Evolution of vertical phase separation in P3HT:PCBM thin films induced by thermal annealing

The achievement of the desirable morphology at the nanometer scale of bulk heterojunctions consisting of a conjugated polymer with fullerene derivatives is a prerequisite in order to optimize the power conversion efficiency of organic solar cells. The various experimental conditions such as the choice of solvent, drying rates and annealing have been found to significantly affect the blend morphology and the final performance of the photovoltaic device. In this work, we focus on the effects of post deposition thermal annealing at 140 °C on the blend morphology, the optical and structural properties of bulk heterojunctions that consist of poly(3-hexylthiophene) (P3HT) and a methanofullerene derivative (PCBM). The post thermal annealing modifies the distribution of the P3HT and the PCBM inside the blend films, as it has been found by Spectroscopic Ellipsometry studies in the visible to far-ultraviolet spectral range. Phase separation was identified by AFM and GIXRD as a result of a slow drying process which took place after the spin coating process. The increase of the annealing time resulted to a significant increase of the P3HT crystallinity at the top regions of the blend films. © 2011 Elsevier B.V. All rights reserved.

Thermal annealing effect on the nanomechanical properties and structure of P3HT:PCBM thin films

Nanostructured polymer-fullerene thin films are among the most prominent materials for application in high efficient polymer solar cells. Specifically, poly(3-hexylthiophene) (P3HT) and fullerene derivatives (PCBM) blends are used as the donor/acceptor materials forming a bulk heterojunction. Although P3HT:PCBM properties have been extensively studied, less light has been set on its nanomechanical properties, which affect the device service life. In this work Atomic Force Acoustic Microscopy (AFAM), Atomic Force Spectroscopy and Nanoindentation were used to study the effect of the fullerene presence and the annealing on the P3HT:PCBM nanomechanical behavior. The P3HT:PCBM thin films were prepared by spin coating on glass substrates and then annealed at 100 °C and 145 °C for 30 min. Large phase separation was identified by optical and Atomic Force Microscopy (AFM) for the annealed samples. Needle-like PCBM crystals were formed and an increase of the polymer crystallinity degree with the increase of the annealing temperature was confirmed by X-ray diffraction. AFAM characterization revealed the presence of aggregates close to stiff PCBM crystals, possibly consisting of amorphous P3HT material. AFM force-distance curves showed a continuous change in stiffness in the vicinity of the PCBM crystals, due to the PCBM depletion near its crystals, and the AFM indentation provided qualitative results about the changes in P3HT nanomechanical response after annealing. © 2011 Elsevier B.V. All rights reserved.

Graphene nanoribbon blends with P3HT for organic electronics.

In organic field-effect transistors (OFETs) the electrical characteristics of polymeric semiconducting materials suffer from the presence of structural/morphological defects and grain boundaries as well as amorphous domains within the film, hindering an efficient transport of charges. To improve the percolation of charges we blend a regioregular poly(3-hexylthiophene) (P3HT) with newly designed N = 18 armchair graphene nanoribbons (GNRs). The latter, prepared by a bottom-up solution synthesis, are expected to form solid aggregates which cannot be easily interfaced with metallic electrodes, limiting charge injection at metal-semiconductor interfaces, and are characterized by a finite size, thus by grain boundaries, which negatively affect the charge transport within the film. Both P3HT and GNRs are soluble/dispersible in organic solvents, enabling the use of a single step co-deposition process. The resulting OFETs show a three-fold increase in the charge carrier mobilities in blend films, when compared to pure P3HT devices. This behavior can be ascribed to GNRs, and aggregates thereof, facilitating the transport of the charges within the conduction channel by connecting the domains of the semiconductor film. The electronic characteristics of the devices such as the Ion/Ioff ratio are not affected by the addition of GNRs at different loads. Studies of the electrical characteristics under illumination for potential use of our blend films as organic phototransistors (OPTs) reveal a tunable photoresponse. Therefore, our strategy offers a new method towards the enhancement of the performance of OFETs, and holds potential for technological applications in (opto)electronics.

Fabrication of ZnO and its enhancement of charge injection and transport in hybrid organic/inorganic light emitting devices

ZnO nanocrystals were synthesized by hydrolysis in methanol. X-ray diffraction and photoluminescence spectra confirm that good crystallized ZnO nanoparticles were formed. Utilizing those ZnO nanoparticles and poly [2- methoxy-5 - (3',7'-dimethyloctyloxy)- 1,4-phenylenevinylene] (MDMO-PPV), light emitting devices with indium tin oxide (ITO)/poly(3,4-oxyethyleneoxy-thiophene):poly(styrene sulfonate) (PEDOT:PSS)/ ZnO:MDMO-PPV/Al and ITO/PEDOT:PSS/MDMO-PPV/Al structures were fabricated. Electrolummescence (EL) spectra reveal that EL yield of hybrid MDMO-PPV and ZnO nanocrystals devices increased greatly as compared with pristine MDMO-PPV devices. The current-voltage characteristics indicate that addition of ZnO nanocrystals can facilitate electrical injection and charge transport. The decreased energy barrier to electron injection is responsible for the increased efficiency of electron injection. (c) 2007 Elsevier B.V. All rights reserved.

Enhanced photoresponse from the ordered microstructure of naphthalocyanine-carbon nanotube composite film

Naphthalocyanine-sensitized multi-walled carbon nanotube (NaPc-MWNT) composites have been synthesized through the pi-stacking between naphthalocyanine (NaPc) and carbon nanotubes. The resultant nanocomposites were characterized with a scanning electron microscope (SEM), a transmission electron microscope (TEM), and by UV - vis absorption and photocurrent spectra. The long-range ordering was observed in the NaPc - MWNT composites by using a TEM. The enhancement in the absorption intensity and the broadening of the absorption wavelength observed in the composite films, which were due to the attachment of NaPc on the MWNT surface, is discussed based on the measured UV - vis absorption spectra. Furthermore, the photoconductivity of the poly( 3-hexylthiophene)(PAT6) - NaPc - MWNT composite film was found to increase remarkably in the visible region and broaden towards the red regions. These new phenomena were ascribed to the larger donor/acceptor (D/A) interface and the formation of a biconsecutive D/A network structure, as discussed in consideration of the photoinduced charge transfer between PAT6 and NaPc - MWNT.

Broadband short-range surface plasmon structures for absorption enhancement in organic photovoltaics

We theoretically demonstrate a polarization-independent nanopatterned ultra-thin metallic structure supporting short-range surface plasmon polariton (SRSPP) modes to improve the performance of organic solar cells. The physical mechanism and the mode distribution of the SRSPP excited in the cell device were analyzed, and reveal that the SRSPP-assisted broadband absorption enhancement peak could be tuned by tailoring the parameters of the nanopatterned metallic structure. Three-dimensional finite-difference time domain calculations show that this plasmonic structure can enhance the optical absorption of polymer-based photovoltaics by 39% to 112%, depending on the nature of the active layer (corresponding to an enhancement in short-circuit current density by 47% to 130%). These results are promising for the design of organic photovoltaics with enhanced performance.

Phase transition behavior and molecular orientation of oligo(9,9 '-dioctylfluorene-alt-bithiophene)

A novel conjugated oligomer, oligo(9,9'-dioctylfluorene-alt-bithiophene) (OF8T2), was found to exhibit a unique phase transition between crystalline and liquid-crystalline states, and a liquid-crystalline glass was easily generated, offering better TFT device performance. In thin films, upon annealing the OF8T2 molecules oriented preferentially with their planes of conjugation being normal to the substrate, and both film thickness and annealing temperature were critical to the film morphology and the molecular orientation. When the OF8T2 film was deposited on a rubbed polyimide surface and annealed, the molecules aligned their long axes along the rubbing direction.

Improving performance of polymer photovoltaic devices using an annealing-free approach via construction of ordered aggregates in solution

Low crystalline order has been proved to be one of the main hindrances for achieving high performance devices based on thin films composed of crystallizable polymer. In this work, we use a facile method to substantially improve crystallinity of poly(3-hexylthiophene) (P3HT) in its pure or composite film via the construction of ordered precursors in the solution used for thin film deposition. These improvements have been confirmed by bright-field transmission electron micrography, electron diffraction, UV-Vis absorption and wide-angle X-ray diffraction.

Epitaxy-Assisted Creation of PCBM Nanocrystals and Its Application in Constructing Optimized Morphology for Bulk-Heterojunction Polymer Solar Cells

PCBM (a C-60 derivative) is so far the most successful electron acceptor for bulk-heterojunction polymer photovoltaic (PV) cells. Here we present a novel method epitaxy-assisted creation of PCBM nanocrystals and their homogeneous distribution in the matrix using freshly cleaved mica sheet as the substrate. The highly matched epitaxy relationship between the unit cell of PCBM crystal and crystallographic (001) surface of mica induces abundant PCBM nuclei, which subsequently develop into nanoscale crystals with homogeneous dispersion in the composite film.

The effect of annealing treatment on performance of interdiffused organic photovoltaic devices

We fabricated the interdiffused organic photovoltaic devices, which composed of poly (2-methoxy-5-(2'-ethylhexyloxy)-1, 4-phenylenevinylene) (MEH-PPV) and buckminsterfullerene (C-60), by annealing treatment. After annealing, C60 diffused into the MEH-PPV layer, in consequence, MEH-PPV/C-60 interfacial area was increased and their interface became closer proximity. The results lead to reduce reverse-bias saturation current (J(s)), and increase the open-circuit voltage (V-OC) and the short-circuit current (J(SC)).

Effects of thermal annealing on polymer photovoltaic cells with buffer layers and in situ formation of interfacial layer for enhancing power conversion efficiency

We have investigated the effects of thermal annealing before and after cathode deposition on poly(3-hexylthiophene)(P3HT)/[6,6]-phenyl C61-butyric acid methyl ester (PCBM) blend photovoltaic cells with different cathode buffer layers. The introduction of cathode buffer layer such as lithium fluoride (LiF) and calcium oxide (CaO) in pre-annealing cells can increase the open-circuit voltage (V-oc) and the power conversion efficiency (PCE). Post thermal annealing after cathode deposition further enhanced the PCE of the cells with LiF/Al cathode.

Synthesis and characterization of phenylene-thiophene all-conjugated diblock copolymers

Grignard metathesis (GRIM) polymerization for all-conjugated diblock copolymers comprising poly (2,5-dihexyloxy-1,4-phenylene) (PPP) and poly(3-hexylthiophene) (P3HT) blocks were systematically studied with LiCl as additive and 1,2-bis (diphenylphosphino) ethane nickel dichloride (Ni(dppe)Cl-2) or 1,3-bis(diphenylphosphino) propane nickel dichloride (Ni(dppp)Cl-2) as catalyst. It was found that the addition order of the monomers was crucial for the success of copolymerization. With the monomer addition in the order of phenyl and then thienyl Grignard reagents, all-conjugated PPP-b-P3HT diblock copolymers with different block ratios were successfully synthesized. In contrast, the inverted addition order only afforded a mixture containing both block copolymers and deactivated or end-capped homopolymers.

Constructing Thin Polythiophene Film Composed of Aligned Lamellae via Controlled Solvent Vapor Treatment

Thin poly(3-butylthiophene) (P3BT) film composed of aligned lamellae attached to the edge of the original film has been achieved via a controlled solvent vapor treatment (C-SVT) method. The polarized optical microscopy operated at both single-polarization and cross-polarization modes has been used to investigate the alignment of the fiber-like lamellae. A numerical simulation method is used to quantitatively calculate angle distributions of the lamellae deviated from the film growth direction. Prepatterned P3BT film edge acts as nuclei which densely initialize subsequent crystal growth by exhausting the materials transported from the partially dissolved film. The growth of new film upon crystallization is actually a self-healing process where the two-dimensional geometric confinement is mainly responsible for this parallel alignment of P3BT crystals. The solvent vapor pressure should be carefully chosen so as to induce crystal growth but avoid liquid instability which will destroy the continuity of the film.