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.     

Fluorine functionalized asymmetric indo [2,3-b]quinoxaline framework based D-A copolymer for fullerene polymer solar cells

Innovating molecular structure of copolymer donor materials is still one of the prominent approach to obtain high-performance polymer solar cells (PSCs). In this paper, two novel wide bandgap (WBG) copolymers, namely PBDTTS-IQ and PBDTTS-DFIQ, based on asymmetric planar aromatic core indo [( Li et al., 2012; Wang et al., 2020) 2,32,3-b]quinoxaline (IQ) as acceptor unit through tuning side chains with fluorine (F) atom engineering and exemplary alkylthio-thienyl substituted benzodithiophene (BDTTS) donor group, are synthesized and finally employed as the photovoltaic donor materials for fullerene polymer solar cells (PSCs). After blending with PC₇₁BM acceptor, the PBDTTS-DFIQ:PC₇₁BM blend film presented better efficient exciton dissociation and charge extraction, more balanced electron/hole mobility (μ_h/μ_e), and nice morphology in comparison with PBDTTS-IQ:PC₇₁BM blend film. Encouragingly, the PBDTTS-DFIQ:PC₇₁BM based PSCs exhibits a higher power conversion efficiency (PCE) of 7.4% than that of the device based on the PBDTTS-IQ:PC₇₁BM blend with a PCE of 4.96%, which thanks to an enhancement of open-circuit voltage (V_oc) of 0.84 V, short current density (J_sc) of 13.26 mA cm⁻² and fill factor (FF) of 66.00% simultaneously. These results demonstrate that this asymmetric IQ framework is a wonderful acceptor moiety to build light-harvesting copolymers for highly efficient PSCs.     

Insights into the influence of fluorination positions on polymer donor materials on photovoltaic performance

To explore the influence of fluoro substitution position and number on optical, electrochemical and photovoltaic properties, three novel donor-acceptor (D-A) alternative copolymers (PHF, PFH and PFF) were synthesized by Stille polycondensation of 2,3-diphenyl-5,8-di(thiophen-2-yl)quinoxaline (DTQx) acceptor unit and indacenodithiophene (IDT) donor unit. As films, PHF and PFF comprising two fluoro substituents on the lateral phenyl groups displayed a broad absorption ranging from 350 to 700 nm; whereas PFH containing two fluorine atoms on the polymer main chain exhibited a slightly narrower absorption ranging from 350 to 650 nm. In addition, fluoro substitution on the polymer main chain can lower the HOMO level of the resulted polymers. As expected, PFH and PFF possess deeper HOMO energy level than PHF. Polymer solar cells (PSCs) were fabricated with these three polymers as donor materials and PC₇₁BM as acceptor material. PHF based PSCs gave a power conversion efficiency (PCE) of 7.2% with a V_oc of 0.84 V, a J_sc of 12.46 mA/cm² and an FF of 0.69. And PFH based PSCs showed a PCE of 6.19% with a V_oc of 0.93 V, a J_sc of 9.57 mA/cm² and an FF 0.70. However, a PCE of only 2.9% with a V_oc of 0.92 V, a J_sc of 4.61 mA/cm² and an FF of 0.68 was obtained for PFF based PSCs. Transmission electron microscopy (TEM) and resonant soft X-ray scattering (R-SoXS) studies indicated that the introduction of four fluorine atoms at each repeating unit can spoil the morphology of active layer. These results highlight the importance of fluorination position and number to the performance of PSCs.     

Dithienopyrrole-benzodithiophene based donor materials for small molecular BHJSCs: Impact of side chain and annealing treatment on their photovoltaic properties

Two small molecular organic materials denoted as ICT1 and ICT2 with A-D₁-D₂-D₁-A architecture have been synthesized and their thermal, photo-physical, electrochemical and photovoltaic properties are explored. Synthesized materials have n-butylrhodanine acceptor (A), dithienopyrrole (DTP) (D₁) and benzodithiophene (BDT) (D₂) (Alkoxy BDT and alkylthiophene BDT, respectively for ICT1 and ICT2) donor moieties. Both the materials have good solubility (up to 25 mg/mL) in most common organic solvents and have excellent thermal stability with the decomposition temperature (T_d) as 348 and 382 °C, respectively for ICT1 and ICT2. Both ICT1 and ICT2 have broad and intense visible region absorption (molar excitation coefficient is 1.71 × 10⁵ and 1.65 × 10⁵ mol⁻¹ cm⁻¹, respectively for ICT1 and ICT2) and have suitable HOMO and LUMO energy levels for PC₇₁BM acceptor. Bulk heterojunction solar cells with ITO/PEDOT:PSS/blend/Al structure are fabricated using these materials. The BHJSCs fabricated by spin cast of ICT1:PC₇₁BM and ICT2:PC₇₁BM (1:2 wt ratio) blend from chloroform showed power conversion efficiency (PCE) of 2.77% (J_sc = 6.84 mA/cm², V_oc = 0.92 V and FF = 0.44) and 3.27% (J_sc = 7.26 mA/cm², V_oc = 0.96 V and FF = 0.47), respectively. Annealing the active layer significantly improved the PCE of these BHJSCs to 5.12% (J_sc = 10.15 mA/cm², V_oc = 0.87 V and FF = 0.58) and 5.90% (J_sc = 10.68 mA/cm², V_oc = 0.92 V and FF = 0.60), respectively for ICT1 and ICT2 donors. The enhancement in the PCE is due to higher light harvesting ability of the active layer, better nanoscale morphology for efficient and balanced charge transport and effective exciton dissociation at the donor-acceptor interface.     

Synthesis and photovoltaic properties low bandgap D-A copolymers based on fluorinated thiadiazoloquinoxaline

In this communication, we report the design a low bandgap D-A copolymer consist of fluorinated thiadiazoloquinoxaline (TDQ) as strong acceptor and benzothiophene (BT), denoted as P(ffFlTDQ_x-BT) exhibit broad absorption profile covering from 350 nm to 1000 nm with optical bandgap of 1.26 eV. P(ffFlTDQ_x-BT) showed highest occupied molecular orbital (HOMO) energy level of −5.46 eV which is deeper than that for nonfluorinated counterpart copolymer. The photovoltaic properties were evaluated using conventional devices with a structure of ITO/PEDOT:PSS/P(ffFlTDQ_x-BT):PC₇₁BM/Al. After the optimizations of the P(ffFlTDQ_x-BT) to PC₇₁BM weight ratios, and concentration of the solvent additive (DIO), the devices showed overall power conversion efficiency of 7.27%. The higher value of PCE of this device is higher than that of nonfluorinated copolymer (5.80%) is attributed to the higher values of both J_sc and FF, related to the higher hole mobility and better exciton dissociation efficiency. Moreover, employing a low boiling point solvent additive, i.e. o-chlorobenzaldehyde (CBA) (boiling point 132 °C) for active layer deposition and after the optimization of concentration of CBA, the resulted PSC showed overall PCE of 8.10%, which is higher than the PSC based on active processed with DIO/CB, related to the better balanced charge transport, induced by the fast removal of residues of solvent. To our best of our knowledge, PCE of 8.10% is also the highest for the PSCs with low bandgap of below 1.30 eV.     

Perylene diimide-benzodithiophene D-A copolymers as acceptor in all-polymer solar cells

Two n-type conjugated D-A copolymers with perylene diimide (PDI) as acceptor unit and benzodithiophene (BDT) as donor unit, P(PDI-BDT-Ph) and P(PDI-BDT-Th), were synthesized and applied as electron acceptor in all-polymer solar cells (all-PSCs). P(PDI-BDT-Ph) and P(PDI-BDT-Th) films exhibit similar absorption spectra in the visible region with optical bandgap (E_g) of 1.65 eV and 1.55 eV respectively, and the identical LUMO level of −3.89 eV. The all-PSCs based on P(PDI-BDT-Ph) as acceptor and PTB7-Th as donor demonstrated a power conversion efficiency (PCE) of 4.31% with a short-circuit current density (J_sc) of 11.94 mA cm⁻², an open-circuit voltage (V_oc) of 0.81 V, and a fill factor (FF) of 44.49%. By contrast, the corresponding all-PSCs with P(PDI-BDT-Th) as acceptor showed a relative lower PCE of 3.58% with a J_sc of 11.36 mA cm⁻², V_oc of 0.79 V, and FF of 40.00%.     

Benzothiadiazole-pyrrolo[3,4-b]dithieno[2,3-f:3′,2′-h]quinoxalindione-based random terpolymer incorporating strong and weak electron accepting [1,2,5]thiadiazolo[3,4g]quinoxalinefor polymer solar cells

We report the synthesis of a D-A random terpolymer denoted as P2 consists of one thiophene donor unit and three acceptor benzothiadiazole (BT), pyrrolodithienoquinoxalinedione (PDQD) and thiadiazoloquinoxaline (TDQ) units by Stille-coupling reaction and investigated its optical and electrochemical properties. We have compared its properties with the parent copolymer P1. The P2 exhibits bandgap of about 1.18 eV which is lower than that of P1 (1.50 eV), indicating strength of accepting units controls both the optical and electrochemical bandgap. We have used terpolymer P2 as electron donor along with [6,6]-phenyl C₇₁ butyric acid methyl ester (PC₇₁BM) as electron acceptor for the fabrication of solution processed bulk heterojunction polymer solar cells (PSCs). PSC based on an optimized P2:PC₇₁BM (1:2 by weight) active layer processed with 3v % DIO/DCB solution, displayed a power conversion efficiency (PCE) of 7.22%, which is higher than that for P1 based polymer solar cell (PCE = 6.56%) processed under same conditions. The higher value of PCE for P2:PC₇₁BM may be related to more favorable phase separated morphology of active layer as compared to P1:PC₇₁BM, beneficial for the exciton dissociation and charge transport, as evidenced from the larger hole mobility.     

Two new A-D-A type small molecule acceptors based on C2v-symmetric dithienocyclopentaspiro[fluorene-9,9′-xanthene] core for polymer solar cells

A C_2v-symmetric core, dithienocyclopentaspiro[fluorene-9,9′-xanthene], was used as the central block for the first time to design and synthesize A-D-A type small molecule acceptors for nonfullerene polymer solar cells (PSCs), and two new small molecule acceptors of TSFX-2F and TSFX-4F were synthesized based on the C_2v-symmetric core. The two TSFX-based acceptors show high thermal stability, strong absorption in the wavelength region of 550–750 nm and appropriate energy levels. The PSCs with the broad bandgap polymer J71 as donor and TSFX-2F as acceptor demonstrated power conversion efficiency (PCE) of 9.42% with open circuit voltage (V_oc) of 0.89 V, short circuit current density (J_sc) of 15.27 mA cm⁻² and fill factor (FF) of 69.30%, while the PSC based on J71:TSFX-4F shows a PCE of 8.47% with V_oc of 0.83 V, J_sc of 15.48 mA cm⁻² and FF of 66.16%. The higher V_oc of the PSC based on J71: TSFX-2F is benefitted from the up-shifted LUMO energy level of the TSFX-2F acceptor, and its higher FF can be ascribed to the higher and more balanced hole and electron mobilities of the J71: TSFX-2F active layer. This work demonstrates that the new C_2v-symmetric building block is a promising central D-unit for the design and synthesis of new structured norfullerene acceptors for high-performance PSCs.     

Enhancing efficiency for additive–free blade–coated small–molecule solar cells by thermal annealing

Blade coating was successfully applied to realise high-efficiency small-molecule organic solar cells (OSCs) with a solution-processed active layer comprising a small organic molecule DR3TBDTT with a benzo[1,2–b:4,5–b′]dithiophene (BDT) unit as the central building block as the donor and [6,6]–phenyl–C71–butyric acid methyl ester (PC₇₁BM) as the acceptor. Using chloroform as the solvent, a DR3TBDTT/PC₇₁BM blend active layer without an additive was effectively formed through blade coating. The power conversion efficiency (PCE) of small organic molecule solar cells was enhanced by 3.7 times through thermal annealing at 100 °C. This method produces OSCs with a high PCE of up to 6.69%, with an open circuit voltage (V_oc) of 0.97 V, a short-circuit current density (J_sc) of 12.60 mA/cm², and a fill factor (FF) of 0.55.     

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%.     

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.     

Fluorination as an effective tool to increase the photovoltaic performance of indacenodithiophene-alt-quinoxaline based wide-bandgap copolymers

To investigate the effect of the fluoride phenyl side-chains into quinoxaline (PQx) unit on the photovoltaic performances of polymers, we demonstrated the synthesis and characterization of two novel wide-bandgap (WBG) copolymers, PIDT-DTPQx and PIDT-DTFPQx, in which indacenodithiophene (IDT), 2,3-diphenylquinoxaline (PQx) (and/or 2,3-bis(4-fluorophenyl)quinoxaline (FPQx)) and thiophene (T) were used as the donor (D) unit, acceptor (A) unit and π-bridge, respectively. Compared to the non-fluorine substituted PIDT-DTPQx, fluorine substituted PIDT-DTFPQx presents a deep HOMO energy level and a high hole mobility. Obviously, improved the V_oc, J_sc, and FF simultaneously, giving rise to overall efficiencies in the PIDT-DTFPQx/PC₇₁BM-based PSCs. A highest PCE of 5.78% was obtained with a V_oc of 0.86 V, J_sc of 10.84 mA cm⁻² and FF of 61.7% in the PIDT-DTFPQx/PC₇₁BM-based PSCs, while PIDT-DTPQx based devices also demonstrated a PCE of 5.11%, under the illumination of AM 1.5G (100 mW cm⁻²). Note that these PCE values were achieved for PSCs without any extra treatments. Furthermore, these optimal devices have a film thickness of about 175 nm for the polymer/PC₇₁BM-based active layers. The results provide that introduction of the fluorine atom into quinoxaline unit by side-chain engineering is one of the effective strategies to construct the promising polymer donor materials for future application of large-area polymer solar cells.     

Investigations into inward positioned 3,3′-Dihexylditheinylbenzothiadiazole (DTBTh)-Benzodithiophene (BDT) based polymer solar cells by controlling molecular weight and alkyl side chain

In previous studies, PSCs based on polymers with an inward alkyl positioned DTBT unit showed poor power conversion efficiency mainly due to the greatly distorted polymer backbone structure caused by severe steric hindrance between the alkyl groups on the flanking thiophene of DTBT and the BT unit. In this study, PSCs based on polymers with an inward alkyl positioned DTBT unit are markedly improved by controlling the molecular weight and alkyl chain length. Two BDT-DTBTs and one BDT-BT polymers were synthesized by engineering alkylthienyl chains on BDT and by installing these with a short alkyl chain on the inward alkyl positioned DTBT. Extraordinary bathochromic shifts in the absorption maxima at 146 nm for PA and 165 nm for PB were observed going from solution to a solid film state, suggesting great differences in the polymer structures of the two states. Optical and electrochemical measurements were taken, and the HOMO levels of PA, PB, and PC were determined to be −5.76, −5.66, and −5.71 eV, respectively, indicating very low-lying HOMO energy levels. The optimized PSCs based on PA, PB, and PC exhibit power conversion efficiencies (PCEs) of 3.75%, 2.42%, and 2.30%, respectively, with V_oc (0.77–0.86 V), J_sc (6.9–8.7 mA/cm²), and FF (38–52%). We believe that the highest PCE for the PSCs based on PA may be attributed to the high molecular weight and improved processability relative to those of PB and PC. A theoretical study suggests that the polymer backbones of PA and PB are highly distorted between the donor unit and the acceptor unit, by as much as 49°, possibly by the steric hindrance between BT and the inward positioned methyl group on the flanking thiophene. Therefore, the conjugations for the HOMO p-orbitals of PA and PB are highly localized throughout the backbone while the conjugations for the HOMO p-orbitals of PC are well delocalized. The AFM study revealed that DIO additive greatly changed the morphology of the polymer blend from an amorphous state into distinct nanoscale phase separated states, leading to a great improvement in PCEs. The XRD study revealed that all polymers are amorphous.     

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%.     

Properties of inverted polymer solar cells based on novel small molecular electrolytes as the cathode buffer layer

Novel small-molecule electrolytes were designed and synthesized for use in the cathode interlayer in bulk-heterojunction polymer solar cells (PSCs). The synthesized materials consist of polar quaternary ammonium bromide with the addition of multiple hydroxyl groups, which are N,N,N,N,N,N-hexakis(2-hydroxyethyl)butane-1,4-diaminium bromide (C4) and N,N,N,N,N,N-hexakis(2-hydroxyethyl)hexane-1,6-diaminium bromide (C6). The materials generate a favorable interface dipole through the quaternary ammonium bromide. In addition, the multiple polar hydroxyl groups increased the interface dipole magnitude. The power conversion efficiency of the devices with the interlayer was up to 9.20% with a J_sc of 17.22 mA/cm², a V_oc of 0.75 V, and an FF of 71.3%. The PCE of devices with an interlayer show better long-term stability than a device without an interlayer. Our strategy shows that it is possible to enhance the efficiency of PSCs by simple approaches without complicated syntheses.     

Efficient solution processed D1-A-D2-A-D1 small molecules bulk heterojunction solar cells based on alkoxy triphenylamine and benzo[1,2-b:4,5-b′]thiophene units

Two molecules denoted as VC96 and VC97 have been synthesized for efficient (η = 6.13% @ 100 mW/cm² sun-simulated light) small molecule solution processed organic solar cells. These molecules have been designed with the D₁-A-D₂-A-D₁ structure bearing different central donor unit, same benzothiadiazole (BT) as π-acceptor and end capping triphenylamine. Moreover, the optical and electrochemical properties (both experimental and theoretical) of these molecules have been systematically investigated. The solar cells prepared from VC96:PC₇₁BM and VC97:PC₇₁BM (1:2) processed from CF (chloroform) exhibit a PCE (power conversion efficiency) of η = 4.06% (J_sc = 8.36 mA/cm², V_oc = 0.90 V and FF = 0.54) and η = 3.12% (J_sc = 6.78 mA/cm², V_oc = 0.92 V and FF = 0.50), respectively. The higher PCE of the device with VC96 as compared to VC97 is demonstrated to be due to the higher hole mobility and broader IPCE spectra. The devices based on VC96:PC₇₁BM and VC97:PC₇₁BM processed with solvent additive (3 v% DIO, 1,8-diiodooctane) showed PCE of η = 5.44% and η = 4.72%, respectively. The PCE device of optimized VC96:PC₇₁BM processed with DIO/CF (thermal annealed) has been improved up to 6.13% (J_sc = 10.72 mA/cm², V_oc = 0.88 V and FF = 0.61). The device optimization results from the improvement of the balanced charge transport and better nanoscale morphology induced by the solvent additive plus the thermal annealing.     

Improved efficiency of solution processed small molecules organic solar cells using thermal annealing

A solution processable A-D-A-D-A structure small molecule DCAEH5TBT using a BT unit as the core has been designed and synthesized for application in BHJ solar cells. The device employing DCAEH5TBT/PC₆₁BM as active layer shows PCE of 2.43% without any post treatment. After thermal annealing (150 °C, 10 min), the PCE of this molecule based device increased to 3.07%, with J_sc of 7.10 mA/cm², V_oc of 0.78 V and FF of 55.4%, which indicates that high performance of solution processed small molecule based solar cells can be achieved using thermal annealing by carefully design molecule structure.     

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.     

Synthesis of a Modified PC70BM and Its Application as an Electron Acceptor with Poly(3‐hexylthiophene) as an Electron Donor for Efficient Bulk Heterojunction Solar Cells

A simple and effective modification of phenyl‐C₇₀‐butyric acid methyl ester (PC₇₀BM) is carried out in a single step after which the material is used as electron acceptor for bulk heterojunction polymer solar cells (PSCs). The modified PC₇₀BM, namely CN‐PC₇₀BM, showed broader and stronger absorption in the visible region (350–550 nm) of the solar spectrum than PC₇₀BM because of the presence of a cyanovinylene 4‐nitrophenyl segment. The lowest unoccupied molecular energy level (LUMO) of CN‐PC₇₀BM is higher than that of PC₇₀BM by 0.15 eV. The PSC based on the blend (cast from tetrahydrofuran (THF) solution) consists of P3HT as the electron donor and CN‐PC₇₀BM as the electron acceptor and shows a power conversion efficiency (PCE) of 4.88%, which is higher than that of devices based on PC₇₀BM as the electron acceptor (3.23%). The higher PCE of the solar cell based on P3HT:CN‐PC₇₀BM is related to the increase in both the short circuit current (J_sc) and the open circuit voltage (V_oc). The increase in J_sc is related to the stronger light absorption of CN‐PC₇₀BM in the visible region of the solar spectrum as compared to that of PC₇₀BM. In other words, more excitons are generated in the bulk heterojunction (BHJ) active layer. On the other hand, the higher difference between the LUMO of CN‐PC₇₀BM and the HOMO of P3HT causes an enhancement in the V_oc. The addition of 2% (v/v) 1‐chloronapthalene (CN) to the THF solvent during film deposition results in an overall improvement of the PCE up to 5.83%. This improvement in PCE can be attributed to the enhanced crystallinity of the blend (particularly of P3HT) and more balanced charge transport in the device.     

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.