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A new PC61BM-based fullerene, [6,6]-phenyl-C61 butyric acid pentafluorophenyl ester (PC61BPF) is designed and synthesized. This new n-type material can replace PC61BM to form a P3HT:PC61BPF binary blend or serve as an additive to form a P3HT:PC61BM:PC61BPF ternary blend. Supramolecular attraction between the pentafluorophenyl group of PC61BPF and the C60 cores of PC61BPF/PC61BM can effectively suppress the PC61BPF/PC61BM materials from severe aggregation. By doping only 8.3 wt% PC61BPF, device PC61BPF651 exhibits a PCE of 3.88% and decreases slightly to 3.68% after heating for 25 h, preserving 95% of its original value. When PC61BP with non-fluorinated phenyl group is used to substitute PC61BPF, the stabilizing ability disappears completely. The efficiencies of PC61BP651 and PC61BP321 devices significantly decay to 0.44% and 0.11%, respectively, after 25 h isothermal heating. Most significantly, this strategy is demonstrated to be effective for a blend system incorporating a low band-gap polymer. By adding only 10 wt% PC61BPF, the PDTBCDTB:PC71BM-based device exhibits thermally stable morphology and device characteristics. These findings demonstrate that smart utilization of supramolecular interactions is an effective and practical strategy to control morphological evolution.

The versatility of a fl uoro-containing low band-gap polymer, poly[2,6-(4,4bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b’]dithiophene)-alt-4,7-(5-fl uoro2,1,3-benzothia-diazole)] (PCPDTFBT) in organic photovoltaics (OPVs) applications is demonstrated. High boiling point 1,3,5-trichlorobenzene (TCB) is used as a solvent to manipulate PCPDTFBT:[6,6]-phenyl-C 71 -butyric acid methyl ester (PC 71 BM) active layer morphology to obtain high-performance single-junction devices. It promotes the crystallization of PCPDTFBT polymer, thus improving the charge-transport properties of the active layer. By combining the morphological manipulation with interfacial optimization and device engineering, the single-junction device exhibits both good air stability and high power-conversion effi ciency (PCE, of 6.6%). This represents one of the highest PCE values for cyclopenta[2,1-b;3,4-b’]dithiophene (CPDT)-based OPVs. This polymer is also utilized for constructing semitransparent solar cells and double-junction tandem solar cells to demonstrate high PCEs of 5.0% and 8.2%, respectively.

Indolo[3,2-b]indole, containing two fused indole units, is an unexplored but promising electron-rich molecule for constructing donor–acceptor materials due to its planar, symmetric, and extended conjugated structure. We have successfully developed a new synthetic pathway to prepare 2,7-diboronic ester-indolo[3,2-b]indole, which was then reacted with dithienodiketopyrrolo-pyrrole acceptor to afford a new acceptor–donor–acceptor (A–D–A) conjugated molecule, 2,7-bis(dithienodiketopyrrolo-pyrrole)indolo[3,2-b]indole (2,7-DPPIIDPP). II is used to stand for indolo[3,2-b]indole in order to emphasize that this compound is constructed from two indole units. The A–D–A linkage through the 2,7-positions of II not only preserves the phenylene units in the para-conjugation but also renders stronger electron-donating strength. This material exhibited good thermal stability, high crystallinity, and broad UV/Vis absorption. The solution-processed bulk heterojunction device using the configuration of ITO/PEDOT:PSS/2,7-DPPIIDPP:PC71BM/Ca/Al exhibited a Voc of 0.72 V, a Jsc of 6.88 mA/cm2, and an FF of 49.6 %, leading to a power conversion efficiency (PCE) of 2.45 %.

A new class of ladder-type dithienosilolo-carbazole (DTSC), dithienopyrrolo-carbazole (DTPC), and dithienocyclopenta-carbazole (DTCC) units is developed in which two outer thiophene subunits are covalently fastened to the central 2,7-carbazole cores by silicon, nitrogen, and carbon bridges, respectively. The heptacyclic multifused monomers are polymerized with the benzothiadiazole (BT) acceptor by palladium-catalyzed cross-coupling to afford three alternating donor-acceptor copolymers poly(dithienosilolo-carbazole-alt-benzothiadiazole) (PDTSCBT), poly(dithienocyclopenta-carbazole-alt-benzothiadiazole) (PDTCCBT), and poly(dithienopyrrolo-carbazole-alt-benzothiadiazole) (PDTPCBT). The silole units in DTSC possess electron-accepting ability that lowers the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of PDTSCBT, whereas stronger electron-donating ability of the pyrrole moiety in DTPC increases the HOMO and LUMO energy levels of PDTPCBT. The optical bandgaps (Egopt) deduced from the absorption edges of thin film spectra are in the following order: PDTSCBT (1.83 eV) > PDTCCBT (1.64 eV) > PDTPCBT (1.50 eV). This result indicated that the donor strength of the heptacyclic arenes is in the order: DTPC > DTCC > DTSC. The devices based on PDTSCBT and PDTCCBT exhibited high hole mobilities of 0.073 and 0.110 cm2 V−1 s−1, respectively, which are among the highest performance from the OFET devices based on the amorphous donor-acceptor copolymers. The bulk heterojunction photovoltaic device using PDTSCBT as the p-type material delivered a promising efficiency of 5.2% with an enhanced open circuit voltage, Voc, of 0.82 V.

Research on polymer solar cells (PSC) using organic p-type (donor) and n-type (acceptor) semiconductors has attracted tremendous scientific and industrial interest in recent years. The charge generation and charge transport play equally important roles in determining the device efficiency. To dramatically increase the area of the donor–acceptor interface for efficient charge separation, a bulk heterojunction (BHJ) is adopted to form an interpenetrating network of donor and acceptor materials. This configuration decreases the distance that excitons need to travel to reach the heterojunction interface, thus reducing exciton recombination. However, the donor and acceptor are randomly interspersed; pathways for charges to reach the electrodes through the active layer are disordered. Free charges are likely to encounter an opposite charge, resulting in charge recombination and reduced current. 4] Moreover, space charge may be built up if charges are locally trapped on isolated domains. Furthermore, an increase in the thickness of the BHJ layer to enhance absorption is usually accompanied by deteriorated charge collection. Consequently, controlling phase separation toward optimal morphology in BHJ by external treatments, such as thermal or solvent annealing, is an important but challenging task. To provide a direct path for charge transport while maintaining a large interfacial area, the ideal architecture of the donor and acceptor is the periodic, vertically aligned, and interpenetrating ordered bulk heterojunction (OBHJ). The electrons and holes have straight and independent pathways to the electrodes to shorten the carrier transport length and reduce the probability of charge recombination. Several elegant studies have attempted to demonstrate this conceptual architecture, for example by a template-assisted strategy or self-assembly of block copolymer. However, realization of high-performance OBHJ devices has not been successful. We envision that designing a system that combines a BHJ for efficient charge generation with an OBHJ for efficient charge transport and collection would be a more practical strategy. Such a configuration is specifically suitable for solar cells with inverted architecture, because an electron-selective layer is required at the bottom of the active layer for electron extraction and hole blocking. For instance, the upper BHJ active layer of an inverted solar cell is infiltrated into vertically aligned nanorods extending from a bottom layer of an inorganic semiconductor (e.g. ZnO or TiO2). [18–20] However, owing to the poor electrical coherence at the organic/inorganic interface, the improvement in efficiency is moderate (PCE ranges from 2.1 to 2.7%). Recently, we reported a cross-linkable fullerene material, [6,6]-phenyl-C61-butyric styryl dendron ester (PCBSD). The formation of a cross-linked PCBSD (C-PCBSD, Figure 1a) planar layer allows realization of a multilayer inverted device by all-solution processing. By using indene–C60 bisadduct (ICBA, Figure 1a) with a higher-lying lowest unoccupied molecular orbital (LUMO) energy level to serve as the acceptor in the blend, an inverted solar cell device based on the ITO/ZnO/C-PCBSD/ICBA:P3HT/PEDOT:PSS/Ag configuration achieved an enhanced power conversion efficiency

The successful design and synthesis of two styryl-functionalized fullerene derivatives, [6,6]-phenyl-C61-butyric acid styryl dendron ester (PCBSD) and [6,6]-phenyl-C61-butyric acid styryl ester (PCBS) is presented. The polymerizable PCBS or PCBSD materials are incorporated into a poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) blend to form an active layer of ternary blend. The blending systems are first thermally annealed at 110 C for 10 min to induce optimal morphology, followed by heating at 150 C for 10 min to trigger the in situ polymerization of styrene groups. Through chemical crosslinking of PCBSD, the initial morphology of the blend (P3HT:PCBM:PCBSD = 6:5:1 in weight) can be effectively fixed and stably preserved. The device based on this blend shows extremely stable device characteristics, delivering an average power conversion efficiency (PCE) of 3.7% during long-term thermal treatment. By molecular engineering to reduce the insulating portion, PCBS with higher C60 content (71 wt%) possesses better electron-transport properties than PCBSD (58 wt%). Encouragingly, at a low doping concentration of PCBS in the blend (P3HT:PCBM:PCBS = 6:5:1 in weight), linear-polymerized PCBS can stabilize the morphology against thermal heating. This device exhibits more balanced charge mobility to achieve an average PCE of 3.8% over 25 h heating at 150 °C.

We have synthesized six p-type copolymers, CPDT-co-TPADCN, CPDT-co-TPADTA, CPDT-co-TPATCN, CPDT-co-DFADCN, CPDT-co-DFADTA, and CPDT-co-DFATCN, consisting of a cyclopenta[2,1-b:3,4-b']dithiophene (CPDT) unit and an organic dye in an alternating arrangement. Triphenylamine (TPA) or difluorenylphenyl amine (DFA) units serve as the electron donors, whereas dicyanovinyl (DCN), 1,3-diethyl-2-thiobarbituric acid, or tricyanovinyl (TCN) units act as the electron acceptors in the dyes. The target polymers were prepared via Stille coupling, followed by postfunctionalization to introduce the electron acceptors to the side chains. Because of the strongest withdrawing ability of TCN acceptor to induce efficient intramolecular charge transfer, CPDT-co-TPATCN and CPDT-co-DFATCN exhibit the broader absorption spectra covering from 400 to 900 nm and the narrower optical band gaps of 1.34 eV. However, the CPDT-co-TPATCN:PC 71 BM and CPDT-co-DFATCN:PC 71 BM based solar cells showed the power conversion efficiencies (PCEs) of 0.22 and 0.31%, respectively, due to the inefficient exciton dissociation. The DFA-based polymers possess deeper-lying HOMO energy levels than the TPA-based polymer analogues, leading to the higher V oc values and better efficiencies. The device based on CPDT-co-DFADTA:PC 71 BM blend achieved the best PCE of 1.38% with a V oc of 0.7 V, a J sc of 4.57 mA/cm 2 , and a fill factor of 0.43.

Pentacyclic diindeno[1,2-b:2',1'-d]thiophene (DIDT) unit is a rigid and coplanar conjugated molecule. To the best of our knowledge, this attractive molecule has never been incorporated into a polymer and thus its application in polymer solar cells has never been explored. For the first time, we report the detailed synthesis of the tetra-alkylated DIDT molecule leading to its dibromo- and diboronic ester derivatives, which are the key monomers for preparation of DIDT-based polymers. Two donor-acceptor alternating polymers, poly(diindenothiophene-alt-benzothiadiazole) PDIDTBT and poly(diindenothiophene-alt-dithienylbenzothiadiazole) PDIDTDTBT, were synthesized by using Suzuki polymerization. Copolymer PTDIDTTBT was also prepared by using Stille polymerization. Although PTDIDTTBT is prepared through a manner of random polymerization, we found that the different reactivities of the dibromo-monomers lead to the resulting polymer having a block copolymer arrangement. With the higher structural regularity, PTDIDTTBT, symbolized as (thiophene-alt-DIDT)(0.5)-block-(thiophene-alt-BT)(0.5), shows the higher degree of crystallization, stronger π-π stacking, and broader absorption spectrum in the solid state, as compared to its alternating PDIDTDTBT analogue. Bulk heterojunction photovoltaic cells based on ITO/PEDOT:PSS/polymer:PC(71)BM/Ca/Al configuration were fabricated and characterized. PDIDTDTBT/PC(71)BM and PTDIDTTBT/PC(71)BM systems exhibited promising power-conversion efficiencies (PCEs) of 1.65 % and 2.00 %, respectively. Owing to the complementary absorption spectra, as well as the compatible structures of PDIDTDTBT and PTDIDTTBT, the PCE of the device based on the ternary blend PDIDTDTBT/PTDIDTTBT/PC(71)BM was further improved to 2.40 %.

In order to fulfill the promise of organic electronic devices, performance-limiting factors, such as the energetic discontinuity of the material interfaces, must be overcome. Here, improved performance of polymer light-emitting diodes (PLEDs) is demonstrated using self-assembled monolayers (SAMs) of triarylamine-based hole-transporting molecules with phosphonic acid-binding groups to modify the surface of the indium tin oxide (ITO) anode. The modified ITO surfaces are used in multilayer PLEDs, in which a green-emitting polymer, poly[2,7-(9,9-dihexylfluorene)-co-4,7-(2,1,3-benzothiadiazole)] (PFBT5), is sandwiched between a thermally crosslinked hole-transporting layer (HTL) and an electron-transporting layer (ETL). All tetraphenyl-diamine (TPD)-based SAMs show significantly improved hole-injection between ITO and the HTL compared to oxygen plasma-treated ITO and simple aromatic SAMs on ITO. The device performance is consistent with the hole-transporting properties of triarylamine groups (measured by electrochemical measurements) and improved surface energy matching with the HTL. The turn-on voltage of the devices using SAM-modified anodes can be lowered by up to 3 V compared to bare ITO, yielding up to 18-fold increases in current density and up to 17-fold increases in brightness at 10 V. Variations in hole-injection and turn-on voltage between the different TPD-based molecules are attributed to the position of alkyl-spacers within the molecules.

Novel fluorene-based blue-light-emitting copolymers with an ultraviolet-blue-light (UV-blue-light) emitting host and a blue-light emitting component, 4-N,N-diphenylaminostilbene (DPS) have been designed and synthesized by using the palladium-catalyzed Suzuki coupling reaction. It was found that both copolymers poly [2,7-(9,9-dioctylfluorene)-alt-1,3-(5-carbazol-phenylene)] (PFCz) DPS1 and PFCz-DPS1-OXD show pure blue-light emission even with only 1 % DPS units because of the efficient energy transfer from the UV-blue-light emitting PFCz segments to the blue-light-emitting DPS units. Moreover, because of the efficient energy transfer/charge trapping in these copolymers, PFCz-DPS1 and PFCz-DPS1-OXD show excellent device performance with a very stable pure blue-light emission. By using a neutral surfactant poly[9,9-bis(6'-(diethanolamino)-hexyl)-fluorene] (PFN-OH) as the electron injection layer, the device based on PFCz-DPS1-OXD5 with the configuration of ITO/PEDOT:PSS/PVK/polymer/PFN-OH/Al showed a maximum quantum efficiency of 2.83 % and a maximum luminous efficiency of 2.50 cd A -1 . Its CIE 1931 chromaticity coordinates of (0.156, 0.080) match very well with the NTSC standard blue pixel coordinates of (0.14, 0.08). These results indicate that this kind of dopant/host copolymer could be a promising candidate for blue-light-emitting polymers with high efficiency, good color purity, and excellent color stability.

A series of new hydrophobic two-photon absorbing (2PA) chromophores with varied electron-donating groups in quasi-linear and multibranched structures are synthesized to correlate their structure/photophysical property relationships. The feasibility of using these large two-photon absorption cross-sectional (δ, expressed in GM = 1 × 10–50 cm4 s photon–1 molecule–1) materials in aqueous solution is also explored. All four hydrophobic 2PA materials can be encapsulated into micelles generated by dispersing an amphiphilic block copolymer, poly(methacrylic acid)-block-polystyrene (PMAA-b-PS), into water. The micellar nanostructures are characterized using dynamic light scattering, atomic force microscopy, and transmission electron microscopy. After these dyes are incorporated into micelles, they exhibit strong fluorescence in water. It is found that the quantum yield and δ values of these chromophores are strongly dependent on the diameters of the micelles, concentrations of the PMAA-b-PS, and molecular structures of the 2PA chromophores. One of the compounds that has a strong triarylamino donor and a multibranched structure exhibits a large δ value of 2790 GM and high quantum yield (0.56) in micelle-containing water. Although this value is smaller than the original value of 5300 GM in toluene, it is still substantially larger than the values of most water-soluble 2PA materials, which have δ values of less than 100 GM.

A range of silanylene-spaced divinylbenzene copolymers (1) and the corre- sponding monomers (2) have been synthesized by the rhodium-catalyzed hydrosilyla- tion of the corresponding bisalkynes with bissilyl hydrides, and the photophysical properties of 1 and 2 have been investigated. The silicon moiety in 1 serves as an insulating tetrahedral spacer that makes 1 highly folded. The two chromophores may be in close proximity such that a ground-state intrachain interaction between two conjugated moieties through space might occur. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2218 -2231, 2003

phenylenevinylene)s L4. Fluorene-Based Conjugated Polymers L4.1. Fluorene-Based Copolymers ContainingElectron-Rich MoietiesM4.2. Fluorene-Based Copolymers ContainingElectron-Deficient MoietiesN4.3. Fluorene-Based Copolymers ContainingPhosphorescent ComplexesQ5. Carbazole-Based Conjugated Polymers R5.1. Poly(2,7-carbazole)-Based Polymers R5.2. Indolo[3,2

Heteroaromatics-containing polymers comprise a huge class of materials that have received considerable attention due to their interesting electrical, electrochemical, and optical properties. In this review, the recent advances on the use of organometallic cross-coupling reactions for the synthesis of heteroaromatic conjugated polymers for the optoelectronic interests and applications are summarised.

Second hole-transport layer (HTL) with perfect solvent-resistance is formed via spin-coating then thermally crosslinking on top of a pre-crosslinked HTL or p-type conducting polymer layer. By judiciously choosing the energy levels of the hole-transport moieties, cascade hole-injection can be realized for a light-emitting layer with phosphorescent blue emitters (and white thereafter).