Improving Thermal and Photostability of Polymer Solar Cells by Robust Interface Engineering.

As the power conversion efficiency (PCE) of organic photovoltaics (OPVs) approaches 19%, increasing research attention is being paid to enhancing the device's long-term stability. In this study, a robust interface engineering of graphene oxide nanosheets (GNS) is expounded on improving the thermal and photostability of non-fullerene bulk-heterojunction (NFA BHJ) OPVs to a practical level. Three distinct GNSs (GNS, N-doped GNS (N-GNS), and N,S-doped GNS (NS-GNS)) synthesized through a pyrolysis method are applied as the ZnO modifier in inverted OPVs. The results reveal that the GNS modification introduces passivation and dipole effects to enable better energy-level alignment and to facilitate charge transfer across the ZnO/BHJ interface. Besides, it optimizes the BHJ morphology of the photoactive layer, and the N,S doping of GNS further enhances the interaction with the photoactive components to enable a more idea BHJ morphology. Consequently, the NS-GNS device delivers enhanced performance from 14.5% (control device) to 16.5%. Moreover, the thermally/chemically stable GNS is shown to stabilize the morphology of the ZnO electron transport layer (ETL) and to endow the BHJ morphology of the photoactive layer grown atop with a more stable thermodynamic property. This largely reduces the microstructure changes and the associated charge recombination in the BHJ layer under constant thermal/light stresses. Finally, the NS-GNS device is demonstrated to exhibit an impressive T80 lifetime (time at which PCE of the device decays to 80% of the initial PCE) of 2712 h under a constant thermal condition at 65 °C in a glovebox and an outstanding photostability with a T80 lifetime of 2000 h under constant AM1.5G 1-sun illumination in an N2 -controlled environment.

Amino-Acid-Induced Preferential Orientation of Perovskite Crystals for Enhancing Interfacial Charge Transfer and Photovoltaic Performance.

Interfacial engineering of perovskite solar cells (PSCs) is attracting intensive attention owing to the charge transfer efficiency at an interface, which greatly influences the photovoltaic performance. This study demonstrates the modification of a TiO2 electron-transporting layer with various amino acids, which affects charge transfer efficiency at the TiO2 /CH3 NH3 PbI3 interface in PSC, among which the l-alanine-modified cell exhibits the best power conversion efficiency with 30% enhancement. This study also shows that the (110) plane of perovskite crystallites tends to align in the direction perpendicular to the amino-acid-modified TiO2 as observed in grazing-incidence wide-angle X-ray scattering of thin CH3 NH3 PbI3 perovskite film. Electrochemical impedance spectroscopy reveals less charge transfer resistance at the TiO2 /CH3 NH3 PbI3 interface after being modified with amino acids, which is also supported by the lower intensity of steady-state photoluminescence (PL) and the reduced PL lifetime of perovskite. In addition, based on the PL measurement with excitation from different side of the sample, amino-acid-modified samples show less surface trapping effect compared to the sample without modification, which may also facilitate charge transfer efficiency at the interface. The results suggest that appropriate orientation of perovskite crystallites at the interface and trap-passivation are the niche for better photovoltaic performance.

Impact of constitution of the terthiophene-vinylene conjugated side chain on the optical and photovoltaic properties of two-dimensional polythiophenes.

The effects of the spatial arrangement of the conjugated side chains of two-dimensional polymers on their optical, electrochemical, molecular-packing, and photovoltaic characteristics were investigated. Accordingly, novel polythiophenes with horizontally (PBTTTV-h) and vertically (PBTTTV-v) grafted terthiophene­vinylene (TTV) conjugated side chains were synthesized that display two and one UV-vis peaks, respectively; the difference is due to the different constitutions of the conjugated side-chains. Because the spatial arrangement affects the molecular self-assembly, PBTTTV-h shows stronger crystallinity than PBTTTV-v, which enhances the charge mobility in devices. Moreover, PBTTTV-h has a lower HOMO energy level (−5.49 eV) than PBTTTV-v (−5.40 eV). Bulk heterojunction solar cells fabricated from PBTTTV-h/PC71BM and PBTTTV-v/PC71BM exhibit power conversion efficiencies of 4.75% and 4.00%, respectively, and Voc values of 800 and 730 mV, respectively, under AM1.5G illumination (100 mW cm(−2)). Thus, the architecture of the TTV conjugated side chains affects the optical, electrochemical, and photovoltaic properties; this study provides more ideas for improving 2-D conjugated polymers for semiconductor devices.

Quasi-2D Perovskite Crystalline Layers for Printable Direct Conversion X-Ray Imaging.

Polycrystalline perovskite film-based X-ray detector is an appealing technology for assembling large scale imager by printing methods. However, thick crystalline layer without trap and solvent residual is challenging to fabricate. Here, the authors report a solution method to produce high quality quasi-2D perovskite crystalline layers and detectors that are suitable for X-ray imaging. By introducing n-butylamine iodide into methylammonium lead iodide precursor and coating at elevated temperatures, compact and crystalline layers with exceptional uniformity are obtained on both rigid and flexible substrates. Photodiodes built with the quasi-2D layers exhibit a low dark current and stable operation under constant electrical field over 96 h in dark, and over 15 h under X-ray irradiation. The detector responds sensitively under X-ray, delivering a high sensitivity of 1214 µC Gyair -1  cm-2 and a sensitivity gain is observed when operated under higher fields. Finally, high resolution images are demonstrated using a single pixel device that can resolve 80-200 µm features. This work paves the path for printable direct conversion X-ray imager development.

Cesium Lead Halide Perovskite Nanocrystals Assembled in Metal-Organic Frameworks for Stable Blue Light Emitting Diodes.

All inorganic cesium lead trihalide nanocrystals are promising light emitters for bright light emitting diodes (LEDs). Here, CsPb(BrCl)1.5 nanocrystals in metal-organic frameworks (MOF) thin films are demonstrated to achieve bright and stable blue LEDs. The lead metal nodes in the MOF thin film react with Cs-halide salts, resulting in 10-20 nm nanocrystals. This is revealed by X-ray scattering and transmission electron microscopy. Employing the CsPbX3 -MOF thin films as emission layers, bright deep blue and sky-blue LEDs are demonstrated that emit at 452 and 476 nm respectively. The maximum external quantum efficiencies of these devices are 0.72% for deep blue LEDs and 5.6% for sky blue LEDs. More importantly, the device can maintain 50% of its original electroluminescence (T50 ) for 2.23 h when driving at 4.2 V. Detailed optical spectroscopy and time-of-flight secondary ion mass spectroscopy suggest that the ion migration can be suppressed that maintains the emission brightness and spectra. The study provides a new route for fabricating stable blue light emitting diodes with all-inorganic perovskite nanocrystals.

Chromatic Fulleropyrrolidine as Long-Lived Metal-Free Catalyst for CO2 Photoreduction Reaction.

Conversion of CO2 into carbonaceous fuels with the aid of solar energy has been an important research subject for decades. Owing to their excellent electron-accepting capacities, fullerene derivatives have been extensively used as n-type semiconductors. This work reports that the fulleropyrrolidine functionalized with 4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole, abbreviated as DTBT-C60 , could efficiently catalyze the photoreduction of CO2 to CO. The novel C60 -chromophore dyad structure facilitated better usage of solar light and effective dissociation of excitons. Consequently, the DTBT-C60 exhibited a promising CO yield of 144 µmol gcat -1 under AM1.5G solar illumination for 24 h. Moreover, the isotope experiments demonstrated that water molecules could function as an electron source to reactivate DTBT-C60 . Impressively, DTBT-C60 exhibited an extremely durable catalytic activity for more than one week, facilitating the practical application of photochemical CO2 reaction.

Naphthalene Diimide-Based Donor-Acceptor-Donor Small Molecules as Metal-Free Organocatalysts for Photocatalytic CO2 Reaction.

The application of organic small molecules as metal-free photocatalysts for light-driven photoreduction of carbon dioxide (CO2) has seldom been explored. This work developed four naphthalene diimide (NDI)-derived donor-acceptor-donor small molecules with different numbers of thiophene units, namely, NDI-2T, NDI-TT, NDI-4T, and NDI-6T, as metal-free photocatalysts to catalyze the reduction of CO2 under irradiation with an air mass 1.5G solar simulator at one-sun intensity. The structure-property relationship was investigated by exploring the effects of the electron-donating ability of the donor units on the optical properties, redox potential, electron-hole distribution, and exciton lifetime. NDI-6T exhibited the most red-shifted absorption, longest exciton lifetime, and strongest electron-hole separation. However, the large upshift in oxidation potential because of the elevated electron-donating ability of the hexathiophene unit significantly reduced the driving force for catalyst regeneration, leading to poor catalytic performance. Alternatively, NDI-4T possessed proper redox potentials, reduced charge-transfer resistance, and excellent photocurrent intensity; therefore, it effectively converted CO2 to a single product of CO in the presence of water as an electron donor without a sacrificial reagent or cocatalyst with a product yield of 168.6 µmol gcat-1 24 h-1, which was considerably higher than those of NDI-TT (111.9 µmol gcat-1 24 h-1), NDI-2T (88.4 µmol gcat-1 24 h-1), and NDI-6T (40.5 µmol gcat-1 24 h-1). This study provides a practical guideline for the molecular design of conjugated organic molecules as promising photocatalysts for CO2 photoreduction.

Correlating interface heterostructure, charge recombination, and device efficiency of poly(3-hexyl thiophene)/TiO2 nanorod solar cell.

The charge recombination rate in poly(3-hexyl thiophene)/TiO(2) nanorod solar cells is demonstrated to correlate to the morphology of the bulk heterojunction (BHJ) and the interfacial properties between poly(3-hexyl thiophene) (P3HT) and TiO(2). The recombination resistance is obtained in P3HT/TiO(2) nanorod devices by impedance spectroscopy. Surface morphology and phase separation of the bulk heterojunction are characterized by atomic force microscopy (AFM). The surface charge of bulk heterojunction is investigated by Kelvin probe force microscopy (KPFM). Lower charge recombination rate and lifetime have been observed for the charge carriers in appropriate heterostructures of hybrid P3HT/TiO(2) nanorod processed via high boiling point solvent and made of high molecular weight P3HT. Additionally, through surface modification on TiO(2) nan,orod, decreased recombination rate and longer charge carrier lifetime are obtained owing to creation of a barrier between the donor phases (P3HT) and the acceptor phases (TiO(2)). The effect of the film morphology of hybrid and interfacial properties on charge carrier recombination finally leads to different outcome of photovoltaic I-V characteristics. The BHJ fabricated from dye-modified TiO(2) blended with P3HT exhibits 2.6 times increase in power conversion efficiency due to the decrease of recombination rate by almost 2 orders of magnitude as compared with the BHJ made with unmodified TiO(2). In addition, the interface heterostructure, charge lifetime, and device efficiency of P3HT/TiO(2) nanorod solar cells are correlated.

Use of polyethylenimine-modified magnetic nanoparticles for highly specific enrichment of phosphopeptides for mass spectrometric analysis.

Phosphopeptides have been isolated and concentrated by use of polyethyleneimine (PEI)-modified magnetic nanoparticles as an extremely specific affinity probe. The particles specifically captured phosphopeptides from a tryptic digest of a protein mixture that contained 0.07% (mole/mole) phosphoproteins, which is the highest specificity obtained to date. The time required for enrichment of the phosphopeptides was 1 min only. PEI-modified magnetic nanoparticles carry positive charges over a wide range of pH-between 3 and 11. This feature means the particles are effectively dispersed in solution during phosphopeptide capture. Mass spectrometric analysis revealed the very high efficiency of enrichment of phosphopeptides that contain both single and multiply-phosphorylated sites. The detection limit in the analysis of phosphopeptides obtained from both bovine α-casein and ß-casein by matrix-assisted laser desorption/ionization mass spectrometry was 5 fmol. This approach was also used to enrich the phosphopeptides in a protein digest obtained from non-fat milk.

Exohedral Functionalization of Fullerene by Substituents Controlling of Molecular Organization for Spontaneous C60 Dimerization in Liquid Crystal Solutions and in a Bulk Controlled by a Potential.

A study was carried out on the possibility of orderly and spontaneous dimerization at room temperature of C60 cages in fullerene liquid crystal fullerene dyads (R-C60). For this purpose, dyads with a structural elements feature supporting π-stacking and Van der Waals interactions were tested, due to the presence of terthiophene donors linked through an α-position or dodecyloxy chains. In addition, this possibility was also tested and compared to dyads with shorter substituents and the pristine C60. Research has shown that only in dyads with the features of liquid crystals, π-dimerization of C60 units occurs, which was verified by electrochemical and spectroelectrochemical (ESR) measurements. Cyclic voltammetry and differential voltammetry studies reveal π-dimerization in liquid crystal dyad solution even without the possibility of previous polymerization (cathodic or anodic) under conditions in the absence of irradiation and without the availability of reaction initiators, and even with the use of preliminary homogenization. These dyads undergo six sequential, one-electron reductions of π-dimer (R-C60···C60-R), where two electrons are added successively to each of the two fullerene cages and first form two radical anion system (R-C60)•-(R-C60)•- without pairing with the characteristics of two doublets. Similarly, the second reductions of π-dimer occur at potentials that are close to the reduction potential for the conversion to a system of two triplet dianions (R-C60)2-(R-C60)2-. Electron paramagnetic resonance spectra indicate a significant interaction between C60 cages. Interestingly, the strength of intermolecular bonds is so significant that it can overcome Coulombic repulsion, even with such highly charged particles as dianions and trianions. Such behavior has been revealed and studied so far only in covalently bonded C60 dimers.

Facile Fabrication of Self-Assembly Functionalized Polythiophene Hole Transporting Layer for High Performance Perovskite Solar Cells.

Crystallinity and crystal orientation have a predominant impact on a materials' semiconducting properties, thus it is essential to manipulate the microstructure arrangements for desired semiconducting device performance. Here, ultra-uniform hole-transporting material (HTM) by self-assembling COOH-functionalized P3HT (P3HT-COOH) is fabricated, on which near single crystal quality perovskite thin film can be grown. In particular, the self-assembly approach facilitates the P3HT-COOH molecules to form an ordered and homogeneous monolayer on top of the indium tin oxide (ITO) electrode facilitate the perovskite crystalline film growth with high quality and preferred orientations. After detailed spectroscopy and device characterizations, it is found that the carboxylic acid anchoring groups can down-shift the work function and passivate the ITO surface, retarding the interface carrier recombination. As a result, the device made with the self-assembled HTM show high open-circuit voltage over 1.10 V and extend the lifetime over 4,300 h when storing at 30% relative humidity. Moreover, the cell works efficiently under much reduced light power, making it useful as power source under dim-light conditions. The demonstration suggests a new facile way of fabricating monolayer HTM for high efficiency perovskite devices, as well as the interconnecting layer needed for tandem cell.

C60(OH)12 and Its Nanocomposite for High-Performance Lithium Storage.

Organic carbon materials, such as graphene and nanotubes, with a high specific capacity show promise in improving the energy density for lithium ion batteries (LiBs). Here, we report on the synthesis and characterization of C60(OH)12 and the C60(OH)12/graphene oxide (GO) composite and demonstrate their use as anode materials in LiBs. We find that the C60(OH)12/GO composite forms due to the chemical reactions between the carboxyl and epoxy groups of GO and the hydroxyl of C60(OH)12 nanoparticles and that C60(OH)12 uniformly grows on the surface of GO nanosheets. Using a suite of spectroscopy probes, we unequivocally show the mixing between C60(OH)12 and GO at the molecular level, which leads to superior battery performances. This composite has a reversible capacity of 1596 mAh g-1 at 0.2 A g-1, higher than the capacities of C60(OH)12 and GO. This composite has a superior cycling stability and excellent rate performance, making it a promising organic anode material for high-performance LiBs.

Mechanistic Insights into the Effect of Polymer Regioregularity on the Thermal Stability of Polymer Solar Cells.

Thermal stability is a bottleneck toward commercialization of polymer solar cells (PSCs). The effect of PCBM aggregation on a multilength scale on the bulk-heterojunction (BHJ) structure, performance, and thermal stability of PSCs is studied here by grazing-incidence small- and wide-angle X-ray scattering. The evolution of hierarchical BHJ structures of a blend film tuned by regioregularity of polymers from the as-cast state to the thermally unstable state is systematically investigated. The thermal stability of PSCs with high polymer regioregularity values can be improved because of the good mutual interaction between polymer crystallites and fullerene aggregates. The insights obtained from this study provide an approach to manipulate the film structure on a multilength scale and to enhance the thermal stability of P3HT-based PSCs.

Effect of Fullerene Passivation on the Charging and Discharging Behavior of Perovskite Solar Cells: Reduction of Bound Charges and Ion Accumulation.

Ion accumulation of organometal halide perovskites (OHPs) induced by electrode polarization of perovskite solar cells (PSCs) under illumination has been intensely studied and associated with a widely observed current-voltage hysteresis behavior. This work is dedicated to the investigation of the behavior of charged species at the compact TiO2/OHP interface with respect to electrode polarization in PSC devices. By providing a comprehensive discussion of open-circuit voltage ( VOC) buildup and VOC decay under illumination and in the dark for the PSCs modified with [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) at the TiO2/OHP interface and their corresponding electrochemical impedance spectroscopies (EISs), a justified mechanism is proposed attempting to elucidate the dynamics of interfacial species with respect to the time and frequency domains. Our results demonstrate that the retarded VOC buildup and decay observed in PSC devices are related to the formation of bound charges in TiO2, which is essential to neutralize the oppositely charged ions accumulating at the OHP side. Besides, inserting a thicker PCBM at the TiO2/OHP interface as a passivation layer can alleviate the electrode polarization more efficiently as verified by the low dielectric constant measured from EIS. Moreover, photoluminescence measurements indicate that PCBM at the TiO2/OHP interface is capable of passivating a trap state and improving charge transfer. However, with respect to the time scale investigated in this work, the reduction of the hysteresis behavior on a millisecond scale is more likely due to less bound charge formation at the interface rather than shallow trap-state passivation by PCBM. After all, this work comprehensively demonstrates the interfacial properties of PSCs associated with PCBM passivation and helps to further understand its impact on charging/discharging as well as device performance.

Novel Two-Dimensional Conjugated Polymer Containing Fluorinated Bithiophene as Donor and Benzoselenodiazole as Acceptor Units with Vinyl-Terthiophene Pendants for Polymer Photovoltaic Cells.

Novel two-dimensional conjugated copolymer, abbreviated as PDTBSeVTT-2TF, containing electron-deficient 4,7-di(thiophen-2-yl)benzo[c][1,2,5]selenodiazole (DTBSe) unit, conjugated vinyl-terthiophene (VTT) side chain and 3,3'-difluoro-2,2'-bithiophene (2TF) was designed and synthesized using microwave-assisted Stille cross-coupling polymerization. UV⁻visible absorption and cyclic voltammetry studies revealed that this copolymer possesses a strong and broad absorption in the range of 300⁻800 nm and a narrow optical bandgap (Eg) of 1.57 eV with low-lying HOMO and LUMO energy levels. Further, the bulk heterojunction polymer solar cells (PSCs) were fabricated using PDTBSeVTT-2TF as donor and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) as acceptor with an inverted device structure of ITO/ZnO/PDTBSeVTT-2TF:PC71BM/V2O5/Ag. The processing temperature of blend solution for preparing PDTBSeVTT-2TF:PC71BM active layer showed obvious impact on the photovoltaic performance of solar devices. The cell fabricated from the blend solution at 65 °C exhibited enhanced power conversion efficiencies (PCE) of 5.11% with a Jsc of 10.99 mA/cm-2 compared with the one at 50 °C, which had a PCE of 4.69% with a Jsc of 10.10 mA/cm-2. This enhancement is due to the dissolution of PDTBSeVTT-2TF clusters into single molecules and small aggregates, improving the miscibility between the polymer and PC71BM and thus increasing the donor/acceptor interface.

Development of Conjugated Polymers for Memory Device Applications.

This review summarizes the most widely used mechanisms in memory devices based on conjugated polymers, such as charge transfer, space charge traps, and filament conduction. In addition, recent studies of conjugated polymers for memory device applications are also reviewed, discussed, and differentiated based on the mechanisms and structural design. Moreover, the electrical conditions of conjugated polymers can be further fine-tuned by careful design and synthesis based on the switching mechanisms. The review also emphasizes and demonstrates the structure-memory properties relationship of donor-acceptor conjugated polymers for advanced memory device applications.

Insights into the Morphological Instability of Bulk Heterojunction PTB7-Th/PCBM Solar Cells upon High-Temperature Aging.

The impact of the morphological stability of the donor/acceptor mixture under thermal stress on the photovoltaic properties of bulk heterojunction (BHJ) solar cells based on the poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']-dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]-thiophene)-2-carboxylate-2,6-diyl]/phenyl-C61-butyric acid methyl ester (PTB7-Th/PC61BM) blend is extensively investigated. Both optical microscopy and transmission electron microscopy micrographs show that long-term high-temperature aging stimulates the formation of microscale clusters, the size of which, however, is about 1 order of magnitude smaller than those observed in thermally annealed poly(3-hexylthiophene)/PC61BM composite film. The multilength-scale evolution of the morphology of PTB7-Th/PC61BM film from the scattering profiles of grazing incidence small-angle and wide-angle X-ray scattering indicates the PC61BM molecules spatially confine the self-organization of polymer chains into large domains during cast drying and upon thermal activation. Moreover, some PC61BM molecules accumulate into ∼30-40 nm clusters, the number of which increases with heating time. Therefore, the hole mobility in the active layer decays much more rapidly than the electron mobility, leading to unbalanced charge transport and degraded cell performance. Importantly, the three-component blend that is formed by replacing a small amount of PC61BM in the active layer with the bis-adduct of PC61BM (bis-PC61BM) exhibits robust morphology against thermal stress. Accordingly, the PTB7-Th/PC61BM:bis-PC61BM (8 wt %) device has an extremely stable power conversion efficiency.

Near-Infrared-Absorbing and Dopant-Free Heterocyclic Quinoid-Based Hole-Transporting Materials for Efficient Perovskite Solar Cells.

New heterocyclic quinoid-based hole transporting materials (HTMs) with a rigid quinoid core [3,6-di(2H-imidazol-2-ylidene)cyclohexa-1,4-diene] have been synthesized. The new HTMs have good hole mobility (>10-4  cm2 V-1 s-1 ) and very intense absorption in the near-infrared region extending to >800 nm. High performance perovskite solar cells can be fabricated using these HTMs without dopant. The best cell efficiency under simulated AM 1.5 G illumination reaches 12.22 %, which is comparable with that (12.58 %) using doped 2,2',7,7'-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene (spiro-OMeTAD) as the HTM.

Coexistence of Two Electronic Nano-Phases on a CH3NH3PbI3-xClx Surface Observed in STM Measurements.

Scanning tunneling microscopy is utilized to investigate the local density of states of a CH3NH3PbI3-xClx perovskite in cross-sectional geometry. Two electronic phases, 10-20 nm in size, with different electronic properties inside the CH3NH3PbI3-xClx perovskite layer are observed by the dI/dV mapping and point spectra. A power law dependence of the dI/dV point spectra is revealed. In addition, the distinct electronic phases are found to have preferential orientations close to the normal direction of the film surface. Density functional theory calculations indicate that the observed electronic phases are associated with local deviation of I/Cl ratio, rather than different orientations of the electric dipole moments in the ferroelectric phases. By comparing the calculated results with experimental data we conclude that phase A (lower contrast in dI/dV mapping at -2.0 V bias) contains a lower I/Cl ratio than that in phase B (higher contrast in dI/dV).

Synthesis and Characterization of Two-Dimensional Conjugated Polymers Incorporating Electron-Deficient Moieties for Application in Organic Photovoltaics.

A series of novel p-type conjugated copolymers, PTTVBDT, PTTVBDT-TPD, and PTTVBDT-DPP, cooperating benzo[1,2-b:4,5-b']dithiophene (BDT) and terthiophene-vinylene (TTV) units with/without thieno[3,4-c]pyrrole-4,6-dione (TPD) or pyrrolo[3,4-c]pyrrole-1,4-dione (DPP) via Stille polymerization were synthesized and characterized. Copolymer PTTVBDT shows a low-lying HOMO energy level and ordered molecular-packing behavior. Furthermore, two terpolymers, PTTVBDT-TPD and PTTVBDT-DPP, display stronger absorption ability, alower-lying HOMO energy level, and preferred molecular orientation, due to the replacement TTV-monomer units with electron-deficient groups. Furthermore, bulk-heterojunction organic solar cells were fabricated using blends of the PTTVBDT-TPD, and PC61BM gave the best power conversion efficiency of 5.01% under the illumination of AM 1.5G, 100 mW·cm-2; the short circuit current (Jsc) was 11.65 mA·cm-2 which displayed a 43.8% improvement in comparison with the PTTVBDT/PC61BM device. These results demonstrate a valid strategy combining the two-dimensional molecular structure with random copolymerization strikes promising conjugated polymers to achieve highly efficient organic photovoltaics.