Alkylated fullerene derivatives for solution-processable organic thin-film transistors and bulkheterojunction solar cells.

In this paper, we report synthesis and characterization of alkylated fullerene derivatives for solution-processable organic thin film transistors and solar cells. Their physical, thermal, and semiconducting properties have been studied. Organic thin-film transistors fabricated from C60TH-Oc exhibit electron mobilities as high as 3.2 x 10(-2) cm2 V(-1) s(-1) with 32 V of a threshold voltage. The best power conversion efficiency (PCE) was observed in a layered structure P3HT:C60TH-Oc (PCE = 0.44%), which was a twice value of P3HT:C60TH-Dd (PCE = 0.23%).

Ultrafast exciton dissociation followed by nongeminate charge recombination in PCDTBT:PCBM photovoltaic blends.

The precise mechanism and dynamics of charge generation and recombination in bulk heterojunction polymer:fullerene blend films typically used in organic photovoltaic devices have been intensively studied by many research groups, but nonetheless remain debated. In particular the role of interfacial charge-transfer (CT) states in the generation of free charge carriers, an important step for the understanding of device function, is still under active discussion. In this article we present direct optical probes of the exciton dynamics in pristine films of a prototypic polycarbazole-based photovoltaic donor polymer, namely poly[N-11''-henicosanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT), as well as the charge generation and recombination dynamics in as-cast and annealed photovoltaic blend films using methanofullerene (PC(61)BM) as electron acceptor. In contrast to earlier studies we use broadband (500-1100 nm) transient absorption spectroscopy including the previously unobserved but very important time range between 2 ns and 1 ms, which allows us not only to observe the entire charge carrier recombination dynamics but also to quantify the existing decay channels. We determine that ultrafast exciton dissociation occurs in blends and leads to two separate pools of products, namely Coulombically bound charge-transfer (CT) states and unbound (free) charge carriers. The recombination dynamics are analyzed within the framework of a previously reported model for poly(3-hexylthiophene):PCBM (Howard, I. A. J. Am. Chem. Soc. 2010, 132, 14866) based on concomitant geminate recombination of CT states and nongeminate recombination of free charge carriers. The results reveal that only ~11% of the initial photoexcitations generate interfacial CT states that recombine exclusively by fast nanosecond geminate recombination and thus do not contribute to the photocurrent, whereas ~89% of excitons create free charge carriers on an ultrafast time scale that then contribute to the extracted photocurrent. Despite the high yield of free charges the power conversion efficiency of devices remains moderate at about 3.0%. This is largely a consequence of the low fill factor of devices. We relate the low fill factor to significant energetic disorder present in the pristine polymer and in the polymer:fullerene blends. In the former we observed a significant spectral relaxation of exciton emission (fluorescence) and in the latter of the polaron-induced ground-state bleaching, implying that the density of states (DOS) for both excitons and charge carriers is significantly broadened by energetic disorder in pristine PCDTBT and in its blend with PCBM. This disorder leads to charge trapping in solar cells, which in turn causes higher carrier concentrations and more significant nongeminate recombination. The nongeminate recombination has a significant impact on the IV curves of devices, namely its competition with charge carrier extraction causes a stronger bias dependence of the photocurrent of devices, in turn leading to the poor device fill factor. In addition our results demonstrate the importance of ultrafast free carrier generation and suppression of interfacial CT-state formation and question the applicability of the often used Braun-Onsager model to describe the bias dependence of the photocurrent in polymer:fullerene organic photovoltaic devices.

Photopatterning of cell-adhesive-modified poly(ethyleneimine) for guided neuronal growth.

We describe photopatterning technique that employs the photodegradation of cell-adhesive-modified poly(ethyleneimine) (m-PEI) to fabricate precise micropatterns on the indium tin oxide (ITO) substrate for guided neuronal growth. The photodegradation of m-PEI coated on hydroxyl group-terminated ITO substrate created micropatterns over a large area through deep UV irradiation. The photopatterned m-PEI layer can effectively guide neurite outgrowth and control neurite extensions from individual neurons.

Selective binding and detection of magnetic labels using PHR sensor via photoresist micro-wells.

We have developed a novel platform for selective binding of magnetic labels on planar Hall resistance sensor (PHR) for biosensing applications. The photoresist (PR) micro wells were prepared on the PHR sensor junctions to trap the magnetic bead at specified locations on the sensor surface and thin layer of Au was sputtered in the PR wells immobilize bimolecular. The Au surface is functionalized with single-stranded oligonucleotide and further biotin was used to immobilize streptavidin coated magnetic labels (Dynabeads Myone 1.0 microm, Invitrogen Co.). After removal of the PR wells on the sensor surface the non specific binding magnetic labels were successfully removed and only the chemically bounded magnetic labels were remained on the Au surface for detection of biomolecules using PHR sensor. We controlled the number of magnetic labels on the PHR sensor surface by using different sizes of the PR well on the junctions. The specifically bounded magnetic labels were successfully detected by characterizing the individual PHR sensor junctions. This technique enables the complete control over the magnetic labels for selective binding of biomolecules on the sensor surface for increasing the sensitivity of the PHR sensor as well as removal of the non specific bindings on the sensor surface.

Efficient Inverted Solar Cells Using Benzotriazole-Based Small Molecule and Polymers.

We synthesized medium-band-gap donor-acceptor (D-A) -type conjugated polymers (PBTZCZ-L and PBTZCZ-H) consisting of a benzotriazole building block as an acceptor and a carbazole unit as a donor. In comparison with the polymers, a small conjugated molecule (BTZCZ-2) was developed, and its structural, thermal, optical, and photovoltaic properties were investigated. The power conversion efficiency (PCE) of the BTZCZ-2-based solar cell devices was less than 0.5%, considerably lower than those of polymer-based devices with conventional device structures. However, inverted solar cell devices configured with glass/ITO/ZnO:PEIE/BTZCZ-2:PC71BM/MoO3/Ag showed a tremendously improved efficiency (PCE: 5.05%, Jsc: 9.95 mA/cm2, Voc: 0.89 V, and FF: 57.0%). We believe that this is attributed to high energy transfer and excellent film morphologies.

Thieno[3,2-b]thiophene-based conjugated polyfluorene copolymer for efficient polymer solar cell.

We have synthesized and characterized a polyfluorene derivative composed of octyl-substituted thieno[3,2,-b]thiophene and 2,1,3-benzothiadiazole as an acceptor unit. The best power conversion efficiencies of the polymer were showed with 1.63% and 2.31% by using PCBM and PC71BM, respectively.

Fine neurite patterns from photocrosslinking of cell-repellent benzophenone copolymer.

We have synthesized photocrosslinkable benzophenone copolymer, Poly(St-co-MBz), and fabricated cell-repellent patterns of Poly(St-co-MBz) on covalently bound poly-D-lysine (PDL) layer via the photocrosslinking. We have successfully obtained fine grid line pattern with line width of 3 µm and fine neurite, presumably axon, patterns with excellent pattern fidelity. We found that benzophenone unit can be crosslinked under the exposure of UV (with the intensity of ∼77 mW/cm² at 280 nm and ∼60 mW/cm² at 365 nm) without photo-oxidative damage to PDL, poly-L-lysine, and polyethyleneimine.

Enhancement of neuronal cell adhesion by covalent binding of poly-D-lysine.

We have prepared the poly-d-lysine (PDL) bound surfaces for neuron cell culture by covalent binding between the poly-d-Lysine and substrates and investigated neuronal cell adhesion properties and cell growth morphology. The number of neuronal cell and the number of neurite per neuronal cell on PDL bound surfaces was much more than those on PDL coated surfaces and also the neuronal cells on PDL bounded surfaces survived a longer time. On the pattern of covalently bound PDL, neuronal cells and their neurites are confined within the grid line leading to patterned neuronal networks with the long-term survival.

Sensitized near-IR luminescence of lanthanide complexes based on push-pull diketone derivatives.

Lanthanide complexes with two push-pull diketone derivatives as sensitizers have been developed as synthons for near-infrared emitting materials. The ligand substituents consist of a carbazole moiety with hole-transport properties and an aromatic or heteroaromatic unit. According to quantitative NMR analysis and complementary HPLC experiments, the diketones are predominantly in their enolic form in polar solvents such as THF and MeCN at room temperature. The preferred cis-enol form contributes strongly to the binding of lanthanide ions (Ln = Nd, Gd, Er). The resulting tris(diketonate) ternary complexes with terpyridine (Ln = Nd, Er) display sizeable near-IR emission with long luminescence lifetimes.

Sensitized emission of luminescent lanthanide complexes based on 4-naphthalen-1-yl-benzoic acid derivatives by a charge-transfer process.

The photophysical properties of 4-naphthalen-1-yl-benzoic acid ligands and their Eu(III)-cored complexes were systematically investigated to elucidate the effective energy-transfer pathway in luminescent lanthanide complexes. A series of 4-naphthalen-1-yl-benzoic acid ligands, such as 4-naphthalen-1-yl-benzoic acid (NA-1), 4-[4-(4-methoxyphenyl)-naphthalen-1-yl]-benzoic acid (NA-2), and 4-{4-[4-(4-methoxyphenyl)-naphthalen-1-yl]-benzyloxy}-benzoic acid (NA-3), were synthesized and utilized for the synthesis of their Eu(III)-cored complexes, corresponding to NAC-1, NAC-2, and NAC-3. The fluorescence spectra of NA-1 and NA-2 show large Stokes shifts with increasing solvent polarity. These large Stokes shifts might be dominantly due to the formation of an intramolecular charge transfer (ICT) complex in the excited state. Also, the intensive luminescence of the Eu(III) ions by the photoexcitation of the ligand in NAC-1 and NAC-2 in polar solvents supports that the energy transfer from the ligand to the Eu(III) ion takes place efficiently. In the case of NA-3, which has a -CH2OPh- group that acts as a blocking group, there is no dependence of the fluorescence spectrum on the solvent nature and no luminescence of the Eu(III) ions by the photoexcitation of the ligand, indicating no formation of the ICT state. This can be due to the fact that the formation of the ICT state in NA-3 was prevented because the -OCH2- group acts as a blocking group by interrupting the pi-conjugation between the benzoic acid and the naphthalene unit. From these photophysical studies, we suggest that the ICT state plays a very important role in the energy-transfer pathway from the ligand to the Eu(III) ion. To our best knowledge, this is the first demonstration of sensitized emission of luminescent lanthanide complexes based on 4-naphthalen-1-yl-benzoic acid derivatives by the charge-transfer process.