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.     

Inside Front Cover: Perfect Bi4Ti3O12 Single‐Crystal Films via Flux‐Mediated Epitaxy (Adv. Funct. Mater. 4/2006)

Flux‐mediated epitaxy has been developed for ferroelectric Bi₄Ti₃O₁₂ single‐crystal film growth, as shown on the inside cover. The key point is the selection of an appropriate flux material. A combinatorial high‐throughput screening technique reported by Matsumoto and co‐workers on p. 485 has led to the successful discovery of the novel flux composition, Bi–Cu–O, for Bi₄Ti₃O₁₂ single‐crystal film growth. This flux‐mediated epitaxy is not limited to oxide epitaxy, but is also widely applicable to various promising materials for the realization of non‐Si‐based electronics, such as nitrides, carbides, and halides. Excellent crystallinity of material films and atomic control of their surface/interface, sufficient for the realization of their optimal physical properties, are technological premises for modern functional‐device applications. Bi₄Ti₃O₁₂ and related compounds attract much interest as highly insulating, ferroelectric materials for use in ferroelectric random‐access memories. However, it has been difficult thus far for Bi₄Ti₃O₁₂ films to satisfy such requirements when formed using vapor‐phase epitaxy, owing to the high volatility of Bi in a vacuum. Here, we demonstrate that flux‐mediated epitaxy is one of the most promising and widely applicable concepts to overcome this inevitable problem. The key point of this process is the appropriate selection of a multi‐component flux system. A combinatorial approach has led to the successful discovery of the novel flux composition of Bi–Cu–O for Bi₄Ti₃O₁₂ single‐crystal film growth. The perfect single‐crystal nature of the stoichiometric Bi₄Ti₃O₁₂ film formed has been verified through its giant grain size and electric properties, equivalent to those of bulk single crystals. This demonstration has broad implications, opening up the possibility of preparing stoichiometric single‐crystal oxide films via vapor‐phase epitaxy, even if volatile constituents are required.     

Cover Picture: Toward Large‐Scale Alignment of Electrohydrodynamic Patterning of Thin Polymer Films (Adv. Funct. Mater. 15/2006)

By integrating lithography and self‐assembly via electrohydrodynamic instabilities, Russel and co‐workers are able to guide initially flat polymer films to evolve into periodic arrays of pillars over regions much greater in extent than their natural domain sizes, as detailed on p. 1992. Novel structures that involve a combination of linear ridges and pillars are also produced, mainly as as result of the dynamic merging among preformed pillars. To pattern thin polymer films via electrohydrodynamic instabilities, we design and utilize two different kinds of mask patterns to guide pillars into alignment over regions much greater in extent than their natural domain sizes. First, narrow protruding ridges that intersect to form regular patterns on the mask trigger the growth of pillars beneath. Later, square and triangular packings of pillars develop in the regions enclosed by those ridges, preserving the registry from one domain to the next over a much larger area than within individual domains in unpatterned portions of the mask. Second, small square protrusions that are prealigned into a large regular array on the mask guide the formation of square packings of pillars in domains that conform to the mask, forming a large array of pillars. Novel structures involving a combination of linear ridges and pillars are also produced mainly due to the dynamic merging among preformed pillars. Finally, we find vertex symmetry of the mask pattern is necessary for generating and preserving ordered patterns on the polymer film.     

Cover Picture: Structural Modifications to Polystyrene via Self‐Assembling Molecules (Adv. Funct. Mater. 3/2005)

The cover shows tensile failure of a sample of pure polystyrene (left), and a polystyrene sample with greater impact strength containing 1% by weight of dispersed nanoribbons (right), as reported in work by Stupp and co‐workers on p. 487. The nanoribbons are formed by self‐assembly of molecules known as dendron rodcoils (DRCs) in styrene monomer, resulting in the formation of a gel. This gel can then be polymerized thermally. We have previously reported that small quantities of self‐assembling molecules known as dendron rodcoils (DRCs) can be used as supramolecular additives to modify the properties of polystyrene (PS). These molecules spontaneously assemble into supramolecular nanoribbons that can be incorporated into bulk PS in such a way that the orientation of the polymer is significantly enhanced when mechanically drawn above the glass‐transition temperature. In the current study, we more closely evaluate the structural role of the DRC nanoribbons in PS by investigating the mechanical properties and deformation microstructures of polymers modified by self‐assembly. In comparision to PS homopolymer, PS containing small amounts (≤ 1.0 wt.‐%) of self‐assembling DRC molecules exhibit greater Charpy impact strengths in double‐notch four‐point bending and significantly greater elongations to failure in uniaxial tension at 250 % prestrain. Although the DRC‐modified polymer shows significantly smaller elongations to failure at 1000 % prestrain, both low‐ and high‐prestrain specimens maintain tensile strengths that are comparable to those of the homopolymer. The improved toughness and ductility of DRC‐modified PS appears to be related to the increased stress whitening and craze density that was observed near fracture surfaces. However, the mechanism by which the self‐assembling DRC molecules toughen PS is different from that of conventional additives. These molecules assemble into supramolecular nanoribbons that enhance polymer orientation, which in turn modifies crazing patterns and improves impact strength and ductility.     

Cover Picture: A Route to Self‐Organized Honeycomb Microstructured Polystyrene Films and Their Chemical Characterization by ToF‐SIMS Imaging (Adv. Funct. Mater. 7/2007)

The cover shows a composition of different characterization images of an auto‐organized polystyrene film obtained through breath‐figure imprinting, as reported by Sami Yunus and co‐workers on p. 1079. Water‐droplet condensation, represented as a synthetic perspective image (top), is responsible for ordered microstructuring during film formation. The following perspectives are taken from SEM and from three negative ToF‐SIMS images that allow deduction of the surface chemical composition. The background is an SEM picture of a polydimethylsiloxane molding of the self‐organized film. A new type of polymer compound that allows the formation of highly ordered microstructured films by casting from a volatile solvent in the presence of humidity, and its characterization by ToF‐SIMS (time‐of‐flight secondary‐ion mass spectrometry) are presented. A honeycomb structure is obtained by activation of 2,2,6,6‐tetramethyl‐1‐piperidinyloxyl (TEMPO)‐terminated polystyrene (PS) with p‐toluenesulfonic acid (PTSA). The mechanism of this activation reaction, leading to a more polar PS termination, is deduced from simple experiments and supported by ToF‐SIMS characterization. Positive and negative ToF‐SIMS imaging allows different chemical regions correlating to the film morphology to be distinguished. This new, straightforward activation process, together with ToF‐SIMS chemical imaging, provides a better understanding of the phenomena underlying the formation of these films by directly linking the role of polar terminations to the microscale self‐organization. This new method, transposable to other organic acids, suggests interesting new perspectives in the field of self‐organized chemical and topographical patterning.     

Cover Picture: Sequential Nucleation and Growth of Complex Nanostructured Films (Adv. Funct. Mater. 3/2006)

A sequential nucleation and growth process has been developed to construct complex nanostructured films step‐by‐step from aqueous solutions, as reported by Liu, Voigt, and co‐workers on p. 335. This method can be applied to a wide range of materials, and can be combined with top–down techniques to create spatially resolved micropatterns. The cover figure shows images of oriented nanowires, nanoneedles, nanotubes, nanoplates and stacked columns, wagon‐wheels, hierarchical films based on wagon‐wheels, hierarchically ordered mesophase silicate, and micropatterned flower‐like structures. Nanostructured films with controlled architectures are desirable for many applications in optics, electronics, biology, medicine, and energy/chemical conversions. Low‐temperature, aqueous chemical routes have been widely investigated for the synthesis of continuous films, and arrays of oriented nanorods and nanotubes. More recently, aqueous‐phase routes have been used to produce films composed of more complex crystal structures. In this paper, we discuss recent progress in the synthesis of complex nanostructures through sequential nucleation and growth processes. We first review the use of multistage, seeded‐growth methods to synthesize a wide range of nanostructures, including oriented nanowires, nanotubes, and nanoneedles, as well as laminated films, columns, and multilayer heterostructures. We then describe more recent work on the application of sequential nucleation and growth to the systematic assembly of large arrays of hierarchical, complex, oriented, and ordered crystal architectures. The multistage aqueous chemical route is shown to be applicable to several technologically important materials, and therefore may play a key role in advancing complex nanomaterials into applications.     

Cover Picture: Formation of Metal Nano‐ and Micropatterns on Self‐Assembled Monolayers by Pulsed Laser Deposition Through Nanostencils and Electroless Deposition (Adv. Funct. Mater. 10/2006)

The cover illustrates two‐step fabrication of metal micro‐ and nanostructures on self‐assembled monolayers (SAMs) by pulsed laser deposition and electroless deposition. Metal–SAM–metal junctions are a key component of molecular electronic devices. Pt was deposited in a micropattern by pulsed laser deposition through a stencil. XPS maps show how the Pt pattern is developed into a Cu pattern using electroless deposition as reported by Ravoo, Brugger, Reinhoudt, Blank, and co‐workers on p. 1337. The Cu pattern can also be observed by optical microscopy (background). Patterns of noble‐metal structures on top of self‐assembled monolayers (SAMs) on Au and SiO₂ substrates have been prepared following two approaches. The first approach consists of pulsed laser deposition (PLD) of Pt, Pd, Au, or Cu through nano‐ and microstencils. In the second approach, noble‐metal cluster patterns deposited through nano‐ and microstencils are used as catalysts for selective electroless deposition (ELD) of Cu. Cu structures are grown on SAMs on both Au and SiO₂ substrates and are subsequently analyzed using X‐ray photoelectron spectroscopy element mapping, atomic force microscopy, and optical microscopy. The combination of PLD through stencils on SAMs followed by ELD is a new method for the creation of (sub)‐micrometer‐sized metal structures on top of SAMs. This method minimizes the gas‐phase deposition step, which is often responsible for damage to, or electrical shorts through, the SAM.     

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.