Cover Picture: Self‐Organization of Ink‐jet‐Printed Triisopropylsilylethynyl Pentacene via Evaporation‐Induced Flows in a Drying Droplet (Adv. Funct. Mater. 2/2008)

Charge carrier transport in organic electronic devices is influenced by the crystalline microstructure and morphology of the organic semiconductor film. Evaporation behavior during drying plays a vital role in controlling the film morphology and the distribution of solute in inkjet‐printed films. On p. 229, Kilwon Cho and co‐workers demonstrate the influence of the evaporation‐induced flow in a single droplet on the crystalline microstructure and film morphology of inkjet‐printed 6,13‐bis((triisopropylsilylethynyl) pentacene. The results provide an excellent method for direct‐write fabrication of high‐performance organic electronics. We have demonstrated the influence of evaporation‐induced flow in a single droplet on the crystalline microstructure and film morphology of an ink‐jet‐printed organic semiconductor, 6,13‐bis((triisopropylsilylethynyl) pentacene (TIPS_PEN), by varying the composition of the solvent mixture. The ringlike deposits induced by outward convective flow in the droplets have a randomly oriented crystalline structure. The addition of dichlorobenzene as an evaporation control agent results in a homogeneous film morphology due to slow evaporation, but the molecular orientation of the film is undesirable in that it is similar to that of the ring‐deposited films. However, self‐aligned TIPS_PEN crystals with highly ordered crystalline structures were successfully produced when dodecane was added. Dodecane has a high boiling point and a low surface tension, and its addition to the solvent results in a recirculation flow in the droplets that is induced by a Marangoni flow (surface‐tension‐driven flow), which arises during the drying processes in the direction opposite to the convective flow. The field‐effect transistors fabricated with these self‐aligned crystals via ink‐jet printing exhibit significantly improved performance with an average effective field‐effect mobility of 0.12 cm² V^–1 s^–1. These results demonstrate that with the choice of appropriate solvent ink‐jet printing is an excellent method for the production of organic semiconductor films with uniform morphology and desired molecular orientation for the direct‐write fabrication of high‐performance organic electronics.     

Self‐Organization of Ink‐jet‐Printed Triisopropylsilylethynyl Pentacene via Evaporation‐Induced Flows in a Drying Droplet

We have demonstrated the influence of evaporation‐induced flow in a single droplet on the crystalline microstructure and film morphology of an ink‐jet‐printed organic semiconductor, 6,13‐bis((triisopropylsilylethynyl) pentacene (TIPS_PEN), by varying the composition of the solvent mixture. The ringlike deposits induced by outward convective flow in the droplets have a randomly oriented crystalline structure. The addition of dichlorobenzene as an evaporation control agent results in a homogeneous film morphology due to slow evaporation, but the molecular orientation of the film is undesirable in that it is similar to that of the ring‐deposited films. However, self‐aligned TIPS_PEN crystals with highly ordered crystalline structures were successfully produced when dodecane was added. Dodecane has a high boiling point and a low surface tension, and its addition to the solvent results in a recirculation flow in the droplets that is induced by a Marangoni flow (surface‐tension‐driven flow), which arises during the drying processes in the direction opposite to the convective flow. The field‐effect transistors fabricated with these self‐aligned crystals via ink‐jet printing exhibit significantly improved performance with an average effective field‐effect mobility of 0.12 cm² V^–1 s^–1. These results demonstrate that with the choice of appropriate solvent ink‐jet printing is an excellent method for the production of organic semiconductor films with uniform morphology and desired molecular orientation for the direct‐write fabrication of high‐performance organic electronics.     

Inkjet‐Printed Single‐Droplet Organic Transistors Based on Semiconductor Nanowires Embedded in Insulating Polymers

Fabrication of organic field‐effect transistors (OFETs) using a high‐throughput printing process has garnered tremendous interest for realizing low‐cost and large‐area flexible electronic devices. Printing of organic semiconductors for active layer of transistor is one of the most critical steps for achieving this goal. The charge carrier transport behavior in this layer, dictated by the crystalline microstructure and molecular orientations of the organic semiconductor, determines the transistor performance. Here, it is demonstrated that an inkjet‐printed single‐droplet of a semiconducting/insulating polymer blend holds substantial promise as a means for implementing direct‐write fabrication of organic transistors. Control of the solubility of the semiconducting component in a blend solution can yield an inkjet‐printed single‐droplet blend film characterized by a semiconductor nanowire network embedded in an insulating polymer matrix. The inkjet‐printed blend films having this unique structure provide effective pathways for charge carrier transport through semiconductor nanowires, as well as significantly improve the on‐off current ratio and the environmental stability of the printed transistors.     

Tailoring Morphology and Structure of Inkjet‐Printed Liquid‐Crystalline Semiconductor/Insulating Polymer Blends for High‐Stability Organic Transistors

Inkjet printing of semiconducting polymers is desirable for realizing low‐cost, large‐area printed electronics. However, sequential inkjet printing methods often suffer from nozzle clogging because the solubility of semiconducting polymers in organic solvents is limited. Here, it is demonstrated that the addition of an insulating polymer to a semiconducting polymer ink greatly enhances the solubility and stability of the ink, leading to the stable ejection of ink droplets. This bicomponent blend comprising a liquid‐crystalline semiconducting copolymer, poly(didodecylquaterthiophene‐alt‐didodecylbithiazole) (PQTBTz‐C12), and an insulating commodity polymer, polystyrene, is extremely useful as a semiconducting layer in organic field‐effect transistors (OFETs), providing fine control over the phase‐separated morphology and structure of the inkjet‐printed film. Tailoring the solubility‐induced phase separation of the two components leads to a bilayer structure consisting of a polystyrene layer on the top and a highly crystalline PQTBTz‐C12 layer on the bottom. The blend film is used as the semiconducting layer in OFETs, reducing the semiconductor content to several tens of pictograms in a single device without degrading the device performance. Furthermore, OFETs based on the PQTBTz‐C12/polystyrene film exhibit much greater environmental and electrical stabilities compared to the films prepared from homo PQTBTz‐C12, mainly due to the self‐encapsulated structure of the blend film.     

Room‐Temperature Printing of Organic Thin‐Film Transistors with π‐Junction Gold Nanoparticles

Printing semiconductor devices under ambient atmospheric conditions is a promising method for the large‐area, low‐cost fabrication of flexible electronic products. However, processes conducted at temperatures greater than 150 °C are typically used for printed electronics, which prevents the use of common flexible substrates because of the distortion caused by heat. The present report describes a method for the room‐temperature printing of electronics, which allows thin‐film electronic devices to be printed at room temperature without the application of heat. The development of π‐junction gold nanoparticles as the electrode material permits the room‐temperature deposition of a conductive metal layer. Room‐temperature patterning methods are also developed for the Au ink electrodes and an active organic semiconductor layer, which enables the fabrication of organic thin‐film transistors through room‐temperature printing. The transistor devices printed at room temperature exhibit average field‐effect mobilities of 7.9 and 2.5 cm² V^?1 s^?1 on plastic and paper substrates, respectively. These results suggest that this fabrication method is very promising as a core technology for low‐cost and high‐performance printed electronics.     

Low‐Temperature‐Processed Printed Metal Oxide Transistors Based on Pure Aqueous Inks

Additive patterning of transparent conducting metal oxides at low temperatures is a critical step in realizing low‐cost transparent electronics for display technology and photovoltaics. In this work, inkjet‐printed metal oxide transistors based on pure aqueous chemistries are presented. These inks readily convert to functional thin films at lower processing temperatures (T ≤ 250 °C) relative to organic solvent‐based oxide inks, facilitating the fabrication of high‐performance transistors with both inkjet‐printed transparent electrodes of aluminum‐doped cadmium oxide (ACO) and semiconductor (InO_x ). The intrinsic fluid properties of these water‐based solutions enable the printing of fine features with coffee‐ring free line profiles and smoother line edges than those formed from organic solvent‐based inks. The influence of low‐temperature annealing on the optical, electrical, and crystallographic properties of the ACO electrodes is investigated, as well as the role of aluminum doping in improving these properties. Finally, the all‐aqueous‐printed thin film transistors (TFTs) with inkjet‐patterned semiconductor (InO_x ) and source/drain (ACO) layers are characterized, which show ideal low contact resistance (R _c < 160 Ω cm) and competitive transistor performance (µ _lin up to 19 cm² V^?1 s^?1, Subthreshold Slope (SS) ≤150 mV dec^?1) with only low‐temperature processing (T ≤ 250 °C).     

Polymer Dielectrics and Orthogonal Solvent Effects for High‐Performance Inkjet‐Printed Top‐Gated P‐Channel Polymer Field‐Effect Transistors

We investigated the effects of a gate dielectric and its solvent on the characteristics of top‐gated organic field‐effect transistors (OFETs). Despite the rough top surface of the inkjet‐printed active features, the charge transport in an OFET is still favorable, with no significant degradation in performance. Moreover, the characteristics of the OFETs showed a strong dependency on the gate dielectrics used and its orthogonal solvents. Poly(3‐hexylthiophene) OFETs with a poly(methyl methacrylate) dielectric showed typical p‐type OFET characteristics. The selection of gate dielectric and solvent is very important to achieve high‐performance organic electronic circuits.     

Direct Patterning of Self‐Assembled Monolayers by Stamp Printing Method and Applications in High Performance Organic Field‐Effect Transistors and Complementary Inverters

Self‐assembled monolayer (SAM) is usually applied to tune the interface between dielectric and active layer of organic field‐effect transistors (OFETs) and other organic electronics, a time‐saving, direct patterning approach of depositing well‐ordered SAMs is highly desired. Here, a new direct patterning method of SAMs by stamp printing or roller printing with special designed stamps is introduced. The chemical structures of the paraffin hydrocarbon molecules and the tail groups of SAMs have allowed to use their attractive van der Waals force for the direct patterning of SAMs. Different SAMs including alkyl and fluoroalkyl silanes or phosphonic acids are used to stamp onto different dielectric surfaces and are characterized by water contact angle, atomic force microscopy, X‐ray diffraction, and attenuated total reflectance Fourier transform infrared. The p‐type dinaphtho[2,3‐b:2′,3′‐f]thieno[3,2‐b]thiophene (DNTT) and n‐type F₁₆CuPc OFETs show competitive mobility as high as 3 and 0.018 cm² V^?1 s^?1, respectively. This stamp printing method also allows to deposit different SAMs on certain regions of same substrate, and the complementary inverter consists of both p‐type and n‐type transistors whose threshold voltages are tuned by stamp printing SAMs and shows a gain higher than 100. The proposed stamp or roller printing method can significantly reduce the deposition time and compatible with the roll‐to‐roll fabrication.     

Direct Ink‐Jet Printing of Ag–Cu Nanoparticle and Ag‐Precursor Based Electrodes for OFET Applications

The field of organic electronics has seen tremendous progress over the last years and all‐solution‐based processes are believed to be one of the key routes to ultra low‐cost roll‐to‐roll device and circuit fabrication. In this regard a variety of functional materials has been successfully designed for inkjet printing. While orthogonal‐solvent approaches have frequently been used to tackle the solubility issue in multilayer solution processing, the focus of this work lies on printed metal electrodes for organic field‐effect transistors (OFET) and their curing concepts. Two metallic inkjet‐printable materials are studied: i) a silver‐copper nanoparticle based dispersion and ii) a soluble organic silver‐precursor. Photoelectron spectroscopy reveals largely metallic properties of the cured materials, which are compared with respect to OFET performance and process‐related issues. Contact resistance of the prepared metal electrodes is significantly larger than that of evaporated top‐contact gold electrodes. As direct patterning via inkjet printing limits the reliably achievable channel length to values well above 10 μm, the influence of contact resistance is rather small, however, and overall device performance is comparable.     

High‐Performance Top‐Gated Organic Field‐Effect Transistor Memory using Electrets for Monolithic Printed Flexible NAND Flash Memory

High‐performance top‐gated organic field‐effect transistor (OFET) memory devices using electrets and their applications to flexible printed organic NAND flash are reported. The OFETs based on an inkjet‐printed p‐type polymer semiconductor with efficiently chargeable dielectric poly(2‐vinylnaphthalene) (PVN) and high‐k blocking gate dielectric poly(vinylidenefluoride‐trifluoroethylene) (P(VDF‐TrFE)) shows excellent non‐volatile memory characteristics. The superior memory characteristics originate mainly from reversible charge trapping and detrapping in the PVN electret layer efficiently in low‐k/high‐k bilayered dielectrics. A strategy is devised for the successful development of monolithically inkjet‐printed flexible organic NAND flash memory through the proper selection of the polymer electrets (PVN or PS), where PVN/‐ and PS/P(VDF‐TrFE) devices are used as non‐volatile memory cells and ground‐ and bit‐line select transistors, respectively. Electrical simulations reveal that the flexible printed organic NAND flash can be possible to program, read, and erase all memory cells in the memory array repeatedly without affecting the non‐selected memory cells.     

Cover Picture: High Definition Digital Fabrication of Active Organic Devices by Molecular Jet Printing (Adv. Funct. Mater. 15/2007)

A new method for direct patterning of organic optoelectronic/electronic devices using a reconfigurable and scalable printing method is reported by Vladimir Bulovic and co‐workers on p. 2722. The printing technique is applied to the fabrication of high‐resolution printed organic light emitting devices (OLEDs) and organic field effect transistors (OFETs). Remarkably, the final print‐deposited films are evaporated onto the substrate (rather than solvent printed), giving high‐quality, solvent‐free, molecularly flat structures that match the performance of comparable high‐performance unpatterned films. We introduce a high resolution molecular jet (MoJet) printing technique for vacuum deposition of evaporated thin films and apply it to fabrication of 30 μm pixelated (800 ppi) molecular organic light emitting devices (OLEDs) based on aluminum tris(8‐hydroxyquinoline) (Alq₃) and fabrication of narrow channel (15 μm) organic field effect transistors (OFETs) with pentacene channel and silver contacts. Patterned printing of both organic and metal films is demonstrated, with the operating properties of MoJet‐printed OLEDs and OFETs shown to be comparable to the performance of devices fabricated by conventional evaporative deposition through a metal stencil. We show that the MoJet printing technique is reconfigurable for digital fabrication of arbitrary patterns with multiple material sets and high print accuracy (of better than 5 μm), and scalable to fabrication on large area substrates. Analogous to the concept of “drop‐on‐demand” in Inkjet printing technology, MoJet printing is a “flux‐on‐demand” process and we show it capable of fabricating multi‐layer stacked film structures, as needed for engineered organic devices.     

Rheological and Drying Considerations for Uniformly Gravure‐Printed Layers: Towards Large‐Area Flexible Organic Light‐Emitting Diodes

Printing organic semiconductor inks by means of roll‐to‐roll compatible techniques will allow a continuous, high‐volume fabrication of large‐area flexible optoelectronic devices. The gravure printing technique is set to become a widespread process for the high throughput fabrication of functional layers. The gravure printing process of a poly‐phenylvinylene derivative light‐emitting polymer dissolved in a two solvent mixture on poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is studied. The surface tensions, contact angles, viscosities, and drying times of the formulations are investigated as a function of the solvent volume fraction and polymer concentration. The properties of the ink grant a homogeneous printed layer, suitable for device fabrication, when the calculated film leveling time is shorter than a critical time, at which the film has been frozen due to loss of solvent via evaporation. The knowledge obtained from the printing process is applied to fabricate organic light‐emitting diodes (OLEDs) on flexible substrates, yielding a luminance of ≈5000 cd m^?2.     

Inkjet‐Printed Organic Electrodes for Bottom‐Contact Organic Field‐Effect Transistors

A graphite thin film was investigated as the drain and source electrodes for bottom‐contact organic field‐effect transistors (BC OFETs). Highly conducting electrodes (10² S cm^?1) at room temperature were obtained from pyrolyzed poly(l,3,4‐oxadiazole) (PPOD) thin films that were prepatterned with a low‐cost inkjet printing method. Compared to the devices with traditional Au electrodes, the BC OFETs showed rather high performances when using these source/drain electrodes without any further modification. Being based on a graphite‐like material these electrodes possess excellent compatibility and proper energy matching with both p‐ and n‐type organic semiconductors, which results in an improved electrode/organic‐layer contact and homogeneous morphology of the organic semiconductors in the conducting channel, and finally a significant reduction of the contact resistance and enhancement of the charge‐carrier mobility of the devices is displayed. This work demonstrates that with the advantages of low‐cost, high‐performance, and printability, PPOD could serve as an excellent electrode material for BC OFETs.     

Control of Ambipolar and Unipolar Transport in Organic Transistors by Selective Inkjet‐Printed Chemical Doping for High Performance Complementary Circuits

The selective tuning of the operational mode from ambipolar to unipolar transport in organic field‐effect transistors (OFETs) by printing molecular dopants is reported. The field‐effect mobility (μ_FET) and onset voltage (V_on) of both for electrons and holes in initially ambipolar methanofullerene [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) OFETs are precisely modulated by incorporating a small amount of cesium fluoride (CsF) n‐type dopant or tetrafluoro‐tetracyanoquinodimethane (F4‐TCNQ) p‐type dopant for n‐channel or p‐channel OFETs either by blending or inkjet printing of the dopant on the pre‐deposited semiconductor. Excess carriers introduced by the chemical doping compensate traps by shifting the Fermi level (E_F) toward respective transport energy levels and therefore increase the number of mobile charges electrostatically accumulated in channel at the same gate bias voltage. In particular, n‐doped OFETs with CsF show gate‐voltage independent Ohmic injection. Interestingly, n‐ or p‐doped OFETs show a lower sensitivity to gate‐bias stress and an improved ambient stability with respect to pristine devices. Finally, complementary inverters composed of n‐ and p‐type PCBM OFETs are demonstrated by selective doping of the pre‐deposited semiconductor via inkjet printing of the dopants.     

Control of the Morphology and Structural Development of Solution‐Processed Functionalized Acenes for High‐Performance Organic Transistors

Solution‐processable functionalized acenes have received special attention as promising organic semiconductors in recent years because of their superior intermolecular interactions and solution‐processability, and provide useful benchmarks for organic field‐effect transistors (OFETs). Charge‐carrier transport in organic semiconductor thin films is governed by their morphologies and molecular orientation, so self‐assembly of these functionalized acenes during solution processing is an important challenge. This article discusses the charge‐carrier transport characteristics of solution‐processed functionalized acene transistors and, in particular, focuses on the fine control of the films' morphologies and structural evolution during film‐deposition processes such as inkjet printing and post‐deposition annealing. We discuss strategies for controlling morphologies and crystalline microstructure of soluble acenes with a view to fabricating high‐performance OFETs.     

Polymer‐Based Organic Field‐Effect Transistors with Active Layers Aligned by Highly Hydrophobic Nanogrooved Surfaces

In this study, polymer‐based organic field‐effect transistors (OFETs) that exhibit alignment‐induced mobility enhancement, very small device‐to‐device variation, and high operational stability are successfully fabricated by a simple coating method of semiconductor solutions on highly hydrophobic nanogrooved surfaces. The highly hydrophobic nanogrooved surfaces (water contact angle >110°) are effective at inducing unidirectional alignment of polymer backbone structures with edge‐on orientation and are advantageous for realizing high operational stability because of their water‐repellent nature. The dewetting of the semiconductor solution is a critical problem in the thin film formation on highly hydrophobic surfaces. Dewetting during spin coating is suppressed by surrounding the hydrophobic regions with hydrophilic ones under appropriate designs. For the OFET array with an aligned terrace‐phase active layer of poly(2,5‐bis(3‐hexadecylthiophene‐2‐yl)thieno[3,2‐b]thiophene), the hole mobility in the saturation regime of 30 OFETs with channel current direction parallel to the nanogrooves is 0.513 ± 0.018 cm² V^?1 s^?1, which is approximately double that of the OFETs without nanogrooves, and the intrinsic operational stability is comparable to the operational stability of amorphous‐silicon field‐effect transistors. In other words, alignment‐induced mobility enhancement and high operational stability are successfully achieved with very small device‐to‐device variation. This coating method should be a promising means of fabricating high‐performance OFETs.     

Preliminary Works of Contact via Formation of LCD Backplanes Using Silver Printing

The fabrication of a thin‐film transistor backplane and a liquid‐crystal display using printing processes can eliminate the need for photolithography and offers the potential to reduce the manufacturing costs. In this study, we prepare contact via structures through a poly(methyl methacrylate) polymer insulator layer using inkjet printing. When droplets of silver ink composed of a polymer solvent are placed onto the polymer insulator and annealed at high temperatures, the silver ink penetrates the interior of the polymer and generates conducting paths between the top and bottom metal lines through the partial dissolution and swelling of the polymer. The electrical property of various contact via‐hole interconnections is investigated using a semiconductor characterization system.     

Polypyrrole top-contact electrodes patterned by inkjet printing assisted vapor deposition polymerization in flexible organic thin-film transistors

Highly conductive polymer, polypyrrole (PPy) was successfully patterned as source and drain (S/D) electrodes for flexible pentacene thin film transistors in top-contact structure by combining inkjet printing and vapor deposition polymerization. Facile inkjet printing of initiator and subsequent exposure of pyrrole monomers resulted in selective absorption and polymerization of pyrrole monomers on the patterned initiator region. Pentacene transistors based on printed PPy electrodes exhibited higher electrical characteristics than that of the devices with thermally evaporated Au electrodes. Improved performance of the devices based on PPy electrodes could be attributed to the reduction of contact resistance at the interface between polymer and organic semiconductor. For the replacement of metal electrodes, vapor deposition polymerization assisted inkjet printing technique can provide a versatile method to utilize highly conductive polymer as a functional electrode of flexible organic electronic devices.     

Physicochemically Stable Polymer‐Coupled Oxide Dielectrics for Multipurpose Organic Electronic Applications

A chemically coupled polymer layer is introduced onto inorganic oxide dielectrics from a dilute chlorosilane‐terminated polystyrene (PS) solution. As a result of this surface modification, hydrophilic‐oxide dielectrics gain hydrophobic, physicochemically stable properties. On such PS‐coupled SiO₂ or AlO_x dielectrics, various vacuum‐ and solution‐processable organic semiconductors can develop highly ordered crystalline structures that provide higher field‐effect mobilities (μ_FETs) than other surface‐modified systems, and negligible hysteresis in organic field‐effect transistors (OFETs). In particular, the use of PS‐coupled AlO_x nanodielectrics enables a solution‐processable triethylsilylethynyl anthradithiophene OFET to operate with μ_FET ～ 1.26 cm² V^?1 s^?1 at a gate voltage below –1 V. In addition, a complementary metal‐oxide semiconductor‐like organic inverter with a high voltage gain of approximately 32 was successfully fabricated on a PS‐coupled SiO₂ dielectric.     

Patterning of Flexible Transparent Thin‐Film Transistors with Solution‐Processed ZnO Using the Binary Solvent Mixture

Flexible transparent thin‐film transistors (TTFTs) have emerged as next‐generation transistors because of their applicability in transparent electronic devices. In particular, the major driving force behind solution‐processed zinc oxide film research is its prospective use in printing for electronics. Since the patterning that prevents current leakage and crosstalk noise is essential to fabricate TTFTs, the need for sophisticated patterning methods is critical. In patterning solution‐processed ZnO thin films, several points require careful consideration. In general, as these thin films have a porous structure, conventional patterning based on photolithography causes loss of film performance. In addition, as controlling the drying process is very subtle and cumbersome, it is difficult to fabricate ZnO semiconductor films with robust fidelity through selective printing or patterning. Therefore, we have developed a simple selective patterning method using a substrate pre‐patterned through bond breakage of poly(methyl methacrylate) (PMMA), as well as a new developing method using a toluene–methanol mixture as a binary solvent mixture.