Acceptor Polymers Research Articles

Boosting the Power Factor of Benzodithiophene Based Donor-Acceptor Copolymers/SWCNTs Composites through Doping.

In this study, a benzodithiophene (BDT)-based donor (D)–acceptor (A) polymer containing carbazole segment in the side-chain was designed and synthesized and the thermoelectric composites with 50 wt % of single walled carbon nanotubes (SWCNTs) were prepared via ultrasonication method. Strong interfacial interactions existed in both of the composites before and after immersing into the 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) solution as confirmed by UV-Vis-NIR, Raman, XRD and SEM characterizations. After doping the composites by F4TCNQ, the electrical conductivity of the composites increased from 120.32 S cm−1 to 1044.92 S cm−1 in the room temperature. With increasing the temperature, the electrical conductivities and Seebeck coefficients of the undoped composites both decreased significantly for the composites; the power factor at 475 K was only 6.8 μW m−1 K−2, which was about nine times smaller than the power factor at room temperature (55.9 μW m−1 K−2). In the case of doped composites, although the electrical conductivity was deceased from 1044.9 S cm−1 to 504.17 S cm−1, the Seebeck coefficient increased from 23.76 μV K−1 to 35.69 μW m−1 K−2, therefore, the power factors of the doped composites were almost no change with heating the composite films.

Toward Efficient All-Polymer Solar Cells via Halogenation on Polymer Acceptors.

Although halogenation has been widely regarded as an effective approach to adjust the properties of organic semiconductors, systematic investigation on the comparison of nonhalogenated and halogenated polymer acceptors only received minor attention in all-polymer solar cell (all-PSC) community. Herein, we report three IDIC-based narrow band gap polymer acceptors, PIDIC2T, PIDIC2T2F, and PIDIC2T2Cl, which are composed of IDIC-C16 building blocks as acceptor units, linking pristine bithiophene, fluorinated bithiophene, or chlorinated bithiophene as donor units. Although these three polymer acceptors exhibit nearly identical lowest unoccupied molecular orbital (LUMO) levels of ca. -3.87 eV with a similar optical band gap of ca. 1.54 eV, we found that different halogen species significantly affect the electron mobility and thin-film morphology of the polymer acceptors. All-PSCs were fabricated by pairing three polymer acceptors with a PBDB-T polymer donor, while PIDIC2T2Cl delivered a highest power conversion efficiency (PCE) of 5.34% due to its favorable bulk morphology with smaller root-mean-square (rms) roughness values, which induce the relatively more balanced charge carrier mobilities. By blending the fluorinated analogue of PBDB-T, PM6, further improved VOC, JSC, and fill factor (FF) of devices were achieved (5.46% for PM6:PIDIC2T, 4.96% for PM6:PIDIC2T2F, 7.11% for PM6:PIDIC2T2Cl), which can be due to the synergistic effect of the deeper highest occupied molecular orbital (HOMO) energy level of PM6, enhanced crystallinity, and more matched charge transport. This systematic study provides an insight into the influence of halogenation (fluorination and chlorination) on the optoelectrical properties of n-type organic semiconductors and demonstrates an efficient strategy that the design guideline for polymer acceptors can be enriched by backbone halogenation to further develop high-performance all-PSCs.

High-Performance All-Polymer Solar Cells: Synthesis of Polymer Acceptor by a Random Ternary Copolymerization Strategy.

Demonstrated in this work is a simple random ternary copolymerization strategy to synthesize a series of polymer acceptors, PTPBT-ETx , by polymerizing a small-molecule acceptor unit modified from Y6 with a thiophene connecting unit and a controlled amount of an 3-ethylesterthiophene (ET) unit. Compared to PTPBT of only Y6-like units and thiophene units, PTPBT-ETx (where x represents the molar ratio of the ET unit) with an incorporated ET unit in the ternary copolymers show up-shifted LUMO energy levels, increased electron mobilities, and improved blend morphologies in the blend film with the polymer donor PBDB-T. And the all-polymer solar cell (all-PSC) based on PBDB-T:PTPBT-ET0.3 achieved a high power conversion efficiency over 12.5 %. In addition, the PTPBT-ET0.3 -based all-PSC also exhibits long-term photostability over 300 hours.

High‐Performance All‐Polymer Solar Cells: Synthesis of Polymer Acceptor by a Random Ternary Copolymerization Strategy

AbstractDemonstrated in this work is a simple random ternary copolymerization strategy to synthesize a series of polymer acceptors, PTPBT‐ETx, by polymerizing a small‐molecule acceptor unit modified from Y6 with a thiophene connecting unit and a controlled amount of an 3‐ethylesterthiophene (ET) unit. Compared to PTPBT of only Y6‐like units and thiophene units, PTPBT‐ETx (where x represents the molar ratio of the ET unit) with an incorporated ET unit in the ternary copolymers show up‐shifted LUMO energy levels, increased electron mobilities, and improved blend morphologies in the blend film with the polymer donor PBDB‐T. And the all‐polymer solar cell (all‐PSC) based on PBDB‐T:PTPBT‐ET0.3 achieved a high power conversion efficiency over 12.5 %. In addition, the PTPBT‐ET0.3‐based all‐PSC also exhibits long‐term photostability over 300 hours.

High-Performance All-Polymer Solar Cells Enabled by n-Type Polymers with an Ultranarrow Bandgap Down to 1.28 eV.

Compared to organic solar cells based on narrow-bandgap nonfullerene small-molecule acceptors, the performance of all-polymer solar cells (all-PSCs) lags much behind due to the lack of high-performance n-type polymers, which should have low-aligned frontier molecular orbital levels and narrow bandgap with broad and intense absorption extended to the near-infrared region. Herein, two novel polymer acceptors, DCNBT-TPC and DCNBT-TPIC, are synthesized with ultranarrow bandgaps (ultra-NBG) of 1.38 and 1.28 eV, respectively. When applied in transistors, both polymers show efficient charge transport with a highest electron mobility of 1.72 cm2 V-1 s-1 obtained for DCNBT-TPC. Blended with a polymer donor, PBDTTT-E-T, the resultant all-PSCs based on DCNBT-TPC and DCNBT-TPIC achieve remarkable power conversion efficiencies (PCEs) of 9.26% and 10.22% with short-circuit currents up to 19.44 and 22.52 mA cm-2 , respectively. This is the first example that a PCE of over 10% can be achieved using ultra-NBG polymer acceptors with a photoresponse reaching 950 nm in all-PSCs. These results demonstrate that ultra-NBG polymer acceptors, in line with nonfullerene small-molecule acceptors, are also available as a highly promising class of electron acceptors for maximizing device performance in all-PSCs.

Bisisoindigo–Benzothiadiazole Copolymers: Materials for Ambipolar and n-Channel OTFTs with Low Threshold Voltages

The development of design strategies in both ambipolar and electron-conducting organic thin-film transistor (OTFT) materials is important for producing high-performance materials and devices in organic electronics. Isoindigo donor–acceptor polymers have been well studied as hole-conducting materials in OTFTs, while more electron-deficient, acceptor-rich isoindigo polymers have been underexplored. In this report, two common design strategies in isoindigo-based polymers, acceptor–acceptor polymers and core-expanded isoindigo structures, are combined to create copolymers of bisisoindigo, a core-expanded derivative of isoindigo, and electron-deficient benzothiadiazoles. These polymers exhibit the low energy lowest unoccupied molecular orbitals (LUMOs) required for electron transport and show ambipolar OTFT performance with hole and electron mobilities up to 4.0 × 10–3 and 1.4 × 10–3 cm2 V–1 s–1, respectively. Additionally, changing the source and drain contacts from Au to LiF/Al significantly lowered the threshold voltage due to improved alignment of the polymer and electrode energy levels. Comparisons of the optoelectronic properties between these polymers and previously reported bisisoindigo donor–acceptor polymers indicate that the increased acceptor strength lowers the frontier molecular orbital energies, while the dithienyl-benzothiadiazole unit impacts the film morphology by altering the shape of the polymer backbone.

A Conjugated Polymer Containing Arylazopyrazole Units in the Side Chains for Field‐Effect Transistors Optically Tunable by Near Infra‐Red Light

AbstractOptically tunable field‐effect transistors (FETs) with near infra‐red (NIR) light show promising applications in various areas. Now, arylazopyrazole groups are incorporated in the side chains of a semiconducting donor–acceptor (D‐A) polymer. The cis–trans interconversion of the arylazopyrazole can be controlled by 980 nm and 808 nm NIR light irradiation, by utilizing NaYF4:Yb,Tm upconversion nanoparticles and the photothermal effect of conjugated D‐A polymers, respectively. This reversible transformation affects the interchain packing of the polymer thin film, which in turn reversibly tunes the semiconducting properties of the FETs by the successive 980 nm and 808 nm light irradiation. The resultant FETs display fast response to NIR light, good resistance to photofatigue, and stability in storage for up to 120 days. These unique features will be useful in future memory and bioelectronic wearable devices.

Designed Polymer Donors to Match an Amorphous Polymer Acceptor in All-Polymer Solar Cells

All-polymer solar cells (all-PSCs) based on amorphous polymer acceptors show different phase separation behaviour from that with conventional semi-crystalline polymer acceptors. In this work, to ma...

High Open-circuit Voltage and Low Voltage Loss in All-polymer Solar Cell with a Poly(coronenediimide-vinylene) Acceptor

Reducing the voltage loss (Vloss) is a critical factor in optimizing the open-circuit voltage (Voc) and overall power-conversion efficiency (PCE) of polymer solar cells. In the current work, by designing a novel electron-accepting unit of coronenediimide (CDI) and using it as the main functional building block, a new polymer acceptor CDI-V is developed and applied to fabricate all-polymer solar cells. Compared with the perylenediimide-based polymer acceptors we previously reported, the current CDI-V polymer possesses a noticeably elevated lowest unoccupied molecular orbital (LUMO). Thereby, by virtue of the enlarged energy gap between the donor HOMO and acceptor LUMO, a high Voc value of 1.05 V is achieved by the all-polymer photovolatic device, along with an impressively low Vloss of 0.55 V. As remarkably, in spite of an extremely small LUMO level offset of 0.01 eV exhibited by the donor and acceptor polymers, effective charge separation still takes place in the all-polymer device, as evidenced by a proper short-circuit current (Jsc) of 9.5 mA·cm2 and a decent PCE of 4.63%.

The new era for organic solar cells: polymer acceptors

The new era for organic solar cells: polymer acceptors

Toward the Prediction and Control of Glass Transition Temperature for Donor–Acceptor Polymers

AbstractSemiconducting donor–acceptor (D–A) polymers have attracted considerable attention toward the application of organic electronic and optoelectronic devices. However, a rational design rule for making semiconducting polymers with desired thermal and mechanical properties is currently lacking, which greatly limits the development of new polymers for advanced applications. Here, polydiketopyrrolopyrrole (PDPP)‐based D–A polymers with varied alkyl side‐chain lengths and backbone moieties are systematically designed, followed by investigating their thermal and thin film mechanical responses. The experimental results show a reduction in both elastic modulus and glass transition temperature (Tg) with increasing side‐chain length, which is further verified through coarse‐grained molecular dynamics simulations. Informed from experimental results, a mass‐per‐flexible bond model is developed to capture such observation through a linear correlation between Tg and polymer chain flexibility. Using this model, a wide range of backbone Tg over 80 °C and elastic modulus over 400 MPa can be predicted for PDPP‐based polymers. This study highlights the important role of side‐chain structure in influencing the thermomechanical performance of conjugated polymers, and provides an effective strategy to design and predict Tg and elastic modulus of future new D–A polymers.

Increasing N2200 Charge Transport Mobility to Improve Performance of All Polymer Solar Cells by Forming a Percolation Network Structure.

The poor electron transport ability of the polymer acceptor is one of the factors restricting the performance of all-polymer solar cells. The percolation network of conjugated polymers can promote its charge transfer. Hence, we aim to find out the critical molecular weight (MW) of N2200 on the forming of the percolation network and to improve its charge mobility and thus photovoltaic performance of J51:N2200 blend. Detailed measurements demonstrate that when the MW of N2200 is larger than 96k, a percolation network structure is formed due to the chain tangled and multi-chain aggregations. Analysis of kinetic experiments reveals that it is the memory of the N2200 long chain conformation and the extent of aggregation in solution are carried into cast films for the formation of the percolation network. Thus, the electron mobility increases from 5.58 × 10−6 cm2V−1s−1 (N220017k) to 9.03 × 10−5 cm2V−1s−1 when the MW of N2200 is >96k. It led to a balance between hole and electron mobility. The μh/μe decrease from 16.9 to 1.53, causing a significant enhancement in the PCEs, from 5.87 to 8.28% without additives.

Novel polymer acceptors achieving 10.18% efficiency for all-polymer solar cells

Polymer acceptors based on extended fused ring π skeleton has been proven to be promising candidates for all-polymer solar cells (all-PSCs), due to their remarkable improved light absorption than the traditional imide-based polymer acceptors. To expand structural diversity of the polymer acceptors, herein, two polymer acceptors PSF-IDIC and PSi-IDIC with extended fused ring π skeleton are developed by copolymerization of 2,2′-((2Z,2′Z)-((4,4,9,9-tetrahexadecyl-4,9-dihydro-s-indaceno [1,2-b:5,6-b']dithiophene-2,7-diyl)bis(methanylylidene))bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (IDIC-C16) block with sulfur (S) and fluorine (F) functionalized benzodithiophene (BDT) unit and silicon (Si) atom functionalized BDT unit, respectively. Both polymer acceptors exhibit strong light absorption. The PSF-IDIC exhibits similar energy levels and slightly higher absorption coefficient relative to the PSi-IDIC. After blended with the donor polymer PM6, the functional atoms on the polymer acceptors show quite different effect on the device performance. Both of the acceptors deliver a notably high open circuit voltage (VOC) of the devices, but PSi-IDIC achieves higher VOC than PSF-IDIC. All-PSC based on PM6:PSi-IDIC attains a power conversion efficiency (PCE) of 8.29%, while PM6:PSF-IDIC-based device achieves a much higher PCE of 10.18%, which is one of the highest values for the all-PSCs reported so far. The superior device performance of PM6:PSF-IDIC is attributed to its higher exciton dissociation and charge transport, decreased charge recombination, and optimized morphology than PM6:PSi-IDIC counterpart. These results suggest that optimizing the functional atoms of the side chain provide an effective strategy to develop high performance polymer acceptors for all-PSCs.

Ultranarrow Bandgap Naphthalenediimide-Dialkylbifuran-Based Copolymers with High-Performance Organic Thin-Film Transistors and All-Polymer Solar Cells.

A new polymer acceptor poly{(N,N'-bis(2-ethylhexyl)-1,4,5,8-naphthalenedicarboximide-2,6-diyl)-alt-5,5-(3,3'-didodecyl-2,2'-bifuran)} (NDI-BFR) made from naphthalenediimide (NDI) and furan-derived head-to-head-linked 3,3'-dialkyl-2,2'-bifuran (BFR) units is reported in this study. Compared to the benchmark polymer poly(naphthalenediimide-alt-bithiophene) (N2200), NDI-BFR exhibits a larger bathochromic shift of absorption maxima (842 nm) with a much higher absorption coefficient (7.2 × 104 m-1 cm-1 ), leading to an ultranarrow optical bandgap of 1.26 eV. Such properties ensure good harvesting of solar light from visible to the near-infrared region in solar cells. Density functional theory calculation reveals that the polymer acceptor NDI-BFR possesses a higher degree of backbone planarity versus the polymer N2200. The polymer NDI-BFR exhibits a decent electron mobility of 0.45 cm2 V-1 s-1 in organic thin-film transistors (OTFTs), and NDI-BFR-based all-polymer solar cells (all-PSCs) achieve a power conversion efficiency (PCE) of 4.39% with a very small energy loss of 0.45 eV by using the environmentally friendly solvent 1,2,4-trimethylbenzene. These results demonstrate that incorporating head-to-head-linked BFR units in the polymer backbone can lead to increased planarity of the polymer backbone, reduced optical bandgap, and improved light absorbing. The study offers useful guidelines for constructing n-type polymers with narrow optical bandgaps.

Tuning of electronic properties of novel donor–acceptor polymers containing oligothiophenes with electron-withdrawing ester groups

To investigate the substituent effects introduced into oligothiophene units, a series of novel donor–acceptor conjugated polymers containing ester-substituted oligothiophenes were synthesized by the direct C–H arylation polycondensation of bis(ester-substituted thienyl)benzothiadiazole and dibromo-substituted oligothiophenes. The ultraviolet–visible absorption spectra of three polymers showed two absorption bands in the visible light wavelength region, ascribed to π–π* transition and the intramolecular charge transfer bands. The oxidation potentials of the polymers exhibited a negative shift with an increase in the chain length of the oligothiophene units. By comparing these polymers with alkyl-substituted analogues, it was found that the introduction of electron-withdrawing ester groups induced a negative shift in the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels and affected the LUMO rather than the HOMO energy levels. As a preliminary experiment, organic photovoltaic cells using these polymers were prepared, and their photoelectric conversion characteristics were investigated in relation to their chemical structures.

10.13% Efficiency All‐Polymer Solar Cells Enabled by Improving the Optical Absorption of Polymer Acceptors

The limited light absorption capacity for most polymer acceptors hinders the improvement of the power conversion efficiency (PCE) of all‐polymer solar cells (all‐PSCs). Herein, by simultaneously increasing the conjugation of the acceptor unit and enhancing the electron‐donating ability of the donor unit, a novel narrow‐bandgap polymer acceptor PF3‐DTCO based on an A–D–A‐structured acceptor unit ITIC16 and a carbon–oxygen (C–O)‐bridged donor unit DTCO is developed. The extended conjugation of the acceptor units from IDIC16 to ITIC16 results in a red‐shifted absorption spectrum and improved absorption coefficient without significant reduction of the lowest unoccupied molecular orbital energy level. Moreover, in addition to further broadening the absorption spectrum by the enhanced intramolecular charge transfer effect, the introduction of C–O bridges into the donor unit improves the absorption coefficient and electron mobility, as well as optimizes the morphology and molecular order of active layers. As a result, the PF3‐DTCO achieves a higher PCE of 10.13% with a higher short‐circuit current density (Jsc) of 15.75 mA cm−2 in all‐PSCs compared with its original polymer acceptor PF2‐DTC (PCE = 8.95% and Jsc = 13.82 mA cm−2). Herein, a promising method is provided to construct high‐performance polymer acceptors with excellent optical absorption for efficient all‐PSCs.

D‐A Polymer with a Donor Backbone ‐ Acceptor‐side‐chain Structure for Organic Solar Cells

AbstractWe report the design, synthesis, and properties of a novel type of donor (D)‐acceptor (A) polymer, poly(3‐(([2,2′:5′,2′′‐terthiophen]‐3‐yl‐5,5“‐diyl)methylene)‐1‐(2‐octyldodecyl)indolin‐2‐one) (PTIBT), with a donor backbone and acceptor side chains (Type II D‐A polymer) as donor for organic solar cells (OSCs) as opposed to the conventional D‐A polymers having both donor and acceptor units on backbone (Type I D‐A polymers). PTIBT having a backbone consisting of thiophene donor units and side chains containing indolin‐2‐one acceptor units was synthesized very conveniently in three steps. This polymer has a high dielectric constant of 7.70, which is beneficial for the exciton diffusion and dissociation in the active blend layer in an OSC. In addition, PTIBT was found to have a low‐lying HOMO energy level of −5.41 eV and a wide band gap of 1.80 eV in comparison to its counterpart Type I D‐A polymer. In organic thin film transistors (OTFTs), PTIBT showed typical p‐type semiconductor performance with hole mobilities of up to 1.81×10−2 cm2 V−1 s−1. When PTIBT and ITIC were used as donor and acceptor to form a blend active layer, the best OSC device showed a JSC of 15.19 mAcm−2, a VOC of 0.66 V, and a fill factor of 0.57, resulting in a power conversion efficiency (PCE) of up to 5.72%.

Low-Bandgap n-Type Polymer Based on a Fused-DAD-Type Heptacyclic Ring for All-Polymer Solar Cell Application with a Power Conversion Efficiency of 10.7.

An n-type polymer (A701) is designed and synthesized with an alternative A'-DAD-A'-D' backbone, where 1,1-dicyanomethylene-3-indanone (IC), dithienothiophen[3,2-b]-pyrrolobenzothiadiazole (TPBT), and benzodithiophene (BDT) are used as A', DAD, and D' units, respectively. A701 shows enhanced light absorption with a narrow bandgap of 1.42 eV and a high absorption coefficient of 6.85 × 104 cm-1 at 780 nm. It displays an uplifted LUMO (the lowest unoccupied molecular orbital) level of -3.80 eV. By introducing a high point solvent additive of 1,8-diiodooctane (DIO), all-polymer solar cells (all-PSCs) based on the PBDB-T:A701 blend exhibit efficient exciton dissociation, enhanced charge transport, and decreased bimolecular recombination. Thus, a high open-circuit voltage (VOC) of 0.92 V, a short-circuit current (JSC) of 18.27 mA cm-2, and a fill factor (FF) of 0.64 are attained, affording an impressive power conversion efficiency (PCE) of 10.70%. The low voltage loss of 0.50 V and high efficiency of 10.7% are among the top values for all-PSCs. Our results indicate that the fused DAD-type heptacyclic ring can be utilized to construct not only nonfullerene small molecular acceptors but also promising polymer acceptors.

Quantification of Photophysical Processes in All‐Polymer Bulk Heterojunction Solar Cells

All‐polymer solar cells lag behind the state‐of‐the‐art in small molecule nonfullerene acceptor (NFA) bulk heterojunction (BHJ) organic solar cells (OSCs) for reasons still unclear. Herein, the efficiency‐limiting processes in all‐polymer solar cells are investigated using blends of the common donor polymer PBDT‐TS1 with different acceptor polymers, namely P2TPD[2F]T and P2TPDBT[2F]T. Combining data from steady‐state optical spectroscopy and time‐resolved photoluminescence, transient absorption, and time‐delayed collection field experiments, provides not only a concise but also quantitative assessment of the losses due to limited photon absorption, geminate and nongeminate charge carrier recombination, field‐dependent charge generation, and inefficient carrier extraction. Although both systems exhibit a similar charge separation efficiency in the absence of external bias, charge separation is significantly enhanced in P2TPDBT[2F]T‐based blends when biased. Kinetic parameters obtained via pulsed laser spectroscopy are used to reproduce the experimentally measured device current–voltage (J–V) characteristics and indicate that low fill factors originate either from nongeminate recombination competing with charge extraction, or from a pronounced field dependence of charge generation, depending on the acceptor polymer. The methodology presented here is generic and can be used to quantify the loss processes in BHJ OSCs including both all‐polymer and small molecule NFA systems.

Introducing Porphyrin Units by Random Copolymerization Into NDI-Based Acceptor for All Polymer Solar Cells.

Naphthalene diimide (NDI)-based polymer N2200 is a promising organic polymer acceptor for all-polymer solar cells (all-PSCs), but its inherent shortcomings like poor extinction coefficient and strong aggregation limit further performance optimization of all-PSCs. Here, a series of random copolymers, PNDI-Px, were designed and synthesized by introducing porphyrin unit into NDI-based polymer as acceptors for all-PSCs. These random copolymers show a higher absorption coefficient and raised the lowest unoccupied molecular orbital (LUMO) energy levels compared to N2200. The crystallinity can also be fine-tuned by regulation of the content of porphyrin unit. The random copolymers are matched with polymer donor PBDB-T for the application in all-polymer solar cells. The best power conversion efficiency (PCE) of these PNDI-Px-based devices is 5.93%, ascribed to the overall enhanced device parameters compared with the N2200-based device. These results indicate that introducing porphyrin unit into polymer is a useful way to fine-tune the photoelectric performance for efficient all-PSCs.