Photo-induced isomerization of poly 4′-(6-acryloxy) hexyloxy-4-methoxyazobenzene ultra-thin solid film prepared by Langmuir–Blodgett technique

The photo-induced response of an ultra thin polymeric film of poly 4′-(6-acryloxy) hexyloxy-4-methoxyazobenzene (P5) is investigated. A monolayer of P5 at a gas–water interface possesses a mean molecular area of 28.0 Å²/monomer-repeat. Multilayer films of P5 were prepared by horizontal deposition at a surface pressure of 25 mN/m². The uniformity of the transfer process is shown by UV–vis absorption spectra where a linear relationship between the absorption maxima and the number of transferred layer was observed. The average layer thickness of the transferred film determined by XRD measurements is 34.0 Å. This is longer than the length of the azobenzene side group. The transferred film shows a blue shift of the π–π¹ transition from 357 nm for the P5 in solution to 340 nm for the P5 in the film. This suggests the formation of H-aggregate with a head-to-head arrangement of the dipole within the film. The optical property of the transferred film is changed by the irradiation of the film with the UV light at 385 nm. An irreversible change in its molecular packing in the film is seen in the shift of the UV–vis absorption maxima and the change in morphology as observed by AFM. The film morphology changes from being a smooth film into an island-like surface when exposed to the UV irradiation. The layer structure in the film is destroyed. A mass transport is observed during the cis–trans thermal back isomerization process. This suggests that movement of the P5 took place in both the trans–cis isomerization process and the cis–trans back isomerization process. The first movement leads to a molecular expansion while the second, to a molecular contraction.     

Tetraalkoxylated-PPV derivative: An efficient and pure green electroluminescent polymer with good solution processability

A new solution-processable tetraalkoxy-substituted poly(1,4-phenylenevinylene) derivative, poly{[2-(3′,7′-dimethyloctyloxy)-3,5,6-trimethoxy]-1,4-phenylenevinylene} (TALK-PPV), was synthesized through a dehydrohalogenation polymerization route, and its light-emitting properties were investigated. The TALK-PPV showed highly blue-shifted UV–visible absorption and PL emission spectra compared to the dialkoxy-substituted PPV derivatives. This is because of the disturbance to the π-conjugation caused by a steric hindered structure. The TALK-PPV thin film exhibited an absorption peak at 446 nm, with an onset at 515 nm. Its PL emission maximum was at 554 nm. Cyclic voltammetric analysis showed the HOMO and LUMO energy levels of the TALK-PPV to be 5.77 and 3.36 eV, respectively. Light-emitting devices were fabricated with an ITO (indium-tin oxide)/PEDOT/polymer/Ca/Al configuration. The TALK-PPV component leads to pure green light emission with a CIE 1931 chromaticity of (0.20, 0.74) at 100 cd/m² brightness, which is very close to the standard green (0.21, 0.71) demanded by the NTSC (National Television System Committee). The maximum brightness of this device was 24,900 cd/m² with an efficiency of 1.45 cd/A.     

Radiative and non-radiative relaxation of excitons in strain-compensated quantum dots

We have investigated the population dynamics of excitons in strain-compensated InAs quantum dots (QDs) using a pump–probe technique under resonant excitation. Precise control of polarization directions of incident pulses enabled us to selectively estimate population lifetimes for two orthogonally polarized exciton ground states according to polarization selection rules. Measured decay times of the probe transmissions were highly dependent on the polarization directions of the exciton states. We found that the ratio of the decay times for the orthogonally polarized states is in quantitative agreement with the ratio of square of the transition dipole moments. This indicates that radiative recombination processes have a dominant effect on the population dynamics and that non-radiative and spin relaxations are negligible in our QDs. As a result, we can estimate the radiative lifetimes to be 1.0±0.1 and 1.7±0.2 ns for orthogonally polarized exciton ground states.     

Luminescence study of self-trapped excitons in CdMoO4

Luminescence properties of CdMoO₄ crystals have been investigated in a wide temperature range of T=5–300 K. The luminescence-excitation spectra are examined by using synchrotron radiation as a light source. A broad structureless emission band appears with a maximum at nearly 550 nm when excited with photons in the fundamental absorption region (<350 nm) at T=5 K. This luminescence is ascribed to a radiative transition from the triplet state of a self-trapped exciton (STE) located on a (MoO₄)^2? complex anion. Time-resolved luminescence spectra are also measured under the excitation with 266 nm light from a Nd:YAG laser. It is confirmed that triplet luminescence consists of three emission bands with different decay times. Such composite nature is explained in terms of a Jahn–Teller splitting of the triplet STE state. The triplet luminescence at 550 nm is found to be greatly polarized in the direction along the crystallographic c axis at low temperatures, but change the degree of polarization from positive to negative at T>180 K. This remarkable polarization is accounted for by introducing further symmetry lowering of tetrahedral (MoO₄)^2? ions due to a uniaxial crystal field, in addition to the Jahn–Teller distortion. Furthermore, weak luminescence from a singlet state locating above the triplet state is time-resolved just after the pulse excitation, with a polarization parallel to the c axis. The excited sublevels of STEs responsible for CdMoO₄ luminescence are assigned on the basis of these experimental results and a group-theoretical consideration.     

Improvement of polarization extinction in silicon waveguide devices

The SOI based waveguide devices are found to be highly polarization sensitive. Unwanted polarization excitations can be attenuated by integrating a TE- or TM-pass polarizer. A large attenuation of TM-polarized light has been observed when a thin film of metal is coated on the top of silicon rib waveguide, while TE-polarized light remains almost unaffected. The attenuation of TM-polarized light is attributed to the plasmonic absorption of the evanescent field in the metal cladding. Typically, with an Al cladding of thickness ～ 100 nm and a length of 1 mm on top of a single-mode (λ ～ 1550 nm) SOI rib waveguide structure, TE vs TM extinction ratio of ～ 15 dB has been obtained. Integrating such waveguide polarizers in a directional coupler and MZI based DWDM channel interleaver, we have also achieved an improvement in polarization extinction by ～ 15 dB.     

Absorption spectra response of XRQA radiochromic film to x-ray radiation

Gafchromic XRQA, radiochromic film is a high sensitivity auto developing x-ray analysis films designed and available for kilovoltage x-ray, dose and QA assessment applications. The film is designed for reflective analysis with a yellow transparent top filter and white opaque backing materials. This allows the film to be visually inspected for colour changes with a higher level of contrast than clear coated radiochromic films such as Gafchromic EBT version 1. The spectral absorption properties in the visible wavelengths have been investigated and results show two main peaks in absorption located at 636 nm and 585 nm. These peaks are located in the same position as EBT Gafchromic film highlighting a similar chemical monomer/polymer for radiation sensitivity. A much higher sensitivity however is found at kilovoltage energies with an average 1.55 OD units per 20 cGy irradiation variation measured at 636 nm using 150 kVp x-rays. This is compared to approximately 0.12 OD units per 20 cGy measured at 636 nm for EBT film at 6 MV x-ray energy. That is, the XRQA film is more than 10 times more sensitive than EBT1 film. The visual colour change is enhanced by the yellow polyester coating. However this does not affect the absorption spectra properties in the red region of analysis which is the main area for use using desktop scanners in reflection mode.     

Spectral characteristics and fluorescence quenching of N,N′-bis(4-pyridyl)-3,4:9,10-perylenebis(dicarboximide) (BPPD)

The photophysical properties such as electronic absorption, molar absorptivity, emission spectra, fluorescence quantum yield and fluorescence lifetime of N,N′-bis(4-pyridyl)-3,4:9,10-perylene bis(dicarboximide) (BPPD) have been measured in different solvents. Both electronic absorption and fluorescence spectra are not sensitive to medium polarity, while the fluorescence quantum yield (?_f) is solvent dependent. The ground state geometry has been computed by using density functional theory (DFT), the transition from HOMO to LUMO from perylene core with maximum absorption at 512 nm and HOMO–LUMO energy difference equal 2.53 eV. BPPD dye undergoes molecular aggregation to dimmer or higher aggregates in dimethyl sulfoxide (DMSO). Crystalline solids of BPPD gives excimer-like emission at 676 nm. The fluorescence quenching of BPPD is also studied using hydrated ferric oxide nanoparticle (FeOOH), and the Stern–Volmer rate constants (K_sv) were calculated as 8×10⁶ and 9.2×10⁶ M^?1 in ethanol and ethylene glycol, respectively.     

Improvement of all-optical switching performance based on azo dye-doped polymer film using two cross-linearly polarized pump beams

We propose a method for improving the characteristics of all-optical switching based on azo dye-doped polymers. Using alternately two cross-linearly polarized beams (532 nm, continuous light wave (CW)) to pump azo dye–ethyl red (ER) doped polymer methyl methacrylate (PMMA) film, the modulation depth of the all-optical switching reached 96% at the pump powers of 4.8 mW and 1.6 mW and the modulation frequency of 1000 Hz. For comparison, we used respectively the single linearly polarized beam (4.8 mW) and the alternately linear–circular polarized beams (4.8 mW and 1.6 mW) to pump the film at the modulation frequency of 1000 Hz, the obtained modulation depths of the all-optical switching were 36% and 45.8%, respectively. Furthermore, the experimental measurement and analysis showed that the turn off speed of the all-optical switching could be obviously increased by use of our pump method.     

Photocatalytic degradation of ciprofloxacin drug in water using ZnO nanoparticles

We report the synthesis of nanostructure ZnO semiconductor with ～2.1 nm diameter using a chemical precipitation method. The resulting nanoparticles were characterized by X-ray diffraction analysis (XRD), Fourier-transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The optical properties were investigated by UV–vis and fluorescence techniques. The absorption spectra exhibit a sharp absorption edge at ～334 nm corresponding to band gap of ～3.7 eV. The fluorescence spectra displayed a near-band-edge ultraviolet excitonic emission at ～410 nm and a green emission peak at ～525 nm, due to a transition of a photo-generated electron from the conduction band to a deeply trapped hole. The photocatalytic activity of the prepared ZnO nanoparticles has been investigated for the degradation of ciprofloxacin drug under UV light irradiation in aqueous solutions of different pH values. The results showed that the photocatalytic degradation process is effective at pH 7 and 10, but it is rather slow at pH 4. Higher degradation efficiency (～50%) of the drug was observed at pH 10 after 60 min. Photodegradation of the drug follows a pseudo-first-order kinetics.     

Structural and optical properties of chromotrope 2R thin films of different thicknesses

Chromotrope 2R (CHR) films of different thicknesses have been prepared using spin coater. The material has been characterized using FT-IR, DTA and X-ray diffraction. The XRD of the material in powder and thin film forms showed polycrystalline structure with triclinic phase. Preferred orientation at the (1 1 4) plane is observed for the deposited films. Initial indexing of the XRD pattern was performed using “Crystalfire” computer program. Miller indices, h k l, values for each diffraction line in X-ray diffraction (XRD) spectrum were calculated and indexed for the first time. The DTA thermograms of CHR powder have been recorded in the temperature range 25–350 °C with different heating rates. The spectra of the infra-red absorption allow characterization of vibration modes for the powder and thin film. The effect of film thickness on the optical properties has been studied in the UV-visible-NIR regions. The films show high transmittance exceeding 0.90 in the NIR region λ > 800 nm. The intensity of the absorption peaks for λ < 800 nm are enhanced as the film thickness increase. The absorption bands are attributed to the (π–π*) and (n–π*) molecular transitions. The optical properties have been analyzed according to the single-oscillator model and the dispersion energy parameters as well as the free charge carrier concentration have been determined. The optical energy gap as well as the oscillator strength and electric dipole strength have been calculated.     

Photophysical parameters and laser performance of 3-(4′-dimethylaminophenyl)-1-(2-furanyl)prop-2-en-1-one (DMAFP): A new laser dye

The spectral properties such as singlet absorption, molar absorptivity, emission spectra, fluorescence quantum yield and excited state lifetime of 3-(4′-dimethylaminophenyl)-1-(2-furanyl)prop-2-en-1-one (DMAFP) have been determined in different solvents. DMAFP dye exhibits a large red shift in both electronic absorption and emission spectra as the solvent polarity increases, indicating a large change in the dipole moment of molecules upon excitation. A crystalline solid of DMAFP gives an excimer like emission at 566 nm due to the excitation of molecular aggregates. This is expected from the idealized crystal structure of the dye that belongs to the B-type class of Steven's classification. The ground and excited state protonation constants of DMAFP are calculated and amounted to 1.71 and 8.3, respectively. DMAFP acts as a good laser dye upon pumping with nitrogen laser (λ_ex=337.1 nm) in chloroform, methylene chloride and dioxane and gives laser emission in the range 460–590 nm. The laser parameters such as the tuning range, gain coefficient (α), emission cross section (σ_e) and half-life energy (E_1/2) are calculated. The photoreactivity and net photochemical quantum yield of DMAFP in chloromethane solvents are also studied.     

Room temperature near-field photoluminescence of zinc-blend and wurtzite ZnO structures

Near-field photoluminescence (PL) was measured from ZnO film, composed of nanocrystallites with zinc-blend (ZB) and wurtzite (W) structures, on a sapphire (0 0 0 1) substrate at room temperature (RT). The size of nanocrystallites was in the range of 30–50 nm. Using a fiber probe with aperture size of 80 nm, two near-field emission peaks attributed to one ZB and one W structures were observed. The difference in the emission energies was 0.10 eV close to the calculated bandgap difference between ZB and W structures. The intensity of emission peak from ZB structure with lower energy was stronger than that from W structure, which is supposed to be resulted from the quenched excitonic effect of W structure.     

Ohmic contact and space-charge-limited current in molybdenum oxide modified devices

The effect of indium-tin oxide (ITO) surface treatment on hole injection of devices with molybdenum oxide (MoO₃) as a buffer layer on ITO was studied. The Ohmic contact is formed at the metal/organic interface due to high work function of MoO₃. Hence, the current is due to space charge limited when ITO is positively biased. The hole mobility of N, N′-bis-(1-napthyl)-N, N′-diphenyl-1, 1′biphenyl-4, 4′-diamine (NPB) at various thicknesses (100–400 nm) has been estimated by using space-charge-limited current measurements. The hole mobility of NPB, 1.09×10⁻⁵ cm²/V s at 100 nm is smaller than the value of 1.52×10⁻⁴ cm²/V s at 400 nm at 0.8 MV/cm, which is caused by the interfacial trap states restricted by the surface interaction. The mobility is hardly changed with NPB thickness for the effect of interfacial trap states on mobility which can be negligible when the thickness is more than 300 nm.     

Dual-wavelength laser polarimeter and its performance capabilities

A dual-wavelength optical polarimetric approach has been proposed as a means of elimination of the systematic errors and estimation of the optical anisotropy parameters for a single DKDP crystal. Our HAUP-related polarimeter uses two semiconductor lasers with the neighbouring wavelengths of 635 nm and 650 nm. Based on the temperature dependence analysis of small characteristic azimuths of light polarization with respect to the axis of the sample, we found the parameters of imperfections of polarization system. We acquired eigen waves ellipticities in a DKDP crystal and found perpendicular to the optic axis value of the optical rotatory power. Our results correlate positively with previously measured data for KDP crystals.     

Out-of-plane ellipsometry measurements of nanoparticles on surfaces for thin film coated wafer inspection

Measurements of the diameter and size distribution of nanoparticles on wafers are critical parameters in the semiconductor industry, essential to control transistor quality and increase production rate. A goniometric optical scatter instrument (GOSI) has been developed that employs polarized light scattering to make measurements of the diameter and size distribution of nanoparticles on bare and thin film coated wafers. This scatter instrument is capable of distinguishing various types of optical scattering characteristics, which correspond to the diameters of the nanoparticles and thin film thickness, on or near the surfaces using the Mueller matrix calculation in Bobbert and Vlieger (1986) [1]. The experimental results of the GOSI system show good agreement with theoretical predictions for nanoparticles of diameter 100, 200, and 300 nm on wafers coated with thin films of 2, 5, and 10 nm thickness. These results demonstrate that the polarization of light scattered by nanoparticles can be used to determine the size of particulate contaminants on bare and thin film coated silicon wafers.     

Circularly polarized lasing over wide wavelength range in spin-controlled (1 1 0) vertical-cavity surface-emitting laser

We investigated the emission wavelength dependence of the lasing polarization in a (1 1 0)-oriented vertical-cavity surface-emitting laser (VCSEL) with GaAs/AlGaAs quantum wells under optical spin injection at room temperature. Lasing was observed in the one circularly polarized mode over a wide wavelength range from 838 to 857 nm, in which a degree of circular polarization higher than 0.8 was maintained. The optical gain spectrum that contributed to the circularly polarized lasing is discussed based on the optical selection rules and the measured polarization-resolved photoluminescence spectra of the active layers.     

Exciton-polariton state in nanocrystalline SiC films

We studied the features of optical absorption in the films of nanocrystalline SiC (nc-SiC) obtained on the sapphire substrates by the method of direct ion deposition. The optical absorption spectra of the films with a thickness less than ~500 nm contain a maximum which position and intensity depend on the structure and thickness of the nc-SiC films. The most intense peak at 2.36 eV is observed in the nc-SiC film with predominant 3C-SiC polytype structure and a thickness of 392 nm. Proposed is a resonance absorption model based on excitation of exciton polaritons in a microcavity. In the latter, under the conditions of resonance, there occurs strong interaction between photon modes of light with λ_ph=521 nm and exciton of the 3С polytype with an excitation energy of 2.36 eV that results in the formation of polariton. A mismatch of the frequencies of photon modes of the cavity and exciton explains the dependence of the maximum of the optical absorption on the film thickness.     

The preparation and characterization of nanoparticle TiO2/Ti films and their photocatalytic activity

Nanoparticle TiO₂/Ti films were prepared by a sol–gel process using Ti(OBu)₄ as raw material, the as-prepared film samples were also characterized by TG-DTA, XRD, TEM, SEM, XPS, DRS, PL, SPS and EFISPS testing techniques. TiO₂ nanoparticles experienced two processes of phase transition, i.e. amorphous to anatase and anatase to rutile at the calcining temperature range from 450 to 700 °C. TiO₂ nanoparticles calcined at 600 °C had similar composition, structure, morphology and particle size with the internationally commercial P-25 TiO₂ particles. Thus, the conclusion that 600 °C might be the most appropriate calcining temperature during the preparation process of nanoparticle TiO₂/Ti film photocatalysts could be made by considering the main factors such as the properties of TiO₂ nanoparticles, the adhesion of nanoparticle TiO₂ film to Ti substrate, the effects of calcining temperature on Ti substrate and the surface characteristics and morphology of nanoparticle TiO₂/Ti film for the practice view. The Ti element mainly existed on the nanoparticle TiO₂/Ti(3) film calcined at 600 °C as the chemical state of Ti⁴⁺, while O element mainly existed as three kinds of chemical states, i.e. crystal lattice oxygen, hydroxyl oxygen and adsorbed oxygen with increasing band energy. Its photoluminescence (PL) spectra with a peak at about 380 nm could be observed using 260 nm excitation, possibly resulting from the electron transition from the bottom of conduction band to the top of valence band. The PL peak position was nearly the same as the onset of its diffuse reflection spectra (DRS) and surface photovoltage spectroscopy (SPS), demonstrating that the effects of the quantum size on optical property were greater than that of the Coulomb and surface polarization. The PL spectra with two peaks related to the anatase and rutile, respectively, could be observed using the excited wavelength of 310 nm. Weak PL spectra could be observed using the excited wavelength of 450 nm, resulting from surface states. In addition, during the experimental process of the photocatalytic degradation phenol, the photocatalytic activity of nanoparticle TiO₂/Ti film with three layers calcined at 600 °C was the highest.     

Excellent UV absorption in spin-coated thin films of oleic acid modified zinc oxide nanorods embedded in Polyvinyl alcohol

The aim of the study is to investigate the optical properties of spin-coated, highly transparent nanocomposite films of oleic acid modified ZnO (Zinc oxide) nanorods embedded in Polyvinyl alcohol (PVA) matrix. Pristine and oleic acid (OA) modified ZnO nanorods have been prepared by wet chemical synthesis and are characterized by X-ray diffraction, FESEM, TEM and FT–IR spectroscopy techniques. The optical properties of ZnO/PVA films are studied using UV–visible absorption and Photoluminescence (PL) spectroscopy. The results show that the optical absorption of the films in the UV region is quite high and more than 95% absorption is observed in films prepared from OA modified ZnO nanorods. The excellent UV absorption at around 300 nm offers prospects of applications of these films as efficient UV filters in this wavelength region. The PL spectrum of pristine ZnO nanorods shows almost white light emission whereas OA modified ZnO nanorods have a more intense peak centered in the blue region. The PL emission of OA modified ZnO/PVA film shows appreciable increase in intensity compared to the film obtained with pristine ZnO. The surface modification of ZnO by the polymer matrix removes defect states within ZnO and facilitates sharp near band edge PL emission at 364 nm.     

Electronic properties of the polycrystalline tin dioxide interface with conjugated organic layers

The results on the electronic structure of the unoccupied electronic states of the polycrystalline SnO₂ in the energy range from 5 eV to 25 eV above the Fermi level are presented. The modification of the electronic structure and of the surface potential upon deposition of the ultrathin films of copper phthalocyanine (CuPc) and of perylene tetracarboxylic acid dianhydride (PTCDA) film onto the SnO₂ surface were studied using the very low energy electron diffraction (VLEED) method and the total current spectroscopy (TCS) measurement scheme. A substantial attenuation of the TCS signal coming from the SnO₂ surface was observed upon formation of a 1.5–2 nm thick organic deposit layer while no new spectral features from the deposit were distinguishable. It was observed that the electronic structure typical for the organic films was formed within the organic deposit thickness range from 2 nm to 7 nm. The interfacial charge transfer was characterized by the formation of the polarization layer up to 5 nm thick in the organic films. The PTCDA deposition on SnO₂ was accompanied by the negative charge transfer onto the organic layer and to the 0.65 eV increase the surface work function. At the CuPc/SnO₂ interface, the negative charge was transferred to the SnO₂ surface and the overall surface work function decreased by 0.15 eV.