D.Y. Paraschuk

Ultrafast Charge Photogeneration Dynamics in Ground-State Charge-Transfer Complexes Based on Conjugated Polymers

The charge photogeneration and early recombination in MEH-PPV-based charge-transfer complexes (CTCs) and in MEH-PPV/PCBM blend as a reference are studied by ultrafast visible-pump-IR-probe spectroscopy. After excitation of the CTC band, an immediate (<100 fs) electron transfer is observed from the polymer chain to the acceptor with the same yield as in the MEH-PPV/PCBM blend. The forward charge transfer in the CTCs is followed by an efficient (approximately 95%) and fast (<30 ps) geminate recombination. For comparison, the recombination efficiency obtained in the MEH-PPV/PCBM blend does not exceed a mere 50%. Polarization-sensitive experiments demonstrate high (approximately 0.3) values of transient anisotropy for the CTCs polaron band. In contrast, in the MEH-PPV/PCBM blend the dipole moment orientation of the charge-induced transition is less correlated with the polarization of the excitation photon. According to these data, photogeneration and recombination of charges in the CTCs take place locally (i.e., within a single pair of a polymer conjugation segment and an acceptor) while in the MEH-PPV/PCBM blend exciton migration precedes the separation of charges. Results of the ultrafast experiments are supported by photocurrent measurements on the corresponding MEH-PPV/acceptor photodiodes.

Effect of doping on performance of organic solar cells

Conventional models of planar and bulk heterojunction organic solar cells have been extended by introducing doping in the active layer. We have studied the performance of organic solar cells as a function of dopant concentration. For bulk heterojunction cells, the modeling shows that for the most studied material pair (poly-3-hexylthiophene, P3HT, and phenyl-C61-butyric acid methyl ester, PCBM) doping decreases the short-circuit current density (JSC), fill factor (FF) and efficiency. However, if bulk heterojunction cells are not optimized, namely, at low charge carrier mobilities, unbalanced mobilities or non-ohmic contacts, the efficiency can be increased by doping. For planar heterojunction cells, the modeling shows that if the acceptor layer is n doped, and the donor layer is p doped, the open-circuit voltage, JSC, FF and hence the efficiency can be increased by doping. Inversely, when the acceptor is p doped, and the donor is n doped; FF decreases rapidly with increasing dopant concentrations so that the current-voltage curve becomes S shaped. We also show that the detrimental effect of nonohmic contacts on the performance of the planar heterojunction cell can be strongly weakened by doping.

Efficient two-step photogeneration of long-lived charges in ground-state charge-transfer complexes of conjugated polymer doped with fullerene

Polarization-sensitive time-resolved visible-infrared pump-probe experiments demonstrate that one can efficiently generate long-lived charges in donor-acceptor charge transfer complex (CTC) of conjugated polymer doped with fullerene, MEH-PPV/dinitroanthraquinone/C(60). In particular, a strong enhancement of the photoinduced charge generation is observed in the red part of the spectrum, i.e. inside the polymer band gap, which makes the current material attractive for photovoltaic applications. The spectroscopic results indicate that enhanced generation of charges is due to a consecutive photoinduced electron transfer from the polymer to the CTC-acceptor in the first step and then, in the second step, to the fullerene. The LUMO energy difference between the CTC-acceptor and fullerene appears to be a key parameter for efficient charge separation in these ternary systems. The results are also discussed in respect to the charge generation processes in widely used polymer-fullerene blends, where formation of weak CTCs has recently been discovered.

Oligothiophene-based monolayer field-effect transistors prepared by Langmuir-Blodgett technique

Quinquethiophene-based monolayer organic field-effect transistors (OFETs) prepared by Langmuir-Blodgett (LB) technique show hole mobilities up to 10−2 cm2/Vs and On/Off ratios up to 106. Functional logic LB monolayer devices operating in air have been demonstrated. The performance of LB OFETs is comparable to self-assembled monolayer field-effect transistors (SAMFETs) devices prepared by self-assembly from solution using the same organosilicon oligothiophene despite the LB OFET monolayer is weakly bounded to the dielectric surface. Taking into account that the LB technique is a fast and rather easy process, these findings highlight a high potential of LB technique for ultrathin organic electronics.

Dramatic enhancement of photo-oxidation stability of a conjugated polymer in blends with organic acceptor

Photo-oxidation of a prototype conjugated polymer poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) in blended films with 2,4,7-trinitrofluorenone (TNF) is drastically suppressed upon exposure to green laser radiation under ambient conditions that was observed by using Fourier transform infrared spectroscopy. By increasing the TNF concentration in MEH-PPV, we have found that the photo-oxidation rate and the photoluminescence intensity drop together in a correlated way by three orders of magnitude. We suggest that triplet exciton formation in the MEH-PPV/TNF blends is deeply suppressed blocking the photo-oxidation. These findings may open a way to intrinsically photostable conjugated polymer materials for photonic and photoelectric applications.

Highly Luminescent Solution-Grown Thiophene-Phenylene Co-Oligomer Single Crystals

Thiophene-phenylene co-oligomers (TPCOs) are among the most promising materials for organic light emitting devices. Here we report on record high among TPCO single crystals photoluminescence quantum yield reaching 60%. The solution-grown crystals are stronger luminescent than the vapor-grown ones, in contrast to a common believe that the vapor-processed organic electronic materials show the highest performance. We also demonstrate that the solution-grown TPCO single crystals perform in organic field effect transistors as good as the vapor-grown ones. Altogether, the solution-grown TPCO crystals are demonstrated to hold great potential for organic electronics.

Acceptor-Enhanced Local Order in Conjugated Polymer Films.

Disorder in conjugated polymers is a general drawback that limits their use in organic electronics. We show that an archetypical conjugated polymer, MEH-PPV, enhances its local structural and electronic order upon addition of an electronic acceptor, trinitrofluorenone (TNF). First, acceptor addition in MEH-PPV results in a highly structured XRD pattern characteristic for semicrystalline conjugated polymers. Second, the surface roughness of the MEH-PPV films increases upon small acceptor addition, implying formation of crystalline nanodomains. Third, the low-frequency Raman features of the polymer are narrowed upon TNF addition and indicate decreased inhomogeneous broadening. Finally, the photoinduced absorption and surface photovoltage spectroscopy data show that photoexcited and dark polymer intragap electronic states assigned to deep defects disappear in the blend. We relate the enhanced order to formation of a charge-transfer complex between MEH-PPV and TNF in the electronic ground state. These findings may be of high importance to control structural properties as they demonstrate an approach to increasing the order of a conjugated polymer by using an acceptor additive.

Highly-emissive solution-grown furan/phenylene co-oligomer single crystals

Solution-processed furan/phenylene co-oligomer single crystals combine high photoluminescence quantum yield (>65%) and efficient charge transport (mobility 0.12 cm2 V−1 s−1) making them promising materials for printable organic optoelectronics.

Luminescent Organic Semiconducting Langmuir Monolayers

In recent years, monolayer organic field-effect devices such as transistors and sensors have demonstrated their high potential. In contrast, monolayer electroluminescent organic field-effect devices are still in their infancy. One of the key challenges here is to create an organic material that self-organizes in a monolayer and combines efficient charge transport with luminescence. Herein, we report a novel organosilicon derivative of oligothiophene-phenylene dimer D2-Und-PTTP-TMS (D2, tetramethyldisiloxane; Und, undecylenic spacer; P, 1,4-phenylene; T, 2,5-thiophene; TMS, trimethylsilyl) that meets these requirements. The self-assembled Langmuir monolayers of the dimer were investigated by steady-state and time-resolved photoluminescence spectroscopy, atomic force microscopy, X-ray reflectometry, and grazing-incidence X-ray diffraction, and their semiconducting properties were evaluated in organic field-effect transistors. We found that the best uniform, fully covered, highly ordered monolayers were semiconducting. Thus, the ordered two-dimensional (2D) packing of conjugated organic molecules in the semiconducting Langmuir monolayer is compatible with its high-yield luminescence, so that 2D molecular aggregation per se does not preclude highly luminescent properties. Our findings pave the way to the rational design of functional materials for monolayer organic light-emitting transistors and other optoelectronic devices.

Fill factor in organic solar cells can exceed the Shockley-Queisser limit

The ultimate efficiency of organic solar cells (OSC) is under active debate. The solar cell efficiency is calculated from the current-voltage characteristic as a product of the open-circuit voltage (VOC), short-circuit current (JSC), and the fill factor (FF). While the factors limiting VOC and JSC for OSC were extensively studied, the ultimate FF for OSC is scarcely explored. Using numerical drift-diffusion modeling, we have found that the FF in OSC can exceed the Shockley-Queisser limit (SQL) established for inorganic p–n junction solar cells. Comparing charge generation and recombination in organic donor-acceptor bilayer heterojunction and inorganic p–n junction, we show that such distinctive properties of OSC as interface charge generation and heterojunction facilitate high FF, but the necessary condition for FF exceeding the SQL in OSC is field-dependence of charge recombination at the donor-acceptor interface. These findings can serve as a guideline for further improvement of OSC.