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Two new nonfused ring nonfullerene electron acceptors, NFAs, (dicarbazolyl)bis(2-(3-oxo-2,3-dihydro-1 H -inden-1-ylidene)malononitrile) ( MDCzM-4H ) and -(2-(5,6-fluoro-3-oxo-2,3-dihydro-1 H -inden-1-ylidene)malononitrile) ( MDCzM-4F ), thus exhibiting an A-D 2 -A motif, were synthesized and characterized. As thin films, they exhibit the lowest energy absorption signature near 540 nm, extending down to ∼700 nm. This band is due to an intramolecular charge transfer process from the DCz (nonfused dicarbazoyl; DCz ) moiety to the malononitrile-based units ( M ) based on density functional theory calculations (DFT), which are also corroborated by time-dependent DFT (TDDFT) computations. Both NFAs fluoresce in the near-IR region exhibiting a band maximum peaking near 750 nm with biphasic lifetimes in the 75-410 ps time scale. Electrochemical measurements permitted the determination of their HOMO (∼-5.7 eV) and LUMO (∼-4.0 eV) energies. The absorption bands are complementary to those of the commercial copolymer PTB7-Th , which was used to prepare binary blends for photovoltaic cell performance assessments (ITO/PEDOT:PSS/active layer/PFN-Br/Ag). The power conversion efficiencies (PCE) are found to be 10.17% for MDCzM-4H / PTB7-Th (short-circuit current J SC = 15.87 mA cm -2 ; open-circuit voltage V OC = 1.03 V; fill factor FF = 0.622) and 14.09% for MDCzM-4F / PTB7-Th ( J SC = 20.92 mA cm -2 ; V OC = 0.965 V; FF = 0.698). The use of nonfused ring NFAs achieving such high performances is significant and reveals a path toward simpler NFAs for use in organic photovoltaics.

Researchers have been motivated to develop photovoltaic systems that can efficiently convert artificial light into power with the growing use of indoor electrical devices for the Internet of Things. Understanding the impact of molecular design strategies involving morphological optimization through the terminal group of the non-fullerene acceptors (NFAs) is crucial. This is critically important to enhancing the photovoltaic efficiency of organic photovoltaic devices under diverse irradiation conditions. Halogenation of terminal groups proves to be a standout approach for adjusting energy levels, refining light-harvesting capabilities, crystallinity, and bolstering the intermolecular stacking in NFAs. Herein, we have designed two simple NFAs, DICTF-4F and DICTF-4Cl , to explore the dihalogenation (F and Cl) effect on the terminal group on the optical and electrochemical properties. After combining with the BODIPY-thiophene-backboned donor polymer P(BdP-HT), the organic solar cells (OSCs) using an optimized active layer with P(BdP-HT): DICTF-4F and P(BdP-HT): DICTF-4Cl attained a power conversion efficiency (PCE) of about 8.03 and 14.16%, respectively, under 1 sun illumination. Moreover, the OSC-based P(BdP-HT): DICTF-4Cl active layer showed a PCE approaching 24% under 1000 lx indoor conditions.

Organic solar cells (OSCs) have emerged as a promising technology for renewable energy generation, and researchers are constantly exploring ways to improve their efficiency. For prediction of photovoltaic properties in OSCs, many machine learning models have been used in the past. All the models are used with fixed molecular descriptors and molecular fingerprints as input for power conversion efficiency (PCE) prediction. Recently, the graph neural network (GNN), which can model graph structures of the molecule, has received increasing attention as a method that could potentially overcome the limitations of fixed descriptors by learning the task-specific representations using graph convolutions. In this study, we have used the directed message passing neural network (D-MPNN), an emerging type of GNN for predicting PCE of organic solar cells, and the results are compared for the same train and test set with fixed descriptors and fingerprints. The excellent performance demonstrated by the D-MPNN model in this investigation highlights its potential for predicting PCE, surpassing the limitations of conventional fixed descriptors.

In recent years, non-fused non-fullerene acceptors (NFAs) have attracted increasing consideration due to several advantages, which include simple preparation, superior yield, and low cost. In the work reported here, we designed and synthesized three new NFAs with the same cyclopentadithiophenevinylene (CPDTV) trimer as the electron-donating unit and different terminal units (IC for FG10 , IC-4F for FG8 , and IC-4Cl for FG6 ). Both halogenated NFAs, i.e., FG6 and FG8 , show red-shifted absorption spectra and higher electron mobilities (more pronounced for FG6 ) in comparison with FG10 . Moreover, the dielectric constants of these materials also increased upon halogenation of the IC terminal units, thus leading to a reduction in the exciton binding energy, which is favorable for dissociation of excitons and subsequent charge transfer despite the driving force (highest occupied molecular orbital and lowest unoccupied molecular orbital offsets) being very small. The organic solar cells (OSCs) constructed using these acceptors and PBDB-T, as the donor, showed PCE values of 15.08, 12.56, and 9.04% for FG6 , FG8 , and FG10 , respectively. The energy loss for the FG6 -based device was the lowest (0.45 eV) of all the devices, and this may be attributed to it having the highest dielectric constant, which leads to a reduction in the binding energy of exciton and a small driving force for hole transfer from FG6 to PBDB-T. The results indicate that the NFA containing the CPDTV oligomer core and halogenated terminal units can efficiently spread the absorption spectrum to the NIR zone. Non-fused NFAs have a bright future in the quest to obtain efficient OSCs with low cost for marketable purposes.

Herein, simple acceptor-donor-acceptor (A-D-A)-type small molecules denoted as DICTF and DRCTF with modification in terminal units were synthesized and used as electron acceptors. With the tuning of the electron-withdrawing units in electron acceptors, their photovoltaic properties were investigated when combined with low-band-gap BODIPY-thiophene-backboned donor material, named P(BdP-HT). The P(BdP-HT):DICTF-based organic solar cells (OSCs) displayed excellent efficiency of around 11.94%, which is superior to the P(BdP-HT):DRCTF counterpart (8.78%). Although the open-circuit voltage ( V OC ) of the P(BdP-HT):DRCTF-based OSC is greater than that for the P(BdP-HT):DICTF counterpart, the rise in the short-circuit current density ( J SC ) may be attributed to the fact that the P(BdP-HT):DICTF blend displayed impressive panchromatic absorption compared to P(BdP-HT):DRCTF. The improved fill factor (FF) is responsible for the balanced transport of charges in the P(BdP-HT):DICTF-based device. Moreover, the P(BdP-HT):DRCTF- and P(BdP-HT):DICTF-based OSCs showed 17.68 and 21.84%, respectively, under indoor illumination (1000 lx). To the best of our observation, this might be the first report on BODIPY-based donors with power conversion efficiency (PCE) of 21.84% under indoor illumination conditions.

Recently, the power conversion efficiency (PCE) of organic solar cells (OSCs) has significantly progressed with a rapid increase from 10 to 19% due to state-of-the-art research on nonfullerene acceptor molecules and various device processing strategies. However, OSCs still exhibit significant open circuit voltage loss (Δ V OC ∼ 0.6 V) due to high energetic offsets and molecular disorder. In this work, we present a systematic investigation to determine the effects of energetic offset and disorder on different recombination losses in open circuit voltage ( V OC ) using 13 different photoactive layers, wherein the PCE and Δ V OC vary in the ranges of 2.21-14.74% and 0.561-1.443 V, respectively. The detailed voltage loss analysis of all these devices was carried out, and voltage losses were correlated with energetic offset and disorder. This has enabled us to identify the key features for minimizing the voltage loss like: (1) a low energy offset between the donor and acceptor molecular states is essential to attain a nonradiative voltage loss (Δ V OC, nrad ) as low as ∼200 meV and (2) Urbach energy, which is a measure of the materials' disorder and packing, should be low for the minimization of the radiative voltage loss (Δ V OC, rad ). In addition, time-resolved photoluminescence spectroscopy was employed to further understand the exciton dynamics of pristine materials and donor-acceptor blends. It was observed that the absorbers with ultralong exciton lifetime (∼1000 ps) produce higher efficiencies. The current study emphasizes the importance of simultaneously testing photovoltaic performance and active layer exciton dynamics for rational device optimization and opens new prospects for designing novel molecules with fine-tuning of energetic offset and disorder with longer exciton lifetime which is the effective strategy to boost the efficiency of OSCs to their modified Shockley-Queisser (SQ) limit by minimizing radiative and nonradiative voltage losses.

The structural flexibility of organic semiconductors offers vast a search space, and many potential candidates (donor and acceptor) for organic solar cells (OSCs) are yet to be discovered. Machine learning is extensively used for material discovery but performs poorly on extrapolation tasks with small training data sets. Active learning techniques can guide experimentalists to extrapolate and find the most promising D:A combination in a significantly small number of experiments. This study uses an active learning technique with a predictive random forest model to iteratively find the most optimal D:A combinations in the search space using various acquisition functions. Active learning results with five different acquisition functions (MM, MEI, MLI, MU, and UCB) are compared. Results reveal that acquisition functions that combine exploitation and exploration (MEI, MLI, and UCB) perform far better than purely exploiting (MM) and purely exploring (MU) acquisition functions. Interestingly, the proposed model can overcome the bottleneck of extrapolating small training data sets and find most promising D:A combinations in relatively fewer experiments.

We report the design of novel medium bandgap nonfullerene small molecule acceptor NFSMA SPS-TDPP-2CNRh with A 2 -π-A 1 -π-A 2 architecture, with the molecular engineering of this material comprising a strong electron-accepting backbone unit DPP (A 1 ) as the acceptor, which is attached to the dicyanomethylene-3-hexylrhodanine (A 2 ) acceptor via a furan (π-spacer) linker. We systematically studied its structural and optoelectronic properties. The incorporation of dicyanomethylene-3-hexylrhodanine and furan enhance the light absorption and electrochemical properties by extending π-conjugation and is anticipated to improve V OC by decreasing the LUMO level. The long alkyl chain units were responsible for the better solubility and aggregation of the resultant molecule. Binary BHJ-OSCs constructed with polymer P as the donor and SPS-TDPP-2CNRh as the acceptor resulted in a PCE of 11.49% with improved V OC = 0.98 V, J SC = 18.32 mA/cm 2 , and FF = 0.64 for P: SPS-TDPP-2CNRh organic solar cells. A ternary solar cell device was also made using Y18-DMO and SPS-TDPP-2CNRh as acceptors having complementary absorption profiles and polymer P as the donor, resulting in a PCE of 15.50% with improved J SC = 23.08 mA/cm 2 , FF = 0.73, and V OC = 0.92 V for the P: SPS-TDPP-2CNRh :Y18-DMO solar cell. The ternary OSCs with SPS-TDPP-2CNRh as the host acceptor in the P:Y18-DMO binary film were shown to have improved PCE values, which is mainly attributed to the effective photoinduced charge transfer through multiple networks and the use of excitons from SPS-TDPP-2CNRh and Y18-DMO. Moreover, in the ternary BHJ active layers, the superior stable charge transport that was observed compared to the binary counterparts may also lead to an increase in the fill factor. These results demonstrate that combining medium bandgap and narrow bandgap NFSMAs with a wide bandgap polymer donor is a successful route to increasing the overall PCE of the OSCs via the ternary BHJ concept.

The widespread use of nonfullerene-based electron-accepting materials has triggered a rapid increase in the performance of organic photovoltaic devices. However, the number of efficient acceptor compounds available is rather limited, which hinders the discovery of new, high-performing donor:acceptor combinations. Here, we present a new, efficient electron-accepting compound based on a hitherto unexplored family of well-known molecules: gold porphyrins. The electronic properties of our electron-accepting gold porphyrin, named VC10 , were studied by UV-Vis spectroscopy and by cyclic voltammetry (CV) , revealing two intense optical absorption bands at 500-600 and 700-920 nm and an optical bandgap of 1.39 eV. Blending VC10 with PTB7-Th, a donor polymer, which gives rise to an absorption band at 550-780 nm complementary to that of VC10 , enables the fabrication of organic solar cells (OSCs) featuring a power conversion efficiency of 9.24% and an energy loss of 0.52 eV. Hence, this work establishes a new approach in the search for efficient acceptor molecules for solar cells and new guidelines for future photovoltaic material design.

Organic solar cells (OSCs) that contain small molecules only were prepared with FG1 as the donor, a narrow band gap non-fullerene acceptor MPU4 , and a wide band gap PC 71 BM. The OSCs based on optimized FG1 : MPU4 (1:1.2) and FG1 :PC 71 BM (1:1.5) active layers, respectively, gave power conversion efficiencies (PCEs) of 11.18% with a short circuit current ( J SC ) of 19.54 mA/cm 2 , open circuit voltage ( V OC ) of 0.97 V, and fill factor (FF) of 0.59, and 6.62% with a J SC of 12.50 mA/cm 2 , V OC of 0.84 V, and FF of 0.63%, respectively. A PCE of 13.26% was obtained from the optimized ternary FG1 :PC 71 BM: MPU4 (1:0.3:0.9) OSCs and this arises because of the boost in a J SC of 21.91 mA/cm 2 and FF of 0.68. The V OC of the ternary OSCs (0.89 V) lies between those for the OSCs based on FG1 : MPU4 and FG1 :PC 71 BM, which indicates the formation of an alloy of the two acceptors. The increase in J SC and FF in the ternary OSCs may result from the efficient energy transfer from PC 71 BM to MPU4 as well as more charge-transfer donor/acceptor interfaces, enhanced charge carrier mobilities resulting in better adjusted charge transport, and lower bimolecular and trap-assisted recombination. The appropriate phase separation, increased crystallinity, and reduced π-π stacking distance in the ternary active layer are consistent with the enhancement in the FF for OSCs based on a ternary active layer. The results of this work suggest the merging of the fullerene acceptor into the non-fullerene acceptor to form a fullerene/non-fullerene acceptor alloy, and this may be a viable approach to obtain high-performance OSCs.

In recent years, tremendous growth has been seen for solution-processed bulk heterojunction solar cells (BHJSCs) using fullerene-free molecular acceptors. Herein, we report the synthesis, characterization of a coumarin-based organic semiconducting molecule C1, and its use in BHJSCs as an electron donor. The compound exhibited an absorption band at 472 nm in chloroform solution with an optical energy gap of 2.33 eV. The HOMO/LUMO energy levels of C1 were found to be ideal for use in BHJSCs. Using PC 71 BM and a fullerene-free acceptor IT-4F, the device generated power conversion efficiencies (PCEs) of 6.17 and 8.31%, respectively. The success of the device based on a fullerene-free acceptor is a result of complementary absorption and well-matched energy levels, resulting in an improved photocurrent and photovoltage in the device. Moreover, ternary solar cells fabricated by employing C1 (20 wt%) as a secondary donor, i.e., an active layer of C1:PM6:IT-4F (0.2:0.8:1.5), generated an enhanced PCE of 11.56% with a high short-circuit current density ( J SC ) of 16.42 mA cm -2 , an open-circuit voltage ( V OC ) of 1.02 V, and a fill factor of 0.69 under 1 sun spectral illumination, which is ∼8% higher than that for the PM6:IT-4F-based binary device (PCE = 10.70%). The increased PCE for the ternary organic solar cell may be related to the efficient exciton generation and its dissociation via Forster resonance energy transfer, which guarantees enough time for an exciton to diffuse toward the D/A interfaces.

A new low-molecular-weight porphyrin-based polymer, PPPyDPP , with pyridine-capped diketopyrrolopyrrole (DPP) has been synthesized, and its optical and electrochemical properties were investigated. The polymer is prepared with a low content of homocoupling units and gives a widely spread absorption from 400 to 900 nm with a narrow optical band gap of 1.46 eV. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels are respectively located at -5.27 and -3.78 eV, respectively. PPPyDPP was used as the electron donor, whereas [6,6]-phenyl-C 71 -butyric acid methyl ester (PC 71 BM) and bis(rhodanine)indolo-[3,2- b ]-carbazole ( ICzRd 2 ), a nonfullerene small molecule, were used as acceptors for the fabrication of solution-processed bulk heterojunction polymer solar cells. Overall power conversion efficiencies (PCEs) of 7.31 and 9.16% (record high for porphyrin-containing polymers) were obtained for PC 71 BM and ICzRd 2 , respectively. A high V oc of 1.01 V and a low E loss of 0.45 eV may explain this new record.

Two D-A-D small molecules with a DPP acceptor core and Zn-porphyrin donor with different electron-donating substituents, namely, 2,6-bis(dodecyloxy)phenyl and 5-hexylthieno[3,2- b]thiophen-2-yl at mesopositions, VC4 and VC5, were synthesized, and their optical and electrochemical properties were investigated. The results reveal that both molecules are suitable as donors for organic solar cells (OSCs) in which PC 71 BM is employed as the acceptor. Overall power conversion efficiencies of 8.05% ( J sc = 13.83 mA/cm 2 , V oc = 0.91 V, and FF = 0.64) and 8.89% ( J sc = 16.98 mA/cm 2 , V oc = 0.79 V, and FF = 0.663) were obtained, respectively. The high V oc value for the VC4-based OSC correlates with the deeper HOMO, whereas the high J sc value for VC5 may be attributed to the extended absorption spectrum toward the longer wavelength region. Moreover, the relatively high FF value for VC5-based OSCs as compared to the VC4 counterparts may be related to the more balanced charge transport in the active layer, reduced charge recombination, and efficient charge collection. The energy loss for VC5 is smaller (0.52 eV) than that for VC4 (0.56 eV).

Dyes based on charge-transfer (CT) characteristics are attractive candidates for organic photovoltaics due to their intense and broad absorption window. In these molecular frameworks, electron-rich donors and electron-deficient acceptors are covalently linked to achieve an effective CT process. Corrole, a tetrapyrrolic congener of porphyrin, is an excellent example of an electron-rich molecule with a large molar extinction coefficient. BODIPY, on the other hand, is a well-known electron-deficient bypyrrolic boron difluoride complex with intense absorption complementary to the corrole. A combination of these two structural motifs should result in a dyad having a wide absorption window, which will be suitable for organic photovoltaics. Herein, a corrole derivative has been envisaged as an efficient donor for solution-processed bulk heterojunction solar cells with PC 71 BM as an acceptor for the first time. The current molecule exhibits broad absorption in the visible range in solution as well as in thin films, with a high molar extinction coefficient and a low band gap of 1.79 eV. Frontier molecular orbital energy levels were found to be complementary to those of the well-known acceptor PC 71 BM. The optimized devices based on Cor-BODIPY:PC 71 BM showed a high power conversion efficiency (PCE) of 6.6% with J sc = 11.46 mA/cm 2 , V oc = 0.90 V, and FF = 0.61. A remarkable value of incident photon-to-current conversion efficiency (IPCE) of 61% has also been observed.

Low bandgap A-π-D copolymer, P(BdP-DEHT), consisting of alternating BOronDIPYrromethene (BODIPY) and thiophene units bridged by ethynyl linkers, and its porphyrin-enriched analogue, P(BdP/Por-DEHT), were prepared, and their optical and electrochemical properties were studied. P(BdP-DEHT) exhibits strong absorption in the 500-800 nm range with an optical bandgap of 1.74 eV. On the basis of cyclic voltammetry, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels are evaluated to be -5.40 and -3.66 eV, respectively. After the anchoring of zinc(II) porphyrin on the BODIPY unit, P(BdP/Por-DEHT) displays broadened absorption, thanks to porphyrins, and the optical bandgap decreases to 1.59 eV because of extension of BODIPY conjugation. The resulting estimated HOMO and LUMO energy levels, respectively, move to -5.32 and -3.73 eV. After optimization of the P(BdP-DEHT) or P(BdP/Por-DEHT) to PC 71 BM weight ratio to 1:2 in dichlorobenzene solution, the bulk heterojunction polymer solar cells show overall power conversion efficiencies (PCEs) of 3.03 and 3.86%, respectively. After solvent vapor annealing (SVA) treatment in CH 2 Cl 2 for 40 s, the PCEs increased to 7.40% [V oc of 0.95 V, J sc of 12.77 mA/cm 2 , and fill factor (FF) of 0.61 with energy loss of 0.79 eV] and 8.79% (V oc of 0.92 V, J sc of 14.48 mA/cm 2 , and FF of 0.66 with energy loss of 0.67 eV). The increase in the PCE for P(BdP/Por-DEHT)-based devices is mainly attributed to the enhancement in J sc and FF, which may be related to the broader absorption spectra, lower band gap, and better charge transport of P(BdP/Por-DEHT) compared to P(BdP-DEHT). This could also be related to the optimized nanoscale morphology of the active layer for both efficient exciton dissociation and charge transport toward the electrodes and a balanced charge transport in the device, induced by the SVA treatment of the active layer.

Two novel regular terpolymers that are of D-A1-D-A2 type and contain benzothiadiazole and 2,5-dibromo-8-dodecanoylbenzo[1,2-b:3,4-b':5,6-d″]trithiophene (P1) or 2,8-dibromo-5-dodecanoylbenzene[1,2-b:3,4-b':5,6-d″]trithiophene (P2) acceptor units with the same thiophene donor were synthesized through Stille coupling, and their optical and electrochemical properties were investigated. The highest occupied molecular orbital (HOMO) and lowest unoccupied (LUMO) molecular orbital energy levels of these terpolymers indicate that there is sufficient LUMO offset with PCBM for efficient exciton dissociation, and their deeper HOMO levels ensure the high open-circuit voltage for the resultant bulk heterojunction solar cells. Measurements on the solar cell devices also confirm that compared to those based on P2 the devices based on P1 possess a higher short-circuit photocurrent (J sc ) as well as a higher fill factor (FF), which is attributed to the lower bandgap and higher hole mobility for P1, whereas the V oc is higher for the devices that are based on P2, which may be a result of P2 having a lower HOMO energy level than P1. The optimized polymer solar cells fabricated using P1:PC 71 BM (DIO/CF) and P2:PC 71 BM (CF/DIO) for the active layers showed a PCE of 7.19% and 6.34%, respectively. Atomic force microscopy (AFM) images of P1:PC 71 BM blend films show that they exhibit more suitable morphology with favorable interpenetrating networks, which favors high J sc and FF. Moreover, P1 exhibits a more crystalline nature than P2 that also favors the charge transport. This may be a result of better molecular packing, more distinct phase separation of the blended films, as well as a reduction of charge recombination.

A D1-A-A'-π-D2 type (D = donor; A = acceptor) unsymmetrical small molecule denoted as BTD3 containing different end group donor moieties has been designed and synthesized for use as a donor in the solution processable bulk heterojunction (BHJ) solar cell. The BTD3 exhibits a low HOMO-LUMO gap of 1.68 eV and deeper HOMO energy level (-5.5 eV). Its LUMO energy level (-3.65 eV) is compatible with the LUMO level of PC71BM to facilitate the electron transfer from BTD3 to PC71BM in the BHJ solar cell. The solution processed BHJ solar cell with optimized BTD3:PC71BM active layer processed with THF solvent exhibited a PCE of 3.15% with Jsc = 7.45 mA/cm(2), Voc = 0.94 V, and FF = 0.45. Moreover, the device with optimized concentration of 3 vol. % 1-chloronaphthalene (CN) additive, i.e., CN/THF, showed significant enhancement in PCE up to 4.61% (Jsc = 9.48 mA/cm(2), Voc = 0.90 V, and FF = 0.54). The improvement in the PCE has been attributed to the appropriate nanoscale phase separation morphology, balance charge transport, and enhancement in the light harvesting ability of the active layer.

We have designed and synthesized a new thiocyante-free ruthenium complex containing 2,6-bis(1-methylbenzimidazol-2-yl)pyridine, coded as SPS-G3, and it has been used as an efficient photosensitizer for dye-sensitized solar cells (DSSCs). Upon sensitization of SPS-G3 on nanocrystalline TiO2 film, the DSSC test cell yielded a large short-circuit photocurrent (16.15 mA cm(-2)), an open circuit voltage of 0.52 V, and a fill factor (FF) of 0.72, resulting in an overall power conversion efficiency (PCE) of 6.04% under simulated AM 1.5 solar irradiation (100 mW cm(-2)). DSSCs were prepared by adding various concentrations of multiwall carbon nanotubes (MWCNTs) (up to 0.5 wt %) into the TiO2 nanoparticles. Optimization of MWCNT concentration (0.3 wt %) lead to PCE values as high as 7.76%, while the test cells employing pure TiO2 photoanode obtained an efficiency of 6.04%. The results indicate that the PCE of MWCNTs/TiO2 composite DSSCs are dependent on the quantity of MWCNTs loading on the photoanodes. A small amount (0.3 wt %) clearly enhances the PCE of DSSC, while the excessive MWCNT loading lowers the photovoltaic performance of the DSSC. The increase in the PCE has been attributed to the decrease in charge-transport resistance, charge-transport time, and electron lifetime, which are estimated from electrochemical impedance spectra.

The morphology of the photoactive layer used in the bulk heterojunction photovoltaic devices is crucial for efficient charge generation and their collection at the electrodes. We investigated the solvent vapor annealing and thermal annealing effect of an alternating phenylenevinylene copolymer P:PCBM blend on its morphology and optical properties. The UV-visible absorption spectroscopy shows that both solvent and thermal annealing can result in self-assembling of copolymer P to form an ordered structure, leading to enhanced absorption in the red region and hole transport enhancement. By combining the solvent and thermal annealing of the devices, the power conversion efficiency is improved. This feature was attributed to the fact that the PCBM molecules begin to diffuse into aggregates and together with the ordered copolymer P phase form bicontinuous pathways in the entire layer for efficient charge separation and transport. Furthermore, the measured photocurrent also suggests that the space charges no longer limit the values of the short circuit current (J(sc)) and fill factor (FF) for solvent-treated and thermally annealed devices. These results indicate that the higher J(sc) and PCE for the solvent-treated and thermally annealed devices can be attributed to the phase separation of active layers, which leads to a balanced carrier mobility. The overall PCE of the device based on the combination of solvent annealing and thermal annealing is about 3.7 %.

Two novel soluble compounds T and A that contain a central dihexyloxy-p-phenylenevinylene unit, intermediate moieties of thiophene or anthracene, respectively, and terminal cyano-vinylene nitrophenyls were synthesized and characterized. They showed moderate thermal stability and relatively low glass transition temperatures. These compounds displayed similar optical properties. Their absorption was broad and extended up to about 750 nm with the longer-wavelength maximum around 640 nm and an optical band gap of approximately 1.70 eV. From the current-voltage characteristics of the devices using both compounds T and A, it was concluded that both compounds behave as p-type organic semiconductors with hole mobility on the order of 10(-5) cm(2)/(V s). The power conversion efficiency (PCE) of the devices based on these compounds was 0.019% and 0.013% for compounds A and T, respectively. When compounds A and T were blended with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), the PCE dramatically increased up to 1.66% and 1.36% for devices with A:PCBM and T:PCBM, respectively. The efficiencies of the devices were further enhanced upon thermal annealing up to 2.49% and 2.33% for devices based on A:PCBM and T:PCBM, respectively.

The effect of the incorporation of a low-band-gap small-molecule BTD-TNP on the photovoltaic properties of vinylene copolymer P:PCBM bulk heterojunction solar cells has been investigated. The introduction of this small molecule increases both the short-circuit photocurrent and the overall power conversion efficiency of the photovoltaic device. The incident photon-to-current efficiency (IPCE) of the device based on P:PCBM:BTD-TNP shows two distinct bands, which correspond to the absorption bands of P:PCBM and BTD-TNP. Furthermore, it was found that the IPCE of the device has also been enhanced even at the wavelengths corresponding to the absorption band of P:PCBM, when the thermally annealed blend was used in the device. This indicates that the excitons that are generated in copolymer P are dissociated into charge carriers more effectively in the presence of the BTD-TNP small molecule at the copolymer P:PCBM interface by energy transfer from P to the small molecule. Therefore, we conclude that the BTD-TNP small molecule acts as light-harvesting photosensitizer and also provides a path for the generated exciton in copolymer P toward the P:PCBM interface for efficient charge separation. The overall power conversion efficiency for the P:PCBM:BTD-TNP photovoltaic device is about 1.27%, which has been further enhanced up to 2.6%, when a thermally annealed blend layer is used.