Jingjing Yao

Significant Improvement of Semiconducting Performance of the Diketopyrrolopyrrole–Quaterthiophene Conjugated Polymer through Side-Chain Engineering via Hydrogen-Bonding

Three diketopyrrolopyrrole (DPP)-quaterthiophene conjugated polymers, pDPP4T-1, pDPP4T-2, and pDPP4T-3, in which the molar ratios of the urea-containing alkyl chains vs branching alkyl chains are 1:30, 1:20, and 1:10, respectively, were prepared and investigated. In comparison with pDPP4T without urea groups in the alkyl side chains and pDPP4T-A, pDPP4T-B, and pDPP4T-C containing both linear and branched alkyl chains, thin films of pDPP4T-1, pDPP4T-2, and pDPP4T-3 exhibit higher hole mobilities; thin-film mobility increases in the order pDPP4T-1 < pDPP4T-2 < pDPP4T-3, and hole mobility of a thin film of pDPP4T-3 can reach 13.1 cm(2) V(-1) s(-1) after thermal annealing at just 100 °C. The incorporation of urea groups in the alkyl side chains also has an interesting effect on the photovoltaic performances of DPP-quaterthiophene conjugated polymers after blending with PC71BM. Blended thin films of pDPP4T-1:PC71BM, pDPP4T-2:PC71BM, and pDPP4T-3:PC71BM exhibit higher power conversion efficiencies (PCEs) than pDPP4T:PC71BM, pDPP4T-A:PC71BM, pDPP4T-B:PC71BM, and pDPP4T-C:PC71BM. The PCE of pDPP4T-1:PC71BM reaches 6.8%. Thin films of pDPP4T-1, pDPP4T-2, and pDPP4T-3 and corresponding thin films with PC71BM were characterized with AFM, GIXRD, and STEM. The results reveal that the lamellar packing order of the alkyl chains is obviously enhanced for thin films of pDPP4T-1, pDPP4T-2, and pDPP4T-3; after thermal annealing, slight inter-chain π-π stacking emerges for pDPP4T-2 and pDPP4T-3. Blends of pDPP4T-1, pDPP4T-2, and pDPP4T-3 with PC71BM show a more pronounced micro-phase separation. These observations suggest that the presence of urea groups may further facilitate the assemblies of these conjugated polymers into nanofibers and ordered aggregation of PC71BM.

New Electron-Donor/Acceptor-Substituted Tetraphenylethylenes: Aggregation-Induced Emission with Tunable Emission Color and Optical-Waveguide Behavior

Herein, we report the synthesis of new tetraphenylethylene derivatives 1-5 that feature electron-donating (methoxy) and -accepting (dicyanomethane) groups as AIE-active molecules with tunable emission colors. The crystal structures of compounds 3 and 4 are described and the intermolecular interactions within their crystals agree with the observation that they exhibit strong solid-state emission. Compounds 1-4 exhibit typical AIE behavior and their emission maxima are red-shifted in the order: 1<2<3<4. Such red-shifts are ascribed to the fact that intramolecular interactions between the electron donor and the electron acceptor become stronger with increasing number of methoxy groups. The solid-state emission colors of compounds 1-4 are successfully tuned from yellow-green to red. Compound 5 shows AIE behavior, but its emission is only slightly enhanced after aggregation and its solid shows a low quantum yield. Furthermore, microplates of compound 3 exhibit 2D optical-waveguide behavior.

Controllable Self-Assembly of Di(p-methoxylphenyl)Dibenzofulvene into Three Different Emission Forms

Self-assembly of di(p-methoxylphenyl)dibenzofulvene in the absence and presence of CTAB (cetyl trimethylammonium bromide) leads to three emission forms: strongly yellow-green- and blue-emissive crystalline forms (as microrods), and weakly orange-emissive amorphous form. Each of these three emission forms can be prepared by adjusting the concentration of CTAB.

Highly Sensitive Thin-Film Field-Effect Transistor Sensor for Ammonia with the DPP-Bithiophene Conjugated Polymer Entailing Thermally Cleavable tert-Butoxy Groups in the Side Chains

The sensing and detection of ammonia have received increasing attention in recent years because of the growing emphasis on environmental and health issues. In this paper, we report a thin-film field-effect transistor (FET)-based sensor for ammonia and other amines with remarkable high sensitivity and satisfactory selectivity by employing the DPP-bithiophene conjugated polymer pDPPBu-BT in which tert-butoxycarboxyl groups are incorporated in the side chains. This polymer thin film shows p-type semiconducting property. On the basis of TGA and FT-IR analysis, tert-butoxycarboxyl groups can be transformed into the -COOH ones by eliminating gaseous isobutylene after thermal annealing of pDPPBu-BT thin film at 240 °C. The FET with the thermally treated thin film of pDPPBu-BT displays remarkably sensitive and selective response toward ammonia and volatile amines. This can be attributed to the fact that the elimination of gaseous isobutylene accompanies the formation of nanopores with the thin film, which will facilitate the diffusion and interaction of ammonia and other amines with the semiconducting layer, leading to high sensitivity and fast response for this FET sensor. This FET sensor can detect ammonia down to 10 ppb and the interferences from other volatile analytes except amines can be negligible.

New dithienyl-diketopyrrolopyrrole-based conjugated molecules entailing electron withdrawing moieties for organic ambipolar semiconductors and photovoltaic materials

In this paper we report two DPP-based conjugated molecules DPPBT and DPPTT in which the respective electron withdrawing moieties 2,1,3-benzothiadiazole and thiazolo[5,4-d]thiazole are flanked by two DPP moieties. For comparison, DPPBZ containing 1,4-diethynylbenzene and two DPP moieties were synthesized. HOMO/LUMO energies of DPPBT, DPPTT and DPPBZ were estimated on the basis of cyclic voltammetric data. Owing to the fact that LUMO energies of DPPBT and DPPTT were lowered to ca. −3.5 eV, thin films of both DPPBT and DPPTT exhibit ambipolar semiconducting properties under N2 atmosphere with hole and electron mobilities up to 0.25 cm2 V−1 s−1 and 0.09 cm2 V−1 s−1, respectively. In comparison, thin film of DPPBZ just shows p-type semiconducting property. Notably, ambipolar semiconductors with relatively high carrier mobility are rarely reported for DPP-containing small conjugated molecules. Alternatively, both DPPBT and DPPTT can function as electron donors for photovoltaic materials. Thin films of DPPTT:PC71BM and DPPBT:PC71BM at a weight ratio of 1 : 1 exhibit PCEs of 4.18% and 2.44%, respectively, with VOC higher than 0.95 V.

Conjugated donor–acceptor terpolymers entailing the Pechmann dye and dithienyl-diketopyrrolopyrrole as co-electron acceptors: tuning HOMO/LUMO energies and photovoltaic performances

Three conjugated D–A terpolymers PBPD1, PBPD2, and PBPD3 with the Pechmann dye-derived electron acceptor and dithienyl-diketopyrrolopyrrole as co-acceptors are presented. Their HOMO/LUMO energies and absorptions can be tuned by varying the ratios of two acceptors. Importantly, HOMO energies of these terpolymers are lowered by increasing the content of the Pechmann dye-derived electron acceptor in the conjugated backbones. The thin blend films of PBPD1, PBPD2, and PBPD3 with PC71BM have been tested as active layers for polymer solar cells. The blend of PBPD1:PC71BM shows a high power conversion efficiency of up to 5.21%, which is higher than that with the blend of the dithienyl-diketopyrrolopyrrole-based polymer without the Pechmann dye-derived electron acceptor and PC71BM. In addition, the neat thin films of PBPD1, PBPD2, and PBPD3 exhibit ambipolar semiconducting properties with hole and electron mobilities up to 0.604 cm2 V−1 s−1 and 0.225 cm2 V−1 s−1.

New conjugated molecules with four DPP (diketopyrrolopyrrole) moieties linked by [2,2]paracyclophane as electron acceptors for organic photovoltaic cells

In this paper, we report two conjugated molecules 1 and 2 with four diketopyrrolopyrrole (DPP) moieties, which are linked by [2,2]paracyclophane. The energies of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of 1 and 2 were estimated from the respective onset oxidation and reduction potentials, which were determined on the basis of cyclic voltammetric data. Both 1 and 2 exhibit strong absorption in the visible region. Blended thin films of 1 and 2 with P3HT (poly(3-hexylthiophene)) in different weight ratios were utilized as active layers to fabricate solar cells. The results reveal that blended thin films of P3HT/1 and P3HT/2 at a weight ratio of 2 : 1 yielded the best photovoltaic performance with power conversion efficiencies (PCEs) up to 1.33% and 1.84% after thermal annealing. Blended thin films of P3HT/1 and P3HT/2 were characterized by XRD (X-ray diffraction) and AFM (atomic force microscopy) techniques. The low degree of inter-chain packing order and poor thin-film morphology are responsible for the relatively low PCEs.

The adjustment of bandgap and coplanarity of diketopyrrolopyrrole-based copolymers through fine-tuning of the conjugated backbones and applications in thin film field effect transistors

In order to demonstrate the influence of structural fine-tuning on bandgap and semiconductor performance of π-conjugated polymer materials, three new diketopyrrolopyrrole (DPP) based copolymers P1, P2 and P3 with monomers, i.e., 2-phenylpyridine, 2-(thiophen-2-yl)pyridine and 2-(thiophen-2-yl)thiazole, respectively, have been synthesized using a typical Suzuki cross-coupling polycondensation. The DFT calculations demonstrate that polymer P3 displays high backbone coplanarity in comparison to polymers P1 and P2. Absorption spectra results reveal that P3 exhibits a remarkable red-shifted absorption profile, narrow band gap and broad absorption. The thin film FET measurements show that P3 possesses the highest hole mobility (μh) up to 1.25 cm2 V−1 s−1 and on/off (Ion/off) ratio as high as 108. Those results demonstrate that the fine-tuning of the π-conjugated backbone can significantly affect the band gaps and coplanarities, and ultimately improve the semiconducting performances.