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%.     

Polymer solar cells based low bandgap A1-D-A2-D terpolymer based on fluorinated thiadiazoloquinoxaline and benzothiadiazole acceptors with energy loss less than 0.5 eV

We synthesized an ultra low bandgap terpolymer denoted as P containing fluorinated-fluorene attached thiadiazoloquinoxaline and benzothiadiazole acceptors and thiophene as donor in its backbone and investigated its optical and electrochemical properties. This terpolymer is used for as donor along with PC₇₁BM as electron acceptor in solution processed polymer solar cells (PSCs). The P showed a shows strong absorption band from 650 nm to 1100 nm with an optical bandgap of 1.12 eV and highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of −5.25 eV and −3.87 eV, respectively. After the optimization of P to PC₇₁BM weight ratio, the optimized weight ratio 1:2 in chlorobenzene (CB) solution, the PSC showed overall power conversion efficiency of 4.10% (J_sc of 10.96 mA/cm², V_oc of 0.68 V and FF of 0.55). After the solvent additive (3 v% DIO) followed by subsequent thermal annealing (SA-TA) the PCE has been increased up to 7.54% with J_sc of 16.12 mA/cm², V_oc of 0.65 V and FF of 0.72. The increase in the PCE is related with the enhancement in the both J_sc and FF, attributed optimized nanoscale morphology of the active layer for both efficient exciton dissociation and charge transport towards the electrodes and balanced charge transport in the device, induced by the TSA treatment of the active layer. This is the highest PCE of PSCs with an energy loss about 0.47 eV with the low bandgap of 1.12 eV.     

Structure-property relationship of D-A type copolymers based on thienylenevinylene for organic electronics

A series of D-A type conjugated polymers based on (E)-1,2-bis(3-dodecyllthiophen-2-yl)ethene (TV) as electron donor unit and with different repeating subunits, PTVBO8, PTVBT8, PTVTBO12, and PTVTBT12 were synthesized for use in organic field effect transistors and bulk heterojunction organic photovoltaics. Upon incorporation of alkoxy substituents in acceptor units, benzooxadiazole (BO) and benzothiadiazole (BT), polymer solubility improved and higher molecular weight polymers were obtained. In addition, all copolymers showed favorable thermal stability (T_d > 300 °C), and low band gap properties (1.49–1.67 eV). The thiophene-flanked TV-TBX copolymers, PTVTBO12 and PTVTBT12, exhibited higher molecular weight and superior device performance in both OFETs and OPVs compared with the TV-BX copolymers. The electronic energy levels of copolymers were strongly influenced by the nature of acceptor units, while optical band gaps and shape of molecular orientation of polymer chains were affected by the presence or absence of thiophene spacer. Charge carrier mobilities in TV-TBX copolymers were 1 order of magnitude greater than in TV-BX copolymers. OFETs based on a PTVTBT12 with TG/BC configuration displayed the highest hole mobility of 0.48 cm² V⁻¹ s⁻¹. The photovoltaic device containing a PTVTBO12:PC₇₁BM (1:2 w/w) blend system exhibited best performance with a V_oc of 0.56 V, a short-circuit current density (Jsc) of 13.1 mA cm⁻², a fill factor (FF) of 69%, and a power conversion efficiency (PCE) of 5.0%.     

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.     

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.     

Ternary organic solar cells based on non-fullerene acceptors: A review

Organic solar cells (OSCs) have reached their second golden age in recent two years with a boosted number of publications. Non-fullerene acceptor (NFA) materials have become a rising star in the field which are widely applied in organic solar cells because of their excellent optoelectronic properties, such as strong light-harvesting ability and tunable energy level. Unlike the low synthetic flexibility and high production cost of fullerene materials, NFAs exhibit flexible structures, and relatively low fabrication costs. Recently, the ternary strategy has become another hot research topic in the field, which introduces a third component into the binary host system for OSCs. The application of a ternary strategy can break the limits of light absorption brought by the host system, improve the morphology and energy level alignment for the active layer and thus improved the efficiency of organic solar cell devices. Benefiting from the advancement in both NFA and ternary strategy, the power conversion efficiency (PCE) of organic solar cell has exceeded over 17.5% to date. A comprehensive review of the recent progress in NFA based ternary OSCs (TOSCs) is needed in the field. Herein, this review mainly focuses on recent research on ternary organic solar cells using NFA materials during the last two years. Firstly, device physics and frequently used active materials in NFA based TOSCs are summarized and discussed. Then, the recent reported high-performance NFA based TOSCs are reviewed. Finally, the outlook and future research direction in the field are proposed. This review aims to provide an insight into NFA based TOSCs and help researchers to explore the full potential of OSCs.     

Synthesis and photophysical properties of semiconductor molecules D1-A-D2-A-D1-type structure based on derivatives of quinoxaline and dithienosilole for organics solar cells

A novel small molecule with D1-A-D2-A-D1 structure denoted as DTS(QxHT₂)₂ based on quinoxaline acceptor and dithienosilone donor units was synthesized and its optical and electrochemical properties were investigated. The thin film of DTS(QxHT₂)₂ showed a broad absorption profile covering the solar spectrum from 350 nm to 780 nm with an optical bandgap of 1.63 eV. The energy levels estimated from the cyclic voltammetry indicate that this small molecule is suitable as donor along with PC₇₁BM as acceptor for the fabrication solution processed bulk heterojunction solar cells for efficient exciton dissociation and high open circuit voltage. The organic solar cells based on optimized DTS(QxHT2)2:PC₇₁BM active layers processed with chloroform and DIO/CF showed overall power conversion efficiency of 3.16% and 6.30%, respectively. The higher power conversion efficiency of the solar cell based on the DIO/CF processed active layer is attributed to enhanced short circuit photocurrent and fill factor may be related to better phase separation between donor and acceptor in the active layer and more balanced charge transport, induced by the solvent additive. The power conversion efficiency of the organic solar cell was further improved up to 7.81% based on active layer processed with solvent additive, using CuSCN as hole transport layer instead of PEDOT:PSS and mainly attributed to increased fill factor and open circuit voltage due the formation of better Ohmic contact between the active layer and the CuSCN layer.     

Recent progress in high efficiency polymer solar cells by rational design and energy level tuning of low bandgap copolymers with various electron-withdrawing units

AbstractThis review collects recent five-year publications on low bandgap semiconducting polymers, which are composed of electron donor (D) and electron acceptor (A) units, exhibiting the power conversion efficiency (PCE) higher than 6%. When the photovoltaic performances of different types of D−A semiconducting copolymers are compared after the copolymers are classified into several categories according to the type of A-units, it is realized that diketopyrrolopyrrole (DPP)-based copolymers exhibit high J_SCs owing to low bandgaps and low V_OCs due to high-lying HOMO levels, while thienopyrroledione (TPD)-based copolymers exhibit high V_OCs due to their deep HOMO levels and low J_SCs because of wide bandgaps. Benzothiadiazole- and thienothiophene-based copolymers show intermediate values of V_OC and J_SC between DPP- and TPD-based ones. For further enhancement of photovoltaic performance, DPP-based copolymers may be designed to have deeper HOMO level with the minimum widening of bandgap while TPD-based polymers may be designed to have lower bandgap with the minimum rise of HOMO level. Hence, the energy level tuning must be considered so as to minimize the adverse effect.     

Hexa-peri-hexabenzocoronene and diketopyrrolopyrrole based D-A conjugated copolymers for organic field effect transistor and polymer solar cells

Hexa-peri-hexabenzocoronene (HBC) is a disc-shaped conjugated molecule with strong π-π stacking property, high intrinsic charge mobility and good self-assembly property. But for a long time, the organic photovoltaic (OPV) solar cells based on HBC small organic molecules demonstrated low power conversion efficiencies (PCEs). In this study, a series of polymers named as PHBCDPPC20, PHBCDPPC8, PHBCDPPF and PHBCDPPDT were designed and synthesized through copolymerization of HBC with bulky mesityl substituents and strong electron-withdrawing diketopyrrolopyrrole (DPP) with different alkyl side chains and various π-bridges. Introduction of DPP unit into the HBC derivatives broadened the absorption spectra and lowered the band gaps. Bulky mesityl substituents attached to periphery of HBC prevented polymers from self-aggregating into too large domain size in the blend films of photovoltaic devices. The different π-bridges have significant effect on the structure conformation of the polymers. The polymer PHBCDPPDT with bithiophene π-bridges demonstrated the broadest absorption for its extensive π-conjugation and more coplanar conformation compared with the thiophene π-bridge one. PHBCDPPC20, PHBCDPPC8, PHBCDPPF and PHBCDPPDT gave field-effect hole mobilities of 1.35 × 10⁻³, 2.31 × 10⁻⁴, 2.79 × 10⁻⁴ and 8.60 × 10⁻³ cm² V⁻¹ s⁻¹, respectively. The solar cells based on these polymers displayed PCEs of 2.12%, 2.85%, 1.89% and 2.74%. To our knowledge, 2.85% is the highest PCE for the HBC-based photovoltaic materials till now.     

Photovoltaic properties of low band gap copolymers based on phenylenevinylene donor and cyanovinylene 4-nitrophenyl acceptor units

Two novel copolymers P1 and P2 having phenylenevinylene donor and cyanovinylene 4-nitrophenyl acceptor units, were synthesized by heck coupling and employed as electron donor along with PCBM or modified PCBM (F) as electron acceptor for the fabrication of bulk heterojunction (BHJ) photovoltaic devices. These copolymers P1 and P2 showed broad band absorption around 640-700 nm and optical band gap of 1.60 eV and 1.72 eV, respectively. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) estimated from cyclic voltammetry measurement reveals that these values are well suitable for the use of these copolymers as electron donor along with PCBM derivatives as electron acceptor for BHJ active layer. The suitable LUMO off set allows efficient photo-induced charge transfer at the donor/acceptor interfaces in the BHJ photovoltaic device and resulting power conversion efficiency (PCE) of 2.8% and 3.29% for P1 and P2, respectively, when PCBM is used as acceptor. This value has been improved up to 3.52% and 4.36% for the devices based on P1 and P2 when F is used as electron acceptor, instead of PCBM. We have also investigated the effect of solvent annealing on the photovoltaic performance of device based on P1: F and P2: F blends and found that the over all PCE of the devices is 4.36% and 4.88%, respectively. The increase in PCE is mainly due to the improvement in the J_sc, which is due to the increased charge transport in the annealed device as compared to as cast device.     

Efficient bulk heterjunction solar cells based on a low-bandgap polyfluorene copolymers and fullerene derivatives

A low-bandgap polymer (PF-PThCVPTZ) consisted of fluorene and phenothiazine was designed and synthesized. With the donor–acceptor segment, the partial charge transfer can be built in the polymer backbone leading to a wide absorbance. The absorption spectrum of PF-PThCVPTZ exhibits a peak at 510 nm and an absorption onset at 645 nm in the visible range. As blended with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as an electron acceptor, narrow bandgap PF-PThCVPTZ as electron donor shows significant solar cell performance. Under AM 1.5 G, 100 mA/cm² illumination, a power conversion efficiency (PCE) of 1.85% was recorded, with a short circuit current (J_SC) of 5.37 mA/cm², an open circuit voltage (V_OC) of 0.80 V, and a fill factor (FF) of 43.0%.     

Synthesis and characterization of the conjugated polymers tethered with dipolar side chains containing a benzothiadiazole entity for bulk heterojunction solar cells

New conjugated copolymers (P1?P3) containing dipolar side chains connected to the main chain via triphenylamine donors have been synthesized and characterized. The side chains of these polymers have an electron deficient benzothiadiazole moiety in the spacer, but with different acceptors at the end. By changing the acceptor moieties of the side chain, the absorption spectra and HOMO/LUMO gaps of the polymers can be fine-tuned, ranging from 1.86 to 1.59 eV. Solution processed bulk heterojunction (BHJ) solar cells using these polymers as the donor and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) as the acceptor were fabricated and measured under 100 mW cm^?2 of AM 1.5 illumination. The cell based on the blend of P1/PCBM (1:1, w/w) exhibited the highest power conversion efficiency of 1.78%, with open circuit voltage (V_oc) = 0.79 V, short circuit current (J_sc) = 6.63 mA cm^?2 and fill factor (FF) = 0.34, respectively.     

Synthesis and characterization of a new perylene bisimide (PBI) derivative and its application as electron acceptor for bulk heterojunction polymer solar cells

A symmetrical perylene bisimide derivative (PBI) with 2-(4-nitrophenyl)acrylonitrile groups at the 1,7 bay positions of perylene and solubilizing cyclohexyl units was synthesized and characterized. The absorption spectrum of PBI was broad with the most prominent peak at 655 nm and optical band gap of 1.72 eV. The electrochemical investigation indicates that PBI has a LUMO energy level of −3.9 eV which is similar to that of PCBM or PC₇₀BM. Bulk heterojunction solar cell fabricated using a blend of poly(3-hexylthiophene) (P3HT) and PBI (1:1 w/w) as active layer cast from THF exhibited power conversion efficiency (PCE) at 1.56%. However, the device with P3HT:PBI blend deposited from mixed solvent (DIO/THF) improved the PCE to 2.78% which further increased to 3.17% on using the thermal annealed active layer. The improvement in the PCE is attributed to the enhanced crystallinity of the blend (particularly P3HT) and increase in hole mobility leading to balanced charge transport.     

Effects of processing additives on nanoscale phase separation,crystallization and photovoltaic performance of solar cells based on mesogenic phthalocyanine

A study on the effects of processing additives on the nanoscale phase separation, crystallization, and photovoltaic performance of bulk heterojunction (BHJ) thin films made of 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH₂) and [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) via spin-casting for photovoltaic applications is reported. By incorporating various solvents as processing additives to a volume of a few percent, the separation of donor and acceptor phases in C6PcH₂:PCBM thin films, which discussed by taking the photoluminescence quenching, Davydov splitting at the Q-band of the absorbance spectra and the surface nanomorphology into consideration, is improved, and the crystallinity of the discotic C6PcH₂ molecules with hexagonal structures is reinforced. Photovoltaic cells with the optimum phase-separated BHJ materials and high crystallinity of the discotic C6PcH₂ molecules are demonstrated to have a power conversion efficiency of 4.2%.     

Synthesis and photovoltaic properties of D–A–D type small molecules containing diketopyrrolopyrrole (DPP) acceptor central unit with different donor terminal units

Two D–A–D small molecules TDPP (FP)2 and TDPP (BuP)2 coded as CSDPP2 and CSDPP4 respectively were synthesized having same diketopyrrolopyrrole (DPP) as core acceptor and difluoro-phenyl (FP) and dibutyloxy phenyl (BuP) as different end donor units with broad absorption and suitable energy levels. We have used these small molecules as donor components along with the PC₇₀BM as electron acceptor for the preparation of bulk heterojunction (BHJ) active layer in small molecule (SM) organic photovoltaics (OPV) test cells. The optimal power conversion efficiencies obtained with CSDPP2 and CSDPP4 are 2.26% and 3.23% when the BHJ active layer was cast from CF solvent. The PCE has been further enhanced up to 3.03% and 4.65% for CSDPP2 and CSDPP4 when the BHJ active layer was cast from CN/CF solvent. The enhancement in PCE has been explained in terms of change in crystallinity and nanoscale morphology and more balanced charge transport resulting from increased hole mobility.     

D-A-D-A-D push pull organic small molecules based on 5,10-dihydroindolo[3,2-b]indole (DINI) central core donor for solution processed bulk heterojunction solar cells

Two D-A-D-A-D small molecules based on same 5,10-dihydroindolo [3,2-b]indole central donor core and different benzothiadiazole (BT) and fluorine substituted BT (FBT) acceptor units, denoted as p-DINI-(BTTh₃)₂ (1) and p-DINI-(FBTTTh₃)₂ (2), respectively were synthesized and their optical and electrochemical properties were investigated. These molecules were applied as donor along with PC₇₁BM as electron acceptor for the fabrication of solution processed bulk heterojunction organic solar cells. The solar cells prepared from the optimized active blended layer (1:2) cast from dichlorobenzene (DCB) showed overall power conversion efficiency (PCE) of 2.02% and 2.70% for 1 and 2, respectively as donor. The higher PCE of 2 as compared to 1 is attributed to the higher hole mobility and broader IPCE spectra. In order to improve the PCE we have employed a two step treatment of active layer i.e. solvent vapor annealing after thermal annealing (SVA-TA) and the PCE has been enhanced up to 4.14% and 5.27% for optimized 1:PC₇₁BM and 2:PC₇₁BM active layers, respectively. The improvement in the PCE has been resulted from the improvement in the balanced charge transport and better crystallinity of the donor in the blended active layer.     

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.     

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.     

Air-processed high performance ternary blend solar cell based on PTB7-Th:PCDTBT:PC70BM

Ternary bulk heterojunctions (BHJs) are promising candidates that can improve the power conversion efficiencies (PCEs) of organic solar cells (OSCs). In this paper, a ternary OSC with two donors, including one wide bandgap polymer poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT), one low bandgap polymer Poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene-co-3-fluorothieno[3,4-b]thiophene-2-carboxylate] (PTB7-Th), and one acceptor [6,6]-phenyl C70 butyric acid methyl ester (PC₇₀BM), is fabricated in atmospheric conditions. By incorporating a 20% content of PCDTBT, an optimized PCE of 7.86% for ternary OSC is characterized by a short-circuit current density (J_sc) of 15.21 mA cm⁻², a fill factor of 69.70% and an open-circuit voltage (V_oc) of 0.74 V. The V_oc values increased steadily from 0.73 to 0.86 V as the increase of PCDTBT fraction, which indicates that the V_oc of ternary OSC is not limited by the smallest one of the corresponding binary OSC. We show that the J_sc of the ternary OSC is better than those of the binary OSC in virtue of the complementary polymer absorption and cascade energy levels, as well as optimized morphology of the ternary system. Furthermore, the lifetime of the devices with PCDTBT is greatly enhanced. This work indicates that two donors (PTB7-Th/PCDTBT) ternary BHJs system provide a simple and effective method to improve the performance and also the stability of OSCs.     

Synthesis and characterization of a wide bandgap polymer based on a weak donor-weak acceptor structure for dual applications in organic solar cells and organic photodetectors

We synthesized a novel wide bandgap polymer, PDTFBT, forming a weak donor (WD)-weak acceptor (WA) structure for use in organic photodetectors (OPDs) and organic solar cells (OSCs). The fluorination in the D unit and the alkoxy substitution in the A unit induced WD and WA properties, respectively. The WD-WA structure of PDTFBT effectively broadened the bandgap compared to typical D-A structures, and the S-F and S-O dipole-dipole interactions induces a highly planar backbone structure with excellent π-π stacking in the vertical direction. In OPDs, conformationally less disordered PDTFBT polymer retained the constant responsivity and significantly improved the detectivity of PDTFBT:PC₇₁BM devices even with a thick active layer of 470 nm, contrary to the variation in the responsivity of P3HT:PC₆₁BM devices depending on the thickness. In OSCs, the deep HOMO energy level (−5.57 eV) of PDTFBT led to high Voc of 0.92 V in PDTFBT:PC₇₁BM devices, which was 0.3 eV higher than that of P3HT:PC₆₁BM devices (0.62 V), resulting in 1.8-fold enhanced power conversion efficiency. We demonstrated that the WD-WA structure with S-F and S-O interactions is highly promising strategy to make wide bandgap polymers for organic photodetectors and for the bottom cell of tandem architecture.