An easily accessible DPP‐based small molecule ( DMPA‐DTDPP ) has been synthesized by a simple and efficient route. The resulting molecule, when incorporated into a P3HT:PCBM‐based BHJ solar cell, is found to significantly improve the efficiency. The utility of DMPA‐DTDPP as an additive yields an increase in the short circuit current density (Jsc) because DMPA‐DTDPP serves as an energy funnel for P3HT excitons at the P3HT:PCBM interfaces, resulting in an improved overall power conversion efficiency, compared to the P3HT:PCBM control device. Considering the trouble‐free and cost effective synthesis of DMPA‐DTDPP , it may prove very useful in high‐performance solar cells. 相似文献
A series of block copolymers with fixed length of the semiconductor‐block poly(3‐butylthiophene) (P3BT) and varying length of the insulator‐block polystyrene (PS) are synthesized. These copolymers are blended with phenyl‐C61‐butyric acid methyl ester (PCBM) for the bulk heterojunction photoactive layers. With appropriate insulator‐block length and donor–acceptor ratio, the power conversion efficiency increases by one order of magnitude compared with reference devices with pure P3BT/PCBM. PS blocks improve the miscibility of the active layer blends remarkably. The P3BT‐b‐PS crystallizes as nanorods with the P3BT core covered with the PS‐block, which creates a nanoscale tunneling barrier between donor and acceptor leading to more efficient transportation of charge carriers in the semiconductors. 相似文献
To maximize the efficiency of heterojunction organic photovoltaics (HJOPVs), it is imperative to increase not only the open-circuit
voltage (VOC) but also the short-circuit current (ISC). Therefore, it is desirable to find an organic acceptor material that possesses a higher lowest unoccupied molecular orbital
(LUMO) level for higher VOC and can absorb photons in the solar spectrum efficiently for larger ISC. In this paper, in comparison with the typical donor poly(3-hexylthiophene) (P3HT) and acceptor [6,6]-phenyl-C61-butyric acid ester ([60]PCBM), the geometries, electronic structures, absorption spectra, and transport properties of a series
of organic compounds containing 9,9′-bifluorenylidene (9,9′BF) were systematically investigated using density functional and the semiclassical Marcus charge transfer theory calculation
to evaluate their potential severing as acceptor. Our results indicate that the absorption spectra of 99′BF derivatives have better overlap with the solar spectrum than those of [60]PCBM, and higher LUMOs result in a significant
enhancement of VOC when they are used in HJOPVs with P3HT as donor materials. On the other hand, these compounds own higher electron carrier
mobilities comparing with [60]PCBM. The study also demonstrates that the H-shaped compounds based on the 99′BF backbone possess good photophysical and charge transport properties, can be promising organic semiconductor for heterojunction
photovoltaics. 相似文献
To increase the open circuit voltage (VOC) of polymer solar cells (PSCs) based on polythiophene, two new ester group functionalized polythiophene derivatives, PCTDT and PCTBDT, were designed and synthesized via alternating copolymerization of thiophene‐3‐carboxylate (CT) with the 2,2′‐bithiophene (DT) and benzodithiophene (BDT) units, respectively. The resulting copolymers exhibited broad and strong absorptions in the visible region, which was similar to that of the commonly used poly(3‐hexylthiophene) (P3HT). Through cyclic voltammetry measurements, it was found that both copolymers showed lower HOMO energy levels (−5.27 eV for PCTDT and −5.36 eV for PCTBDT) than that of P3HT (−5.03 eV), indicating that the HOMO energy level could be efficiently reduced by introducing the ester group into the polymer side chain. Photovoltaic properties of the copolymers blended with [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) as electron acceptor were investigated. The obtained two devices possessed both relatively large short circuit current (ISC) and higher VOC than that of P3HT:PCBM blend. For PCTBDT:PCBM blend, a power conversion efficiency (PCE) up to 2.32%, an ISC of 6.94 mA · cm−2, and a VOC of 0.80 V were observed while PCTDT:PCBM system demonstrated a PCE of 1.75% with a VOC of 0.68 V.
We prepared conceptually novel, fully rigid, spiro compact electron donor (Rhodamine B, lactam form, RB)/acceptor (naphthalimide; NI) orthogonal dyad to attain the long‐lived triplet charge‐transfer (3CT) state, based on the electron spin control using spin‐orbit charge transfer intersystem crossing (SOCT‐ISC). Transient absorption (TA) spectra indicate the first charge separation (CS) takes place within 2.5 ps, subsequent SOCT‐ISC takes 8 ns to produce the 3NI* state. Then the slow secondary CS (125 ns) gives the long‐lived 3CT state (0.94 μs in deaerated n‐hexane) with high energy level (ca. 2.12 eV). The cascade photophysical processes of the dyad upon photoexcitation are summarized as 1NI*→1CT→3NI*→3CT. With time‐resolved electron paramagnetic resonance (TREPR) spectra, an EEEAAA electron‐spin polarization pattern was observed for the naphthalimide‐localized triplet state. Our spiro compact dyad structure and the electron spin‐control approach is different to previous methods for which invoking transition‐metal coordination or chromophores with intrinsic ISC ability is mandatory. 相似文献
A comparative study of the photophysical performance of the prototypical fullerene derivative PC61BM with a planar small‐molecule acceptor in an organic photovoltaic device is presented. The small‐molecule planar acceptor is 2‐[{7‐(9,9‐di‐n‐propyl‐9H‐fluoren‐2‐yl)benzo[c][1,2,5]thiadiazol‐4‐yl}methylene]malononitrile, termed K12. We discuss photoinduced free charge‐carrier generation and transport in blends of PC61BM or K12 with poly(3‐n‐hexylthiophene) (P3HT), surveying literature results for P3HT:PC61BM and presenting new results on P3HT:K12. For both systems we also review previous work on film structure and correlate the structural and photophysical results. In both cases, a disordered mixed phase is formed between P3HT and the acceptor, although the photophysical properties of this mixed phase differ markedly for PC61BM and K12. In the case of PC61BM the mixed phase acts as a free carrier generation region that can efficiently shuttle carriers to the pure polymer and fullerene domains. As a result, the vast majority of excitons quenched in P3HT:PC61BM blends yield free carriers detected by the contactless time‐resolved microwave conductivity (TRMC) method. In contrast, approximately 85 % of the excitons quenched in P3HT:K12 do not result in free carriers over the nanosecond timescale of the TRMC experiment. We attribute this to poor electron‐transport properties in the mixed P3HT:K12 phase. We propose that the observed differences can be traced to the respective shapes of PC61BM and K12: the three‐dimensional nature of the fullerene cage facilitates coupling between PC61BM molecules irrespective of their relative orientation, whereas for K12 strong electronic coupling is only expected for molecules oriented with their π systems parallel to each other. Comparison between the eutectic compositions of the P3HT:PC61BM and P3HT:K12 shows that the former contains enough fullerene to form a percolation pathway for electrons, whereas the latter contains a sub‐percolating volume fraction of the planar acceptor. Furthermore, the planar K12 co‐assembles with P3HT into a disordered, glassy phase that partly accounts for the poor electron‐transport properties, and may also enhance recombination due to the strong intermolecular interactions between the donor and the acceptor. The implication for the performance of organic photovoltaic devices with the two acceptors is also discussed. 相似文献
A series of novel highly soluble double‐caged [60]fullerene derivatives were prepared by means of lithium‐salt‐assisted [2+3] cycloaddition. The bispheric molecules feature rigid linking of the fullerene spheres through a four‐membered cycle and a pyrrolizidine bridge with an ester function CO2R (R=n ‐decyl, n ‐octadecyl, benzyl, and n ‐butyl; compounds 1 a – d , respectively), as demonstrated by NMR spectroscopy and X‐ray diffraction. Cyclic voltammetry studies revealed three closely overlapping pairs of reversible peaks owing to consecutive one‐electron reductions of fullerene cages, as well as an irreversible oxidation peak attributed to abstraction of an electron from the nitrogen lone‐electron pair. Owing to charge delocalization over both carbon cages, compounds 1 a – d are characterized by upshifted energies of frontier molecular orbitals, a narrowed bandgap, and reduced electron‐transfer reorganization energy relative to pristine C60. Neat thin films of the n ‐decyl compound 1 a demonstrated electron mobility of (1.3±0.4)×10−3 cm2 V−1 s−1, which was comparable to phenyl‐C61‐butyric acid methyl ester (PCBM) and thus potentially advantageous for organic solar cells (OSC). Application of 1 in OSC allowed a twofold increase in the power conversion efficiencies of as‐cast poly(3‐hexylthiophene‐2,5‐diyl) (P3HT)/ 1 devices relative to the as‐cast P3HT/PCBM ones. This is attributed to the good solubility of 1 and their enhanced charge‐transport properties — both intramolecular, owing to tightly linked fullerene cages, and intermolecular, owing to the large number of close contacts between the neighboring double‐caged molecules. Test P3HT/ 1 OSCs demonstrated power‐conversion efficiencies up to 2.6 % ( 1 a ). Surprisingly low optimal content of double‐caged fullerene acceptor 1 in the photoactive layer (≈30 wt %) favored better light harvesting and carrier transport owing to the greater content of P3HT and its higher degree of crystallinity. 相似文献
A new donor‐acceptor‐acceptor (D‐A‐A) type of conjugated molecule, N‐(4‐(N′,N′‐diphenyl)phenylamine)‐4‐(4′‐(2,2‐dicyanovinyl)phenyl) naphthalene‐1,8‐dicarboxylic monoimide ( TPA‐NI‐DCN ), consisting of triphenylamine (TPA) donors and naphthalimide (NI)/dicyanovinylene (DCN) acceptors was synthesized and characterized. In conjunction with previously reported D ‐A based materials, the additional DCN moiety attached as end group in the D‐A‐A configuration can result in a stable charge transfer (CT) and charge‐separated state to maintain the ON state current. The vacuum‐deposited TPA‐NI‐DCN device fabricated as an active memory layer was demonstrated to exhibit write‐once‐read‐many (WORM) switching characteristics of organic nonvolatile memory due to the strong polarity of the TPA‐NI‐DCN moiety. 相似文献
A new‐type of donor–acceptor π‐conjugated (D‐π‐A) fluorescent dyes NI3 – NI8 with a pyridine ring as electron‐withdrawing‐injecting anchoring group have been developed and their photovoltaic performances in dye‐sensitized solar cells (DSSCs) are investigated. The short‐circuit photocurrent densities and solar energy‐to‐electricity conversion yields of DSSCs based on NI3 – NI8 are greater than those for the conventional D‐π‐A dye sensitizers NI1 and NI2 with a carboxyl group as the electron‐withdrawing anchoring group. The IR spectra of NI3 – NI8 adsorbed on TiO2 indicate the formation of coordinate bonds between the pyridine ring of dyes NI3 – NI8 and the Lewis acid sites (exposed Tin+ cations) of the TiO2 surface. This work demonstrates that the pyridine rings of D‐π‐A dye sensitizers that form a coordinate bond with the Lewis acid site of a TiO2 surface are promising candidates as not only electron‐withdrawing anchoring group but also electron‐injecting group, rather than the carboxyl groups of the conventional D‐π‐A dye sensitizers that form an ester linkage with the Brønsted acid sites of the TiO2 surface. 相似文献
Vinyl addition homo‐ and copolymerization of norbornene monomer ( M1 ) functionalized with a PCBM moiety using a Pd(II) catalyst in combination with a 1‐octene chain transfer agent efficiently produces polynorbornenes with side‐chain PCBM groups. Characterization by NMR spectroscopy and elemental analysis reveals that the copolymers constitute a well‐defined polymer structure with controlled incorporation of M1 . Although the homopolymer is insoluble in organic solvents, the copolymers containing 62 mol% ( P2 ) and 50 mol% ( P3 ) of the PCBM moiety are soluble in chlorinated solvents such as o‐dichlorobenzene. The bulk‐heterojunction organic photovoltaic devices fabricated based on the P3HT: P3 blends show that P3 can adequately function as an electron acceptor, leading to a cell with a power conversion efficiency of 1.5%, which is outstanding among the polymeric rivals. 相似文献