Aqueous Processed All-Polymer Solar Cells with High Open-Circuit Voltage Based on Low-Cost Thiophene-Quinoxaline Polymers.

Eco-friendly solution processing and the low-cost synthesis of photoactive materials are important requirements for the commercialization of organic solar cells (OSCs). Although varieties of aqueous-soluble acceptors have been developed, the availability of aqueous-processable polymer donors remains quite limited. In particular, the generally shallow highest occupied molecular orbital (HOMO) energy levels of existing polymer donors limit further increases in the power conversion efficiency (PCE). Here, we design and synthesize two water/alcohol-processable polymer donors, poly[(thiophene-2,5-diyl)-alt-(2-((13-(2,5,8,11-tetraoxadodecyl)-2,5,8,11-tetraoxatetradecan-14-yl)oxy)-6,7-difluoroquinoxaline-5,8-diyl)] (P(Qx8O-T)) and poly[(selenophene-2,5-diyl)-alt-(2-((13-(2,5,8,11-tetraoxadodecyl)-2,5,8,11-tetraoxatetradecan-14-yl)oxy)-6,7-difluoroquinoxaline-5,8-diyl)] (P(Qx8O-Se)) with oligo(ethylene glycol) (OEG) side chains, having deep HOMO energy levels (∼-5.4 eV). The synthesis of the polymers is achieved in a few synthetic and purification steps at reduced cost. The theoretical calculations uncover that the dielectric environmental variations are responsible for the observed band gap lowering in OEG-based polymers compared to their alkylated counterparts. Notably, the aqueous-processed all-polymer solar cells (aq-APSCs) based on P(Qx8O-T) and poly[(N,N'-bis(3-(2-(2-(2-methoxyethoxy)-ethoxy)ethoxy)-2-((2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-methyl)propyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl)-alt-(2,5-thiophene)] (P(NDIDEG-T)) active layer exhibit a PCE of 2.27% and high open-circuit voltage (VOC) approaching 0.8 V, which are among the highest values for aq-APSCs reported to date. This study provides important clues for the design of low-cost, aqueous-processable polymer donors and the fabrication of aqueous-processable OSCs with high VOC.

Dual Polymerized Y-Acceptors of Distinct-Dimensionality Create Neuron-Like Interpenetrating Hierarchical Network towards Efficient and Stable All-Polymer Solar Cells.

All-polymer solar cells have garnered particular attention thanks to their superior thermal, photo, and mechanical stabilities for large-scale manufacturing, yet the performance enhancement remains largely restrained by inherent morphological challenges of the bulk-heterojunction active layer. Herein, a 3D Y-branched polymerized small-molecule acceptor named PYBF, characteristic of high molecular weight and glass transition temperature, is designed and synthesized by precisely linking C3h-symmetric benzotrifuran with Y6 acceptors. In comparison to the benchmark thiophene-bridged linear PYIT acceptor, an optical blue-shift absorption is observed for PYBF yet a slightly higher power conversion efficiency (PCE) of 15.7% (vs 15.14%) is obtained when paired with polymer donor PM6, which benefit from the more crystalline and face-on-oriented PYBF domains. However, the star-like bulky structure of PYBF results in the nucleation-growth dominant phase-separation in polymeric blends, which generates stumpy droplet-like acceptor fibrils and impairs the continuity of acceptor phases. This issue is however surprisingly resolved by incorporating a small amount of PYIT, which leads to the formation of the more interconnective neuron-like dual-acceptor domains by long-chain entanglements of linear acceptors and alleviates bimolecular recombination. Thus, the champion device realizes a respectable PCE of up to ≈17% and importantly exhibits thermal and storage stabilities superior to the linear counterpart.

An Investigation of the Inverted Structure of a PBDB:T/PZT:C1-Based Polymer Solar Cell.

Based on experimental results, this theoretical study presents a new approach for investigating polymers' solar cells. P-type PZT:C1 and N-type PBDB:T were used to construct a blend for use as a photoactive layer for the proposed all-polymer solar cell. Initially, an architecture of an ITO/PEDOT:PSS/PBDB:T/PZT:C1/PFN-Br/Ag all-polymer solar device calibrated with experimental results achieved a PCE of 14.91%. A novel inverted architecture of the same solar device, proposed for the first time in this paper, achieved a superior PCE of 19.92%. Furthermore, the optimization of the doping of the transport layers is proposed in this paper. Moreover, the defect density and the thickness of the polymer are studied, and a PCE of 22.67% was achieved by the optimized cell, which is one of the highest PCEs of polymer solar devices. Finally, the optimized polymer solar cell showed good stability amidst temperature variations. This theoretical study sheds light on the inverted structure of all-polymer solar devices.

All-Polymer Solar Cells and Photodetectors with Improved Stability Enabled by Terpolymers Containing Antioxidant Side Chains.

It is of vital importance to improve the long-term and photostability of organic photovoltaics, including organic solar cells (OSCs) and organic photodetectors (OPDs), for their ultimate industrialization. Herein, two series of terpolymers featuring with an antioxidant butylated hydroxytoluene (BHT)-terminated side chain, PTzBI-EHp-BTBHTx and N2200-BTBHTx (x = 0.05, 0.1, 0.2), are designed and synthesized. It was found that incorporating appropriate ratio of benzothiadiazole (BT) with BHT side chains on the conjugated backbone would induce negligible effect on the molecular weight, absorption spectra and energy levels of polymers, however, which would obviously enhance the photostability of these polymers. Consequently, all-polymer solar cells (all-PSCs) and photodetectors were fabricated, and the all-PSC based on PTzBI-EHp-BTBHT0.05: N2200 realized an optimal power conversion efficiency (PCE) approaching ~ 10%, outperforming the device based on pristine PTzBI-EHp: N2200. Impressively, the all-PSCs based on BHT-featuring terpolymers displayed alleviated PCEs degradation under continuous irradiation for 300 h due to the improved morphological and photostability of active layers. The OPDs based on BHT-featuring terpolymers achieved a lower dark current at - 0.1 bias, which could be stabilized even after irradiation over 400 h. This study provides a feasible approach to develop terpolymers with antioxidant efficacy for improving the lifetime of OSCs and OPDs.

Improved Stability of All-Polymer Solar Cells Using Crosslinkable Donor and Acceptor Polymers Bearing Vinyl Moieties in the Side-Chains.

Crosslinkable polymers have attracted tremendous attention in various fields of science and technology, owing to their potential utilization in applications requiring dimensional and morphological stability under thermal and mechanical stress. In this study, random terpolymers were successfully synthesized by introducing thiophene-based monomers bearing vinyl functional groups in the side-chain of the polymer donor (PBDBT-BV20) and polymer acceptor (N2200-TV10) structures. The physical properties of the blend films of PBDBT-BV20 and N2200-TV10 before and after thermal crosslinking were extensively investigated and compared to those of the homogeneous individual polymer films. The results revealed that a network polymer with donor and acceptor polymer chains, which can lock the internal morphology, could be achieved by inducing crosslinking between the vinyl groups in the mixed state of PBDBT-BV20 and N2200-TV10. In addition, the power conversion efficiency (PCE) of the polymer solar cells (PSCs) containing the blend films that were crosslinked by a two-step thermal annealing process was improved. The enhanced PCE could be attributed to the individual crystallization of PBDBT-BV20 and N2200-TV10 in the blend phase at 120 °C and then thermal crosslinking at 140 °C. In addition, the PSCs with the crosslinked blend film exhibited an excellent shelf-life of over 1200 h and a thermally stable PCE. Furthermore, the crosslinked blend film exhibited excellent mechanical stability under bending stress in flexible PSCs using plastic substrates.

Enhancement of All-Polymer Solar Cells by Addition of a Chlorinated Polymer and Formation of an Energy Cascade in a Nonhalogenated Solvent.

Ternary organic solar cells (OSCs) containing a three-component photoactive layer with cascading energy alignments could benefit the charge transfer and improve the open-circuit voltage and power conversion efficiency. Herein, we report the incorporation of a derived chlorinated polymer, J52-Cl, as a guest donor into the donor J52 and acceptor N2200 blend film. The lowest unoccupied molecular orbital and the highest occupied molecular orbital levels of J52-Cl are between the corresponding energy levels of J52 and N2200, and this leads to generation of a cascade of energy levels. Photoluminescence measurements and the J-V of devices containing the donors indicated that this incorporation of J52-Cl could promote the charge transfer of the solar cells. The contribution from J52-Cl reduced the energy loss of J52-based binary devices significantly from 0.932 to 0.797 eV and the nonradiative energy loss from 0.399 to 0.269 eV, leading to an enhancement of Voc from 0.79 to 0.93 V. This introduction of chlorinated polymers also improves the intermolecular interactions and leads to a favorable morphology with appropriate phase separation and interpenetrating networks. As expected, the power conversion efficiency of ternary all-polymer solar cells (all-PSCs) processed in o-xylene solvent was increased from 8.55 to 11.02%. These results indicate that the ternary devices with the appropriate cascade of energy levels can fine tune the device's open-circuit voltage and finally improve the photovoltaic performance of OSCs.

8.78% Efficient All-Polymer Solar Cells Enabled by Polymer Acceptors Based on a B←N Embedded Electron-Deficient Unit.

In the field of all-polymer solar cells (all-PSCs), all efficient polymer acceptors that exhibit efficiencies beyond 8% are based on either imide or dicyanoethylene. To boost the development of this promising solar cell type, creating novel electron-deficient units to build high-performance polymer acceptors is critical. A novel electron-deficient unit containing B←N bonds, namely, BNIDT, is synthesized. Systematic investigation of BNIDT reveals desirable properties including good coplanarity, favorable single-crystal structure, narrowed bandgap and downshifted energy levels, and extended absorption profiles. By copolymerizing BNIDT with thiophene and 3,4-difluorothiophene, two novel conjugated polymers named BN-T and BN-2fT are developed, respectively. It is shown that these polymers possess wide absorption spectra covering 350-800 nm, low-lying energy levels, and ambipolar film-transistor characteristics. Using PBDB-T as the donor and BN-2fT as the acceptor, all-PSCs afford an encouraging efficiency of 8.78%, which is the highest for all-PSCs excluding the devices based on imide and dicyanoethylene-type acceptors. Considering that the structure of BNIDT is totally different from these classical units, this work opens up a new class of electron-deficient unit for constructing efficient polymer acceptors that can realize efficiencies beyond 8% for the first time.

11.2% All-Polymer Tandem Solar Cells with Simultaneously Improved Efficiency and Stability.

All-polymer solar cells (all-PSCs) that contain both p-type and n-type polymeric materials blended together as light-absorption layers have attracted much attention, since the blend of a polymeric donor and acceptor should present superior photochemical, thermal, and mechanical stability to those of small molecular-based organic solar cells. In this work, the interfacial stability is studied by using highly stable all-polymer solar cell as a platform. It is found that the thermally deposited metal electrode atoms can diffuse into the active layer during device storage, which consequently greatly decreases the power conversion efficiency. Fortunately, the diffusion of metal atoms can be slowed down and even blocked by using thicker interlayer materials, high-glass-transition-temperature interlayer materials, or a tandem device structure. Learning from this, homojunction tandem all-PSCs are successfully developed that simultaneously exhibit a record power conversion efficiency over 11% and remarkable stability with efficiency retaining 93% of the initial value after thermally aging at 80 °C for 1000 h.

Nanoscale Domain Imaging of All-Polymer Organic Solar Cells by Photo-Induced Force Microscopy.

Rapid nanoscale imaging of the bulk heterojunction layer in organic solar cells is essential to the continued development of high-performance devices. Unfortunately, commonly used imaging techniques such as tunneling electron microscopy (TEM) and atomic force microscopy (AFM) suffer from significant drawbacks. For instance, assuming domain identity from phase contrast or topographical features can lead to inaccurate morphological conclusions. Here we demonstrate a technique known as photo-induced force microscopy (PiFM) for imaging organic solar cell bulk heterojunctions with nanoscale chemical specificity. PiFM is a relatively recent scanning probe microscopy technique that combines an AFM tip with a tunable infrared laser to induce a dipole for chemical imaging. Coupling the nanometer resolution of AFM with the chemical specificity of a tuned IR laser, we are able to spatially map the donor and acceptor domains in a model all-polymer bulk heterojunction with resolution approaching 10 nm. Domain size from PiFM images is compared to bulk-averaged results from resonant soft X-ray scattering, indicating excellent quantitative agreement. Further, we demonstrate that in our all-polymer system, the AFM topography, AFM phase, and PiFM show poor correlation, highlighting the need to move beyond standard AFM for morphology characterization of bulk heterojunctions.

Fabrication of Completely Polymer-Based Solar Cells with p- and n-Type Semiconducting Block Copolymers with Electrically Inert Polystyrene.

It is widely recognized that fullerene derivatives show several advantages as n-type materials in photovoltaic applications. However, conventional [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) exhibits weak absorption in the visible region, and poor morphological stability, due to the facile aggregation. For further improvement of the device performance and durability, utilization of n-type polymeric materials instead of PCBM is considered to be a good way to solve the problems. In this study, we fabricated completely polymer-based solar cells utilizing p- and n-type block copolymers consisting of poly(3-hexylthiophene) (P3HT) and poly{[N,N'-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} [P(NDI2OD-T2)], respectively, containing common polystyrene (PSt) inert blocks, which decreased the size of phase separated structures. Electron mobility in synthesized P(NDI2OD-T2)-b-PSt film enhanced by a factor of 8 compared with homopolymer. The root mean square roughness of the blend film of two block copolymers (12.2 nm) was decreased, compared with that of the simple homopolymers blend (18.8 nm). From the current density-voltage characteristics, it was confirmed that the introduction of PSt into both P3HT and P(NDI2OD-T2) improves short-circuit current density (1.16 to 1.73 mA cm-2) and power-conversion efficiency (0.24% to 0.32%). Better performance is probably due to the uniformity of the phase separation, and the enhancement of charge mobility.

Role of Polymer Segregation on the Mechanical Behavior of All-Polymer Solar Cell Active Layers.

An all-polymer bulk heterojunction (BHJ) active layer that removes the use of commonly used small molecule electron acceptors is a promising approach to improve the thermomechanical behavior of organic solar cells. However, there has been limited research on their mechanical properties. Here, we report on the mechanical behavior of high-performance blade-coated all-polymer BHJ films cast using eco-friendly solvents. The mechanical properties considered include the elastic modulus, crack onset strain, and cohesive fracture energy. We show that the mechanical behavior of the blend is largely unaffected by significant changes in the segregation characteristics of the polymers, which was varied systematically through solvent formulation. In comparison to a polymer:fullerene BHJ counterpart, the all-polymer films were found to have lower stiffness and increased ductility. Yet, the fracture energy of the all-polymer films is not significantly improved compared to that of the polymer:fullerene films. This study highlights that improved mechanical behavior of all-polymer systems cannot be assumed, and that details of the molecular structure, molecular weight, and film morphology play an important role in both the optoelectronic and mechanical properties. Furthermore, we show that simple composite modeling provides a predictive tool for the mechanical properties of the polymer blend films, providing a framework to guide future optimization of the mechanical behavior.

Effects of Inserting Thiophene as a π-Bridge on the Properties of Naphthalene Diimide-alt-Fused Thiophene Copolymers.

On the basis of naphthalene diimide (NDI) units connected to thiophene (T), thienothiophene (TT), or dithienothiophene (DTT) units via a thiophene π-bridge, three new copolymers-PDTNDI-T, PDTNDI-TT, and PDTNDI-DTT, respectively-were synthesized and used in the fabrication of all-polymer solar cells (all-PSCs). The relationships between the structures of the polymers and their optoelectronic properties and photovoltaic performances as electron acceptors in all-PSCs were investigated in detail. As the number of copolymerized heteroaromatic rings in the DTNDI-based polymers increased, the power conversion efficiencies of the resulting all-PSCs were found to decrease. This decreasing trend in the photovoltaic performance is opposite to the results reported previously for NDI-based polymers lacking the thiophene π-bridge and naphthodithiophene diimide-based polymers. In addition, the three polymers were found to exhibit distinct molecular orientations: a face-on orientation for PDTNDI-T and edge-on orientations for PDTNDI-TT and PDTNDI-DTT. Our results indicate that large fused aromatic rings are not necessarily advantageous in the design of NDI-based polymers containing π-conjugated bridges.

Charge Transport in Intermixed Regions of All-Polymer Solar Cells Studied by Conductive Atomic Force Microscopy.

Charge transport in intermixed regions of all-polymer solar cells based on a blend of poly(3-hexylthiophene) (P3HT; electron donor) with poly[2,7-(9,9-didodecylfluorene)-alt-5,5-(4',7'-bis(2-thienyl)-2',1',3'-benzothiadiazole)] (PF12TBT; electron acceptor) was studied by conductive atomic force microscopy (C-AFM). For a blend film fabricated from a chlorobenzene solution, intermixed regions were detected between the P3HT-rich and PF12TBT-rich domains. The overall hole current in the intermixed regions remained almost constant, both before and after thermal annealing at 80 °C, but it increased in the P3HT-rich domains. For a blend film fabricated from a chloroform solution, the entire observed area constituted an intermixed region, both before and after thermal annealing. The overall hole current in this film was significantly improved following thermal annealing at 120 °C. These finely mixed structures with efficient charge transport yielded a maximum power conversion efficiency of 3.5%. The local charge-transport properties in the intermixed region, as observed via C-AFM, was found to be closely related to the photovoltaic properties, rather than the bulk-averaged properties or topological features.

High-efficiency all-polymer solar cells based on a pair of crystalline low-bandgap polymers.

All-polymer solar cells based on a pair of crystalline low-bandgap polymers (NT and N2200) are demonstrated to achieve a high short-circuit current density of 11.5 mA cm-2 and a power conversion efficiency of up to 5.0% under the standard AM1.5G spectrum with one sun intensity. The high performance of these NT:N2200-based cells can be attributed to the low optical bandgaps of the polymers and the reasonably high and balanced electron and hole mobilities of the NT:N2200 blends due to the crystalline nature of the two polymers.