A Supramolecular Complex in Small-Molecule Solar Cells based on Contorted Aromatic Molecules

"Ball and socket" motif: The contorted dibenzotetrathienocoronene (6-DBTTC) forms a complex with the C(70) fullerene PC(70) BM embedded in an amorphous phase of PC(70) BM. The materials are processable into organic solar cells in solution. The power conversion efficiency is maximal when there is a 1:2 molar ratio of 6-DBTTC to PC(70) BM. Formation of the supramolecular complex directly affects charge separation in the active layer.     

6,7-dialkoxy-2,3-diphenylquinoxaline based conjugated polymers for solar cells with high open-circuit voltage

6,7-Dialkoxy-2,3-diphenylquinoxaline based narrow band gap conjugated polymers, poly[2,7-(9-octyl-9H-carbazole)-alt-5,5-(5,8-di-2-thinenyl-(6,7-dialkoxy-2,3-diphenylquinoxaline))] (PCDTQ) and poly[2,7-(9,9-dioctylfluorene)-alt-5,5-(5,8-di-2-thinenyl-(6,7-dialkoxy-2,3-diphenylquinoxaline))] (PFDTQ), have been synthesized by Suzuki polycondensation. Their optical, electrochemical, transport and photovoltaic properties have been investigated in detail. Hole mobilities of PCDTQ and PFDTQ films spin coated from 1,2-dichlorobenzene (DCB) solutions are 1.0 × 10-4 and 4.1 × 10-4 cm2V-1s-1, respectively. Polymer solar cells were fabricated with the as-synthesized polymers as the donor and PC61BM and PC71BM as the acceptor. Devices based on PCDTQ:PC71BM (1:3) and PFDTQ:PC71BM (1:3) fabricated from DCB solutions demonstrated a power conversion efficiency (PCE) of 2.5% with a Voc of 0.95 V and a PCE of 2.5% with a Voc of 0.98 V, respectively, indicating they are promising donor materials.     

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.     

Over 16.7% efficiency of ternary organic photovoltaics by employing extra PC71BM as morphology regulator

Ternary organic photovoltaics(OPVs) are fabricated with PBDB-T-2 Cl:Y6(1:1.2, wt/wt) as the host system and extra PC_(71)BM as the third component. The PBDB-T-2 Cl:Y6 based binary OPVs exhibit a power conversion efficiency(PCE) of 15.49% with a short circuit current(J_(SC)) of 24.98 m A cm~(-2), an open circuit voltage(V_(OC)) of 0.868 V and a fill factor(FF) of 71.42%. A 16.71%PCE is obtained in the optimized ternary OPVs with PBDB-T-2 Cl:Y6:PC_(71)BM(1:1.2:0.2, wt/wt) active layer, resulting from the synchronously improved J_(SC) of 25.44 m A cm~(-2), FF of 75.66% and the constant V_(OC)of 0.868 V. The incorporated PC_(71)BM may prefer to mix with Y6 to finely adjust phase separation, domain size and molecular arrangement in ternary active layers, which can be confirmed from the characterization on morphology, 2 D grazing incidence small and wide-angle X-ray scattering, as well as Raman mapping. In addition, PC_(71)BM may prefer to mix with Y6 to form efficient electron transport channels, which should be conducive to charge transport and collection in the optimized ternary OPVs. This work provides more insight into the underlying reasons of the third component on performance improvement of ternary OPVs, indicating ternary strategy should be an efficient method to optimize active layers for synchronously improving photon harvesting, exciton dissociation and charge transport, while keeping the simple cell fabrication technology.     

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.     

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.     

聚合物:富勒烯薄膜光伏电池的反常高温热稳定性研究

聚合物太阳能电池光电转换效率已接近商业化要求,但稳定性差却成为其实用化瓶颈因素.高温暴晒是聚合物太阳能电池实用化必须面临的环境,因此提高聚合物太阳能电池的热稳定性至关重要.本文以典型的Poly(3-hexylthiophene-2,5-diyl(P3HT):[6,6]-Phenyl-C61-butyric acid methyl ester(PC61BM)基聚合物太阳能电池为研究模型,考察其在不同加热温度下(50~110℃)持续工作时的器件效率变化行为,结果发现电池在高温下表现出一种非常规的性能衰减再回升的行为,具体表现为高温下电池首先表现指数式急速衰减(20%~25%),随后发生反常的性能快速恢复至接近初始效率,之后电池保持超长的高温稳定性.光学显微镜和激光光束诱导电流成像结果证明,顶电极覆盖可以有效抑制活性层中PC61BM的聚集结晶,因而电池的反常热诱导稳定性提升与PC61BM的大量聚集结晶无关.活性层薄膜的紫外可见吸收光谱和器件外量子效率的表征结果证明,持续高温加热没有促进PC61BM二聚体的形成,反而有利于PC61BM二聚体的解离.综合实验分析结果,推测PC61BM在光照下的快速二聚反应及其高温解离是导致电池表现出反常热稳定性提升行为的主要原因.实验结果揭示了初期制备的聚合物太阳能电池实际处于一种亚稳态,对器件进行短暂的前期热退火有利于稳定活性层结构,消除亚稳态,有效提升器件稳定性.本研究工作不仅对富勒烯基聚合物太阳能电池的热诱导反常稳定性提升机理机制给出了解释,而且提供了一种提高聚合物太阳能电池稳定性的新策略.     

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％.     

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     

Phase diagram of P3HT:PC70BM thin films based on variable-temperature spectroscopic ellipsometry

In this article, we present the research on the influence of the composition of thin films of a blend of poly (3-hexylthiophene −2,5-diyl) - P3HT with fullerene derivatives [6,6]-phenyl-C71-butyric acid methyl ester – PC70BM and [6,6]-phenyl-C61-butyric acid methyl ester – PC60BM on their thermal transitions. The influence of molar mass (Mw) of P3HT (Mw = 65.2; 54.2 and 34.1 kDa) and PCBM (PC60BM – Mw = 911 g/mol and PC70BM – Mw = 1031 g/mol) is examined in details. The article presents significantly expanded research compared to our previous work on thermal transitions in thin films of blend P3HT (Mw = 65.2 kDa) with PC60BM. For this reason, we also compare current results with previous ones. Here, we present for the first time a phase diagram of thin films of the P3HT(Mw = 65.2 kDa):PC70BM blend using variable-temperature ellipsometry. Our research reveals the presence of characteristic temperatures of pure phases in thin films of P3HT: PCBM blends. It turns out that the cold crystallization temperature of the P3HT phase in P3HT(Mw = 65.2 kDa):PC70BM blend films is lower than corresponding temperature in P3HT(Mw = 65.2 kDa):PC60BM blend films. At the same time, the cold crystallization temperature of the PC70BM phase behaves inversely. We demonstrate also that variable-temperature spectroscopic ellipsometry is a very sensitive technique for studying thermal transitions in these thin films. In addition, we show that the entire phase diagram can be determined based on the raw ellipsometric data analysis, e.g. using a delta angle at wavelength λ = 280 nm.     

Synthesis and investigation of photovoltaic properties for polymer semiconductors based on porphyrin compounds as light-harvesting units

We reported on two polymer semiconducting copolymers based on porphyrin compounds, poly[9,9-dioctylfluorene-co-5,15-bis(hexoxybenzyl)-10,20-bis(benzo-4-yl)porphyrin] (PFPor) and poly[9-(heptadecan-9-yl)carbazole-co-5,15-bis(hexoxybenzyl)-10,20-bis(benzo-4-yl)porphyrin] (PCPor), for use as organic photovoltaic materials. The thermal, optical, electrochemical, and photovoltaic properties of the two polymers were investigated. In addition, PC₆₁BM and PC₇₁BM were introduced as acceptor materials to confirm the acceptor effect in bulk heterojunction photovoltaic devices. Moreover, in order to establish acceptor effects, morphologies of polymer/PCBM blend films were analyzed through atomic force microscopy (AFM). PFPor and PCPor exhibited the best device performance with power conversion efficiencies (PCE) of 0.62% and 0.76%, respectively, upon the introduction of PC₇₁BM as the acceptor in the device where 86 wt.% of the PC₇₁BM was contained in the active layer (pol:PC₇₁BM = 1:6, w/w).     

High performance low band gap polymer solar cells with a non-conventional acceptor

A novel C70 fullerene derivative was designed and synthesized by [4+2] cyclic addition reaction between indene derivative (methyl 1H-indene-3-carboxylate) and C70. The absorption and photoluminescence of H120 and its mixed films with different polymer donor materials were investigated, as well as its electrochemical property and electron mobility. It was found that H120 has 0.05 eV higher LUMO level than that of PC(70)BM. Its electron mobility reached 6.32 × 10(-4) cm(2) V(-1) s(-1), which is slightly lower than 9.55 × 10(-4) cm(2) V(-1) s(-1) of PC(70)BM. The photovoltaic devices based on P3HT, and two high efficiency low band gap polymers, PBDTTT-C and PBDTTDPP as donors, with H120 as an acceptor gave power conversion efficiencies of 4.2%, 6.0% and 6.2%, respectively.     

Rare solvent annealing effective benzo(1,2-b:4,5-b')dithiophene-based low band-gap polymer for bulk heterojunction organic photovoltaics

A newly synthesized benzo(1,2-b:4,5-b')dithiophene-based low band-gap copolymer pBCN is amenable to solvent annealing in the fabrication of organic photovoltaics, of which power conversion efficiency is greatly improved to 4.2% with PC(61)BM or 4.9% with PC(71)BM.     

Development of a new benzo(1,2-b:4,5-b')dithiophene-based copolymer with conjugated dithienylbenzothiadiazole-vinylene side chains for efficient solar cells

A new benzodithiophene-based copolymer PTG1 with dithienylbenzothiadiazole-vinylene side chains exhibits excellent film-forming ability, a deep HOMO energy level, and a good miscibility with PC(71)BM. Bulk heterojunction polymer solar cells fabricated from PTG1 and PC(71)BM showed a promising power conversion efficiency over 4.0%.     

Novel phenanthrocarbazole based donor–acceptor random and alternating copolymers for photovoltaics

A series of 6H‐phenanthro[1,10,9,8‐cdefg]carbazole (PC) and benzothiadiazole (BT) based donor–acceptor (D‐A) random copolymers PPC‐T‐BT_3/1, PPC‐T‐BT_2/1, PPC‐T‐BT_1/1, PPC‐T‐BT_1/2, and PPC‐T‐BT_1/3 were easily prepared by varying the molar ratio of PC to BT from 3:1, 2:1, 1:1, 1:2, to 1:3, respectively. The corresponding alternating D‐A copolymer poly{6H‐phenanthro[1,10,9,8‐cdefg]carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole} (PPCDTBT) was also synthesized for comparison. Compared with PPCDTBT, PPC‐T‐BT_1/1, PPC‐T‐BT_1/2, and PPC‐T‐BT_1/3 obtained more pronounced intramolecular charge transfer band and extended absorption. Power conversion efficiency of these copolymer‐based devices strongly depends on the D/A molar ratio, related to the spectrum absorption and active layer morphology. Among the polymer solar cells based on random copolymers, PPC‐T‐BT_2/1:PC₆₁BM based device achieved the best efficiency of 1.9%, which is close to the efficiency of PPCDTBT:PC₆₁BM based device (2.3%). Therefore, it is concluded that the random copolymer can achieve the comparable performance to alternating copolymer by precisely adjusting the D/A molar ratio on small scales. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4885–4893     

Large open-circuit voltage polymer solar cells by poly(3-hexylthiophene) with multi-adducts fullerenes

Polymer solar cells (PSCs) made by poly(3-hexylthiophene) (P3HT) with multi-adducts fullerenes, [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM), PC61BM-bisadduct (bisPC61BM) and PC61BM-trisadduct (trisPC61BM), were reported. Electrochemistry studies indicated that PC61BM, bisPC61BM and trisPC61BM had step-up distributional lowest unoccupied molecular orbital (LUMO) energy. PSCs made by P3HT with above PC61BMs show a trend of enlarged open-circuit voltages, which is in good agreement with the energy difference between the LUMO of PC61BMs and the HOMO of P3HT. On the contrary, reduced short-circuit currents (Jsc) were observed. The investigation of photo responsibility, dynamics analysis based on photo-induced absorption of composite films, P3HT:PC61BMs and n-channel thin film field-effect transistors of PC61BMs suggested that the short polaron lifetimes and low carrier mobilities were response for reduced Jsc. All these results demonstrated that it was important to develop an electron acceptor which has both high carrier mobility, and good compatibility with the electron donor conjugated polymer for approaching high performance PSCs.     

Tetrathienoanthracene-based copolymers for efficient solar cells

A series of semiconducting copolymers (PTAT-x) containing extended π-conjugated tetrathienoanthracene units have been synthesized. It was shown that the extended conjugation system enhanced the π-π stacking in the polymer/PC(61)BM blend films and facilitated the charge transport in heterojunction solar cell devices. After structural fine-tuning, the polymer with bulky 2-butyloctyl side chains (PTAT-3) exhibited a PCE of 5.6% when it was blended with PC(61)BM.     

Thieno[3,2-b]thiophene-diketopyrrolopyrrole-containing polymers for high-performance organic field-effect transistors and organic photovoltaic devices

We report the synthesis and polymerization of a novel thieno[3,2-b]thiophene-diketopyrrolopyrrole-based monomer. Copolymerization with thiophene afforded a polymer with a maximum hole mobility of 1.95 cm(2) V(-1) s(-1), which is the highest mobility from a polymer-based OFET reported to date. Bulk-heterojunction solar cells comprising this polymer and PC(71)BM gave a power conversion efficiency of 5.4%.     

TYPE I AND TYPE II MECHANISMS IN THE PHOTOSENSITIZED LYSIS OF PHOSPHATIDYLCHOLINE LIPOSOMES BY HEMATOPORPHYRIN

Abstract The lysis of phosphatidylcholine (PC) liposomes was sensitized to visible light (>500nm) by hematoporphyrin (HP) incorporated in the liposomes (0.09-1.5%, wt/wt) or in the external buffer (1-15 μM). The lytic mechanism changed from the Type II pathway mediated by singlet oxygen (¹O₂) at low HP concentrations to the anoxic, Type I pathway at high HP concentrations. Spectral measurements of HP in aqueous and organic solvents indicate that the HP was not aggregated (monomers and/or dimers) for Type II sensitization and aggregated for Type I conditions. High concentrations of azide (>0.1 M) or DABCO (>0.5 M) were protective with high HP concentration under oxic and anoxic conditions, which cannot involve the scavenging of ¹O₂. Feasible protective mechanisms are quenching of the HP triplet state by high azide and repair of the damaged membrane by DABCO via an electron transfer process. There was significant protection against lysis under Type I conditions by low concentrations of ferricyanide (>1 mM), indicative of an electron transfer mechanism. The incorporation of 22 mol % cholesterol in PC liposomes with 1% HP had no effect on the lytic efficiency for oxic and anoxic conditions. Dipalmitoylphosphatidylcholine liposomes incorporating 1% HP showed negligible photosensitized lysis at 50°C compared with PC liposomes with 1% HP at 25°C. The promotion of photosensitized lysis by hydrodynamic agitation observed in prior work with methylene blue (Grossweiner and Grossweiner, 1982) was significant with HP sensitization for both Type I and Type II conditions. Actinometry with PC liposomes incorporating 1% HP indicated that photosensitized lysis was very inefficient, requiring many absorbed quanta per lysed liposome. Preliminary experiments with crude hematoporphyrin derivative (Hpd) showed similar concentration effects on lytic efficiency, where PC liposomes incorporating 0.1% (wt/wt) Hpd were strongly sensitized by oxygen, whereas sensitization by oxygen was insignificant with 3.1% Hpd. The results with HP and crude Hpd indicate that lytic damage in a biomembrane does not necessarily require oxygenation.     

Efficient ternary blend bulk heterojunction solar cells with tunable open-circuit voltage

To explore the potential of ternary blend bulk heterojunction (BHJ) photovoltaics as a general platform for increasing the attainable performance of organic solar cells, a model system based on poly(3-hexylthiophene) (P3HT) as the donor and two soluble fullerene acceptors, phenyl-C(61)-butyric acid methyl ester (PC(61)BM) and indene-C(60) bisadduct (ICBA), was examined. In all of the solar cells, the overall ratio of polymer to fullerene was maintained at 1:1, while the composition of the fullerene component (PC(61)BM:ICBA ratio) was varied. Photovoltaic devices showed high short-circuit current densities (J(sc)) and fill factors (FF) (>0.57) at all fullerene ratios, while the open-circuit voltage (V(oc)) was found to vary from 0.61 to 0.84 V as the fraction of ICBA was increased. These results indicate that the V(oc) in ternary blend BHJ solar cells is not limited to the smallest V(oc) of the corresponding binary blend solar cells but can be varied between the extreme V(oc) values without significant effect on the J(sc) or FF. By extension, this result suggests that ternary blends provide a potentially effective route toward maximizing the attainable J(sc)V(oc) product (which is directly proportional to the solar cell efficiency) in BHJ solar cells and that with judicious selection of donor and acceptor components, solar cells with efficiencies exceeding the theoretical limits for binary blend solar cells could be possible without sacrificing the simplicity of a single active-layer processing step.