Growth of Highly Oriented Ultrathin Crystalline Organic Microstripes: Effect of Alkyl Chain Length.

The growth of organic semiconductor with controllable morphology is a crucial issue for achieving high-performance devices. Here we present the systematic study of the effect of the alkyl chain attached to the functional entity on controlling the growth of oriented microcrystals by dip-coating. Alkylated DTBDT-based molecules with variable chain lengths from n-butyl to n-dodecyl formed into one-dimensional micro- or nanostripe crystals at different pulling speeds. The alignment and ordering are significantly varied with alkyl chain length, as is the transistor performance. Highly uniform oriented and higher-molecular-order crystalline stripes with improved field-effect mobility can be achieved with an alkyl-chain length of around 6. We attribute this effect to the alkyl-chain-length-dependent packing, solubility, and self-assembly behavior.

High-efficiency crystalline white organic light-emitting diodes.

Crystalline white organic light-emitting diodes (C-WOLEDs) are promising candidates for lighting and display applications. It is urgently necessary, however, to develop energy-saving and high-efficiency C-WOLEDs that have stable and powerful emission to meet commercial demands. Here, we report a crystalline host matrix (CHM) with embedded nanoaggregates (NA) structure for developing high-performance C-WOLEDs by employing a thermally activated delayed fluorescence (TADF) material and orange phosphorescent dopants (Phos.-D). The CHM-TADFNA-D WOLED exhibit a remarkable EQE of 12.8%, which is the highest performance WOLEDs based on crystalline materials. The device has a quick formation of excitons and a well-designed energy transfer process, and possesses a fast ramping of luminance and current density. Compared to recently reported high-performance WOLEDs based on amorphous material route, the C-WOLED achieves a low series-resistance Joule-heat loss ratio and an enhanced photon output, demonstrating its significant potential in developing the next-generation WOLEDs.

Efficient organic photovoltaic cells with vertically ordered bulk heterojunctions.

Nanoscale morphology has been proved to be the key parameter deciding the exciton dissociation and charge transportation in bulk heterojunction (BHJ) solar cells. In this paper, we report a kind of small molecular organic photovoltaic cell (OPV) with a vertically ordered BHJ prepared by the weak epitaxial growth method. By this method, zinc phthalocyanine (ZnPc) can easily be formed into a highly ordered and continuous thin film and C60 is inclined to become dispersed crystalline grains in ZnPc film. Furthermore, we can control both the size and distribution density of C60 crystalline grains in ZnPc thin film without destroying the order of the ZnPc thin film. The OPVs with the vertically ordered BHJ show a high fill factor and a power conversion efficiency over 3% has been achieved.

Crystalline organic thin films for crystalline OLEDs (II): weak epitaxy growth of phenanthroimidazole derivatives.

The ordered molecular arrangement of crystalline organic semiconductors facilitates high carrier mobility and light emission in organic light-emitting diode (OLED) devices. It has been demonstrated that the weak epitaxy growth (WEG) process is a valuable crystallization route for fabricating crystalline thin-film OLEDs (C-OLEDs). Recently, C-OLEDs based on crystalline thin films of phenanthroimidazole derivatives have exhibited excellent luminescent properties such as high photon output at low driving voltage and high power efficiency. Achieving effective control of organic crystalline thin film growth is crucial for the development of new C-OLEDs. Herein, we report the studies on morphology structure and growth behavior of the phenanthroimidazole derivative WEG thin films. The oriented growth of WEG crystalline thin films is determined by channeling and lattice matching between the inducing layer and active layer. Large-size and continuous WEG crystalline thin films can be obtained by controlling the growth conditions.

An Efficient Blue-Emission Crystalline Thin-Film OLED Sensitized by "Hot Exciton" Fluorescent Dopant.

Crystalline thin-film organic light-emitting diodes (C-OLEDs) can achieve a large light emission and a low Joule-heat loss under low driving voltage due to the high carrier mobility of the crystalline thin films. However, it is urgent for the C-OLEDs to improve their external quantum efficiency (EQE). Here, a novel strategy is proposed using a doped "hot exciton" material to sensitize a high PLQY blue emitter in C-OLEDs. Benefiting from the capability of the "hot exciton" material harnessing triplet/singlet excitons, the C-OLED exhibits an efficiency breakthrough with a maximum EQE of 6.2%, a much enhanced blue photon output with pure blue emission Commission International de L'Eclairage (CIE) (0.14, 0.15), a low turn-on/operation voltage of 2.6 V(@1 cd m-2 )/3.8 V (@1000 cd m-2 ), and a maximum power efficiency (PE) of 9.4 lm W-1 . This work unlocks the potential of C-OLEDs for achieving high photon output with high EQE.

Novel conjugated polymers based on dithieno[3,2-b:6,7-b]carbazole for solution processed thin-film transistors.

Two conjugated polymers (CPs) P-tCzC12 and P-tCzC16 comprising alternating dithieno[3,2-b:6,7-b]carbazole and 4,4'-dihexadecyl-2,2'-bithiophene units have been designed and synthesized. Upon thermal annealing, they can form ordered thin films in which the polymer backbones dominantly adopted an edge-on orientation respective to the substrate with a lamellar spacing of ≈24 Å and a π-stacking distance of ≈3.7 Å. Organic thin-film transistors (OTFTs) were fabricated by solution casting. A hole mobility of 0.39 cm(2) V(-1) s(-1) has been demonstrated with P-tCzC16. This value is the highest among the CPs containing heteroacenes larger than 4 rings.

Highly ordered thin films of 5,5''-bis(3'-fluoro-biphenyl-4-yl)-2,2' : 5',2''-terthiophene with two meso-phases.

The growth process and phase state of 5,5''-bis(3'-fluoro-biphenyl-4-yl)-2,2' : 5',2''- terthiophene (m-F2BP3T) thin films were investigated by atomic force microscopy (AFM), in-plane and out-of-plane X-ray diffraction (XRD), and selected area electron diffraction (SAED). Two meso-phases (thin film phases) of m-F2BP3T films on SiO(2) surface were obtained in the early stages. The m-F2BP3T films initially exhibited two-dimensional (2D) layers (≤4 ML) followed by three-dimensional (3D) island growth. The film structure evolved two thin film phases in the first four layers and the bulk phase was formed from the fifth layer, which occurred concomitantly with the change of the growth mode. Moreover, the variation of weak epitaxy growth behavior of ZnPc from 2D to 3D growth further reflects that the phase state of the first three layers is different from that of the fourth layer, in spite of ZnPc crystals showing just one orientation corresponding to commensurate epitaxy. The novel phase behavior is closely related to the synergistic effects of the outstanding soft matter properties, limited elasticity of organic molecules, and strain originating from the SiO(2) substrate. This study investigates novel phase behavior in organic thin films and provides significant insight into the mechanism of the phase transition.

High-efficiency blue-emission crystalline organic light-emitting diodes sensitized by "hot exciton" fluorescent nanoaggregates.

Sensitizing fluorescent materials is an effective way to maximally use excitons and obtain high-efficiency blue organic light-emitting diodes (OLEDs). However, it is a persistent challenge for present amorphous thin-film OLEDs to improve photon emission under low driving voltage, severely impeding the development of OLED technology. Here, we propose a novel OLED architecture consisting of a crystalline host matrix (CHM) and embedded "hot exciton" nanoaggregates (HENAs), which effectively sensitize blue dopant (D) emission. Owing to the advantages of the crystalline thin-film route, the device exhibits largely enhanced blue photon output [Commission International de L'Eclairage coordinates of (0.15, 0.17)], with a low turn-on/operation voltage of 2.5 V (at 1 cd/m2)/3.3 V (at 1000 cd/m2), an extremely low Joule heat loss ratio (7.8% at 1000 cd/m2), and a maximum external quantum efficiency (EQE) up to 9.14%. These areal photon output features have outperformed the present amorphous thin-film blue OLEDs with high EQE, demonstrating that the CHM-HENA-D OLED is promising for future OLEDs.

Weak epitaxy growth of organic semiconductor thin films.

The fabrication of organic semiconductor thin films is extremely important in organic electronic devices. This tutorial review--which should particularly appeal to chemists and physicists interested in organic thin-film growth, organic electronic devices and organic semiconductor materials--summarizes the method of weak epitaxy growth (WEG) and its application in the fabrication of high quality organic semiconductor thin films. WEG achieves the thin-film fabrication of disk-like organic semiconductor molecules with highly structural order, molecular level smoothness and large size domains on amorphous substrate. The organic field-effect transistor devices based on these thin films exhibit a high charge mobility that is comparable with their corresponding single-crystal devices. Moreover, it provides a way to produce organic superlattices.

Integrated molecular diode as 10 MHz half-wave rectifier based on an organic nanostructure heterojunction.

Considerable efforts have been made to realize nanoscale diodes based on single molecules or molecular ensembles for implementing the concept of molecular electronics. However, so far, functional molecular diodes have only been demonstrated in the very low alternating current frequency regime, which is partially due to their extremely low conductance and the poor degree of device integration. Here, we report about fully integrated rectifiers with microtubular soft-contacts, which are based on a molecularly thin organic heterojunction and are able to convert alternating current with a frequency of up to 10 MHz. The unidirectional current behavior of our devices originates mainly from the intrinsically different surfaces of the bottom planar and top microtubular Au electrodes while the excellent high frequency response benefits from the charge accumulation in the phthalocyanine molecular heterojunction, which not only improves the charge injection but also increases the carrier density.

Monodisperse co-oligomer approach toward nanostructured films with alternating donor-acceptor lamellae.

A series of donor-acceptor (D-A) co-oligomers with oligo(fluorene-alt-bithiophene) and perylene diimide as donor and acceptor segments, respectively, have been designed and synthesized. They can self-assembly into alternating D-A lamellar nanostructured films with the periods depending on the molecular length. These films have been successfully used in fabrication of high-performance single-molecular solar cells with power conversion efficiency up to 1.50%.

Weak epitaxy growth of copper hexadecafluorophthalocyanine (F16CuPc) on p-sexiphenyl monolayer film.

Weak epitaxy growth (WEG) behavior and mechanism of copper hexadecafluorophthalocyanine (F16CuPc) on p-sexiphenyl (p-6P) monolayer film were investigated by atomic force microscopy (AFM), selected area electron diffraction (SEAD), and wide-angle X-ray diffraction (WAXD). High-quality F16CuPc films with high order, large size, and molecular-level smoothness were obtained successfully by WEG method. It was identified that there exists incommensurate epitaxial relation between highly oriented F16CuPc and p-6P films. The geometrical channels of p-6P monolayer surface induce the nucleation and growth of F16CuPc molecules. Two kinds of in-plane structures, referred to as "phase I" and "phase II", coexist in the initial few molecular layers. As thin-film thickness increases, the distance of (001) plane diminishes and phase I disappears. Furthermore, coalescence, dislocation, and high-angle grain boundary between F16CuPc neighboring domains were observed by high-resolution AFM.

The first liquid crystalline phthalocyanine derivative capable of edge-on alignment for solution processed organic thin-film transistors.

Tetraoctyl-substituted vanadyl phthalocyanine (OVPc4C8) as a new NIR-absorbing discotic liquid crystalline material can form highly ordered thin films with edge-on alignment of the molecules and molecular packing mode identical to that in the phase II of OVPc for solution processed OTFTs with mobility up to 0.017 cm(2) V(-1) s(-1).

Weak epitaxy growth and phase behavior of planar phthalocyanines on p-sexiphenyl monolayer film.

We systematically investigated the weak epitaxy growth (WEG) behavior of a series of planar phthalocyanine compounds (MPc), i.e., metal-free phthalocyanine (H2Pc), nickel phthalocyanine (NiPc), copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), iron phthalocyanine (FePc), cobalt phthalocyanine (CoPc), grown on a p-sexiphenyl ( p-6P) monolayer film by selected area electron diffraction (SAED) and atomic force microscopy (AFM). Two types of epitaxial relations, named as incommensurate epitaxy and commensurate epitaxy, were identified between phthalocyanine compounds and the substrate of the p-6P film. The tiny variation of the lattice constant of phthalocyanine compounds can result in different crystal orientations. The change rule of incommensurate and commensurate epitaxy was extracted. The tendency of commensurate epitaxy becomes weaker as the lattice constant b increases, while it gets stronger as the substrate temperature is elevated. Large size and continuous H2Pc films can be obtained by controlling the growth conditions. The WEG method is generally applicable in the whole family of planar phthalocyanine compounds and may be used to fabricate other high-quality organic films.

Weak epitaxy growth of metal-free phthalocyanine on p-sexiphenyl monolayer and double-layer films.

Weak epitaxy growth (WEG) can afford high-mobility thin films of disk-like organic semiconductor of which mobility is up to the level of the corresponding single crystals. We investigated the WEG behavior and mechanism of planar phthalocyanine in the model system of metal-free phthalocyanine (H2Pc) grown on p-sexiphenyl (p-6P) ultrathin films (monolayers and double layers). Highly oriented H2Pc films with molecules standing up exhibited two kinds of different in-plane orientations, i.e., three sets of in-plane orientations and only one set of in-plane orientation, on p-6P monolayer and double-layer films, respectively. The surface geometrical channels of p-6P substrate dominated the oriented nucleation and growth of H2Pc film. Consequently, the H2Pc film showed incommensurate and commensurate epitaxy on p-6P ultrathin films.

Ultrathin-film growth of para-sexiphenyl (I): submonolayer thin-film growth as a function of the substrate temperature.

The para-sexiphenyl (p-6P) monolayer film induces weak epitaxy growth (WEG) of disk-like organic semiconductors, and their charge mobilities are increased dramatically to the level of the corresponding single crystals [Wang et al., Adv. Mater. 2007, 19, 2168]. The growth behavior and morphology of p-6P monolayer film play decisive roles on WEG. Here, we investigated the growth behavior of p-6P submonolayer film as a function of the substrate temperature. Its growth exhibited two different mechanisms at high and low substrate temperature. At high substrate temperature (>60 degrees C), the mechanism of diffusion-limited aggregation controlled the growth of submonolayer thin film with fractal islands, whereas at low substrate temperature (< or =60 degrees C), the submonolayer thin film was composed of the compact islands. Its growth exhibited another growth mechanism in which the stable compact islands were formed by dissociation and reorganization of the metastable disordered film. The substrate temperature of about 180 degrees C may be optimal to fabricate high-quality p-6P monolayer film with large-size domains and low saturated island density of about 0.018 microm(-2).

Ultrathin-film growth of para-sexiphenyl (II): formation of large-size domain and continuous thin film.

The large-size domain and continuous para-sexiphenyl (p-6P) ultrathin film was fabricated successfully on silicon dioxide (SiO2) substrate and investigated by atomic force microscopy and selected area electron diffraction. At the optimal substrate temperature of 180 degrees C, the first-layer film exhibits the mode of layer growth, and the domain size approaches 100 microm(2). Its saturated island density (0.018 microm(-2)) is much smaller than that of the second-layer film (0.088 microm(-2)), which begins to show the Volmer-Weber growth mode. The characteristic of liquid-like crystal of p-6P monolayer film and the adequate diffusion of p-6P molecules dominate the formation of large-size domain. The coalescence of large-size domains offers the possibility to grow high-quality p-6P monolayer film which provides excellent substrate for weak epitaxy growth of phthalocyanine compounds.

Organic High Electron Mobility Transistors Realized by 2D Electron Gas.

A key breakthrough in inorganic modern electronics is the energy-band engineering that plays important role to improve device performance or develop novel functional devices. A typical application is high electron mobility transistors (HEMTs), which utilizes 2D electron gas (2DEG) as transport channel and exhibits very high electron mobility over traditional field-effect transistors (FETs). Recently, organic electronics have made very rapid progress and the band transport model is demonstrated to be more suitable for explaining carrier behavior in high-mobility crystalline organic materials. Therefore, there emerges a chance for applying energy-band engineering in organic semiconductors to tailor their optoelectronic properties. Here, the idea of energy-band engineering is introduced and a novel device configuration is constructed, i.e., using quantum well structures as active layers in organic FETs, to realize organic 2DEG. Under the control of gate voltage, electron carriers are accumulated and confined at quantized energy levels, and show efficient 2D transport. The electron mobility is up to 10 cm2 V-1 s-1 , and the operation mechanisms of organic HEMTs are also argued. Our results demonstrate the validity of tailoring optoelectronic properties of organic semiconductors by energy-band engineering, offering a promising way for the step forward of organic electronics.

A self-immolative and DT-diaphorase-activatable prodrug for drug-release tracking and therapy.

DT-diaphorase, which catalyzes the reduction of various biological substances like quinones, is overexpressed in some malignant tumors. However, exploiting this attractive property for the controlled release of an active drug from a prodrug is yet to be fully taken advantage of. Herein we report a DT-diaphorase-based prodrug for concomitant drug-release imaging and cancer chemotherapy. This prodrug system is composed of two camptothecin (CPT) moieties as the active anticancer drug, a DT-diaphorase-responsive quinone propionic acid moiety and a set of self-immolative linkers. The presence of DT-diaphorase leads to the release of two CPT molecules and restores the fluorescence of the latter, thereby realizing the fluorescence monitoring of the DT-diaphorase level as well as the tracking of CPT release. Upon internalization by DT-diaphorase overexpressing cells, the prodrug can release fluorescent CPT and exhibit high cytotoxicity (half-maximal inhibitory concentration 0.71 µM) towards the cancer cells. This prodrug features on-demand enzyme-biomarker-triggered drug release as well as self-monitoring of drug release, therapeutic effect and biomarker level. This new strategy may provide an effective approach for constructing prodrugs with enhanced drug loading as well as controllability for drug release and tracking.