Inside Front Cover: Environmental Optical Sensitivity of Gold Nanodecahedra (Adv. Funct. Mater. 9/2007)

As reported on p. 1443 by Isabel Pastoriza‐Santos and Luis M. Liz‐Marzán, the high sensitivity of localized surface plasmon resonances towards changes in the refractive index of the surrounding medium for regular gold nanodecahedra render them strong candidates for (bio)sensing applications. Whereas a monolayer of decahedra deposited on a glass slide looks pink in air, it turns blue when immersed in isopropanol. The sensitivity of localized surface plasmon resonances with respect to changes in the refractive index of the surrounding medium is measured for small (< 60 nm side length) and large (ca. 150 nm side length) regular gold nanodecahedra (pentagonal bipyramids), and compared to rigorous solutions of Maxwell's equations for bicones based upon the boundary element method (BEM). Small particles are prepared through ultrasound‐induced reduction of HAuCl₄ by N,N‐dimethylformamide (DMF) on presynthesized penta‐twinned Au seeds, whereas large decahedra are grown using smaller ones as seeds. Excellent agreement between experimental and calculated spectra is found for dispersions and monolayers of particles in different solvents, as well as for the effect of uniform silica layers of various thicknesses grown on them. These results are expected to be useful for the development of novel biosensors.     

Highly Efficient Organic THz Generator Pumped at Near‐Infrared: Quinolinium Single Crystals

A novel highly efficient ionic electro‐optic quinolinium single crystals for THz wave applications is reported. Acentric quinolinium derivatives, HMQ‐T (2‐(4‐hydroxy‐3‐methoxystyryl)‐1‐methylquinolinium 4‐methylbenzenesulfonate) and HMQ‐MBS (2‐(4‐hydroxy‐3‐methoxystyryl)‐1‐methylquinolinium 4‐methoxybenzenesulfonate) exhibit high order parameters cos³θ_p = 0.92 and cos³θ_p = 1.0, respectively, as well as a large macroscopic optical nonlinearity, which is in the range of the benchmark stilbazolium DAST (N,N‐dimethylamino‐N’‐methylstilbazolium 4‐methylbenzenesulfonate) and phenolic polyene OH1 (2‐(3‐(4‐hydroxystyryl)‐5,5‐dimethylcyclohex‐2‐enylidene)malononitrile) crystals. As‐grown unpolished bulk HMQ‐T crystals with a side length of about 6 mm and thickness of 0.56 mm exhibit 3.1 times higher THz generation efficiency than 0.37 mm thick OH1 crystals and about 8.4 times higher than 1 mm thick inorganic standard ZnTe crystals at the near‐infrared fundamental wavelength of 836 nm. Therefore, HMQ crystals with high order parameter obviously have a very high potential for high power THz‐wave generation and its applications.     

Bifacial potential of single‐ and double‐sided collecting silicon solar cells

Bifacial applications are a promising way to increase the performance of photovoltaic systems. Two silicon solar cell concepts suitable for bifacial operation are the passivated emitter, rear totally diffused (PERT) and the both sides collecting and contacted (BOSCO) cell concepts. This work investigates the bifacial potential of these concepts by means of in‐depth numerical device simulation and experiment with a focus on the impact of varying material quality. It is shown that the PERT cell concept (representing a structure with front‐side emitter only) requires high‐minority‐carrier‐diffusion‐length substrates with L_bulk > 3 × W (with cell thickness W) to exploit its bifacial potential, while the BOSCO cell (representing a structure with double‐sided emitter) can already utilise its bifacial potential on substrates with significantly lower diffusion lengths down to L_bulk ≈ 0.5 × W. Experimentally, BOSCO cells with and without activated rear‐side emitter are compared. For rear‐side illumination, the activated rear‐side emitter is measured to increase internal quantum efficiency at wavelengths λ < 850 nm by up to 45%_abs (factor of 9) and 30%_abs (factor of 2) for cells processed on p‐type multicrystalline silicon substrates with L_bulk ≈ 0.3 × W and L_bulk ≈ 2.6 × W, respectively. For PERT cells processed on n‐type Czochralski‐grown silicon substrates, an according increase in internal quantum efficiency for rear‐side illumination of more than 20%_abs (factor of 1.3) is measured when changing from a substrate with L_bulk ≈ 3.0 to 10.0 × W. The performed simulations and experiments demonstrate that the BOSCO cell concept is a promising candidate to successfully exploit bifacial gain also on low‐ to medium‐diffusion‐length substrates such as p‐type multicrystalline silicon, while PERT cells require a high‐diffusion‐length substrate to utilise their bifacial potential. Furthermore, the BOSCO cell concept is shown to be a promising option to achieve highest output power densities, even when using lower quality and therefore possibly more cost‐effective silicon substrates. Copyright © 2016 John Wiley & Sons, Ltd.     

Photocrosslinkable Nanocomposite Multilayers for Responsive 1D Photonic Crystals

A straightforward method to increase the refractive index of photocrosslinkable polymers by incorporation of high index inorganic nanoparticles is demonstrated and shown to enhance the reflection efficiency of thermochromic 1D photonic multilayers. The refractive index of spin‐coated and UV‐crosslinked films based on poly(para‐methyl styrene) (PpMS) copolymers is increased from 1.57 for the copolymer alone to as high as 1.67 for nanocomposite samples with a volume fraction of 0.38 of ZrO₂ nanoparticles. Thermochromic photonic multilayers consisting of alternating films of PpMS–ZrO₂ with poly(N‐isopropylacrylamide) (PNIPAM) copolymers shows the increases in reflectance as large as 2.5‐fold compared to PpMS/PNIPAM multilayers lacking particles. In addition, ZrO₂ nanoparticles are used to increase the refractive index of PNIPAM‐based films up to 1.68 with a volume fraction of 0.49 of nanoparticles, enabling the fabrication of alternating PNIPAM–ZrO₂/PNIPAM multilayers with a well‐defined Bragg peak that shifts from 635 nm at 6 °C to 410 nm at 48 °C, and reflectance intensities as high as ≈0.30.     

Red Phosphorescent Iridium Complex Containing Carbazole‐Functionalized β‐Diketonate for Highly Efficient Nondoped Organic Light‐Emitting Diodes

A novel red phosphorescent iridium complex containing a carbazole‐functionalized β‐diketonate, Ir(DBQ)₂(CBDK) (bis(dibenzo[f,h]quinoxalinato‐N,C²) iridium (1‐(carbazol‐9‐yl)‐5,5‐dimethylhexane‐2,4‐diketonate)) is designed, synthesized, and characterized. The electrophosphorescence properties of a nondoped device using the title complex as an emitter with a device configuration of indium tin oxide (ITO)/N,N′‐diphenyl‐N,N′‐bis(1‐naphthyl)‐1,1′‐diphenyl‐4,4′‐diamine (NPB; 20 nm)/iridium complex (20 nm)/2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline (BCP; 5 nm)/tris(8‐hydroxyquinoline) (AlQ; 30 nm)/Mg_0.9Ag_0.1 (200 nm)/Ag (80 nm) are examined. The results show that the nondoped device achieves a maximum lumen efficiency as high as 3.49 lm W^–1. To understand this excellent result observed, two reference complexes Ir(DBQ)₂(acac), where acac is the acetyl acetonate anion, and Ir(DBQ)₂(FBDK), [bis(dibenzo[f,h]quinoxalinato‐N,C²) iridium (1‐(9‐methyl‐fluoren‐9‐yl)‐6,6‐dimethylheptane‐3,5‐diketonate)], have also been synthesized, and as emitters they were examined under the same device configuration. The maximum lumen efficiency of the former compound is found to be 0.26 lm W^–1 while that for the latter is 0.37 lm W^–1, suggesting that the excellent performance of Ir(DBQ)₂(CBDK) can be attributed mainly to an improved hole‐transporting property that benefits the exciton transport. In addition, a bulky diketonate group separates the emitter centers from each other, which is also important for organic light‐emitting diodes.     

Quadratic Optical Nonlinearities of N‐Methyl and N‐Aryl Pyridinium Salts

Four series of dyes with dimethylamino electron donor groups and N‐R‐pyridinium (R = methyl Me, phenyl Ph, 2,4‐dinitrophenyl 2,4‐DNPh, or 2‐pyrimidyl 2‐Pym) electron acceptors are studied as their hexafluorophosphate salts. The intramolecular charge‐transfer (ICT) energies (E_max) of these compounds decrease within each of the series in the order R = Me > Ph > 2,4‐DNPh > 2‐Pym, as the electron‐accepting ability of the pyridinium ring increases. Hyper‐Rayleigh scattering with femtosecond 1300 or 800 nm lasers yields fluorescence‐free first hyperpolarizabilities β, and static first hyperpolarizabilities β₀[H] are obtained via the two‐state model. Dipole moment changes Δμ₁₂ for the ICT transitions obtained from Stark spectroscopy afford β₀[S] values by using β₀ = 3Δμ₁₂(μ₁₂)²/2(E_max)² (μ₁₂ = transition dipole moment). The β₀[S] data show that the combination of pyridyl N‐arylation with conjugation extension affords large increases in β₀. The β₀[H] data generally agree with this conclusion, but resonance effects may explain some apparent anomalies. X‐ray structural studies on various salts reveal that the use of tosylate anions is not a generally applicable approach to engineering noncentrosymmetric structures of pyridinium salts. However, trans‐N‐phenyl‐4‐(4‐dimethylaminophenyl‐4‐buta‐1,3‐dienyl)pyridinium hexafluorophosphate adopts the polar space group Cc, and shows a very large powder second harmonic generation efficiency from a 1907 nm laser, which is similar to that of the well‐studied material trans‐4′‐(dimethylamino)‐N‐methyl‐4‐stilbazolium tosylate (DAST).     

Self‐Assembly of Diblock‐Copolymer Micelles for Template‐Based Preparation of PbTiO3 Nanograins

A bottom‐up fabrication route for PbTiO₃ nanograins grown on predefined TiO₂ nanostructures used as seeds is presented. The structuring of the TiO₂ seeds is performed using a self‐organized template constructed from a gold‐loaded micellar monofilm. With this fabrication process, TiO₂ seeds and PbTiO₃ grains with diameters of 12 and 30 nm, respectively, are prepared without the need for electron‐beam lithography. The dimensions of the structure imposed by the micellar template are transferred through all the processing steps to the final PbTiO₃ grains. Furthermore, it is shown that the intermicelle distance and the degree of order in the dried monofilm is mainly determined by the preparation conditions, such as the pulling velocity in the dipping process and the strength of the surface–micelle interaction, and not necessarily by the architectural properties (block length and ratio) of the diblock copolymers that build the micelles. The intermicelle spacing in the dried film is much smaller than the micelle dimensions in solution, and approaches the dimensions of a fully collapsed micelle when the dipping process is performed slowly enough.     

Resistive Switching Memory Integrated with Nanogenerator for Self‐Powered Bioimplantable Devices

Resistive random access memory (ReRAM) devices powered by piezoelectric nanogenerators (NGs) have been investigated for their application to future implantable biomedical devices. Biocompatible (Na_0.5K_0.5)NbO₃ (NKN) films that are grown at 300 °C on TiN/SiO₂/Si and flexible TiN/Polyimide (TiN‐PI) substrates are used for ReRAM and NGs, respectively. These NKN films have an amorphous phase containing NKN nanocrystals with a size of 5.0 nm. NKN ReRAM devices exhibit typical bipolar switching behavior that can be explained by the formation and rupture of oxygen‐vacancy filaments. They have good ReRAM properties such as a large ratio of R_HRS to R_LRS as well as high reliability. The NKN film grown on flexible TiN‐PI substrate exhibits a high piezoelectric strain constant of 50 pm V^?1. The NKN NG has a large open‐circuit output voltage of 2.0 V and a short‐circuit output current of 40 nA, which are sufficient to drive NKN ReRAM devices. Stable switching properties with a large ON/OFF ratio of 10² are obtained from NKN ReRAM driven by NKN NG.     

Chemical Bonding Assembly of Multifunctional Oxide Nanocomposites

The synthesis, functionalization and assembly of metal oxide nanoparticles BaTiO₃ and CoFe₂O₄ is presented. The ferroelectric (BaTiO₃) and ferromagnetic (CoFe₂O₄) oxide nanoparticle surfaces are directly functionalized via the anchoring of phosphonic acid and aminosilane molecules that engender the nanoparticles with terminal carboxylic acid and amine functional groups, respectively. These promote the electrostatic self‐assembly of the particles in non‐polar solvents and permit the synthesis of more chemically robust assemblies linked by the covalent amide bond via the addition of the chemical coupling agent N‐N′‐dicyclohexylcarbodiimide. This functionalization and assembly procedure is applied to two systems: the first comprised of 50 nm BaTiO₃ and 10 nm CoFe₂O₄ particles and the second of 200 nm BaTiO₃ and 12.5 nm CoFe₂O₄ particles. The latter composites possess magnetoelectric properties when processed into dense ceramics and, as a direct result of the assembly performed in solution, have a high degree of homogeneity between the ferroelectric and ferromagnetic phases. The developed functionalization and assembly procedure is considered to be adaptable to the preparation of other hybrid oxide nanomaterials with different property combinations.     

Shunt types in crystalline silicon solar cells

Nine different types of shunt have been found in state‐of‐the‐art mono‐ and multicrystalline solar cells by lock‐in thermography and identified by SEM investigation (including EBIC), TEM and EDX. These shunts differ by the type of their I–V characteristics (linear or nonlinear) and by their physical origin. Six shunt types are process‐induced, and three are caused by grown‐in defects of the material. The most important process‐induced shunts are residues of the emitter at the edge of the cells, cracks, recombination sites at the cell edge, Schottky‐type shunts below grid lines, scratches, and aluminum particles at the surface. The material‐induced shunts are strong recombination sites at grown‐in defects (e.g., metal‐decorated small‐angle grain boundaries), grown‐in macroscopic Si₃N₄ inclusions, and inversion layers caused by microscopic SiC precipitates on grain boundaries crossing the wafer. Copyright © 2004 John Wiley & Sons, Ltd.     

A DCM‐Type Red‐Fluorescent Dopant for High‐Performance Organic Electroluminescent Devices

2‐(2‐tert‐Butyl‐6‐((E)‐2‐(2,6,6‐trimethyl‐2,4,5,6‐tetrahydro‐1H‐pyrrolo[3,2,1‐ij]quinolin‐8‐yl)vinyl)‐4H‐pyran‐4‐ylidene)malononitrile (DCQTB) is designed and synthesized in high yield for application as the red‐light‐emitting dopant in organic light‐emitting diodes (OLEDs). Compared with 4‐(dicyanomethylene)‐2‐tert‐butyl‐6‐(1,1,7,7,‐tetramethyljulolidyl‐9‐enyl)‐4H‐pyran (DCJTB), one of the most efficient red‐emitting dopants, DCQTB exhibits red‐shifted fluorescence but blue‐shifted absorption. The unique characteristics of DCQTB with respect to DCJTB are utilized to achieve a red OLED with improved color purity and luminous efficiency. As a result, the device that uses DCQTB as dopant, with the configuration: indium tin oxide (ITO)/N,N′‐bis(1‐naphthyl)‐N,N′‐diphenyl‐1,1′‐biphenyl‐4,4′‐diamine (NPB; 60 nm)/tris(8‐quinolinolato) aluminum (Alq₃):dopant (2.3 wt %) (7 nm)/2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline (BCP; 12 nm)/Alq₃(45 nm)/LiF(0.3 nm):Al (300 nm), shows a larger maximum luminance (L_max = 6021 cd m^–2 at 17 V), higher maximum efficiency (η_max = 4.41 cd A^–1 at 11.5 V (235.5 cd m^–2)), and better chromaticity coordinates (Commission Internationale de l'Eclairage, CIE, (x,y) = (0.65,0.35)) than a DCJTB‐based device with the same structure (L_max = 3453 cd m^–2 at 15.5 V, η_max = 3.01 cd A^–1 at 10 V (17.69 cd m^–2), and CIE (x,y) = (0.62,0.38)). The possible reasons for the red‐shifted emission but blue‐shifted absorption of DCQTB relative to DCJTB are also discussed.     

Pulsed laser deposition of carbon films: Dependence of film properties on laser wavelength

We have grown thin carbon films by pulsed laser deposition and have investigated the extent to which the properties of such films, as well as the processes responsible for these properties, are laser wavelength dependent. Films were grown by ablating material from a graphite target onto room temperature Si(100) substrates with 1064 and 248 nm laser radiation. The films were analyzed byin situ electron energy loss spectroscopy and byex situ Raman spectroscopy. The results indicated that films grown with 1064 nm ablation were graphitic, while those grown with 248 nm radiation were diamond-like. We have also examined the mass and kinetic energy distributions of the particles ejected from graphite by the two laser wavelengths. The results indicated that irradiation of graphite with 1064 nm laser radiation results in the ejection of a series of carbon cluster ions C _n ⁺ (1 ≤ n ≤ 30) with mean kinetic energies less than 5 eV. Ablation of graphite with 248 nm radiation results in the ejection of primarily C ₂ ⁺ and C ₃ ⁺ with mean kinetic energies of 60 and 18 eV, respectively. These results suggest that large, low energy clusters produce graphitic films, while small, high energy clusters produce films of diamond-like carbon.     

Synthesis and Optical Properties of KYF4/Yb,Er Nanocrystals,and their Surface Modification with Undoped KYF4

KYF₄/Yb³⁺, Er³⁺ nanocrystals with a mean diameter of approximately 13 nm were synthesized at 200 °C in the high boiling organic solvent N‐(2‐hydroxyethyl)ethylenediamine (HEEDA). The particles crystallize in the cubic phase known from α‐NaYF₄ and form transparent colloidal solutions in tetraethylene glycol (TEG) or propanol. Solutions containing 1 wt % of the nanocrystals in TEG display visible upconversion emission upon continuous wave (CW) excitation at 978 nm. Growing undoped KYF₄ on the surface of the KYF₄/Yb³⁺, Er³⁺ nanocrystals increases the upconversion efficiency by more than a factor of 20. The XRD data of these particles, display a slight increase in the mean particle size from 13 to 15.5 nm, indicating that only a part of the subsequently added KYF₄ shell material is deposited onto the particle surface. Nevertheless the performed surface modification obviously leads to core/shell structured particles.     

Synthesis and Characterization of Ferroferriborate (Fe3BO5) Nanorods

Fe₃BO₅ nanorods with diameters from 4 nm to 16 nm and length from 43 nm to 60 nm are synthesized by a facile thermal decomposition of iron acetylacetonate and t‐butylamine borane (TBAB). TBAB is used to control the 1D growth and the aspect ratio of the nanorods. These Fe₃BO₅ nanorods are antiferromagnetic with T_N = 174 K, which is higher than that of bulk Fe₃BO₅ (114 K).     

Organic Thin‐Film Transistors Based on Tolyl‐Substituted Oligothiophenes

Thin films based on the tolyl‐substituted oligothiophenes 5,5′′‐bis(4‐methylphenyl)‐2,2′:5′,2′′‐terthiophene ( 1 ), 5,5′′′‐bis(4‐methylphenyl)‐2,2′:5′,2′′:5′′,2′′′‐quaterthiophene ( 2 ) and 5,5′′′′‐bis(4‐methylphenyl)‐2,2′:5′,2′′:5′′,2′′′:5′′′,2′′′′‐quinqethiophene ( 3 ) exhibit hole‐transport behavior in a thin‐film transistor (TFT) configuration, with reasonable mobilities and high current on/off (I_on/I_off) ratios. Powder X‐ray diffraction (PXRD) reveals that these films, grown by vacuum deposition onto the thermally grown silicon oxide surface of a TFT, are highly crystalline, a characteristic that can be attributed to the general tendency of phenyl groups to promote crystallinity. Atomic force microscopy (AFM) reveals that the films grow layer by layer to form large domains, with some basal domain areas approaching 1000 μm². The PXRD and AFM data are consistent with an “end‐on” orientation of the molecules on the oxide substrate. Variable‐temperature current–voltage (I–V) measurements identified the activation regime for hole transport and revealed shallow level traps in thin films of 1 and 2 , and both shallow and deep level traps in thin films of 3 . The activation energies for thin films of 1 , 2 , and 3 were similar, with values of E_a = 121, 100, and 109 meV, respectively. The corresponding trap densities were N_trap/N_v = 0.012, 0.023, and 0.094, where N_trap is the number of trap states and N_v is the number of conduction states. The hole mobilities for the three compounds were similar (μ ? 0.03 cm² V^–1 s^–1), and the I_on/I_off ratios were comparable with the highest values reported for organic TFTs, with films of 2 approaching I_on/I_off = 10⁹ at room temperature.     

Responsive Macroscopic Materials From Self‐Assembled Cross‐Linked SiO2‐PNIPAAm Core/Shell Structures

A way to obtain macroscopic responsive materials from silicon‐oxide polymer core/shell microstructures is presented. The microparticles are composed of a 60 nm SiO₂‐core with a random copolymer corona of the temperature responsive poly‐N‐isopropylacrylamide (PNIPAAm) and the UV‐cross‐linkable 2‐(dimethyl maleinimido)‐N‐ethyl‐acrylamide. The particles shrink upon heating and form a stable gel in both water and tetrahydrofuran (THF) at 3–5 wt% particle content. Cross‐linking the aqueous gel results in shrinkage when the temperature is increased above the lower critical solution temperature and it regains its original size upon cooling. By freeze drying with subsequent UV irradiation, thin stable layers are prepared. Stable fibers are produced by extruding a THF gel into water and subsequent UV irradiation, harnessing the cononsolvency effect of PNIPAAm in water/THF mixtures. The temperature responsiveness translates to the macroscopic materials as both films and fibers show the same collapsing behavior as the microcore/shell particle. The collapse and re‐swelling of the materials is related to the expelling and re‐uptake of water, which is used to incorporate gold nanoparticles into the materials by a simple heating/cooling cycle. This allows for future applications, as various functional particles (antibacterial, fluorescence, catalysis, etc.) can easily be incorporated in these systems.     

Light Enhanced Electron Transduction and Amplified Sensing at a Nanostructure Modified Semiconductor Interface

Visible and UV light are demonstrated to significantly enhance the sensing properties of an n‐type porous silicon (PS) extrinsic semiconductor interface to which TiO₂ and titanium oxynitride (TiO_2‐xN_x) photocatalytic nanostructures are fractionally deposited. The acid/base chemistry of NH₃, a moderately strong base, and NO₂, a moderately strong acid, couples to the majority charge carriers of the doped semiconductor as the strong acid (TiO₂) enhances the extraction of electrons from NH₃, and the more basic TiO_2‐xN_x decreases the efficiency of electron extraction relative to the untreated interface. In contrast, NO₂ and a TiO₂ or TiO_2‐xN_x nanostructure‐decorated PS interface compete for the available electrons leading to a distinct time dependent electron transduction dynamics as a function of TiO₂ and TiO_2‐xN_x concentration. Only small concentrations of TiO₂ and its oxynitride and no self‐assembly are required to enhance the response of the decorated interface. With light intensities of less than a few lumens/cm²‐sterad‐nm, responses are enhanced by up to 150% through interaction with visible (and UV) radiation. These light intensities should be compared to the sun's radiation level, ≈500 lumens/cm²‐sterad‐nm suggesting the possibility of solar pumped sensors. The observed behavior in these systems is largely explained by the recently developed Inverse Hard/Soft Acid/Base (IHSAB) concept.     

Facile Formation of Uniform Shell‐Crosslinked Nanoparticles with Built‐in Functionalities from N‐Hydroxysuccinimide‐Activated Amphiphilic Block Copolymers

An amphiphilic block copolymer, poly(methylacrylate)₈₂‐block‐poly(N‐(acryloyloxy)succinimide_0.29‐co‐(N‐acryloylmorpholine)_0.71)₁₅₅ (PMA₈₂‐b‐P(NAS_0.29‐co‐NAM_0.71)₁₅₅), was synthesized by reversible addition‐fragmentation chain transfer (RAFT) polymerization and then was supramolecularly assembled into micelles in aqueous solution, followed by chemical crosslinking throughout the shell region upon the introduction of 2,2′‐(ethylenedioxy)‐bis(ethylamine) as a crosslinker to afford well‐defined shell crosslinked nanoparticles (SCKs). The number‐averaged hydrodynamic diameters of the micelles and SCKs were (17 ± 4) nm and (16 ± 3) nm, respectively, by dynamic light scattering (DLS), and (15 ± 2) nm and (13 ± 2) nm, respectively, by transmission electron microscopy (TEM). In an attempt to narrow the particle size distributions, the dodecyl trithiocarbonate chain end of the block copolymer was replaced by a 2‐cyanoisopropyl moiety. Each nanoparticle system was characterized by DLS, electrophoretic light scattering (ELS), TEM, and small‐angle X‐ray scattering (SAXS). SAXS was of particular importance, as it provided definitive observation and quantification of shell contraction and densification upon shell crosslinking. The direct incorporation of NAS into the block copolymers during their preparation allowed for unique crosslinking chemistry to proceed with added diamino crosslinkers. The primary advantages of this system include the ability to conduct in situ synthesis of SCKs that are crosslinked directly and derivatized easily by adding nucleophilic ligands before, during, or after the crosslinking.     

Poled Sol–Gel Materials With Heterocycle Push–Pull Chromophores that Confer Enhanced Second‐Order Optical Nonlinearity

Hybrid organic–inorganic materials doped with zwitterionic push–pull chromophores with high hyperpolarizability have been synthesized by a sol–gel procedure. A large chromophore concentration was reached by using N‐(hydroxyethyl)carbazole as a physical spacer (preventing the dye aggregation). Spin‐coated doped films were electrically poled and second harmonic generation measurements performed in situ. During the thermally assisted poling under a N₂ atmosphere, only the carbazole molecules degraded. Second‐harmonic generation measurements gave an estimation of the nonlinear coefficient, r₃₃, of 38 pm V^–1 at 1064 nm.     

Synthesis of New Europium Complexes and Their Application in Electroluminescent Devices

Several substituted phenanthrolines (L = pyrazino[2,3‐f][1,10]phenanthroline (PyPhen), 2‐methylpyrazino[2,3‐f][1,10]phenanthroline (MPP), dipyrido[3,2‐a:2′,3′‐c]phenazine (DPPz), 11‐methyldipyrido[3,2‐a:2′,3′‐c]phenazine (MDPz), 11,12‐dimethyldipyrido[3,2‐a:2′,3′‐c]phenazine (DDPz), and benzo[i]dipyrido[3,2‐a:2,3‐c]phenazine (BDPz)) were successfully prepared and europium complexes Eu(TTA)₃L (Eu‐L) based on these ligands were synthesized from EuCl₃, 2‐thenoyltrifluoroacetone (TTA) and L in good yields. Irradiation at the absorption band between 320–390 nm of all these europium complexes, except Eu‐BDPz, in solution or in the solid state leads to the emission of a sharp red band at ～ 612 nm, a characteristic Eu³⁺ emission due to the transition ⁵D₀ → ⁷F₂. No emission from the ligands was found. The result indicates that complete energy transfer from the ligand to the center Eu³⁺ ion occurs for these europium complexes. In contrast, the photoluminescence spectrum of Eu‐BDPz exhibits a strong emission at around 550 nm from the coordinated BDPz ligand and a weak emission at 612 nm from the central europium ion. Incomplete energy transfer from the ligand to the central Eu³⁺ ion was observed for the first time. Several electroluminescent devices ( A – I ) using Eu‐PyPhen, Eu‐MPP, Eu‐DPPz, and Eu‐DDPz as dopant emitters with the device configuration: TPD or NPB (50 nm)/Eu:CBP (1.7–7 %, 30 nm)/BCP (20–30 nm)/Alq (25–35 nm) (where TPD: 4,4′‐bis[N‐(p‐tolyl)‐N‐phenylamino]biphenyl; NPB: 4,4′‐bis[1‐naphthylphenylamino]biphenyl; CBP: 4,4′‐N,N′‐dicarbazole biphenyl; BCP: 2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline; Alq: tris[8‐hydroxyquinoline]aluminum) were fabricated. Some of these devices emit saturated red light and are the only europium complex‐based devices that show a brightness of more than 1000 cd m^–2.