2,2-Dicyanovinyl-end-capped oligothiophenes as electron acceptor in solution processed bulk-heterojunction organic solar cells

Three 2,2-dicyanovinyl (DCV) end-capped A-π-D-π-A type oligothiophenes (DCV-OTs) containing dithieno[3,2-b:2′,3′-d]silole (DTSi), cyclopenta[1,2-b:3,4-b′]dithiophene (DTCP) or dithieno[3,2-b:2′,3′-d]pyrrole (DTPy) unit as the central donor part, mono-thiophene as the π-conjugation bridge were synthesized. The absorption spectroscopies, cyclic voltammetry of these compounds were characterized. Results showed that all these compounds have intensive absorption band over 500–680 nm with a LUMO energy level around −3.80 eV, which is slightly higher than that of [6,6]phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM, E_LUMO = −4.01 eV), but lower than that of poly(3-hexylthiophene) (P3HT, E_LUMO = −2.91 eV). Solution processed bulk heterojunction “all-thiophene” solar cells using P3HT as electron donor and the above mentioned oligothiophenes as electron acceptor were fabricated and tested. The highest power conversion efficiency (PCE) of 1.31% was achieved for DTSi-cored compound DTSi(THDCV)₂, whereas PTB7:DTSi(THDCV)₂ based device showed slightly higher PCE of 1.56%. Electron mobilities of these three compounds were measured to be around 10⁻⁵ cm² V⁻¹ s⁻¹ by space charge limited current method, which is much lower than that of PC₆₁BM, and was considered as one of the reason for the low photovoltaic performance.     

Effect of side chains on phenanthrene based D-A type copolymers for polymer solar cells

A series of low band gap conjugated copolymers containing 9,10-modified phenanthrene and diketopyrrolopyrrole (DPP) units were synthesized as electron donor materials for bulk heterojunction organic solar cells. These donor-acceptor type PDPP copolymers have varying solubilizing groups on their identical conjugated backbones. The optical bandgap of PDPP copolymers is about 1.6 eV which corresponds to the long wavelength region of the solar spectrum. Through the incorporation of phenanthrene units into the conjugated backbone instead of commonly used thiophene derivatives, a higher open-circuit voltage of about 0.8 V could be achieved, as a result of their deeper HOMO level. Of all the devices, the P4:PC₆₁BM BHJ system showed the best performance with a V_oc of 0.79 V, a J_sc of 5.97 mA cm⁻², a fill factor of 0.62 and a power conversion efficiency of 2.73% due to superior nanoscale phase separation between the electron donor and electron acceptor materials than in the other polymers arising from short-branched solubilizing groups on the phenanthrene side of its conjugated backbone.     

Vinazene end-capped acceptor-donor-acceptor type small molecule for solution-processed organic solar cells

An acceptor-donor-acceptor (A-D-A) type molecule based on dioctyltertthiophene-benzo[1,2-b:4,5-b′]dithiophene-dioctyltertthiophene central donor and vinazene terminal acceptor was designed and synthesized for solution-processed small molecule bulk-heterojunction (BHJ) solar cells. The thermal and optochemical properties, BHJ morphology and solar cell performance were investigated. The BHJ morphology was systematically optimized by thermal annealing, solvent vapor annealing, and the use of solvent additives. Processed by a combination of thermal annealing and solvent vapor annealing treatments, V-BDT:PC₇₁BM device showed an optimized PCE of 3.73% with a V_OC of 0.89 V, an J_SC of 6.88 mA cm⁻² and a FF of 0.61.     

Efficient ternary blend polymer solar cells with a bipolar diketopyrrolopyrrole small molecule as cascade material

We present a ternary strategy to enhance the power conversion efficiency (PCE) of bulk heterojunction polymer solar cells (PSCs) with a bipolar small molecule as cascade material. A bipolar diketopyrrolopyrrole small molecule (F(DPP)₂B₂), as the second electron acceptor, was incorporated into poly(3-hexylthiophene) (P3HT): [6,6]-phenyl-C₆₁-butyric-acidmethyl-ester (PC₆₁BM) blend to fabricate ternary blend PSCs. The introduction of the bipolar compound F(DPP)₂B₂ can not only broaden the light absorption of the active layer because of its absorption in near infrared region but also play a bridging role between P3HT and PC₆₁BM due to the cascaded energy level structure, thus improving the charge separation and transportation. The optimized ternary PSC with 5 wt% F(DPP)₂B₂ content delivered a high PCE of 3.92% with a short-circuit current density (J_sc) of 9.63 mA cm⁻², an open-circuit voltage (V_oc) of 0.62 V and a fill factor (FF) of 64.90%, showing an 23% improvement of PCE as compared to the binary systems based on P3HT:PC₆₁BM (3.18%) or P3HT:F(DPP)₂B₂ (3.17%). The results indicate that the ternary PSCs with a bipolar compound have the potential to surpass high-performance binary PSCs after carefully device optimization.     

A plasmonically enhanced polymer solar cell with gold–silica core–shell nanorods

We report the use of chemically synthesized gold (Au)–silica core–shell nanorods with the length of 92.5 ± 8.0 nm and diameter of 34.3 ± 4.0 nm for the efficiency enhancement of bulk heterojunction (BHJ) polymer solar cells. Silica coated Au nanorods were randomly blended into the BHJ layers of these solar cells. This architecture inhibits the carrier recombination at the metal/polymer interface and effectively exploits light absorption at the surface plasmon resonance wavelengths of the Au–silica nanorods. To match the two plasmon resonant peaks of the Au–silica nanorods, we employed a low bandgap polymer, poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′] dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) to construct a solar cell. The absorption spectrum of PCPDTBT:[6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₀BM) is relatively wide and matches the two plasmon resonance peaks of Au–silica nanorods, which leads to greater plasmonic effects. We also constructed the poly(3-hexylthiophene):[6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PC₆₀BM) cells for comparison. The absorption spectrum of P3HT:PC₆₀BM only overlaps one of the plasmon resonance peak of Au–silica nanorods. The efficiency of the P3HT:PC₆₀BM device incorporating optimized Au–silica nanorods is enhanced by 12.9% from 3.17% to 3.58%, which is due to the enhanced light absorption. Compared with the P3HT:PC₆₀BM device with Au–silica nanorods, the PCPDTBT:PC₇₀BM device with 1 wt% Au–silica nanorods concentration has a higher efficiency of 4.4% with an increase of 26%.     

Two new D–A conjugated polymers P(PTQD-Th) and P(PTQD-2Th) with same 9-(2-octyldodecyl)-8H-pyrrolo[3,4-b]bisthieno[2,3-f:3′,2′-h]quinoxaline-8,10(9H)-dione acceptor and different donor units for BHJ polymer solar cells application

We report the synthesis, characterization and photovoltaic properties of bulk heterojunction polymer solar cells of new donor–acceptor conjugated copolymers P(PTQD-Th) and P(PTQD-2Th) that incorporate same strong 9-(2-octyldodecyl)-8H-pyrrolo[3,4-b]bisthieno[2,3-f:3′,2′-h]quinoxaline-8,10(9H)-dione as strong acceptor and different weak thiophene (Th) and bi-thiophene (2Th) as donors, respectively. Both the copolymers showed suitable unoccupied lowest molecular orbital (LUMO) energy levels, compatible with the LUMO of PC₇₁BM for efficient electron transfer from copolymer to PC₇₁BM in the blended copolymer: PC₇₁BM thin films. Moreover the deeper highest occupied molecular orbital (HOMO) energy levels of both copolymers ensures the high open circuit voltage (V_oc) of the BHJ polymer solar cells. The optimized P(PTQD-Th):PC₇₁BM and P(PTQD-2Th):PC₇₁BM with weight ratio of 1:2 processed with chloroform solvent showed PCE of 3.65% and 3.96%, respectively. The higher value of J_sc for the device processed with P(PTQD-2Th):PC₇₁BM as compared to that for P(PTQD-Th):PC₇₁BM, attributed to narrower optical bandgap and broader absorption profile for P(PTQD-2Th) as compared to P(PTQD-Th). The PCE values of polymer solar cells were further improved (5.54% and 5.67% for P(PTQD-Th):PC₇₁BM and P(PTQD-2Th):PC₇₁BM, respectively) when small amounts of solvent additive, i.e. 1,8-diiodoctane (DIO) were used for the processing of active layers. The improved PCE has been attributed to both the enhanced values of short circuit current (J_sc) and fill factor (FF) due to the better nanomorphology and charge transport, induced by the high boiling point of solvent additive.     

Polyacetylene-based polyelectrolyte as a universal interfacial layer for efficient inverted polymer solar cells

Here we report that poly(N-dodecyl-2-ethynylpyridiniumbromide) (PDEPB) interlayers between electron-collecting zinc oxide (ZnO) layers and bulk heterojunction (BHJ) layers act as a universal interfacial layer for improving the performances of inverted-type polymer:fullerene solar cells. Three different BHJ layers, poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM), poly[(4,8-bis(2-ethylhexyloxy)-benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl-alt-(N-2-ethylhexylthieno[3,4-c]pyrrole-4,6-dione)-2,6-diyl]] (PBDTTPD):PC₆₁BM, and poly[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]-thiophenediyl] (PTB7) and [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM), were employed so as to prove the role of the PDEPB interlayers. Results showed that the power conversion efficiency (PCE) of polymer:fullerene solar cells with the three different BHJ layers increased in the presence of the PDEPB interlayers prepared from 0.5 mg/ml solutions. The improved PCE was attributed to the conformal coating of the PDEPB layers on the ZnO layers (by atomic force microscopy measurement), lowered work functions of ZnO induced by the PDEPB layers (by Kelvin probe measurement), and reduced interface resistance (by impedance spectroscopy measurement), as supported by the noticeable change in the atom environments of both the ZnO and PDEPB layers (by X-ray photoelectron spectroscopy measurement).     

Synthesis,characterization, and photovoltaic performance of the polymers based on thiophene-2,5-bis((2-ethylhexyl)oxy) benzene-thiophene

Three novel conjugated copolymers based on thiophene-2,5-bis((2-ethylhexyl)oxy)benzene-thiophene (TBT) as electron-donating units, either isoindigo or both isoindigo and diketopyrrolopyrrole (DPP) as electron-withdrawing units have been designed and synthesized by Stille-coupling reaction. All the polymers exhibit high thermal stability, broad absorption in the range of 300–800 nm, and the low-lying energy level of highest occupied molecular orbits (HOMO) (−5.47 to −5.19 eV). After introduced with additional hexylthiophenes and further introduced with DPP units, the polymers PTBT-HTID and PTBT-HTID-DPP show smaller lamellar distance and π–π stacking distance, and the morphology of the corresponding photoactive layers possess more appropriate microphase separation and smaller domain size, which lead to high short circuit current densities (J_sc) and power conversion efficiency (PCE). The polymer photovoltaic devices based on PTBT-HTID-DPP/PC₆₁BM exhibit a high J_sc value of 11.13 mA cm⁻², a fill factor (FF) of 0.57, and the PCE of 4.2%.     

Influence of molar mass ratio,annealing temperature and cathode buffer layer on power conversion efficiency of P3HT:PC71BM based organic bulk heterojunction solar cell

In bulk heterojunction (BHJ) solar cells, the molar mass ratio of donor-acceptor polymers, the annealing temperature (T_an) and the cathode buffer layer plays very consequential role in improving the power conversion efficiency (PCE) by tuning the film morphology and enhancing the charge carrier dynamics. A comprehensive understanding of each of these factors is essential in order to optimize the performance of organic solar cells (OSCs). Albeit there are several fundamental reports regarding these factors, an altogether meticulous correlation of these physical processes with experimental evidence of the photo active layer are required. In this work, we systematically analyzed the influence of different molar mass ratio, the annealing temperature (T_an) and the cathode buffer layer of rrP3HT:PC₇₁BM based BHJ solar cells and their corresponding photovoltaic performances were correlated carefully with their thin film growth structure and energy level diagram. The device having 1:0.8 molar mass ratio of rrP3HT:PC₇₁BM and T_an = 150 °C annealing temperature with Bathocuproine (BCP) as the cathode buffer layer having ITO/PEDOT:PSS/rrP3HT:PC₇₁BM (molar mass ratio = 1:0.8; (T_an = 150 °C)/BCP/Al) configuration showed the best device performance with PCE, ɳ = 4.79%, Jsc = 14.21 mA/cm², V_oc = 0.58 V and FF = 57.8%. This drastic variation in PCE of the device having BCP/Al as the cathode contact compared to the other device configurations is due to the coalesced effects of better hole-blocking capacity of BCP along with Al and better phase separation of the active blend layer at 150 °C annealing temperature. These results explicate the cumulate role of all these physical parameters and their combined contribution to the PCE amendment and overall device performance with rrP3HT:PC₇₁BM based organic BHJ solar cell.     

Synthesis and photovoltaic studies on novel fluorene based cross-conjugated donor-acceptor type polymers

Direct arylation polymerization (DAP) is emerging as a promising green, cheap, simple, and efficient environment friendly method for synthesizing conjugated polymers without involving any organometallic reagent. We report fluorene based novel cross-conjugated alternate and random copolymers for polymer solar cells (PSCs), which were synthesized by DAP and/or Yamamoto polymerization under appropriate reaction conditions to obtain high molecular weight. These cross-conjugated polymers possess absorption maxima in the range of 490–520 nm and have narrow band gap (1.7–2.05 eV) which is suitable for bulk heterojuntion (BHJ) type organic solar cells. Among the synthesized polymers, the highest number average molecular weight (M_n) i.e. 43.1 kg mol⁻¹ was obtained for polymer P2b (poly((9H-fluoren-9-ylidene)methylene)bis((2-ethylhexyl)sulfane)-alt-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole)), and so good polymeric films were formed for P2b. Thus, BHJ films were prepared for P2b for device performance studies and the morphology of these films was studied by atomic force microscopy (AFM). Polymer P2b was blended with the fullerene derivative [6,6]-phenyl C₇₁ butyric acid methyl ester (PC₇₁BM) in different ratios and under the illumination of solar simulator with Air Mass global (AM 1.5G) irradiated at 100 mW cm⁻². Power conversion efficiency (PCE) of 1.4% has been achieved for BHJs in ratio of 1:2 of P2b: PC₇₁BM in simply processed devices. This result indicates that cross-conjugated polymers can be tapped as potential donors for BHJs as the PCE obtained is the highest among this type of cross-conjugated polymers.     

High open-circuit voltage of the solution-processed organic solar cells based on benzothiadiazole–triphenylamine small molecules incorporating π-linkage

Two novel small molecular photovoltaic (PV) materials, BDPTBT and BDATBT were designed and synthesized, consisting of 5,6-bis-(octyloxy)benzo[c][1,2,5]thiadiazole (DOBT) as electron-withdrawing core (A), and triphenylamine (TPA) as electron-donating side group (D). Moreover, the benzene and ethynylbenzene as π-linkage were introduced to form donor–π-acceptor–π-donor (D–π-A–π-D) typed molecular structures, respectively. To fully investigate the linkage effect of a series of small molecules, two reference compounds BDCTBT and BDETBT were also studied systematically, consisting of 2-phenylacrylonitrile and styrene as π-linkage, respectively. As a result, the π-linkage units, benzene, styrene, ethynylbenzene and 2-phenylacrylonitrile played an important role in modifying molecular structure and improving PV performance. Bulk heterojunction (BHJ) solar cells based on BDPTBT/PC₆₁BM and BDATBT/PC₆₁BM yielded the power conversion efficiencies (PCEs) of 2.99% and 2.03%, respectively. Notably, BDATBT based device showed a high open-circuit voltage (Voc) of 1.03 V. Compared to the results we have reported previously, the reference devices based on BDCTBT/PC₆₁BM and BDETBT/PC₆₁BM with the optimized weight ratio showed dramatically enhanced PCEs of 4.84% and 3.40%, respectively, and BDCTBT based device showed a high Voc of 1.08 V. To our knowledge, the Voc of 1.08 V is the highest voltage reported to date for devices prepared from solution-processed small-molecule-donor materials, and the PCE of 4.84% is the highest efficiency reported so far for D–A–D-typed benzothiadiazole (BT)–TPA based solution-processed small molecules PV devices.     

Synthesis and photovoltaic properties of D-A copolymers based on alkylthio-thiophene or alkylthio-selenophene-BDT donor unit and DPP acceptor unit

Two new 2D-conjugated D-A copolymers, PBDTT-S-DPP and PBDTSe-S-DPP, based on benzodithiophene (BDT) donor unit with alkylthio-thiophene or alkylthio-selenophene conjugated side chains and 2,5-bis(2-butyloctyl)-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione) (DPP) acceptor unit, were synthesized for the application as donor materials in polymer solar cells (PSCs). The two polymers were characterized by absorption spectroscopy, cyclic voltammetry, thermogravimetric analysis, theoretical calculation with density functional theory, X-ray diffraction and photovoltaic measurements. The results show that the alkylthio-thiophene/selenophene side groups on BDT unit and intramolecular hydrogen bonding interaction in DPP acceptor unit play important roles in affecting the absorption, HOMO energy levels, molecular planarity and the crystallinity of the polymers. The PSCs based on PBDTT-S-DPP or PBDTSe-S-DPP as donor and PC₇₁BM as acceptor demonstrate power conversion efficiency (PCE) of 5.62% and 5.01%, with relatively higher V_oc of 0.79 V and 0.76 V, respectively.     

Improved photovoltaic performance by enhanced crystallinity of poly(3-hexyl)thiophene

The packing effects induced by the hydrophilic ethylene glycol oligomer side chains occurred in a P3HT:PC₆₁BM mixture upon the addition of small amounts of BP93 (containing 7 mol% PEGT blocks), leading to an enhanced crystallinity among the P3HT molecules, even in a P3HT:PC₆₁BM blend. The enhanced crystallinity improved the charge transport and current density (8.3–11.1 mA/cm²) and increased the power conversion efficiency (3.1–3.9%) in an organic solar cell.     

The effect of processing solvent dependent film aggregation on the photovoltaic performance of squaraine:PC71BM bulk heterojunction solar cells

In this work, we systemically investigated the processing solvent-dependent aggregation behavior of a squaraine dye, 2,4-bis[4-(N,N-dibutylamino)-2,6- dihydroxyphenyl] squaraine (DBSQ), in a DBSQ: [6,6]-phenyl-C71-butyric acid methyl ester (PC₇₁BM) blend film, as well as the aggregation effect on the photovoltaic performance of DBSQ:PC₇₁BM bulk heterojunctions (BHJs). Our finding shows that the aggregation behavior of DBSQ dye in the blend film can be controlled via the proper selection of the processing solvents. For a J-aggregate (head-to-tail molecule alignment) DBSQ:PC₇₁BM active layer based BHJ cells, a power conversion efficiency (PCE) of over 5% can be obtained, which is 75% higher than that of the H-aggregate (parallel molecule packing) active layer based BHJ cells. Our results indicate that the processing solvent controlled J-aggregation formation shall be considered as effective approach to tune the optical and electrical properties of thin films for high-performance BHJ solar cells.     

New ultra low bandgap thiadiazolequinoxaline-based D-A copolymers for photovoltaic applications

In this communication, we designed two low bandgap D-A copolymers with same fluorinated thiadiazoloquinoxaline (TDQ) as acceptor and different donor units benzo[2,1-b;3,4-b′]dithiophene (P1) and benzo[1,2-b:4,5-b′]dithiophene (P2). P1 and P2 exhibit broad absorption profiles covering from 350 nm to 1150 nm and 350–950 nm, respectively with optical bandgaps of 1.06 eV and 1.18 eV, respectively. Both copolymers showed deep highest occupied molecular orbitals (HOMO), i.e. −5.38 eV and −5.26 eV, for P1 and P2. Their photovoltaic properties were evaluated using conventional devices with a structure of ITO/PEDOT:PSS/copolymer:PC₇₁BM/Al. After the optimizations of the copolymer to PC₇₁BM weight ratios, and concentration of the solvent additive (DIO), the devices showed overall power conversion efficiencies of 4.03% and 5.42% for the P1 and P2 based devices, respectively. The higher value of PCE of the P2 based device is attributed to the higher values of J_sc and FF, that is related to the higher hole mobility and better exciton dissociation efficiency. Although the PCEs of these devices are moderate, these ultra low band gap copolymers can be used for their potential application in tandem polymers solar cells. Finally, methanol treatment of the active layer was adopted to increase the PCE of the P2:PC₇₁BM based polymer solar cells that resulted in an improved PCE up to 6.93%.     

Synthesis,optical and electrochemical properties new donor–acceptor (D–A) copolymers based on benzo[1,2-b:3,4-b′:6,5-b″] trithiophene donor and different acceptor units: Application as donor for photovoltaic devices

Two new conjugated D–A polymers P3 (PBTT-d-BTT) and P4 (PBTT-d-TPD) based on same benzo[1,2-b:3,4-b′:6,5-b″] trithiophene (BTT) donor and different acceptors monomers 5,8-dibromo-2-dodecanoylbenzo[1,2-b:3,4-b′:6,5-b″] trithiophene (d-BTT), and 1,3-dibromo-5-(2-ethylhexyl)thieno[3,4]pyrrol-4,6-dione (d-TPD) respectively, were synthesized by Stille cross-coupling reaction and characterized by gel permeation chromatography (GPC), ¹H NMR, UV–Vis absorption, thermal analysis and electrochemical cyclic voltammetry (CV) tests. Photovoltaic properties of the polymers were studied by using the polymers as donor and PC₇₁BM as acceptor with a weight ratio of polymer:PC₇₁BM 1:1, 1:2 and 1:2.5. The optimized photovoltaic device was fabricated with an active layer of a blend P3:PC₇₁BM and P4:PC₇₁BM with a blend ratio of 1:2 showed PCE 3.16% and 2.42%, respectively under illumination of AM 1.5 at 100 mW/cm² with solar simulator. The PCE of the device based on P3:PC₇₁BM processed with DIO/o-DCB has been further improved up to 4.64% with J_sc of 10.52 mA/cm² and FF of 0.58 attributed to the increase in crystalline nature of active layer and more balanced charge transport in the device, induced by DIO additive.     

Filter-Free Narrowband Photomultiplication-Type Planar Heterojunction Organic Photodetectors

Filter-free narrowband photomultiplication-type planar heterojunction (PHJ) organic photodetectors (PM-PHOPDs) are first realized by employing a thick front donor layer and an ultrathin PC₇₁BM layer. The thick front donor layer is employed as an optical field adjusting (OFA) layer. The sequentially coated PC₇₁BM will diffuse slightly into OFA layer, which works as interfacial electron traps to capture photogenerated electrons for assisting hole tunneling injection. The P3HT/PC₇₁BM-based PM-PHOPDs exhibit narrowband response with full-width of half-maximum of 32 nm and external quantum efficiency (EQE) of 1700% at 650 nm under −20 V bias. Due to the enhanced hole transport and reduced charge recombination in PHJ compared to those in bulk heterojunction (BHJ), the EQE of P3HT/PC₇₁BM-based narrowband PM-PHOPDs is twice as P3HT:PC₇₁BM BHJ-based narrowband PM-OPDs under the same bias. The response peak of PM-PHOPDs is adjusted from 650 to 695 or 745 nm by incorporating SMPV1 or DRCN5T in OFA layers due to the red-shifted absorption edge. The EQEs of 3600% at 695 nm and 870% at 745 nm are obtained for P3HT:SMPV1 and P3HT:DRCN5T-based PM-PHOPDs under −20 V bias, respectively. This work provides a smart strategy to achieve narrowband PM-OPDs by designing different OFA layers.     

Enhanced carrier dynamics of PTB7:PC71BM based bulk heterojunction organic solar cells by the incorporation of formic acid

Formic acid (FA) was used as a novel additive in bulk heterojunction (BHJ) solar cells, which contains blends of poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophene-4,6-diyl]] (PTB7) and [6,6]-phenyl-C71-butyric acid methyl ester (PC₇₁BM). The effect of FA on the performance of PTB7:PC₇₁BM based BHJ solar cells is investigated. By the incorporation of FA, the device with the ratio of 6 vol % shows the best power conversion efficiency (PCE) of 9.04%, along with the short-circuit current density (J_sc), open-circuit voltage (V_oc), and fill factor (FF) being 24.11 mA/cm², 0.72 V, and 52.11%, respectively. Experimental results suggest that FA has a strong influence on charge carrier dynamics with a significant increase in J_sc by ∼65% and the dramatically enhanced PCE is mainly due to the increase of absorption and exciton generation of the active layers and the improved charge-carrier mobility of the devices.     

Detailed investigation of dependencies of photovoltaic performances of P3HT:PC61BM based solar cells on anodic work function modified by surface treatment of indium-tin-oxide electrode with benzenesulfonyl chloride derivatives

The photovoltaic (PV) characteristics of bulk-heterojunction (BHJ) solar cells based on poly(3-hexylthiophene) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PC₆₁BM) were improved using indium-tin-oxide (ITO) anode electrodes modified chemically with CH₃O-, H-, Cl-, CF₃-, and NO₂-terminated benzenesulfonyl chlorides as a self-assembled monolayer (SAM). The ITO electrode surfaces were easily treated through the chemical modification of the reactive –SO₂Cl binding group, and the work function (WF) of the modified ITO was effectively changed depending on the permanent dipole moments introduced in the para-position of benzenesulfonyl chloride. We examined the correlation between the ITO WFs corrected by the change in the contact potential difference and the calculated dipole moments of the SAM models. Moreover, we examined the PV characteristics of the P3HT:PC₆₁BM based BHJ organic PV cells using the SAMs or poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)-treated ITOs with different WFs lying within ±0.2 eV from the highest occupied molecular orbital (HOMO) level of P3HT. We found that the enhancement effect of the SAMs on the power-conversion efficiency (η_P) reached a maximum with Cl (η_P = 3.72%), and became larger than that of PEDOT:PSS (η_P = 3.62%). Two distinct J_sc dependencies, increasing and decreasing with the increasing WF of the anode ITO, were observed at higher and lower WFs than the HOMO level of the donor, respectively. Almost constant V_oc values (around 0.6 V) were observed with different SAM-modified ITOs, which suggested that Fermi level pinning was achieved by aligning the anode Fermi level and positive polaronic level of the donor polymer.     

High efficiency polymer solar cells based on alkylthio substituted benzothiadiazole-quaterthiophene alternating conjugated polymers

We have designed and synthesized two alkylthio substituted benzothiadiazole-quaterthiophene based conjugated polymers (P1 and P2) and investigated their photovoltaic performances. Theoretical simulation has demonstrated that the introduction of alkylthio substituents can increase the planarity of the resulted conjugated polymers. The fluorinated polymer P1 possesses a deeper HOMO energy level than the non-fluorinated polymer P2 and can form well-developed fibril networks when blended with PC₇₁BM. PSCs based on P1:PC₇₁BM (1:1.2, by weight) gave a PCE of 7.76% with a V_oc of 0.69 V, a J_sc of 16.30 mA cm⁻² and an FF of 0.69. Our results have demonstrated that alkylthiothiophene could be a useful building block for the construction of high efficiency polymer donor materials used for PSCs.