Generation of Self‐Assembled 3D Mesostructured SnO2 Thin Films with Highly Crystalline Frameworks

Crack‐free, mesoporous SnO₂ films with highly crystalline pore walls are obtained by evaporation‐induced self‐assembly using a novel amphiphilic block‐copolymer template (“KLE” type, poly(ethylene‐co‐butylene)‐block‐poly(ethylene oxide)), which leads to well‐defined arrays of contracted spherical mesopores by suitable heat‐treatment procedures. Because of the improved templating properties of these polymers, a facile heat‐treatment procedure can be applied whilst keeping the mesoscopic order intact up to 600–650 °C. The formation mechanism and the mesostructural evolution are investigated by various state‐of‐the‐art techniques, particularly by a specially constructed 2D small‐angle X‐ray scattering setup. It is found that the main benefit from the polymers is the formation of an ordered mesostructure under the drastic conditions of using molecular Sn precursors (SnCl₄), taking advantage of the large segregation strength of these amphiphiles. Furthermore, it is found that the crystallization mechanism is different from other mesostructured metal oxides such as TiO₂. In the case of SnO₂, a significant degree of crystallization (induced by heat treatment) already starts at quite low temperatures, 250–300 °C. Therefore, this study provides a better understanding of the general parameters governing the preparation of mesoporous metal oxides films with crystalline pore walls.     

Profile Control in Block Copolymer Nanostructures using Bilayer Thin Films for Enhanced Pattern Transfer Processes

Although control over the domain orientation and long‐range order of block copolymer nanostructures self‐assembled in thin films has been achieved using various directed self‐assembly techniques, more challenging but equally important for many lithographic applications is the ability to precisely control the shape of the interface between domains. Here, a novel layer‐by‐layer approach is reported for controlling the interface profile of block copolymer nanostructures and the application of an undercut sidewall profile for an enhanced metal lift‐off process for pattern transfer is demonstrated. Bilayer films of lamellar‐forming poly(styrene‐block‐methyl methacrylate) are assembled and thermally cross‐linked on wafer substrates in a layer‐by‐layer process. The top layer, while being directed to self‐assemble on the lamellae of the underlying layer, has a tunable composition and polystyrene domain width independent of that of the bottom layer. Undercut or negative sidewall profiles in the PS nanostructures are proven to provide better templates for the lift‐off of Au nanowires by achieving complete and defect‐free pattern transfer more than three times faster than comparable systems with vertical sidewall profiles. More broadly, the layer‐by‐layer approach presented here provides a pathway to achieving sophisticated interface profiles and user‐defined 3D block copolymer nanostructures in thin films.     

Flexible and Robust 2D Arrays of Silver Nanowires Encapsulated within Freestanding Layer‐by‐Layer Films

Freestanding layer‐by‐layer (LbL) films encapsulating controlled volume fractions (? = 2.5–22.5 %) of silver nanowires are fabricated. The silver nanowires are sandwiched between poly(allylamine hydrochloride)/poly(styrene sulfonate) (PAH/PSS) films resulting in nanocomposite structures with a general formula of (PAH/PSS)₁₀PAH Ag(PAH/PSS)₁₀PAH. The Young's modulus, toughness, ultimate stress, and ultimate strain are evaluated for supported and freestanding structures. Since the diameter of the nanowires (73 nm) is larger than the thickness of the LbL films (total of about 50 nm), a peculiar morphology is observed with the silver nanowires protruding from the planar LbL films. Nanowire‐containing LbL films possess the ability to sustain significant elastic deformations with the ultimate strain reaching 1.8 %. The Young's modulus increases with increasing nanowire content, reaching about 6 GPa for the highest volume fraction, due to the filler reinforcement effect commonly observed in composite materials. The ultimate strengths of these composites range from 60–80 MPa and their toughness reaches 1000 kJ m^–3 at intermediate nanowire content, which is comparable to LbL films reinforced with carbon nanotubes. These robust freestanding 2D arrays of silver nanowires with peculiar optical, mechanical, and conducting properties combined with excellent micromechanical stability could serve as active elements in microscopic acoustic, pressure, and photothermal sensors.     

Using Directed Self Assembly of Block Copolymer Nanostructures to Modulate Nanoscale Surface Roughness: Towards a Novel Lithographic Process

Nanoscale surface roughness is an important factor in determining the properties of surfaces and can affect the performance of a range of devices prepared by lithographic methods. Here, a method is reported, which enables modulation of the nanoscale roughness of surfaces through the directed self assembly (DSA) of positively charged polymersomes, composed of specifically designed block copolymers, onto negatively charged surfaces. Assembly of the polymersomes on surfaces can result in an increase in the nanoscale surface roughness; however, through a controlled annealing step we can also significantly reduce the nanoscale roughness of the original surface. The ability to decrease the roughness of lithographic patterns is expected to have a significant impact on the manufacture of integrated circuits.     

Atomic Layer Deposition of TiO2 Thin Films on Mixed Self‐Assembled Monolayers Studied as a Function of Surface Free Energy

Mixed self‐assembled monolayers (SAMs) with different ratios of –OH to –CH₃ groups were used to modify the surface free energies of the Si substrates from 64 to 29 mN m^–1. The TiO₂ thin films were grown on the mixed SAM‐coated Si substrates by atomic layer deposition (ALD) from titanium isopropoxide and water. A two‐dimensional growth mode is observed on the SAMs‐coated substrates possessing high surface free energies. As the surface free energy decreases, a three‐dimensional growth mode begins to dominate. These observations indicate that the mixed SAMs can control the growth modes of the atomic layer deposition by modifying of the surface free energies of the substrates.     

Reactive Ion Etching of Cylindrical Polyferrocenylsilane Block Copolymer Micelles: Fabrication of Ceramic Nanolines on Semiconducting Substrates

The diblock copolymers, poly(isoprene‐block‐ferrocenyldimethylsilane) (PI‐b‐PFDMS) and poly(ferrocenyldimethylsilane‐block‐dimethylsiloxane) (PFDMS‐b‐PDMS), form cylindrical micelles with an organometallic polyferrocenylsilane core in a solvent of hexanes. These cylindrical micelles were deposited onto a Si substrate from solution by either spin or dip coating, and upon reactive ion etching, continuous ceramic nanolines with lengths of micrometers and widths as small as 8 nm were created. The nanolines were characterized by scanning force microscopy (SFM) and transmission electron microscopy (TEM), and were shown to contain Fe, Si, and O from X‐ray photoelectron spectroscopy (XPS) studies. The widths of the nanolines could be varied from ca. 8 to 30 nm, depending on the composition of the corona (PI or PDMS). The oriented deposition of these cylindrical micelles can be achieved along pre‐patterned grooves on a resist film using capillary forces. Following treatment with hydrogen or oxygen plasma, oriented ceramic nanolines can be fabricated. The approach reported here represents a relatively simple method to create ceramic nanolines with large aspect ratio on semiconducting substrates.     

A Route to Self‐Organized Honeycomb Microstructured Polystyrene Films and Their Chemical Characterization by ToF‐SIMS Imaging

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.     

Flexible Silk–Inorganic Nanocomposites: From Transparent to Highly Reflective

A novel type of all‐natural, biocompatible, and very robust nanoscale free‐standing biohybrids are reported. They are obtained by integrating a silk fibroin matrix with functional inorganic nanoplatelets using a spin‐assisted layer‐by‐layer assembly. The organized assembly of the silk fibroin with clay (montmorillonite) nanosheets results in highly transparent nanoscale films with significantly enhanced mechanical properties, including strength, toughness, and elastic modulus, as compared to those for the pristine silk nanomaterials. Moreover, replacing clay nanoplatelets with a highly reflective Langmuir monolayer of densely packed silver nanoplates causes a similar enhancement of the mechanical properties, but in contrast to the materials above, highly reflective, mirror‐like, nanoscale flexible films are created. This strategy offers a new perspective for the fabrication of robust all‐natural flexible nanocomposites with exceptional mechanical properties important for biomedical applications, such as reinforced tissue engineering. On the other hand, the ability to convert silk‐based nanoscale films into mirror‐like biocompatible flexible films can be intriguing for prospective photonics and optical exploitation of these nanobiohybrids.     

Continuous,Atmospheric Process to Create Organic Clusters and Nanostructured,Functional Films

An atmospheric process based on compressed CO₂ is used to create stable clusters of small organic molecules. These clusters, 1–10 nm in size, are used as building blocks to assemble thin films on various substrates. Cluster assembly of these films is verified by using low‐angle X‐ray diffraction. The surface quality of these cluster‐assembled films is similar to that of films usually prepared via the vacuum process. Several functional organic light‐emitting diode devices have been prepared, in which only the doped emissive layer has been deposited by our process. The radiometric features and efficiencies of these devices match those of vacuum‐built devices. Atomic force microscopy of these molecular clusters reveals that they are liquid‐like at standard atmospheric conditions. Coatings of these clusters on cloth and stainless steel have been found to be superhydrophobic in nature.     

3D Hexagonal (R‐3m) Mesostructured Nanocrystalline Titania Thin Films: Synthesis and Characterization

A straightforward and reproducible synthesis of crack‐free large‐area thin films of 3D hexagonal (R‐3m) mesostructured nanocrystalline titania (meso‐nc‐TiO₂) using a Pluronic triblock copolymer (P123)/1‐butanol templating system is described. The characterization of the films is achieved using a combination of electron microscopy (high‐resolution scanning electron microscopy and scanning transmission electron microscopy), grazing‐incidence small‐angle X‐ray scattering, in situ high‐temperature X‐ray diffraction, and variable‐angle spectroscopic ellipsometry. The mesostructure of the obtained films is found to be based upon a 3D periodic array of large elliptically shaped cages with diameters around 20 nm interconnected by windows of about 5 nm in size. The mesopores of the film calcined at 300 °C are very highly ordered, and the titania framework of the film has a crystallinity of 40 % being composed of 5.8 nm sized anatase crystallites. The film displays high thermal stability in that the collapse of the pore architecture is incomplete even at 600 °C. The accessible surface area of 3D hexagonal meso‐nc‐TiO₂ estimated by the absorption of methylene blue is nearly twice as large as that of 2D hexagonal meso‐nc‐TiO₂ at the same annealing temperature.     

Multifunctional Nanocrystalline Thin Films of Er2O3: Interplay between Nucleation Kinetics and Film Characteristics

In this study, thin films of Er₂O₃ are deposited by low‐pressure metal–organic chemical vapor deposition (MOCVD) using a tris(isopropylcyclopentadienyl)erbium precursor and O₂ on various substrates, including p‐type Si(100), Si(111), Corning glass, and c‐axis‐oriented α‐Al₂O₃(0001). The resulting films are extensively characterized in order to demonstrate their applicability as antireflective and protective coatings and as high‐k gate dielectrics. The interplay existing among the substrate, the nucleation kinetics, and the resulting structural, morphological, optical, and electrical properties of Er₂O₃ thin films is explored. Fast nucleation governed by surface energy minimization characterizes the growth of (111)‐oriented Er₂O₃ on Si(100), glass, and α‐Al₂O_3. Conversely, nonhomogeneous nucleation leads to polycrystalline Er₂O₃ on Si(111) substrates. Er₂O₃ films grown on Si(100) possess superior characteristics. A high refractive index of 2.1 at 589.3 nm, comparable to the value for bulk single crystalline Er₂O₃, a high transparency in the near UV‐vis range, and an optical bandgap of 6.5 eV make Er₂O₃ interesting as an antireflective and protective coating. A static dielectric constant of 12–13 and a density of interface traps as low as 4.2 × 10¹⁰ cm² eV^–1 for 5–10 nm thick Er₂O₃ layers grown on Si(100) render the present Er₂O₃ films interesting also as high‐k dielectrics in complementary metal oxide semiconductor (CMOS) devices.     

Monomolecular‐Layer Ba5Ta4O15 Nanosheets: Synthesis and Investigation of Photocatalytic Properties

Monomolecular‐layer perovskite Ba₅Ta₄O₁₅ nanosheets with hexagonal structure have been synthesized by a hydrothermal method. The thickness of the nanosheets is about 1.1 nm, which corresponds to a monolayer of Ba₅Ta₄O₁₅ molecules, with the lateral size ranging from 50 to 200 nm. The optimal conditions for the formation of the nanosheets are maintaining the reactants above 270 °C for 24 h. A dissolution–recrystallization mechanism is suggested based on observations of the factors that influence nanosheet formation, such as reaction time, temperature, and basicity. Formation of Ba₅Ta₄O₁₅ nanosheets takes precedence over other nanostructures under high concentrations of OH^– because the hindering effect of OH^– ions on the c‐axis growth is strong. Thus, the extended growth rate of polyhedrons on one monolayer is much faster than the superposition rate of the monolayer, and the crystal grows more easily along the a‐ and b‐planes. The Ba₅Ta₄O₁₅ nanosheets show a high photocatalytic activity in the degradation of Rhodamine B and gaseous formaldehyde. The layered perovskite probably affects the photocatalytic activity by promoting the charge separation and delocalization of photogenerated electrons and holes.     

A Morphological Model for the Solvent‐Enhanced Conductivity of PEDOT:PSS Thin Films

The well‐known enhanced conductivity of poly(3,4‐ethylenedioxythiophene):poly(4‐styrenesulfonate) (PEDOT:PSS) thin films that is obtained by addition of high‐boiling solvents like sorbitol to the aqueous dispersion used for film deposition is shown to be associated with a rearrangement of PEDOT‐rich clusters into elongated domains, as evidenced from STM and AFM. Consistently, temperature dependent conductivity measurements for sorbitol‐treated films reveal that charge transport occurs via quasi 1D variable range hopping (VRH), in contrast to 3D VRH for untreated PEDOT:PSS films. The typical hopping distance of 60–90 nm, extracted from the conductivity measurements is consistent with hopping between the 30–40 nm sized grains observed with scanning probe microscopy.     

Solution Processing Route to Multifunctional Titania Thin Films: Highly Conductive and Photcatalytically Active Nb:TiO2

This paper reports the synthesis of highly conductive niobium doped titanium dioxide (Nb:TiO₂) films from the decomposition of Ti(OEt)₄ with dopant quantities of Nb(OEt)₅ by aerosol‐assisted chemical vapor deposition (AACVD). Doping Nb into the Ti sites results in n‐type conductivity, as determined by Hall effect measurements. The doped films display significantly improved electrical properties compared to pristine TiO₂ films. For 5 at.% Nb in the films, the charge carrier concentration was 2 × 10²¹ cm^?3 with a mobility of 2 cm² V^–1 s^–1 . The corresponding sheet resistance is as low as 6.5 Ω sq^–1 making the films suitable candidates for transparent conducting oxide (TCO) materials. This is, to the best of our knowledge, the lowest reported sheet resistance for Nb:TiO₂ films synthesized by vapour deposition. The doped films are also blue in colour, with the intensity dependent on the Nb concentration in the films. A combination of synchrotron, laboratory and theoretical techniques confirmed niobium doping into the anatase TiO₂ lattice. Computational methods also confirmed experimental results of both delocalized (Ti⁴⁺) and localized polaronic states (Ti³⁺) states. Additionally, the doped films also functioned as photocatalysts. Thus, Nb:TiO₂ combines four functional properties (photocatalysis, electrical conductivity, optical transparency and blue colouration) within the same layer, making it a promising alternative to conventional TCO materials.     

Control of Optical Hysteresis in Block Copolymer Photonic Gels: A Step Towards Wet Photonic Memory Films

Polystyrene‐block‐poly(2‐vinyl pyridine) (PS‐b‐P2VP) block copolymer photonic gels are fabricated that exhibit controllable optical hysteresis in response to a cyclic pH sweep. The optical hysteresis is tuned by controlling the ion‐pairing affinity between various anions and the protonated pyridinium ions on the P2VP block, which is highly dependent on the hydration energy of the ions, the dielectric constant of the solvent, and the ionic strength of the medium. The pH coercivity defining the magnitude of hysteresis of the photonic gels could be varied from 0.26 to 7.4. Photonic gel films with strong optical hysteresis can serve as wet photonic memory films where information can be cyclically recorded and erased at least 15 times and maintained for at least 96 h. The memory colors can be further tuned by selection of the copolymer molecular weight.     

A Top Coat with Solvent Annealing Enables Perpendicular Orientation of Sub‐10 nm Microdomains in Si‐Containing Block Copolymer Thin Films

Achieving sub‐10 nm high‐aspect‐ratio patterns from diblock copolymer self‐assembly requires both a high interaction parameter (χ, which is determined by the incompatibility between the two blocks) and a perpendicular orientation of microdomains. However, these two conditions are extremely difficult to achieve simultaneously because the blocks in a high‐χ copolymer typically have very different surface energies, favoring in‐plane microdomain orientations. A fully perpendicular orientation of a high‐χ block copolymer, poly(styrene‐block‐dimethylsiloxane) (PS‐b‐PDMS) is realized here using partially hydrolyzed polyvinyl alcohol (PVA) top coats with a solvent annealing process, despite the large surface energy differences between PS and PDMS. The PVA top coat on the block copolymer films under a solvent vapor atmosphere significantly reduces the interfacial energy difference between two blocks at the top surface and provides sufficient solvent concentration gradient in the through‐thickness direction and appropriate solvent evaporation rates within the film to promote a perpendicular microdomain orientation. The effects of interfacial energy differences and the swellability of PVA top coats controlled by the degree of hydrolysis on the orientation of micro­domains are examined. The thickness of the BCP film and top coats also affects the orientation of the BCP film.     

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.