 mA/cm2, a Voc of 0.60 V, and an FF of 39%. These results indicate that subtle tuning of the chemical structure can significantly influence Jsc and FF. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2878–2889     

Triplet exciton generation in bulk-heterojunction solar cells based on endohedral fullerenes

Organic bulk-heterojunctions (BHJ) and solar cells containing the trimetallic nitride endohedral fullerene 1-[3-(2-ethyl)hexoxy carbonyl]propyl-1-phenyl-Lu(3)N@C(80) (Lu(3)N@C(80)-PCBEH) show an open circuit voltage (V(OC)) 0.3 V higher than similar devices with [6,6]-phenyl-C[61]-butyric acid methyl ester (PC(61)BM). To fully exploit the potential of this acceptor molecule with respect to the power conversion efficiency (PCE) of solar cells, the short circuit current (J(SC)) should be improved to become competitive with the state of the art solar cells. Here, we address factors influencing the J(SC) in blends containing the high voltage absorber Lu(3)N@C(80)-PCBEH in view of both photogeneration but also transport and extraction of charge carriers. We apply optical, charge carrier extraction, morphology, and spin-sensitive techniques. In blends containing Lu(3)N@C(80)-PCBEH, we found 2 times weaker photoluminescence quenching, remainders of interchain excitons, and, most remarkably, triplet excitons formed on the polymer chain, which were absent in the reference P3HT:PC(61)BM blends. We show that electron back transfer to the triplet state along with the lower exciton dissociation yield due to intramolecular charge transfer in Lu(3)N@C(80)-PCBEH are responsible for the reduced photocurrent.     

Bulk heterojunction polymer solar cells based on binary and ternary blend systems

Polymer solar cells (PSCs) were fabricated using a ternary blend film consisting two conjugated polymers and a soluble fullerene derivative as the donor and acceptor materials, respectively. And, to compare ternary blend system, the single‐component copolymers consisting of the repeating units of each of the copolymers, used in ternary blend solar cells, were designed and synthesized for use as the electron donor materials in binary blend solar cells. We systematically investigated the field‐effect carrier mobilities and the optical, electrochemical, and photovoltaic properties of the copolymers. Under optimized conditions, the binary blend polymer systems showed power conversion efficiencies (PCEs) for the PSCs in the range 3.87–4.16% under AM 1.5 illumination (100 mW cm^?2). All polymers exhibited similar PCEs that did not depend on the ratio of repeating units. The binary blend solar cell containing a single‐component copolymer as the electron donor material performed better than the ternary blend solar cell in this work. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Parallel-like bulk heterojunction polymer solar cells

Here we demonstrate a conceptually new approach, the parallel-like bulk heterojunction (PBHJ), which maintains the simple device configuration and low-cost processing of single-junction BHJ cells while inheriting the major benefit of incorporating multiple polymers in tandem cells. In this PBHJ, free charge carriers travel through their corresponding donor-polymer-linked channels and fullerene-enriched domain to the electrodes, equivalent to a parallel-like connection. The short-circuit current (J(sc)) of the PBHJ solar cell is nearly identical to the sum of those of the individual "subcells", while the open-circuit voltage (V(oc)) is between those of the "subcells". Preliminary optimization of the PBHJ devices gives improvements of up to 40% in J(sc) and 30% in overall efficiency (η) in comparison with single-junction BHJ devices.     

Fullerene derivative acceptors for high performance polymer solar cells

Polymer solar cells (PSCs) are composed of a blend film of a conjugated polymer donor and a soluble fullerene derivative acceptor sandwiched between a PEDOT?:?PSS coated ITO positive electrode and a low workfunction metal negative electrode. The conjugated polymer donor and the fullerene derivative acceptor are the key photovoltaic materials for high performance PSCs. For the acceptors, although [6,6]-phenyl-C(61)-butyric acid methyl ester (PC(60)BM) and its corresponding C(70) derivative PC(70)BM are dominantly used as the acceptors in PSC at present, several series of new fullerene derivatives with higher-lying LUMO energy level and better solubility were reported in recent years for further improving the power conversion efficiency of the PSCs. In this perspective paper, we reviewed the recent research progress on the new fullerene derivative acceptors, including various PC(60)BM-like C(60) derivatives, PC(60)BM bisadduct, PC(70)BM bisadduct, indene-C(60) bisadduct and indene-C(70) bisadduct, trimetallic nitride endohedral fullerenes and other C(60) derivatives with multi side chains. The synthesis and physicochemical properties of PC(60)BM and PC(70)BM were also introduced considering the importance of the two fullerene acceptors.     

Enhanced Hole Transport in Ternary Blend Polymer Solar Cells

Recently, ternary blend polymer solar cells have attracted great attention to improve a short-circuit current density (J_SC) effectively, because complementary absorption bands can harvest the solar light over a wide wavelength range from visible to near-IR region. Interestingly, some ternary blend solar cells have shown improvements not only in J_SC but also in fill factor (FF). Previously, we also reported that a ternary blend solar cell based on a low-bandgap polymer (PTB7-Th), a wide-bandgap polymer (PDCBT), and a fullerene derivative (PCBM) exhibited a higher FF than their binary analogues. Herein, we study charge transport in PTB7-Th/PDCBT/PCBM ternary blend films to address the origin of the improvement in FF. We found that hole polarons are located in PTB7-Th domains and their mobility is enhanced in the ternary blend film.     

Structural tuning of low band gap intermolecular push/pull side-chain polymers for organic photovoltaic applications

A series of novel low band gap donor-acceptor (D-A) type organic co-polymers (BT-F-TPA,BT-CZ-TPA and BT-SI-TPA) consisting of electron-deficient acceptor blocks both in main chains (M1) and at the pendant (M2) were polymerized with different electron rich donor (M3-M5) blocks,i.e.,9,9-dihexyl-9H-fluorene,N-alkyl-2,7-carbazole,and 2,6-dithinosilole,respectively,via Suzuki method.These polymers exhibited relatively low band gaps (1.65-1.88 eV) and broad absorption ranges (680-740 nm).Bulk heterojunction (BHJ) solar cells incorporating these polymers as electron donors,blended with [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) or [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) as electron-acceptors in different weight ratios were fabricated and tested under 100 mW/cm2 of AM 1.5 with white-light illumination.The photovoltaic device containing donor BT-SI-TPA and acceptor PC71BM in 1:2 weight ratio showed the best power conversion efficiency (PCE) value of 1.88％,with open circuit voltage (Voc) =0.75 V,short circuit current density (Jsc) =7.60 mA/cm2,and fill factor (FF) =33.0％.     

以C_(70)衍生物为电子受体的高效聚合物固体薄膜太阳能电池

以PC[70]BM(phenyl C71-butyric acid methyl ester)取代PC[60]BM(phenyl C61-butyric acid methyl ester)作为电子受体材料,以MEH-PPV(poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene])为电子给体材料,制成了本体异质结(bulk heterojunction,BHJ)聚合物太阳能电池.MEH-PPV/PC[70]BM器件在AM1.5G(80 mW/cm2)模拟太阳光的光照条件下得到了3.42%的能量转换效率,短路电流值达到了6.07 mA/cm2,开路电压0.85 V,填充因子为53%.通过紫外可见吸收光谱和外量子效率的研究,发现PC[70]BM作为电子受体,对扩大光谱的吸收范围和增加活性层的吸收系数有明显的作用.同时比较了不同溶剂对该体系器件性能的影响.通过原子力显微镜(AFM)、光暗导I-V曲线等研究,分析了1,2-二氯苯有利于给体相和受体相的微相分离和载流子的传输的原因.     

A novel D-A-π-A organic sensitizer containing a diketopyrrolopyrrole unit with a branched alkyl chain for highly efficient and stable dye-sensitized solar cells

A novel D-A-π-A type organic dye (YCD01) incorporating a diketopyrrolopyrrole unit with a branched alkyl chain was synthesized for dye-sensitized solar cells. YCD01 showed a high conversion efficiency of 7.43% (AM 1.5, 100 mW cm(-2)) with a J(sc) of 13.40 mA cm(-2), a V(oc) of 0.76 V, a FF of 0.73 and an excellent stability.     

Ternary organic solar cells based on polymer donor,polymer acceptor and PCBM components

In this work,ternary organic solar cells(OSCs)combining a fullerene derivative PC71BM with a nonfullerene acceptor N2200-F blended with a polymer donor PM6 were reported.Compared with the binary systems,the highest power conversion efficiency(PCE)of 8.11%was achieved in ternary solar cells with 30 wt%N2200-F content,mainly due to the improved short-circuit current density(Jsc)and fill factor(FF).Further studies showed that the improved Jsc could attribute to the complementary abso rption of the two acceptors and the enhanced FF was originated from the higher hole mobility and the fine-tuned morphology in the ternary system.These results demonstrate that the combination of fullere ne and nonfullerene acceptors in ternary organic solar cells is a promising approach to achieve high-performance OSCs.     

A novel blue dye for near-IR 'dye-sensitised' solar cell applications

A squaraine dye incorporating two carboxylic acid attaching groups has been synthesised and used successfully in both liquid and solid-state solar cells, with solar energy to electricity conversion efficiencies (eta) under AM 1.5 G irradiation (100 mW cm(-2)) of 3.7 and 1.5% and short-circuit current densities (J(sc)s) of 8.6 and 4.2 mA cm(-2), with open-circuit voltages (V(oc)) of 591 and 681 mV and fill factors (FF) of 73 and 53%, respectively.     

Optimal bulk-heterojunction morphology enabled by fibril network strategy for high-performance organic solar cells

A bicontinuous network formed spontaneously upon film preparation is highly desirable for bulk-heterojunction(BHJ) organic solar cells(OSCs). Many donor-acceptor(D-A) type conjugated polymers can self-assemble into polymer fibrils in the solid state and such fibril-assembly can construct the morphological framework by forming a network structure, inducing the formation of ideal BHJ morphology. Our recent works have revealed that the fibril network strategy(FNS) can control the blend morphology in fullerene, non-fullerene and ternary OSCs. It has been shown that the formation of fibril network can optimize phase separation scale and ensure efficient exciton dissociation and charge carriers transport, thus leading to impressive power conversion efficiencies(PCEs) and high fill factor(FF) values. We believe that FNS will provide a promising approach for the optimization of active layer morphology and the improvement of photovoltaic performance, and further promote the commercialization of OSCs.     

Multichromophore light harvesting in hybrid solar cells

A new technologically relevant method for multichromophore sensitizing of hybrid blend solar cells is presented. Two dyes having complementary absorption in the UV-visible regions are individually adsorbed on nanocrystalline TiO(2) powder. These dyed TiO(2) nanoparticles are blended with an organic hole-conductor (HC) Spiro-OMeTAD in desired compositions and applied on a conducting substrate by doctor-blading at room temperature to fabricate multichromophore-sensitized hybrid blend solar cells. The external quantum efficiency (EQE) of the single hybrid layer system fabricated with two dyes, that absorb mainly UV (TPD dye) and visible regions (Ru-TPA-NCS dye), exhibited a clear panchromatic response with the sum of the EQE characteristics of each single dye cell. The first results of a multichromophore-sensitized solid-state solar cell showed J(sc) of 2.1 mA cm(-2), V(oc) of 645 mV, FF of 47% and efficiency of 0.65% at AM 1.5 G, 100 mW cm(-2) illumination intensity. The J(sc) of the multichromophore cell is the sum of the individually dyed solar cells. The process described here is technically very innovative and very simple in procedure. It has potentials to be adopted for panchromatic sensitization using more than two dyes in a single hybrid layer or layer-wise fabrication of a tandem structure at room temperature.     

Vacuum-deposited small-molecule organic solar cells with high power conversion efficiencies by judicious molecular design and device optimization

Three new tailor-made molecules (DPDCTB, DPDCPB, and DTDCPB) were strategically designed and convergently synthesized as donor materials for small-molecule organic solar cells. These compounds possess a donor-acceptor-acceptor molecular architecture, in which various electron-donating moieties are connected to an electron-withdrawing dicyanovinylene moiety through another electron-accepting 2,1,3-benzothiadiazole block. The molecular structures and crystal packings of DTDCPB and the previously reported DTDCTB were characterized by single-crystal X-ray crystallography. Photophysical and electrochemical properties as well as energy levels of this series of donor molecules were thoroughly investigated, affording clear structure-property relationships. By delicate manipulation of the trade-off between the photovoltage and the photocurrent via molecular structure engineering together with device optimizations, which included fine-tuning the layer thicknesses and the donor:acceptor blended ratio in the bulk heterojunction layer, vacuum-deposited hybrid planar-mixed heterojunction devices utilizing DTDCPB as the donor and C(70) as the acceptor showed the best performance with a power conversion efficiency (PCE) of 6.6 ± 0.2% (the highest PCE of 6.8%), along with an open-circuit voltage (V(oc)) of 0.93 ± 0.02 V, a short-circuit current density (J(sc)) of 13.48 ± 0.27 mA/cm(2), and a fill factor (FF) of 0.53 ± 0.02, under 1 sun (100 mW/cm(2)) AM 1.5G simulated solar illumination.     

Facile synthesis of a 56π-electron 1,2-dihydromethano-[60]PCBM and its application for thermally stable polymer solar cells

A facile synthesis was employed to make a 56π-electron methano-PC(61)BM with a very small 1,2-dihydromethano (CH(2)) group. This new fullerene derivative possesses high electron mobility (0.014 cm(2) V(-1) s(-1)) and higher LUMO energy level (0.15 eV) than PC(61)BM. Bulk hetero-junction devices based on using poly(3-hexylthiophene) and methano-PC(61)BM as active layer exhibited better performance and thermal stability than those using the PC(61)BM analogue.     

Synthesis of D-A copolymers based on thiadiazole and thiazolothiazole acceptor units and their applications in ternary polymer solar cells

We have designed and synthesized two wide bandgap new donor-acceptor (D-A) copolymers consisting of the same alkylthiazole-substituted benzo[1,2-b;4,5-b′]dithiophene (BDTTz) donor unit and but different acceptor units, i.e., thiazolo[5,4-d]thiazole (TT_Z) ( P122 ) and 1,3,-4 thiadiazole (TDz) ( P123 ) and investigated their optical and electrochemical properties. We have employed these copolymers as donor and fullerene (PC ₇₁ BM) and narrow bandgap non-fullerene (Y6) as acceptor, to fabricate binary and ternary bulk heterojunction polymer solar cells (PSCs). The overall power conversion efficiency (PCE) of optimized binary bulk heterojunction PSCs based on P122 :Y6 and P123 :Y6 is 12.60% and 13.16%, respectively. The higher PCE for PSCs based on P123 than P122 counterparts may be associated with the broader absorption profile of the P123 and more charge carrier mobilities than that for the P122 active layer. With the incorporation of small amount of PC₇₁BM into either P122 :Y6 or P123 :Y6 binary blend, the corresponding ternary PSCs showed an overall PCE of 14.89% and 15.52%, respectively, which is higher than the binary counterparts using either Y6 or PC₇₁BM as acceptor. Incorporating the PC₇₁BM in the binary host blend increases the absorption in the 300–500 nm wavelength region, generating more excitons in the active ternary layer and helping to dissociate the excitons into free charge carriers more effectively. The more appropriate nanoscale phase separation in the active ternary layer than the binary counterpart may be one of the reasons for higher PCE.     

A ternary organic solar cell with 300 nm thick active layer shows over 14% efficiency

In order to meet the requirements for making organic solar cells(OSCs) through solution printing techniques, great efforts have been devoted into developing high performance OSCs with relatively thicker active layers. In this work, a thick-film(300 nm)ternary OSC with a power conversion efficiency of 14.3% is fabricated by introducing phenyl-C_(61)-butyric-acid-methyl ester(PC_(61)BM) into a PBDB-T-2Cl:BTP-4 F host blend. The addition of PC_(61)BM is found to be helpful for improving the hole and electron mobilities, and thus facilitates charge transport as well as suppresses charge recombination in the active layers, leading to the improved efficiencies of OSCs with relatively thicker active layers. Our results demonstrate the feasibility of employing fullerene derivative PC_(61)BM to construct a high-efficiency thick-film ternary device, which would promote the development of thick layer ternary OSCs to fulfill the requirements of future roll to roll production.     

Controlled conjugated backbone twisting for an increased open-circuit voltage while having a high short-circuit current in poly(hexylthiophene) derivatives

Conjugated polymers with nearly planar backbones have been the most commonly investigated materials for organic-based electronic devices. More twisted polymer backbones have been shown to achieve larger open-circuit voltages in solar cells, though with decreased short-circuit current densities. We systematically impose twists within a family of poly(hexylthiophene)s and examine their influence on the performance of polymer:fullerene bulk heterojunction (BHJ) solar cells. A simple chemical modification concerning the number and placement of alkyl side chains along the conjugated backbone is used to control the degree of backbone twisting. Density functional theory calculations were carried out on a series of oligothiophene structures to provide insights on how the sterically induced twisting influences the geometric, electronic, and optical properties. Grazing incidence X-ray scattering measurements were performed to investigate how the thin-film packing structure was affected. The open-circuit voltage and charge-transfer state energy of the polymer:fullerene BHJ solar cells increased substantially with the degree of twist induced within the conjugated backbone--due to an increase in the polymer ionization potential--while the short-circuit current decreased as a result of a larger optical gap and lower hole mobility. A controlled, moderate degree of twist along the poly(3,4-dihexyl-2,2':5',2'-terthiophene) (PDHTT) conjugated backbone led to a 19% enhancement in the open-circuit voltage (0.735 V) vs poly(3-hexylthiophene)-based devices, while similar short-circuit current densities, fill factors, and hole-carrier mobilities were maintained. These factors resulted in a power conversion efficiency of 4.2% for a PDHTT:[6,6]-phenyl-C(71)-butyric acid methyl ester (PC(71)BM) blend solar cell without thermal annealing. This simple approach reveals a molecular design avenue to increase open-circuit voltage while retaining the short-circuit current.