Diphenylamine‐Substituted Cruciform Oligo(phenylene vinylene): Enhanced One‐ and Two‐Photon Excited Fluorescence in the Solid State

1,4‐di(4′‐N,N‐diphenylaminostyryl)benzene (DPA‐DSB) is a well known compound with a large two‐photon absorption (TPA) section and strong fluorescence in solution. However, the ease with which it crystallizes results in the formation of discontinuous crystalline phases during vacuum deposition processes, thereby greatly limiting its applicability in solid‐state devices. A cruciform dimer of DPA‐DSB, 2,5,2′,5′‐tetra(4′‐N,N‐diphenylaminostyryl)biphenyl (DPA‐TSB) is reported, wherein two DPA‐DSB molecules are linked through a central biphenyl bond. The DPA‐TSB molecules take on a cruciform configuration because of the steric crowding around the central biphenyl core, which has the effect of efficiently suppressing crystalline and intermolecular interactions. The neat DPA‐TSB solid shows strong green–blue fluorescence because of both steady‐state absorption as well as TPA. The DPA‐TSB solid exhibits a photoluminescence (PL) efficiency (η_solid) of 29 % and a solid‐state two‐photon action cross section (δη_solid) of 954 GM (1 GM = 1 × 10^–50 cm⁴ s photon^–1 molecule^–1), which is much greater than for the model compound DPA‐DSB (η_solid = 16 % and δη_solid = 150 GM, where δ is the TPA cross section and η is the fluorescence quantum yield). Based on its high PL efficiency, good film‐forming ability, and strong TPA, DPA‐TSB seems to be a good candidate for applications in solid‐state optical devices.     

Study of Martensitic Phase Transformation in a NiTiCu Thin‐Film Shape‐Memory Alloy Using Photoelectron Emission Microscopy

Thermally induced martensitic phase transformation in a polycrystalline NiTiCu thin‐film shape‐memory alloy is probed using photoelectron emission microscopy (PEEM). In situ PEEM images reveal distinct changes in microstructure and photoemission intensity at the phase‐transition temperatures. In particular, images of the low‐temperature, martensite phase are brighter than that of the high‐temperature, austenite phase, because of the lower work function of the martensite. UV photoelectron spectroscopy shows that the effective work‐function changes by about 0.16 eV during thermal cycling. In situ PEEM images also show that the network of trenches observed on the room‐temperature film disappears suddenly during heating and reappears suddenly during subsequent cooling. These trenches are also characterized using atomic force microscopy at selected temperatures. The implications of these observations with respect to the spatial distribution of phases during thermal cycling in this thin‐film shape‐memory alloy are discussed.     

Chemical Amplification of a Triphenylene Molecular Electron Beam Resist

Molecular resists, such as triphenylene derivatives, are small carbon rich molecules, and thus give the potential for higher lithographic resolution and etch durability, and lower line width roughness than traditional polymeric compounds. Their main limitation to date has been poor sensitivity. A new triphenylene derivative molecular resist, with pendant epoxy groups to aid chemically amplified crosslinking, was synthesized and characterized. The sensitivity of the negative tone, pure triphenylene derivative when exposed to an electron beam with energy 20 keV was ～ 6 × 10^–4 C cm^–2, which increased substantially to ～ 1.5 × 10^–5 C cm^–2 after chemical amplification (CA) using a cationic photoinitiator. This was further improved, by the addition of a second triphenylene derivative, to ～ 7 × 10^–6 C cm^–2. The chemically amplified resist demonstrated a high etch durability comparable with the novolac resist SAL 601. Patterns with a minimum feature size of ～ 40 nm were realized in the resist with a 30 keV electron beam.     

Effect of Molecular Weight on the Structure and Morphology of Oriented Thin Films of Regioregular Poly(3‐hexylthiophene) Grown by Directional Epitaxial Solidification

Regioregular head‐to‐tail (HT)‐coupled poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) with a weight‐average molecular weight (M_w) in the 7.3–69.6 kDa range is crystallized by directional epitaxial solidification in 1,3,5‐trichlorobenzene (TCB) to yield highly oriented thin films. An oriented and periodic lamellar structure consisting of crystalline lamellae separated by amorphous interlamellar zones is evidenced by atomic force microscopy (AFM) and transmission electron microscopy (TEM). Both the overall crystallinity as well as the orientation of the crystalline lamellae decrease significantly with increasing M_w. The total lamellar periodicity is close to the length of “fully extended” chains for M_w = 7.3 kDa (polystyrene‐equivalent molecular weight, eq. PS) and it saturates to a value of ca. (25–28) ± 2 nm for M_w ≥ 18.8 kDa (eq. PS). This behavior is attributed to a transition from an oligomeric‐like system, for which P3HT chains are essentially in a fully extended all‐trans conformation and do not fold, to a semicrystalline system that involves a periodic alternation of crystalline lamellae separated by extended amorphous interlamellar zones, which harbor chain folds, chain ends, and tie molecules. For P3HT with M_w of ca. 7.3 kDa (eq. PS), epitaxial crystallization on TCB allows for the growth of both “edge‐on” and “flat‐on” oriented crystalline lamellae on the TCB substrate. The orientation of the lamellae is attributed to 1D epitaxy. Because of the large size of the “flat‐on” crystalline lamellae, a characteristic single‐crystal electron diffraction pattern corresponding to the [001] zone was obtained by selected area electron diffraction (SAED), indicating that P3HT crystallizes in a monoclinic unit cell with a = 16.0 Å, b = 7.8 Å, c = 7.8 Å, and γ = 93.5°.     

Large‐Scale Synthesis,Annealing, Purification,and Magnetic Properties of Crystalline Helical Carbon Nanotubes with Symmetrical Structures

Crystalline helical carbon nanotubes (HCNTs) are synthesized as the main products in the pyrolysis of acetylene at 450 °C over Fe nanoparticles generated by means of a combined sol–gel/reduction method. Transmission electron microscopy (TEM) images reveal that there are two HCNTs attached to each Fe₃C nanoparticle, and that the two HCNTs are mirror images of each other. Annealing in Ar at 750 °C and purification by immersion in hot (90 °C) HCl solution do not significantly change the structure of the HCNTs, despite the partial removal of Fe nanoparticles by the latter treatment. The magnetic properties of the as‐prepared, annealed, and purified HCNTs have been systematically examined. The annealed sample shows relatively high magnetization due to the ferromagnetic α‐Fe nanoparticles encapsulated in the HCNT nodes. In the case of HCl treatment, relatively pure HCNTs are obtained by the removal of ferromagnetic nanoparticles from the double‐HCNT nodes. The effects of the amount of catalyst used in the synthesis process on the morphology and yield of the carbon products have also been investigated.     

Surface‐Enhanced Raman Scattering Using Microstructured Optical Fiber Substrates

Microstructured optical fibers (MOFs) represent a promising platform technology for fully integrated next generation surface enhanced Raman scattering (SERS) sensors and plasmonic devices. In this paper we demonstrate silver nanoparticle substrates for SERS detection within MOF templates with exceptional temporal and mechanical stability, using organometallic precursors and a high‐pressure chemical deposition technique. These 3D substrates offer significant benefits over conventional planar detection geometries, with the long electromagnetic interaction lengths of the optical guided fiber modes exciting multiple plasmon resonances along the fiber. The large Raman response detected when analyte molecules are infiltrated within the structures can be directly related to the deposition profile of the nanoparticles within the MOFs via electrical characterization.     

Mechanical Properties of Robust Ultrathin Silk Fibroin Films

Robust ultrathin multilayer films of silk fibroin were fabricated by spin coating and spin‐assisted layer‐by‐layer assembly and their mechanical properties were studied both in tensile and compression modes for the first time. The ultrathin films were characterized by a high elastic modulus of 6–8 GPa (after treatment with methanol) with the ultimate tensile strength reaching 100 MPa. The superior toughness is also many times higher than that usually observed for conventional polymer composites (328 kJ m^–3 for the silk material studied here versus typical values of < 100 kJ m^–3). These outstanding properties are suggested to be caused by the gradual development of the self‐reinforcing microstructure of highly crystalline β‐sheets, serving as reinforcing fillers and physical crosslinks, a process that is well known for bulk silk materials but it is demonstrated here to occur in ultrathin films as well, despite their limited dimensions. However, the confined state within films thinner than the lengths of the extended domains causes a significantly reduced elasticity which should be considered in the design of nanosized films from silk materials. Such regenerated silk fibroin films with outstanding mechanical strength have potential applications in microscale biodevices, biocompatible implants, and synthetic coatings for artificial skin.     

Enhanced Dielectric and Crystalline Properties in Ferroelectric Barium Titanate Thin Films

A chemical solution synthesis technique incorporating barium titanate and a high‐temperature liquid phase is developed. In a temperature range conventional to thin‐film growth, the presence of the liquid phase dramatically enhances grain growth, densification, and overall crystalline quality. By controlling the liquid‐phase stoichiometry and molar fraction, thin films with grain sizes greater than 10 μm that pronounce X‐ray peak splitting, low loss, and permittivity values in excess of 3000 at room temperature can be produced. These properties are comparable, and in some cases superior, to those observed in well‐prepared bulk barium titanate. As such, the historical difficulty in reproducing bulklike properties in polycrystalline barium titanate is overcome. These results have broad implications for the expanded use of ferroelectric thin films by demonstrating bulk properties in thin layers and by providing a means of achieving these properties with low thermal budgets.     

Resorbable Dicalcium Phosphate Bone Substitutes Prepared by 3D Powder Printing

Bioceramic bone substitutes with programmed architecture were manufactured at room temperature in this study using a novel 3D printing process that combined 3D powder printing with calcium phosphate cement chemistry. During printing, biphasic α/β‐tricalcium phosphate (Ca₃(PO₄)₂, TCP) powder reacted with a liquid component consisting of phosphoric acid solution to form a matrix of dicalcium phosphate dihydrate (CaHPO₄·H₂O, DCPD, brushite) and unreacted TCP. Printed samples showed compressive strengths between 0.9–8.7 MPa after printing depending on the acid concentration. A further strength improvement to a maximum of 22 MPa could be obtained by additional hardening of the samples in phosphoric acid for three one minute washes. After this treatment, the samples mainly consisted of brushite with minor phases of unreacted TCP and a lesser amount of dicalcium phosphate anhydrate (CaHPO₄, DCPA, monetite). Hydrothermal conversion of brushite to DCPA resulted in an increase of porosity of approximately 13 % and a decrease of strength to 15 MPa, however the resorption rate in vivo was increased as demonstrated after intramuscular implantation over 56 weeks. Major advantages compared with commonly used sintering techniques are the low processing temperature, which enables the fabrication of thermally instable and degradable matrices of secondary calcium phosphates.     

An Epoxy Photoresist Modified by Luminescent Nanocrystals for the Fabrication of 3D High‐Aspect‐Ratio Microstructures

An epoxy‐based negative‐tone photoresist, which is known as a suitable material for high‐aspect‐ratio surface micromachining, is functionalized with red‐light‐emitting CdSe@ZnS nanocrystals (NCs). The proper selection of a common solvent for the NCs and the resist is found to be critical for the efficient incorporation of the NCs in the epoxy matrix. The NC‐modified resist can be patterned by standard UV lithography down to micrometer‐scale resolution, and high‐aspect‐ratio structures have been successfully fabricated on a 100 mm scaled wafer. The “as‐fabricated”, 3D, epoxy‐based surface microstructures show the characteristic luminescent properties of the embedded NCs, as verified by fluorescence microscopy. This issue demonstrates that the NC emission properties can be conveniently conveyed into the polymer matrix without deteriorating the lithographic performance of the latter. The dimensions, the resolution, and the surface morphology of the NC‐modified‐epoxy microstructures exhibit only minor deviations with respect to that of the unmodified reference material, as examined by means of microscopic and metrologic investigations. The proposed approach of the incorporation of emitting and non‐bleachable NCs into a photoresist opens novel routes for surface patterning of integrated microsystems with inherent photonic functionality at the micro‐ and nanometer‐scale for light sensing and emitting applications.