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.     

Direct Photopatterning of Electrochromic Polymers

Propylenedioxythiophene (ProDOT) polymers are synthesized using an oxidative polymerization route that results in methacrylate substituted poly(ProDOTs) having a M_n of 10–20 kDa wherein the methacrylate functionality constitutes from 6 to 60% of the total monomer units. Solutions of these polymers show excellent film forming abilities, with thin films prepared using both spray‐casting and spin‐coating. These polymers are demonstrated to crosslink upon UV irradiation at 350 nm, in the presence of an appropriate photoinitiator, to render the films insoluble to common organic solvents. Electrochemical, spectroelectrochemical, and colorimetric analyses of the crosslinked polymer films are performed to establish that they retain the same electrochromic qualities as the parent polymers with no detriment to the observed properties. To demonstrate applicability for multi‐film processing and patterning, photolithographic patterning is shown, as is desired for fully solution processed and patterned devices.     

Phase‐Separation‐Induced Micropatterned Polymer Surfaces and Their Applications

We report a route to fabricate micropatterned polymer films with micro‐ or nanometer‐scale surface concavities by spreading polymer solutions on a non‐solvent surface. The route is simple, versatile, highly efficient, low‐cost, and easily accessible. The concavity density of the patterned films is tuned from 10⁶ to 10⁹ features cm^–2, and the concavity size is controlled in the range from several micrometers to less than 100 nm, by changing the film‐forming parameters including the polymer concentration, the temperature of the non‐solvent and the interactions between polymer, solvent, and non‐solvent. We further demonstrate that these concavity‐patterned films have significantly enhanced hydrophobicity, owing to the existence of the surface concavities, and their hydrophobicity could be controlled by the concavity density. These films have been used as templates to successfully fabricate convex‐patterned polymer films, inorganic TiO₂ microparticles, and NaCl nanocrystals. Their other potential applications are also discussed.     

Fabrication of Multiscale Gradient Polymer Patterns by Direct Molding and Spatially Controlled Reflow

Size variations of pattern spacing as well as gradient control of the as‐formed polymeric pattern via a spatially controlled reflow process are presented. Micro‐ and nanopatterns of polymethyl methacrylate (PMMA) in the form of line‐and‐space strips are first generated by capillary force lithography (CFL), and the residual layers are removed by ashing process. Subsequently, the exposed PMMA strips underwent a controlled reflow process above the glass transition temperature (T_g) while heating single or both sides of the substrate either in parallel to the line pattern (parallel reflow) or perpendicular to the line pattern (perpendicular reflow). As a result of this controlled reflow, a linear or a parabolic profile of pattern spacing is achieved depending on the heating mode. Furthermore, multiscale gradient patterns are formed with the spacing ranging from 98 nm to 4.23 μm (a difference of two orders of magnitude) in a single patterned layer using the original micropattern of 16 μm width and 8 μm spacing. In order to explain reflow behaviors, a simple theoretical model relating the normalized pattern width to the polymer viscosity is derived based on a leveling kinetics of polymer melt. Also, gradient PMMA channels are fabricated and bonded to a glass substrate, which are used to flow a liquid inside the channels by capillarity‐driven flow.     

PATTERNED POLYMERS: Fabrication of Multiscale Gradient Polymer Patterns by Direct Molding and Spatially Controlled Reflow (Adv. Funct. Mater. 6/2011)

Size variations of pattern spacing as well as gradient control of the as‐formed polymeric pattern via a spatially controlled reflow process are presented. Micro‐ and nanopatterns of polymethyl methacrylate (PMMA) in the form of line‐and‐space strips are first generated by capillary force lithography (CFL), and the residual layers are removed by ashing process. Subsequently, the exposed PMMA strips underwent a controlled reflow process above the glass transition temperature (T_g) while heating single or both sides of the substrate either in parallel to the line pattern (parallel reflow) or perpendicular to the line pattern (perpendicular reflow). As a result of this controlled reflow, a linear or a parabolic profile of pattern spacing is achieved depending on the heating mode. Furthermore, multiscale gradient patterns are formed with the spacing ranging from 98 nm to 4.23 μm (a difference of two orders of magnitude) in a single patterned layer using the original micropattern of 16 μm width and 8 μm spacing. In order to explain reflow behaviors, a simple theoretical model relating the normalized pattern width to the polymer viscosity is derived based on a leveling kinetics of polymer melt. Also, gradient PMMA channels are fabricated and bonded to a glass substrate, which are used to flow a liquid inside the channels by capillarity‐driven flow.     

Direct Fabrication of Fine Gold Patterns from an Aqueous Solution by a UV Laser

A new strategy for directly fabricating fine gold patterns from an aqueous solution with the help of a UV laser is proposed. The solution contains 90 mmol/L of HAuCl₄ and 280 mmol/L of Na₂SO₃. The process involves two steps. The first step is to create the pattern (seed layer) by irradiating the solution layer spread on the substrate by the UV laser beam. The second step is to immerse the patterned or irradiated substrate in the bulk solution for a certain time to grow the film. A 0.1-μm-thick film is yielded in the irradiated area after 30 min immersion in the solution.     

Direct Writing of Metal Nanoparticles by Localized Plasma Electrochemical Reduction of Metal Cations in Polymer Films

A non‐lithographic, dry approach to patterning metal nanoparticles is presented. Solutions of metal salt and polymer are spin‐coated onto a substrate, dried, and exposed to a rastered microscale plasma operated at atmospheric pressure and room temperature. Interaction of the electrons in the plasma with the film results in electrochemical reduction of the metal cations to crystalline metal nanoparticles. The process is highly localized, making it possible to obtain microscale patterns of metal nanoparticles with line widths as small as ～30 μm. We have applied this technique to a wide range of metals such as Ag, Au, Pt, Ir, and Ru, in various polymeric systems such as polyvinyl alcohol (PVA) and poly(methyl methacrylate) (PMMA). Overall, the approach allows the fabrication of transparent, flexible, patterned films of metal nanoparticles at low cost and high throughput for applications ranging from plasmonics to catalysis.     

Direct Surface Patterning from Solutions: Localized Microchemistry Using a Focused Laser

A method for creating microscale‐patterned surfaces by direct‐write lithography is described. A tightly focused, low‐power infrared laser beam is applied to a homogeneous precursor solution containing soluble reagents. When the laser is focused directly at a glass–solution interface, it initiates the local precipitation of a solid product that attaches firmly to the substrate. Operating the laser momentarily forms isolated spots, whereas moving the microscope stage or the laser spot draws continuous lines. The method has been demonstrated for metallic silver and gold, for oxidized copper, and for molybdenum disulfide, suggesting a broad range of suitable materials. Silver patterns were further modified by chemical reactions. Their morphology and physical properties can be altered during deposition by the use of capping agents, which may provide an onset for further functionalization.     

A Non‐Covalent Approach for Depositing Spatially Selective Materials on Surfaces

We describe a new method for depositing patterned materials, based on non‐covalent trapping of ligands in solvent‐templated nanocavities created in aromatic, self‐assembled monolayer or polymer films. A model has been developed and tested to describe nanocavity formation and the ligand adsorption process, which occurs via ligand exclusion from ambient, aqueous solution into the hydrophobic nanocavities. Ligand adsorption rates and ligand adsorbate reactivity with solution species are governed by ligand size/geometry design factors identified using the model. Spatial control of adsorption is achieved via film photochemical changes that inhibit subsequent ligand adsorption/accessibility (UV or X‐ray) or displacement of entrapped ligands (50 keV electron‐beam) during film patterning. The reactivity of the adsorbed ligand is illustrated by the selective binding of Pd^II species that catalyze electroless metal deposition. Fabrication of high‐resolution (≈ 50 nm), positive‐tone patterns in nickel with acceptable feature‐edge acuity and critical dimension control (≈ 5 %) is demonstrated.     

硫掺杂纳米金刚石薄膜的图形化生长

利用电子增强热丝化学气相沉积(EACVD)技术,以CH4/H2/H2S/Ar为工作气体,SiO2/Si为衬底,制备了硫掺杂金刚石薄膜。研究了利用光刻技术实现薄膜的图形化生长。结果表明:以SiO2作掩模的光刻技术能够使得硫掺杂金刚石薄膜在光滑SiO2/Si基片上很好地图形化生长。Hall效应检测表明硫掺杂金刚石薄膜为n型,给出了n型金刚石/p-Si异质结的反向I-V特性曲线。     

Polymer Brush Electrets

The charge storage properties of polymer brushes are reported for the first time. Poly(methyl methacrylate) (PMMA) brushes are explored as electrets to store electrostatic charges. Micrometer‐ and nanometer‐scale patterns of electrostatic charges are successfully fabricated on planar and non‐planar PMMA brush films by means of conductive microcontact printing and atomic force microscope lithography, where the charge storage density and stability are studied in detail with Kelvin force microscopy. Importantly, because PMMA brushes are chemically tethered on the substrate, their charge storage properties can be studied in various organic solvents, in which their bulk counterparts will be dissolved. It is found that patterned charges on PMMA brushes are stable enough in organic media, such as hexane and toluene, for guiding the assembly of Au nanoparticles in organic media and the dewetting of polymer thin films with solvent annealing. The electrets properties shall add a new dimension of functionality, apart from the conventional chemical and physical properties, to polymer brushes for a wide range of applications in materials science, nanotechnology, and electronic devices.     

Highly Customizable All Solution–Processed Polymer Light Emitting Diodes with Inkjet Printed Ag and Transfer Printed Conductive Polymer Electrodes

Inkjet and transfer printing processes are combined to easily form patterned poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) films as top anodes of all solution–processed inverted polymer light emitting diodes (PLEDs) on rigid glass and flexible plastic substrates. An adhesive PEDOT:PSS ink is formulated and fully customizable patterns are obtained using the inkjet printing process. In order to transfer the patterned PEDOT:PSS films, adhesion properties at interfaces during multistep transfer printing processes are carefully adjusted. The transferred PEDOT:PSS film on the plastic substrates shows not only a sheet resistance of 260.6 Ω/□ and a transmittance of 92.1% at 550 nm wavelength but also excellent mechanical flexibility. The PLEDs with spin‐coated functional layers sandwiched between the transferred PEDOT:PSS top anodes and inkjet‐printed Ag bottom cathodes are fabricated. The fabricated PLEDs on the plastic substrates show a high current efficiency of 10.4 cd A^?1 and high mechanical stability. It is noted that because both Ag and PEDOT:PSS electrodes can be patterned with a high degree of freedom via the inkjet printing process, highly customizable PLEDs with various pattern sizes and shapes are demonstrated on the glass and plastic substrates. Finally, with all solution process, a 5 × 7 passive matrix PLED array is demonstrated.     

Soft‐Contact Optical Lithography Using Transparent Elastomeric Stamps and Application to Nanopatterned Organic Light‐Emitting Devices

Conventional photolithography uses rigid photomasks of fused quartz and high‐purity silica glass plates covered with patterned microstructures of an opaque material. We introduce new, transparent, elastomeric molds (or stamps) of poly(dimethylsiloxane) (PDMS) that can be employed as photomasks to produce the same resist pattern as the pattern of the recessed (or non‐contact) regions of the stamps, in contrast to other reports in the literature^[1] of using PDMS masks to generate edge patterns. The exposure dose of the non‐contact regions with the photoresist through the PDMS is lower than that of the contact regions. Therefore, we employ a difference in the effective exposure dose between the contact and the non‐contact regions through the PDMS stamp to generate the same pattern as the PDMS photomask. The photomasking capability of the PDMS stamps, which is similar to rigid photomasks in conventional photolithography, widens the application boundaries of soft‐contact optical lithography and makes the photolithography process and equipment very simple. This soft‐contact optical lithography process can be widely used to perform photolithography on flexible substrates, avoiding metal or resist cracks, as it uses soft, conformable, intimate contact with the photoresist without any external pressure. To this end, we demonstrate soft‐contact optical lithography on a gold‐coated PDMS substrate and utilized the patterned Au/PDMS substrate with feature sizes into the nanometer regime as a top electrode in organic light‐emitting diodes that are formed by soft‐contact lamination.     

Nanopatterning by an Integrated Process Combining Capillary Force Lithography and Microcontact Printing

A novel nanopatterning process was developed by combining capillary force lithography (CFL) and microcontact printing (µCP). Flat polydimethylsiloxane (PDMS) was used as the substrate in CFL, and after chemical functionalization, as the stamp in µCP, which increased the resolution of both methods. The polymer patterns, produced by CFL on a thin polymer film on the flat PDMS substrate, acted as a mask to oxidize the uncovered regions of the PDMS. The chemical patterns were subsequently formed by gas phase evaporation of a fluorinated silane. After removal of the polymer, these stamps were used to transfer thiol inks to a gold substrate by µCP. Gold patterns at a scale of less than 100 nm were successfully replicated by these chemically patterned flat PDMS stamps.     

Direct metallization of gold patterns on polyimide substrate by microcontact printing and selective surface modification

Patterned gold microstructures were fabricated on a polymer substrate by a novel method involving selective electroless plating and microcontact printing. The micro-sized gold patterns were made by the site-selective chemical modification of polyimide substrate films using aqueous potassium hydroxide solution and microcontact printing with a pitch size in the range of 20-200 μm. The base-treated area of the polyimide film became hydrophilic in the regions where the ion-exchange reactions took place for the subsequent metallization. The hydrophilic patterns were sensitized by placing the film in a solution of PdCl₂ and, subsequently, the activated substrate was immersed in an electroless plating solution of Ni and Au to provide well-developed gold patterns on polyimide substrate films.     

Porous Polymer Films with Gradient‐Refractive‐Index Structure for Broadband and Omnidirectional Antireflection Coatings

Porous polymer films that can be employed for broadband and omnidirectional antireflection coatings are successfully shown. These films form a gradient‐refractive‐index structure and are achieved by spin‐coating the solution of a polystyrene‐block‐poly(methyl methacrylate) (PS‐b‐PMMA)/PMMA blend onto an octadecyltrichlorosilane (OTS)‐modified glass substrate. Thus, a gradient distribution of PMMA domains in the vertical direction of the entire microphase‐separated film is obtained. After those PMMA domains are removed, a PS porous structure with an excellent gradient porosity ratio in the vertical direction of the film is formed. Glass substrates coated with such porous polymer film exhibit both broadband and omnidirectional antireflection properties because the refractive index increases gradually from the top to the bottom of the film. An excellent transmittance of >97% for both visible and near‐infrared (NIR) light is achieved in these gradient‐refractive‐index structures. When the incident angle is increased, the total transmittance for three different incident angles is improved dramatically. Meanwhile, the film possesses a color reproduction character in the visible light range.     

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.     

Plastic Electronic Devices Through Line Patterning of Conducting Polymers

A novel method for the preparation of transparent conducting‐polymer patterns on flexible substrates is presented. This method, line patterning, employs mostly standard office equipment, such as drawing software, a laser printer, and commercial overhead transparencies, together with a solution or dispersion of a conducting polymer. The preparation of a seven‐segment polymer‐dispersed liquid‐crystal display using electrodes of the conducting polymer poly(3,4‐ethylenedioxythiophene) doped with poly(4‐styrene sulfonate) (PEDOT/PSS) is described in detail. Furthermore, a method to fabricate an eleven‐key push‐button array for keypad applications is presented. Properties of the electrode films and patterns are discussed using microscopy images, atomic force microscopy, conductivity measurements, and tests of film stability.     

Carbon Nanotube Alignment via Electrohydrodynamic Patterning of Nanocomposites

Electrohydrodynamic (EHD) pattern formation in carbon nanotube‐polymer composite films yields well‐defined patterns on the micrometer scale along with the alignment of carbon nanotubes (CNTs) within these patterns. Conductive pathways in nanotube networks formed during EHD patterning of nanocomposite films results in a substantial increase in the composites’ conductivity at loadings exceeding the percolation threshold. The degree of nanotube alignment can be tuned by adjusting the EHD parameters and the degree of alignment is mirrored by the conductivity across the film. Using etching techniques or by embedding relatively long nanotubes, patterned surfaces decorated by CNT brushes were generated.     

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.