Selective Enrichment of Polydopamine in Mesoporous Nanocarriers for Nuclear‐Targeted Drug Delivery

Small particle size and strong host–guest interactions are prerequisites in the field of nuclear‐targeting nanocarriers for overcoming the multidrug resistance of cancer cells. A novel scheme of synthesizing hybrid organic–inorganic nanocarriers with mesopores is introduced to enhance the delivery efficiency of therapeutic drugs. Specifically, inorganic silica and organic polydopamine (PDA) are integrated inside the pore framework by the assistance of organic silanes terminated by amino/thiol groups. Silica‐etching by hydrothermal treatment leads to the selective enrichment of bioadhesive PDA and size reductions for the hybrids (to ≈30 nm). Interestingly, a high drug loading capacity (523 µg mg⁻¹ for doxorubicin hydrochloride), as well as pH/ glutathione dual‐responsive drug release properties, are realized by the nanocarriers, owing to their high surface area (825 m² g⁻¹) and the π‐stacking and/or hydrophobic–hydrophobic interactions stemming from PDA. More importantly, the conjugation of TAT peptide facilitates the intranuclear localization of the nanocarriers and the release of the encapsulated drugs directly within the nucleoplasm of the multidrug resistant MCF‐7/ADR cancer cells. Therefore, these results provide a controllable method of engineering high‐surface‐area nanocarriers with bioadhesive polymers on the pore surface for advanced drug delivery applications.     

ZnO nanorods–polymer hybrid white light emitting diode grown on a disposable paper substrate

We demonstrate intrinsic white light emission from hybrid light emitting diodes fabricated using an inorganic–organic hybrid junction grown at 50 °C on a paper substrate. Cyclotene was first spin coated on the entire substrate to act as a surface barrier layer for water and other nutrient solutions. The active area of the fabricated light emitting diode (LED) consists of zinc oxide nanorods (ZnO NRs) and a poly(9,9‐dioctylfluorene) (PFO) conducting polymer layer. The fabricated LED shows clear rectifying behavior and a broad band electroluminescence (EL) peak covering the whole visible spectrum range from 420 nm to 780 nm. The color rendering index (CRI) was calculated to be 94 and the correlated color temperature (CCT) of the LED was 3660 K. The low process temperature and procedure in this work enables the use of paper substrate for the fabrication of low cost ZnO–polymer white LEDs for applications requiring flexible/disposable electronic devices. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Drop‐cast and dye‐sensitized ZnO nanorod‐based visible‐light photodetectors

We report the facile fabrication of metal–semiconductor–metal (MSM) photodetectors with dye‐sensitized ZnO nanorods (NRs) operating at wavelengths of ～405–638 nm by a simple drop casting method. The ZnO NRs were synthesized by the hydrothermal synthesis method at 75 °C. The droplet of ethanol solution containing ZnO NRs was dropped between two metal electrodes and dried at 65 °C, which allows the ZnO NRs to be adhered and contacted to both metal electrodes. When a violet light of 405 nm was illuminated into the MSM ZnO NRs‐based photodetector, the photocurrent gain was obtained as ～3.9 × 10³ at the applied bias voltage of 5 V. By increasing the bias voltage from 10 V to 15 V, the device exhibited good recovery performance with a largely reduced reset time from 85.68 s to 2.47 s and an increased on–off ratio from 17.9 to 77.4. To extend the photodetection range towards the long visible spectral region, the ZnO NRs were sensitized by the N719 dye and then drop‐cast. The dye‐sensitized ZnO NRs‐based photodetector also exhibited good photocurrent switching under 638 nm of light illumination. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Significantly reduced leakage currents in organic thin film transistors with Mn‐doped Bi2Ti2O7 high‐k gate dielectrics

We report the fabrication of organic thin‐film transistors (OTFTs) with high‐k gate dielectrics of Mn‐doped Bi₂Ti₂O₇ (BTO) films. 3% Mn‐doped BTO films deposited on polymer substrates by pulsed laser deposition at room temperature exhibit low leakage currents of 2.1 × 10^–8 A/cm² at an applied electric field of 0.3 MV/cm, while undoped BTO films show much higher leakage currents of 4.3 × 10^–4 A/cm². Mn doping effectively reduces the number of oxygen vacancies in the films and improves the electrical properties. Low operation voltage and significantly reduced leakage currents are demonstrated in pentacene‐based OTFTs with the Mn‐doped BTO gate dielectrics. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thick junction broadband organic photodiodes

Inorganic semiconductor‐based broadband photodetectors are ubiquitous in imaging technologies such as digital cameras and photometers. Herein a broadband organic photodiode (OPD) that has performance metrics comparable or superior to inorganic photodiodes over the same spectral range is reported. The photodiode with an active layer comprised of a poly[N‐9′‐heptadecanyl‐2,7‐carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole)]:[6,6]‐phenyl‐C₇₁‐butyric acid methyl ester bulk heterojunction blend had a dark current < 1 nA/cm², specific detectivity of ∼10¹³ Jones, reverse bias −3 dB frequency response of 100 kHz to 1 MHz, and state‐of‐the‐art Linear Dynamic Range for organic photodiodes of nine orders of magnitude (180 dB). The key to these performance metrics was the use of a thick junction (700 nm), which flattened the spectral response, reduced the dark current and decreased performance variations. The strategy also provides a route to large area defect free “monolithic” structures for low noise integrated photo‐sensing, position determination, or contact, non‐focal imaging.     

High‐gain Zn1–xMgx O‐based ultraviolet photodetectors on Al2O3 and LiGaO2 substrates

We report the fabrication and characterization of highly responsive ZnMgO‐based ultraviolet (UV) photodetectors in the metal–semiconductor–metal (MSM) configuration for solar‐blind/visible‐blind optoelectronic application. MSM devices were fabricated from wurtzite Zn_1–xMg_x O/ZnO (x ～ 0.44) thin‐film heterostructures grown on sapphire (α‐Al₂O₃) substrates and w‐Zn_1–xMg_x O (x ～ 0.08), grown on nearly lattice‐matched lithium gallate (LiGaO₂) substrates, both by radio‐frequency plasma‐assisted molecular beam epitaxy (PAMBE). Thin film properties were studied by AFM, XRD, and optical transmission spectra, while MSM device performance was analyzed by spectral photoresponse and current–voltage techniques. Under biased conditions, α‐Al₂O₃ grown devices exhibit peak responsivity of ～7.6 A/W at 280 nm while LiGaO₂ grown samples demonstrate peak performance of ～119.3 A/W, albeit in the UV‐A regime (～324 nm). High photoconductive gains (76, 525) and spectral rejection ratios (～10³, ～10⁴) were obtained for devices grown on α‐Al₂O₃ and LiGaO₂, respectively. Exemplary device performance was ascribed to high material quality and in the case of lattice‐matched LiGaO₂ films, decreased photocarrier trapping probability, presumably due to low‐density of dislocation defects. To the best of our knowledge, these results represent the highest performing ZnO‐based photodetectors on LiGaO₂ yet fabricated, and demonstrate both the feasibility and substantial enhancement of photodetector device performance via growth on lattice‐matched substrates. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Surface‐enhanced Raman scattering and fluorescence emission of gold nanoparticle–multiwalled carbon nanotube hybrids

Multiwalled carbon nanotubes (MWCNTs) are grafted with gold (Au) nanoparticles of different sizes (1–12 and 1–20 nm) to form Au–MWCNT hybrids. The Au nanoparticles pile up at defect sites on the edges of MWCNTs in the form of chains. The micro‐Raman scattering studies of these hybrids were carried using visible to infrared wavelengths (514.5 and 1064 nm). Enhanced Raman scattering and fluorescence is observed at an excitation wavelength of 514.5 nm. It is found that the graphitic (G) mode intensity enhances by 10 times and down shifts by approximately 3 cm⁻¹ for Au–MWCNT hybrids in comparison with pristine carbon nanotubes. This enhancement in G mode due to surface‐enhanced Raman scattering effect is related to the interaction of MWCNTs with Au nanoparticles. The enhancement in Raman scattering and fluorescence for large size nanoparticles for Au–MWCNTs hybrids is corroborated with localized surface plasmon polaritons. The peak position of localized surface plasmons of Au nanoparticles shifts with the change in environment. Further, no enhancement in G mode was observed at an excitation wavelength of 1064 nm. However, the defect mode (D) mode intensity enhances, and peak position is shifted by approximately 40 cm⁻¹ to lower side at the same wavelength. The enhanced intensity of D mode at 1064 nm excitation wavelength is related to the double resonance phenomenon and shift in the particular mode occurs due to more electron phonon interactions near Fermi level. Copyright © 2012 John Wiley & Sons, Ltd.     

Defect removal after low temperature annealing of boron implantations by emitter etch‐back for silicon solar cells

Ion implantation offers new possibilities for silicon solar cell production, e.g. single side doping that can be structured in‐situ with shadow masks. While phosphorus implantations can easily be annealed at low temperature, the annealing of boron implantations is challenging. In this study, we use low energy implantations of boron (1 keV and 5 keV) with a projected range of 5.6 nm and 21.2 nm that form defects causing charge carrier recombination after a low temperature anneal (950 °C, 30 min). An ozone‐based wet chemical etching step is applied to remove this near surface damage. With increasing chemical etch‐back the electrical quality (i.e. emitter saturation current density, J_0e) improves continuously. The calculated limit for J_0e was reached with an abrasion of 35 nm for 1 keV and 85 nm for 5 keV implantations, showing that the relevant defects causing charge carrier recombination are located very close to the surface, corresponding to the as‐implanted profile depth. This emitter etch‐back allows for the fabrication of defect free boron doping profiles with good sheet resistance uniformity (standard deviation <2%). With the resulting characteristics (sheet resistance <100 Ω/sq, surface doping concentration >5 × 10¹⁹ cm^–3, J_0e < 30 fA/cm²), these boron profiles are well suited for silicon solar cells. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

High‐efficiency single etch step apodized surface grating coupler using subwavelength structure

Grating couplers are key elements enabling the coupling of light between planar waveguide circuits and optical fibers. In this work, it is demonstrated using simulations and experiments that a high coupling efficiency can be achieved for an arbitrary buried oxide thickness by judicious adjustment of the grating radiation angle. The coupler strength is engineered by subwavelength structure, allowing straightforward apodization and single etch step fabrication. The design has been implemented using Fourier‐eigenmode expansion and finite difference time domain methods. The measured coupling loss of a continuously apodized grating is −2.16 dB with a 3 dB bandwidth of 64 nm, therefore opening promising prospects for low‐cost and high‐volume fabrication using 193 nm deep‐ultraviolet lithography. It is also shown by simulations that a coupling loss as low as −0.42 dB is predicted for a modified coupler structure with bottom mirror.     

Fabrication of low OH loss holey fibers with varying air hole sizes and their optical properties

We experimentally investigate a flexible fabrication technique for low OH and transmission losses holey fibers with a Ge-doped core and air holes in a silica cladding region. Versatile holey fibers of different size, pitch, and shape of air holes were achieved by controlling the temperature and heating time of the holey fiber preform. In addition, we suppress the OH loss of less than ∼0.323 dB/km at 1383 nm. After fabricating holey fibers, we measure their optical properties including cut-off wavelength, mode field diameter, splicing loss, dispersion, bending loss, and polarization dependent loss based on the size of air holes. The total transmission loss was measured to be ∼0.226 dB/km at 1550 nm by improving the fabrication process. After fabricating optical patch cord based on holey fibers, we measured the long-term stability of the fabricated holey fiber by using the temperature cycling technique for 24 and obtained low power fluctuation of 0.2 dB. We achieve the high quality holey fiber with a low bending loss of ∼0.04 dB/turn under a bending radius of 2.5 mm at 1550 nm. We also obtain a tunable band rejection filter with a number of bending turns.     

Plasmonic Metasurfaces Enabled Ultra‐Compact Broadband Waveguide TM‐Pass Polarizer

Silicon waveguide polarizers offer a simple yet robust approach to address the polarization‐dependent issue of silicon‐based optical components, and hence have found numerous applications in silicon photonics. However, the available silicon waveguide polarizers suffer from the issue of large device footprint, high insertion loss (IL), and/or fabrication complexities. Here, a silicon waveguide transverse magnetic (TM)‐pass polarizer is constructed by coating a silicon waveguide with an ultra‐thin plasmonic metasurface structure that is capable of guiding slow surface wave (SW) mode. The transverse electric (TE) waveguide mode can be converted into SW mode with the involvement of metasurfaces, and hence is intrinsically absorbed and forbidden to pass, while the TM waveguide mode can be well guided due to little influence. A typical metasurface polarizer with an ultra‐short length of 2.4 µm enables the IL of 28.16 dB for the TE mode, and that of 0.53 dB for the TM mode at 1550 nm. Multiple‐band TM‐pass polarizers can be obtained by cascading two or more different metasurface‐coated silicon waveguides along the propagation direction, and a dual‐band TM‐pass polarizer is demonstrated with the IL being of 19.21 and 29.09 dB for the TE mode at 1310 and 1550 nm, respectively.     

Investigation of laser ablation on hybrid sol–gel material applied to kinoform etching

Ultraviolet laser machining of a hybrid organic/inorganic material prepared via a sol–gel process has been studied for the fabrication of kinoforms or surface relief diffractive optical elements. The hybrid mixes silicon and titanium oxides and an organic network in order to improve the mechanical properties. Different material compositions have been investigated. Laser ablation of the hybrid material is observed at low laser fluence (measured threshold fluence of 125 mJ/cm² at 248 nm/6 ns) and shows that the process is well adapted to micro-patterning by laser machining means. The best observed depth resolution is 60± 20 nm and appears to be limited by the ablation setup. Finally, the fabrication of an effective diffractive optical element and its operation at 1.06 μm are described. PACS  81.20.Fw; 79.20.Ds; 42.79.-e     

Photonic‐on‐a‐chip: a thermal actuated Mach‐Zehnder interferometer and a molecular thermometer based on a single di‐ureasil organic‐inorganic hybrid

An integrated photonic‐on‐a‐chip device based on a single organic‐inorganic di‐ureasil hybrid was fabricated for optical waveguide and temperature sensing. The device is composed by a thermal actuated Mach‐Zehnder (MZ) interferometer operating with a switching power of 0.011 W and a maximum temperature difference between branches of 0.89 ºC. The MZ interferometer is covered by a Eu³⁺/Tb³⁺ co‐doped di‐ureasil luminescent molecular thermometer with a temperature uncertainty of 0.1ºC and a spatial resolution of 13 µm. This is an uncommon example in which the same material (an organic‐inorganic hybrid) that is used to fabricate a particular device (a thermal‐actuated MZ interferometer) is also used to measure one of the device intrinsic properties (the operating temperature). The photonic‐on‐a‐chip example discussed here can be applied to sense temperature gradients with high resolution (10⁻³ ºC·µm⁻¹) in chip‐scale heat engines or refrigerators, magnetic nanocontacts and energy‐harvesting machines.     

Raman spectra of nitrogen‐containing organic compounds obtained using a portable instrument at −15 °C at 2860 m above sea level

Well‐resolved Raman spectra of samples of nitrogen‐containing compounds were detected using a portable Raman instrument (Ahura First Defender XL) outdoors at a low ambient temperature of −15 °C and at an altitude of 2860 m (Pitztall, Austria). The portable Raman spectrometer tested here is equipped with a 785‐nm diode laser and a fixed frontal probe. Solid form of formamide, urea, 3‐methylpyridine, aniline, indene, 1‐(2‐aminoethyl)piperazine, indoline and benzofuran were detected unambiguously under high‐mountain field conditions. The main Raman features (strong, medium and partially weak bands) were observed at the correct wavenumber positions (with a spectral resolution 7–10 cm⁻¹) in the wavenumber range 200–1600 cm⁻¹. The results obtained demonstrate the possibility of employing a miniaturised Raman spectrometer as a key instrument for investigating the presence of nitrogen‐containing organic compounds and biomolecules outdoors under low temperature conditions. Within the payload designed by European Space Agency (ESA) and National Aeronautics and Space Administration (NASA) for future missions, focussing not only on Mars, Raman spectroscopy represents an important instrumentation for the detection of organic nitrogen‐containing compounds relevant to life detection on planetary surfaces or near sub‐surfaces. Copyright © 2009 John Wiley & Sons, Ltd.     

Microstructured polymer‐based substrates with broadband absorption for surface‐enhanced Raman scattering

Large area (3 × 3 cm²) substrates for surface‐enhanced Raman scattering were fabricated by combining femtosecond laser microstructuring and soft lithography techniques. The fabrication procedure is as follows: (i) femtosecond laser machining is used to create a silicon master copy, (ii) replicates from polydimethylsiloxane are made, and (iii) a 50‐nm‐thick gold film is deposited on the surface of the replicates. The resulting substrates exhibit strongly enhanced absorption in the spectral region of 350 ∼ 1000 nm and generate enhanced Raman signal with enhancement factor of the order of 10⁷ for 10^{‐ 6} M rhodamine 6G. The main advantages of our substrates are low cost, large active area, and possibility for mass replication. Copyright © 2013 John Wiley & Sons, Ltd.     

Improved efficiencies of hybrid organic light‐emitting diodes using efficient electron injection layer

Hybrid organic‐inorganic light‐emitting diodes were developed with pristine ZnO (2.0 wt%) and Cu‐doped ZnO (2.0 wt%) as electron injection layer and iridium(III)‐bis‐2‐(4‐fluorophenyl)‐1‐(naphthalen‐1‐yl)‐1H‐phenanthro[9,10‐d]imidazole (acetylacetonate) [Ir(fpnpi)₂ (acac)] as green emissive layer (521 nm). The pristine ZnO and Cu‐doped ZnO are deposited at indium tin oxide cathode and emissive layer interface. The electroluminescent performances increased by electron injection layer–Cu‐doped ZnO compared with ZnO‐based device because Cu‐doped ZnO injects electron efficiently result in balanced h⁺ ? e^? recombination in emissive layer than ZnO‐based device. The Cu‐doped ZnO (2.0 %) device shows luminance (L) of 10 982 cd/m² at 23.0 V (ZnO, 1450 cd/m² at 23.0 V).     

Au/TiO2 nanorod‐based Schottky‐type UV photodetectors

TiO₂ nanorods (NRs) were synthesized on fluorine‐doped tin oxide (FTO) pre‐coated glass substrates using hydrothermal growth technique. Scanning electron microscopy studies have revealed the formation of vertically‐aligned TiO₂ NRs with length of ～2 µm and diameter of 110–128 nm, homogenously distributed over the substrate surface. 130 nm thick Au contacts using thermal evaporation were deposited on the n‐type TiO₂ NRs at room temperature for the fabrication of NR‐based Schottky‐type UV photodetectors. The fabricated Schottky devices functioned as highly sensitive UV photodetectors with a peak responsivity of 134.8 A/W (λ = 350 nm) measured under 3 V reverse bias. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Excellent organic/inorganic transparent thin film moisture barrier entirely made by hot wire CVD at 100 °C

We present a silicon nitride/polymer hybrid multilayer moisture barrier for flexible electronics made entirely by hot wire chemical vapor deposition (HWCVD) at substrate temperatures below 100 °C. Using the initiated CVD (iCVD) variant of HWCVD for the polymer layers, these can be extremely thin, while efficiently decoupling the defects in consecutive inorganic layers. Although a single layer of low temperature SiN_x is more prone to have pinholes than its state‐of‐the‐art high temperature equivalent, we have achieved a simple three‐layer structure consisting of two low‐temperature SiN_x layers with a polymer layer in between, which is pinhole free and shows a water vapor transmission rate (WVTR) as low as 5 × 10^–6 g/m²/day at a temperature of 60 °C and a relative humidity of 90%. This WVTR is low enough for organic devices. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ultra‐thin (002)‐oriented Al‐doped zinc oxide transparent electrode grown on oxygen‐controlled homo‐seed layer

Highly (002)‐oriented Al‐doped zinc oxide (AZO) thin films with the thickness of less than 200 nm have been deposited on an oxygen‐controlled homo‐seed layer at 200 °C by DC magnetron sputtering. With the homo‐seed layer being employed, the full‐width at half maximum (FWHM) of the (002) diffraction peak for the AZO ultra‐thin films decreased from 0.33° to 0.22°, and, the corresponding average grain size increased from 26.8 nm to 43.0 nm. The XRD rocking curves revealed that the AZO ultra‐thin film grown on the seed layer deposited in atmosphere of O₂/Ar of 0.09 exhibited the most excellent structural order. The AZO ultra‐thin film with homo‐seed layer reached a resistivity of 4.2 × 10^–4 Ω cm, carrier concentration of 5.2 × 10²⁰ cm^–3 and mobility of 28.8 cm² V^–1 s^–1. The average transmittance of the AZO ultra‐thin film with homo‐seed layer reached 85.4% in the range of 380–780 nm including the substrate. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)