Organic Thin‐Film Transistors Based on Tolyl‐Substituted Oligothiophenes

Thin films based on the tolyl‐substituted oligothiophenes 5,5′′‐bis(4‐methylphenyl)‐2,2′:5′,2′′‐terthiophene ( 1 ), 5,5′′′‐bis(4‐methylphenyl)‐2,2′:5′,2′′:5′′,2′′′‐quaterthiophene ( 2 ) and 5,5′′′′‐bis(4‐methylphenyl)‐2,2′:5′,2′′:5′′,2′′′:5′′′,2′′′′‐quinqethiophene ( 3 ) exhibit hole‐transport behavior in a thin‐film transistor (TFT) configuration, with reasonable mobilities and high current on/off (I_on/I_off) ratios. Powder X‐ray diffraction (PXRD) reveals that these films, grown by vacuum deposition onto the thermally grown silicon oxide surface of a TFT, are highly crystalline, a characteristic that can be attributed to the general tendency of phenyl groups to promote crystallinity. Atomic force microscopy (AFM) reveals that the films grow layer by layer to form large domains, with some basal domain areas approaching 1000 μm². The PXRD and AFM data are consistent with an “end‐on” orientation of the molecules on the oxide substrate. Variable‐temperature current–voltage (I–V) measurements identified the activation regime for hole transport and revealed shallow level traps in thin films of 1 and 2 , and both shallow and deep level traps in thin films of 3 . The activation energies for thin films of 1 , 2 , and 3 were similar, with values of E_a = 121, 100, and 109 meV, respectively. The corresponding trap densities were N_trap/N_v = 0.012, 0.023, and 0.094, where N_trap is the number of trap states and N_v is the number of conduction states. The hole mobilities for the three compounds were similar (μ ? 0.03 cm² V^–1 s^–1), and the I_on/I_off ratios were comparable with the highest values reported for organic TFTs, with films of 2 approaching I_on/I_off = 10⁹ at room temperature.     

Oxide Sandwiched Metal Thin‐Film Electrodes for Long‐Term Stable Organic Solar Cells

Oxide/silver/oxide multilayers as semitransparent top electrode for small molecule organic solar cells (OSCs) are presented. It is shown that two oxide layers sandwiching a central metal layer greatly improve the stability and lifetime of the organic solar cell. Thermally evaporated MoO₃, WO₃, or V₂O₅ layers are employed as an interlayer for subsequent silver deposition and significantly change the morphology of the ultrathin silver layer, improving charge extraction and electrodes series resistance. The transmittance of the electrode is increased by introducing oxide or oxide and organic multilayers as capping layer, which leads to higher photocurrent generation in the absorber layer. Application of 1 nm MoO₃/11 nm Ag/10 nm MoO₃/50 nm Alq₃ multilayer electrodes in OSCs lead to an efficiency of 2.6% for a standard ZnPc:C60 cell, showing superior performance compared to devices with pure silver top contacts. The device lifetime is also strongly increased. MoO₃ layers can saturate and stabilize the inner and outer metal surface, passivating it against most of the degradation mechanisms. With such an oxide/silver/oxide multilayer electrode, the time until the glass encapsulated OSC is degraded to 80% of its starting efficiency is enhanced from 86 h to approximately 4500 h compared to an OSC without an oxide interlayer.     

High‐Performance and Stable Organic Thin‐Film Transistors Based on Fused Thiophenes

A series of new organic semiconductors for organic thin‐film transistors (OTFTs) using dithieno[3,2‐b:2′,3′‐d]thiophene as the core are synthesized. Their electronic and optical properties are investigated using scanning electron microscopy (SEM), X‐ray diffraction (XRD), UV‐vis and photoluminescence spectroscopies, thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). The compounds exhibit an excellent field‐effect performance with a high mobility of 0.42 cm² V^–1 s^–1 and an on/off ratio of 5 × 10⁶. XRD patterns reveal these films, grown by vacuum deposition, to be highly crystalline, and SEM reveals well‐interconnected, microcrystalline domains in these films at room temperature. TGA and DSC demonstrate that the phenyl‐substituted compounds possess excellent thermal stability. Furthermore, weekly shelf‐life tests (under ambient conditions) of the OTFTs based on the phenyl‐substituted compounds show that the mobility for the bis(diphenyl)‐substituted thiophene was almost unchanged for more than two months, indicating a high environmental stability.     

Organic Thin‐Film Photovoltaic Cells Based on Oligothiophenes with Reduced Bandgap

The best polymeric solar cells reported so far are based on a so‐called bulk heterojunction of a polythiophene as donor and a soluble fullerene derivative as acceptor. However, these cells still suffer from an unsatisfying photovoltage, typically below 0.7 V. Here, we show that we can achieve higher photovoltages using a new terthiophene end‐capped with electron withdrawing dicyanovinyl groups (DCV3T) that increase both the ionization energy and even more strongly the electron affinity of the compound. The new material is tested in cells using a photoactive heterojunction to separate the excitons generated in the oligomer and a p‐doped wide‐gap transport layer. The solar cells show an open circuit voltage of up to 1.04 V and a broad spectral sensitivity band ranging from 420 nm to 650 nm. Solar cells based on such oligothiophenes are promising candidates for stacked organic solar cells tailored to the sun‐spectrum. Moreover, we present first examples of a new concept for organic solar cells: By blending DCV3T with fullerene C₆₀, an enhanced generation of triplet excitons on the oligomer can be achieved via a back and forth transfer of excitons (ping‐pong‐effect).     

Electrical Switching and Bistability in Organic/Polymeric Thin Films and Memory Devices

Recently, films created by incorporating metallic nanoparticles into organic or polymeric materials have demonstrated electrical bistability, as well as the memory effect, when subjected to an electrical bias. Organic and polymeric digital memory devices based on this bistable electronic behavior have emerged as a viable technology in the field of organic electronics. These devices exhibit fast response speeds and can form multiple‐layer stacking structures, demonstrating that organic memory devices possess a high potential to become flexible, ultrafast, and ultrahigh‐density memory devices. This behavior is believed to be related to charge storage in the organic or polymer film, where devices are able to exhibit two different states of conductivity often separated by several orders of magnitude. By defining the two states as “1” and “0”, it is now possible to create digital memory devices with this technology. This article reviews electrically bistable devices developed in our laboratory. Our research has stimulated strong interest in this area worldwide. The research by other laboratories is reviewed as well.     

TiO2 Nanoparticle–Photopolymer Composites for Volume Holographic Recording

A new and efficient photopolymer for the recording of volume holograms is presented. The material comprises a mixture of UV‐sensitive acrylates and grafted titanium dioxide nanoparticles with an average size of 4 nm. We report the formation of holographic gratings with refractive‐index modulation amplitudes of up to 15.5 × 10^–3—an improvement of more than a factor of four over the base material without nanoparticles—while maintaining a low level of scattering and a high transparency in the visible‐wavelength range. The influence of the composition of the acrylate system on the final properties of the holographic material is also investigated and discussed. The presence of multifunctional monomers favors the compositional segregation of the different components, while the addition of monofunctional acrylate, highly compatible with the grafting of the nanoparticles, favors the dilution of these nanoparticles.     

Cover Picture: TiO2 Nanoparticle–Photopolymer Composites for Volume Holographic Recording (Adv. Funct. Mater. 10/2005)

TiO2 nanoparticle–photopolymer composites have been employed for volume holographic recording, as reported by Sánchez and co‐workers on p. 1623. Photoinduced segregation of the high refractive index, grafted nanoparticles between polymer‐rich areas leads to improved refractive‐index modulation amplitudes with respect to the base material without nanoparticles. The cover schematically shows a holographic grating registered in this nanocomposite material. These nanocomposite materials should enable the production of holographic optical elements to efficiently control light with angle and wavelength selectivity. This could be used, for example, in liquid‐crystal display technology. A new and efficient photopolymer for the recording of volume holograms is presented. The material comprises a mixture of UV‐sensitive acrylates and grafted titanium dioxide nanoparticles with an average size of 4 nm. We report the formation of holographic gratings with refractive‐index modulation amplitudes of up to 15.5 × 10^–3—an improvement of more than a factor of four over the base material without nanoparticles—while maintaining a low level of scattering and a high transparency in the visible‐wavelength range. The influence of the composition of the acrylate system on the final properties of the holographic material is also investigated and discussed. The presence of multifunctional monomers favors the compositional segregation of the different components, while the addition of monofunctional acrylate, highly compatible with the grafting of the nanoparticles, favors the dilution of these nanoparticles.     

Carbon‐Decorated FePt Nanoparticles

FePt magnetic nanoparticles are an important candidate material for many future magnetic applications. FePt exists as two main phases, that is, a disordered face‐centered cubic (fcc) structure, which is generally prepared by chemical methods at low temperatures, and the high‐temperature chemically ordered face‐centered tetragonal (fct) structure. The fcc FePt, with low coercivity but associated with superparamagnetic properties, may find applications as a magnetic fluid or as a nanoscale carrier for chemical or biochemical species in biomedical areas, while fct FePt is proposed for use in ultrahigh‐density magnetic recording applications. However, for both of these applications an enhancement of the intrinsically weak magnetic properties, the avoidance of magnetic interferences from neighbor particles, and the improved stability of the small magnetic body remain key practical issues. We report a simple synthetic method for producing FePt nanoparticles that involves hydrothermal treatment of Fe and Pt precursors in glucose followed by calcination at 900 °C. This new method produces thermally stable spheroidal graphite nanoparticles (large and fullerene‐like) that encapsulate or decorate FePt particles of ca. 5 nm with no severe macroscopic particle coalescence. Also, a low coercivity of the material is recorded; indicative of small magnetic interference from neighboring carbon‐coated particles. Thus, this simple synthetic method involves the use of a more environmentally acceptable glucose/aqueous phase to offer a protective coating for FePt nanoparticles. It is also believed that such a synthetic protocol can be readily extended to the preparation of other graphite‐coated magnetic iron alloys of controlled size, stoichiometry, and physical properties.     

Template‐Free Preparation of Hollow Sb2S3 Microspheres as Supports for Ag Nanoparticles and Photocatalytic Properties of the Constructed Metal–Semiconductor Nanostructures

A simple and convenient Ostwald ripening route to the morphology‐ and phase‐controlled preparation of hollow Sb₂S₃ microspheres is developed. The hollow spheres are clusters of smaller microspheres if orange amorphous Sb₂S₃ colloid is used as the precursor, whereas, if starting from the yellow precursor, the products are regular hollow spheres. By selecting appropriate experimental conditions for ripening, the phase of the hollow Sb₂S₃ microspheres can be controlled. Amorphous and orthorhombic hollow spheres are prepared by ripening the colloidal precursors at ambient temperature and in an autoclave, respectively. The closed shell of hollow Sb₂S₃ spheres can be easily eroded by hydrochloric acid to form an open structure. By the in situ reduction of adsorbed Ag⁺ on the surface and interior of the hollow spheres, Ag nanoparticles are introduced into them, to form functional metal–semiconductor composites, the weight content of which is controlled by regulating the concentration of the Ag⁺ source and the adsorption time. The composite structures composed of Ag nanoparticles and hollow Sb₂S₃ spheres exhibit a remarkably enhanced absorption covering the UV and visible regions of the electromagnetic spectrum. A study of the photocatalytic properties of the composite structures demonstrates that exposure to both UV and visible light enables them to induce the rapid decomposition of 2‐chlorophenol. The degradation rate increases with a larger weight content of Ag in the composite structure.     

Transparent Nanopaper‐Based Flexible Organic Thin‐Film Transistor Array

Eco‐friendly and low‐cost cellulose nanofiber paper (nanopaper) is a promising candidate as a novel substrate for flexible electron device applications. Here, a thin transparent nanopaper‐based high‐mobility organic thin‐film transistor (OTFT) array is demonstrated for the first time. Nanopaper made from only native wood cellulose nanofibers has excellent thermal stability (>180 °C) and chemical durability, and a low coefficient of thermal expansion (CTE: 5–10 ppm K^‐1). These features make it possible to build an OTFT array on nanopaper using a similar process to that for an array on conventional glass. A short‐channel bottom‐contact OTFT is successfully fabricated on the nanopaper by a lithographic and solution‐based process. Owing to the smoothness of the cast‐coated nanopaper surface, a solution processed organic semiconductor film on the nanopaper comprises large crystalline domains with a size of approximately 50–100 μm, and the corresponding TFT exhibits a high hole mobility of up to 1 cm²V^‐1 s^‐1 and a small hysteresis of below 0.1 V under ambient conditions. The nanopaper‐based OTFT also had excellent flexibility and can be formed into an arbitrary shape. These combined technologies of low‐cost and eco‐friendly paper substrates and solution‐based organic TFTs are promising for use in future flexible electronics application such as flexible displays and sensors.     

Solution‐Processed Metallic Nanowire Electrodes as Indium Tin Oxide Replacement for Thin‐Film Solar Cells

Solution processed silver nanowire (Ag NW) films are introduced as transparent electrodes for thin‐film solar cells. Ag NW electrodes were processed by doctor blade‐coating on glass substrates at moderate temperatures (less than 100 °C). The morphological, optical, and electrical characteristics of these electrodes were investigated as a function of processing parameters. For solar‐cell application, Ag NW electrodes with an average transparency of 90% between 450 and 800 nm and a sheet resistivity of ≈10 Ω per square were chosen. The performance of poly(3‐hexylthiophen‐2,5‐diyl):[6,6]‐phenyl‐C61‐butyric acid methyl ester (P3HT:PCBM) solar cells on Ag NW electrodes was found to match the performance of otherwise identical cells on indium tin oxide. Overall, P3HT:PCBM solar cells with an efficiency of 2.5% on transparent Ag NW electrodes have been realized.     

Hybrid Solar Cells Based on Nanoparticles of CuInS2 in Organic Matrices

We report on solution‐processed hybrid solar cells consisting of a nanocrystalline inorganic semiconductor, CuInS₂, and organic materials. Synthesis of quantized CuInS₂ nanoparticles was performed using a colloidal route, where the particle surface was shielded by an organic surfactant. First attempts were made to use nanocrystalline CuInS₂ with fullerene derivatives to form flat‐interface donor–acceptor heterojunction solar cells. We investigated also bulk heterojunctions by replacing the CuInS₂ single layer by a blend of CuInS₂ and p‐type polymer (PEDOT:PSS; poly(3,4‐ethylenedioxythiophene:poly(styrene sulfonic acid) in the same cell configuration. Bulk heterojunction solar cells show better photovoltaic response with external quantum efficiencies up to 20 %.     

Organic Nanoparticles: Preparation,Self‐Assembly,and Properties

The strong tendency of organic nanoparticles to rapidly self‐assemble into highly aligned superlattices at room temperature when solution‐cast from dispersions or spray‐coated directly onto various substrates is described. The nanoparticle dispersions are stable for years. The novel precipitation process used is believed to result in molecular distances and alignments in the nanoparticles that are not normally possible. Functional organic light‐emitting diodes (OLEDs)—which have the same host–dopant emissive‐material composition—with process‐tunable electroluminescence have been built with these nanoparticles, indicating the presence of novel nanostructures. For example, only changing the conditions of the precipitation process changes the OLED emission from green light to yellow.     

Spontaneous Formation of Ordered Lateral Patterns in Polymer Thin‐Film Structures

The understanding of the lateral morphology stability of thin polymer devices is of fundamental importance. In this work, the lateral morphology in a model system consisting of thin polymer films capped with thin metal layers on a Si substrate is investigated. When the model system is heated above a critical temperature, a characteristic surface topographic structure is observed that has a well‐defined periodicity but random orientation. It is shown that the minimum temperature, T_min, required for the surface pattern to be observed decreases with increasing polymer‐film thickness. Increasing either the metal‐ or polymer‐layer thickness increases the characteristic wavelength of the topography. It is believed that the dominating driving force for the surface corrugated‐pattern formation is the thermal‐expansion‐coefficient mismatch of the capping layer and the substrate. A theoretical model based on local bending of a thin, stiff surface film on a thin, elastic medium is used to provide a quantitative analysis of the surface morphology. The calculated minimum temperature required for the surface morphology and the periodicity of the surface patterns to form are in strong agreement with the experimental results. By contrast, systems with prefabricated topographic patterns within any of the three layers (polymer, metal, substrate) produce highly anisotropic surface topographies aligned perpendicular to the prefabricated topographic structure. It is also found that, in a model system with pre‐patterned polymer films, a much higher critical temperature is required for the surface morphology to be observed. The changes in apparent stability and morphological orientation in the pre‐patterned systems can be understood as a result of the anisotropic release of the lateral surface stress during the heat treatment.     

Cd1–xMnxS Diluted Magnetic Semiconductors as Nanostructured Guest Species in Mesoporous Thin‐Film Silica Host Media

Recently, we demonstrated the possibility of synthesizing ordered nanowires of diluted magnetic II/VI semiconductors inside the channels of mesoporous silica host structures. Here, we expand this procedure from mesoporous powders to mesoporous thin films. Diluted magnetic semiconductors Cd_1–xMn_xS were synthesized within the pores of mesoporous thin‐film silica host structures by a wet‐impregnation technique using an aqueous solution of the respective metal acetates, followed by drying steps and a conversion to sulfide by thermal H₂S treatment. The presence of Cd_1–xMn_xS nanoparticles inside the pores was proved by powder X‐ray diffraction, infrared and Raman spectroscopy, and transmission electron microscopy. Photoluminescence excitation measurements clearly demonstrate the quantum size effect of the incorporated nanostructured guest species. The quality of the nanoparticles incorporated into the mesoporous films is comparable to that of those inside the mesoporous powders.     

Tunneling Current in Polycrystalline Organic Thin‐Film Transistors

Several recent papers have demonstrated that charge‐carrier mobility in organic field‐effect transistors made of vacuum‐evaporated films may become temperature‐independent at low temperature. To account for this behavior, we developed a model based on the polycrystalline nature of these films, where charge transport is mostly limited by grain boundaries. The free‐carrier density in the intergrain regions is controlled by traps, which leads to the formation of back‐to‐back Schottky barriers at each side of the grain boundaries. The height and width of these barriers is estimated from solving Poisson’s equation using the graded‐channel approximation. It is shown that in most cases the barrier width is negligibly small as compared to the physical size of the grain boundaries. In the high‐temperature regime, the conducting channel can be simply described by grains and grain boundaries connected in series, so that the overall resistance reduces to that of the grain boundaries. At low temperatures, tunneling through the barrier becomes predominant, leading to temperature‐independent mobility. A complete two‐dimensional model for charge tunneling through the barriers is developed. A quantitative check of the model is made by least‐squares fitting of the gate voltage‐dependent current measured on an octithiophene transistor at low temperature, which gives a reasonable determination of the trap density and size of the grain boundaries.     

Impact of Materials versus Geometric Parameters on the Contact Resistance in Organic Thin‐Film Transistors

The contact resistance is known to severely hamper the performance of organic thin‐film transistors, especially when dealing with large injection barriers, high mobility organic semiconductors, or short channel lengths. Here, the relative significance of how it is affected by materials‐parameters (mobility and interfacial level‐offsets) and geometric factors (bottom‐contact vs top‐contact geometries) is assessed. This is done using drift‐diffusion‐based simulations on idealized device structures aiming at a characterization of the “intrinsic” situation in the absence of traps, differences in the film morphology, or metal‐atoms diffusing into the organic semiconductor. It is found that, in contrast to common wisdom, in such a situation the top‐contact devices do not always outperform the bottom‐contact ones. In fact, the observed ratio between the contact resistances of the two device structures changes by up to two orders of magnitude depending on the assumed materials parameters. The contact resistance is also shown to be strongly dependent on the hole mobility in the organic semiconductor and influenced by the chosen point of operation of the device.     

Vertically Aligned Nanocomposite Thin Films as a Cathode/Electrolyte Interface Layer for Thin‐Film Solid Oxide Fuel Cells

A thin layer of a vertically aligned nanocomposite (VAN) structure is deposited between the electrolyte, Ce_0.9Gd_0.1O_1.95 (CGO), and the thin‐film cathode layer, La_0.5Sr_0.5CoO₃ (LSCO), of a thin‐film solid‐oxide fuel cell (TFSOFC). The self‐assembled VAN nanostructure contains highly ordered alternating vertical columns of CGO and LSCO formed through a one‐step thin‐film deposition process that uses pulsed laser deposition. The VAN structure significantly improves the overall performance of the TFSOFC by increasing the interfacial area between the electrolyte and cathode. Low cathode polarization resistances of 9 × 10^?4 and 2.39 Ω were measured for the cells with the VAN interlayer at 600 and 400 °C, respectively. Furthermore, anode‐supported single cells with LSCO/CGO VAN interlayer demonstrate maximum power densities of 329, 546, 718, and 812 mW cm^?2 at 550, 600, 650, and 700 °C, respectively, with an open‐circuit voltage (OCV) of 1.13 V at 550 °C. The cells with the interlayer triple the overall power output at 650 °C compared to that achieved with the cells without an interlayer. The binary VAN interlayer could also act as a transition layer that improves adhesion and relieves both thermal stress and lattice strain between the cathode and the electrolyte.     

Photochemical Formation of Au/Cu Bimetallic Nanoparticles with Different Shapes and Sizes in a Poly(vinyl alcohol) Film

Metal nanoparticle (NP)–polymer nanocomposite thin films are attractive for applications in various devices. Since bimetallic NPs provide additional opportunities for tuning the physical properties of the NP components, the development of bimetallic NP nanocomposite thin films should lead to further enhancements of various applications. Au/Cu bimetallic NPs are fabricated in a poly(vinyl alcohol) (PVA) film using a photochemical process. Interestingly, different sizes and shapes of Au/Cu bimetallic NPs are formed in the PVA film, resulting in a uniquely patterned nanocomposite structure. It is determined that the different formation and growth mechanisms of NPs inside and outside the UV‐light irradiation spot leads to the differences in size and shape.     

Materials for Multibit‐per‐Site Optical Data Storage

An approach for multibit‐per‐site optical data storage has been proposed and demonstrated using mesostructured composite films incorporated with uniformly dispersed photoacid generator and pH‐sensitive dye molecules. Upon light illumination, photoacid generator molecules produce acid, which induces a change in the absorption property of pH‐sensitive dye molecules. Because the amount of the generated acid is proportional to the illumination time, the resulting change in the absorption property of mesostructured composite films varies as a function of the illumination time. This function between the absorption property of mesostructured composite films and the illumination time can be used for multibit‐per‐site optical data storage. Recording is performed by using certain discrete values of the illumination time to represent information bits. Reading out is achieved by measuring the absorbance of composite films at a particular wavelength, from which the stored information bits can be determined. In general, N‐bit‐per‐site storage can be realized using 2^N discrete values of the illumination time. This multibit‐per‐site approach for optical data storage is compatible with the current single‐bit‐per‐site technology used for compact disks and digital versatile disks, and will provide significantly larger optical storage capacity. It is also suitable for two‐photon multilayer optical data storage if the photoacid generators and pH‐sensitive dyes are properly designed.