Surface-functionalization-dependent optical properties of II-VI semiconductor nanocrystals

We report a study of the surface-functionalization-dependent optical properties of II-VI zinc-blende semiconductor nanocrystals on the basis of ligand-exchange chemistry, isomaterial core/shell growth, optical spectroscopy, transmission electron microscopy, and X-ray powder diffraction. Our results show that the transition energy and extinction coefficient of the 2S(h3/2)1S(e) excitonic band of these nanocrystals can be strongly modified by their surface ligands as well as ligand associated surface atomic arrangement. The oleylamine exchange of oleate-capped zinc-blende II-VI nanocrystals narrows the energy gap between their first and second excitonic absorption bands, and this narrowing effect is size-dependent. The oleylamine exchange results in the quenching, subsequent recovery, and even enhancing of the photoluminescence emission of these II-VI semiconductor nanocrystals. In addition, the results from our X-ray powder diffraction measurements and simulations completely rule out the possibility that oleate-capped zinc-blende CdSe nanocrystals can undergo zinc-blende-to-wurtzite crystal transformation upon ligand exchange with oleylamine. Moreover, our theoretical modeling results suggest that the surface-functionalization-dependent optical properties of these semiconductor nanocrystals can be caused by a thin type II isomaterial shell that is created by the negatively charged ligands (e.g., oleate and octadecyl phosphonate). Taking all these results together, we provide the unambiguous identification that II-VI semiconductor nanocrystals exhibit surface-functionalization-dependent excitonic absorption features.     

Optical properties of single semiconductor nanocrystals

We present an overview of the current progress in the understanding of the (steady state) optical properties of individual II-VI semiconductor nanocrystals. We begin with a presentation of the conceptual development of the theory required to model the electronic structure of these systems. This is followed by an overview of the current experimental results obtained from the spectroscopy of individual semiconductor nanocrystals, and in particular, we focus on the study of photoluminescence intermittency (blinking) and spectral diffusion. Where possible, we link the experimental observations to the predictions of current theories. We conclude that the surface of small semiconductor crystals plays an important role in determining their optical properties.     

Preparation and photoelectric properties of mesoporous ZnO films

Mesoporous ZnO films doped with Ti⁴⁺ (M-ZnO) have been prepared by doping process and sol–gel method. The films have mesoporous structures and consist of nano-crystalline phase, as evidenced from small angle X-ray diffraction and high resolution transmission electron microscopy. The wide angle X-ray diffraction of M-ZnO films confirms that M-ZnO has hexagonal wurtzite structure and ternary ZnTiO₃ phases. Ultraviolet–visible transmittance spectra, absorbance spectra and energy gaps of the films were measured. The Eg of M-ZnO is 3.25 eV. Photoluminescence intensity of M-ZnO centered at 380 nm increases obviously with the excitation power, which is due to the doping process and enhanced emission efficiency. M-ZnO thin films display a positive photovoltaic effect compared to mesoporous TiO₂ (M-TiO₂) films.     

Photochemical properties of photosystem 1 immobilized in a mesoporous semiconductor matrix

The pigment-protein complex of photosystem 1 (PS1) isolated from cyanobacterium Synechocystis sp. PCC 6803 has been adsorbed on a solid mesoporous film made from TiO₂ nanoparticles. was on The TiO₂ film supported on a glass substrate with a surface area of 1 cm² adsorbs up to 0.045 nmol of PS1. PS1 molecules are distributed in the pores of the mesoporous support. Immobilization has an insignificant effect on the optical and photochemical properties of PS1. A reversible photoinduced EPR signal from the oxidized primary electron donor P700 of immobilized PS1 has been detected. It has been shown by photoelectrochemical methods that the photoexcitation of PS1 results in electron injection from PS1 to the conduction band of TiO₂.     

Molecular optimization of multiply-functionalized mesoporous films with ion conduction properties

Sequential processing of multiply functionalized mesoporous films is shown to yield materials that are compositionally and structurally heterogeneous on mesoscopic and molecular length scales, both of which must be controlled to optimize macroscopic ion-conduction properties. Cubic mesoporous silica films prepared from strongly acidic solutions were subsequently functionalized under highly alkaline conditions to incorporate hydrophilic aluminosilica surface moieties, followed by nonaqueous conditions to introduce perfluorosulfonic-acid surface groups. Such sequential combination of individually incompatible steps yielded stable mesoporous films with high surface hydrophilicities and strong acid functionalities that exhibited high proton conductivities (ca. 9 × 10(-2) S/cm) at elevated temperatures (120 °C). Molecular, mesoscopic, and macroscopic properties of the multiply functionalized films were monitored and correlated at each stage of the syntheses by nuclear magnetic resonance (NMR) spectroscopy, small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), elemental analysis, adsorption, and ion conductivity measurements. In particular, variable-temperature solid-state two-dimensional (2D) (27)Al{(1)H}, (29)Si{(1)H}, (27)Al{(19)F}, and (29)Si{(19)F} HETeronuclear chemical-shift CORrelation (HETCOR) NMR spectra reveal separate surface adsorption and grafting sites for the different functional surface species within the mesopore channels. The hydrophilic aluminosilica and acidic fluoro-group loadings and interaction sites are demonstrated to be strongly affected by the different synthesis and functionalization treatments, which must be separately and collectively optimized to maximize the proton conductivities.     

Chiral II-VI semiconductor nanostructure superlattices based on an amino acid ligand

Reaction of L-cysteine with M(NO3)2 x xH2O (M = Cd, Zn) generates M(L-cysteinate), which feature one-dimensional substructures that can be viewed as fragments of bulk structures of CdS (rock salt high pressure phase) and ZnS (wurtzite) because of the bridging modes accessible to the sulfur atom of L-cysteine. The MS substructures are arranged in a regular and periodic fashion within the crystal via the carboxylate function of L-cysteine. Considering the structural similarities with bulk materials, the optical properties of M(L-cysteinate) were studied and indicate blue shifts of the band gap of 2.59 eV (M = Cd, compared to CdS rock salt) and 1.37 eV (M = Zn, compared to ZnS wurtzite) with respect to the bulk MS structures, due to the low dimensionality of the metal-sulfur arrangement. The chelating nature of the cysteine ligand imposes an unusual mer arrangement of three binding S moieties at Cd with a correspondingly high Cd coordination number in a chalcogenide-based material. Density of states calculations show strong electronic structure similarities with the bulk phases and rationalize the band gap changes.     

Investigation of the properties of organically modified ordered mesoporous silica films

Organically modified, ordered mesoporous silica films, which can provide hydrophobicity and low polarizability to the framework, were prepared using Brij-76 block copolymer as a template. Due to a fast condensation reaction of the silica precursor, mesostructured silica films were not properly synthesized. To circumvent this problem, a synthesis procedure was modified to provide an enhancement of pore periodicity through the incorporation of methyl ligands on the framework. The micropore volume was reduced, and the pore size was enlarged, as the concentration of the methyl ligands on the framework was increased. A mesophase transition from a two-dimensional hexagonal structure to a body-centered cubic (BCC) structure was observed according to the concentration of incorporated methyl ligands. The mechanical properties of the fabricated films were investigated according to the pore ordering and film density. The mechanical properties of the films with random pore geometry show a positive correlation between film density and elastic modulus. Meanwhile, the mechanical behavior of organically modified mesoporous silica films with periodic pore distribution represents a negative correlation within a certain density range, which is advantageous to the low-k materials. Especially, film with a low micropore volume fraction and BCC pore ordering is more applicable to a low-k material due to low dielectric constant and high mechanical strength.     

Optical properties of pentacene and perfluoropentacene thin films

The optical properties of pentacene (PEN) and perfluoropentacene (PFP) thin films on various SiO(2) substrates were studied using variable angle spectroscopic ellipsometry. Structural characterization was performed using x-ray reflectivity and atomic force microscopy. A uniaxial model with the optic axis normal to the sample surface was used to analyze the ellipsometry data. A strong optical anisotropy was observed, and enabled the direction of the transition dipole of the absorption bands to be determined. Furthermore, comparison of the optical constants of PEN and PFP thin films with the absorption spectra of the monomers in solution shows significant changes due to the crystalline environment. Relative to the monomer spectrum, the highest occupied molecular orbital to lowest unoccupied molecular orbital transition observed in PEN (PFP) thin film is reduced by 210 meV (280 meV). A second absorption band in the PFP thin film shows a slight blueshift (40 meV) compared to the spectrum of the monomer with its transition dipole perpendicular to that of the first absorption band.     

Optical properties of polymer films for transparent insulation

Commercially available, highly transparent polymer films for transparent insulation applications were investigated systematically as to their relevant optical properties in the solar and infrared wavelength range. The photometric characterisation in the solar range and the calculation of non-spectral, solar optical film properties using models for scattering-absorbing media have shown, that the solar extinction is dominated by scattering occuring mainly at the surface. For various amorphous and semi-crystalline films the root-mean-square surface roughness correlated well with the solar optical thickness. Regarding high infrared absorptance in the wavelength range of about 10 μm the carbon-oxygen single bond is highly effective for commercial materials with maximum service temperatures of about 100°C. For 50 μm thick films of different polymer types with carbon-oxygen single bonds in the molecular structure a good correlation between the concentration of the functional corbon-oxygen group and the nonspectral, infrared optical thickness was found.     

Optical properties and structure of drawn polyethyleneterephtalate-polyethylene films

Films made by coextrusion of polyethyleneterephtalate and low density polyethylene exhibit specular reflection of light when stretched. Unlike the behaviour of films made of pure PET, where specular reflection is rare and does occur at extremely high stretching rates only, PET/LDPE films show specular reflection independent of the stretching rate.A film, containing 70% PET and 30% LDPE, prepared by coextrusion of the two components, has been investigated by scanning electron microscopy, light microscopy and by measuring the optical properties with a spectrophotometer. The (unstretched) as prepared sample has been compared with a sample stretched to =4.The optical measurements show as a result of the stretching a strong decrease of the transmittance and an increase of the remittance. While there is no drastic change of the dispersion (which is only slight), the increase of the refractive index indicates some straininduced crystallization.The scanning electron micrographs show long, needlelike voids and indicate a fractionation of the two components as a result of the stretching. This fractionation has been investigated by heating the samples up under the light microscope: while the stretched sample shows a separation of the components, the unstretched sample does not.Dedicated to Prof. Dr. F. H. Müller.     

Optical properties of hybrid dendritic-mesoporous titania nanocomposite films

New hybrid optical sensors have been prepared by grafting specifically designed fluorescent, functionalised, phosphorus-containing dendrimers onto a nanocrystalline mesoporous titania thin film formed by evaporation-induced self-assembly. The structural characterisation and optical behaviour of these new fluorescent probes have been studied both in solution and after being grafted onto an inorganic network, which resulted in the discovery of improved probing selectivity in the solid state. This new hybrid sensor exhibits high sensitivity to phenolic OH moieties (especially those from resorcinol and 2-nitroresorcinol), which induce the quenching of fluorescence more efficiently in the solid state than in solution. This effect is a result of the increased spatial proximity of the fluorescent molecules, which is induced by pore confinement that makes the formation of hydrogen bonds between the hydroxyl moieties of the quenchers and the carbonyl groups of the dendrimer easier.     

Mechanistic study of precursor evolution in colloidal group II-VI semiconductor nanocrystal synthesis

The molecular mechanism of precursor evolution in the synthesis of colloidal group II-VI semiconductor nanocrystals was studied using 1H, 13C, and 31P NMR spectroscopy and mass spectrometry. Tri-n-butylphosphine chalcogenides (TBPE; E = S, Se, Te) react with an oleic acid complex of cadmium or zinc (M-OA; M = Zn, Cd) in a noncoordinating solvent (octadecene (ODE), n-nonane-d20, or n-decane-d22), affording ME nanocrystals, tri-n-butylphosphine oxide (TBPO), and oleic acid anhydride ((OA)2O). Likewise, the reaction between trialkylphosphine selenide and cadmium n-octadecylphosphonic acid complex (Cd-ODPA) in tri-n-octylphosphine oxide (TOPO) produces CdSe nanocrystals, trialkylphosphine oxide, and anhydrides of n-octadecylphosphonic acid. The disappearance of tri-n-octylphosphine selenide in the presence of Cd-OA and Cd-ODPA can be fit to a single-exponential decay (kobs = (1.30 +/- 0.08) x 10-3 s-1, Cd-ODPA, 260 degrees C, and kobs = (1.51 +/- 0.04) x 10-3 s-1, Cd-OA, 117 degrees C). The reaction approaches completion at 70-80% conversion of TOPSe under anhydrous conditions and 100% conversion in the presence of added water. Activation parameters for the reaction between TBPSe and Cd-OA in n-nonane-d20 were determined from the temperature dependence of the TBPSe decay over the range of 358-400 K (deltaH++ = 62.0 +/- 2.8 kJ.mol-1, deltaS++ = -145 +/- 8 J.mol-1.K-1). A reaction mechanism is proposed where trialkylphsophine chalcogenides deoxygenate the oleic acid or phosphonic acid surfactant to generate trialkylphosphine oxide and oleic or phosphonic acid anhydride products. Results from kinetics experiments suggest that cleavage of the phosphorus chalcogenide double bond (TOP=E) proceeds by the nucleophilic attack of phosphonate or oleate on a (TOP=E)-M complex, generating the initial M-E bond.     

Optical properties and orientation in polyethylene blown films

We report structural factors affecting the optical properties of blown polyethylene films. Two types of blown polyethylene films of similar degrees of crystallinity were made from (1) single‐site‐catalyst high‐density polyethylene (HDPE; STAR α) and (2) Ziegler–Natta‐catalyst HDPE (ZN) resins. The STAR α film exhibited high clarity and gloss, whereas the ZN film was turbid. Small‐angle X‐ray scattering (SAXS), small‐angle light scattering (SALS), and optical microscopy gave quantitative and qualitative information regarding structure and orientation in the films. A new approach is described for determining the three‐dimensional lamellar normal orientation from SAXS. Both the clear STAR α and turbid ZN films had similar lamellar crystalline structures and long periods but displayed different degrees of orientation. It is demonstrated that optical haze is related to surface features that seem to be linked to the bulk morphology. The relationship between haze and structural orientation is described. The lamellar orientation is linked to rodlike structures seen in optical microscopy and SALS through a stacked lamellar or cylindrite morphology on a nanometer scale and through a fiberlike morphology on a micrometer scale. The micrometer‐scale, rodlike structures seem directly related to surface roughness in a comparison of index‐matched immersion and surface micrographs. The higher haze and lower gloss of the ZN film was caused by extensive surface roughness not observed in the STAR α film. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2923–2936, 2001     

Optical properties of nanostructure boron doped NiO thin films

Boron doped NiO films were prepared by sol–gel method. The effects of B content on the morphological and optical properties of NiO films were studied with atomic force microscopy, and optical characterization method. The average transmittance at the visible region is reached to 75 % for lower doped films (0.1 and 0.2 % B), whereas, the recorded average value of transmittance was about 62 % for doped film with 1 % B throughout the region. The optical energy gap value for pure NiO film was found to be 3.73 eV. These values were affected by B doping with non-monotonic variation and reached to 3.64 eV for 0.1 % B doped NiO. Also, the refractive index dispersion and dielectric constants of the NiO films were studied throughout the investigated range of wavelengths. The obtained results indicate that the optical parameters of the NiO film are controlled with boron doping.     

Optical and dielectrical properties of azo quinoline thin films

In this study, the optical and dielectrical properties of a novel series of quinoline azodyes (5-(4′-derivatives phenyl azo)-8-hydroxy-7-quinolinecarboxaldehyde) (AQL₁–AQL₅) were investigated and the obtained results were analyzed. The X-ray diffraction (XRD) patterns of AQL_n show that the materials in the powder form are a mixture of amorphous and crystalline structure, while the thermally deposited thin films are completely amorphous. The optical constants such as the refractive index, n, the absorption index, k and the absorption coefficient, α, were determined using spectrophotometric measurements of transmittance (T) and reflectance (R) in the wavelength range 200–2500 nm. According to the single oscillator model (SOM), some related parameters such as oscillation energy (E_o), the dispersion energy (E_d), the optical dielectric constant (ε_∞), the lattice dielectric constant (ε_L) and the ratio of free carrier concentration to its effective mass (N/m*) are estimated. The emission spectra of azo quinoline ligands (AQL_n) exhibit dual fluorescence peaks in the region 512–580 nm. This finding reveals the formation of two stoichiometric hydrogen-bonding in the ground and excited state. The dielectrical properties and alternating current conductivity (σ_AC) are investigated in temperature range 298–483 K and frequency range 0.1–100 KHz.     

Optical properties of stretched polymer dispersed liquid crystal films

The basic mechanisms determining the formation of optical anisotropy in stretched, thin polymer dispersed liquid crystal (PDLC) films with micron sized nematic droplets have been studied experimentally and the results analysed in terms of a proposed theoretical model. The experiments were performed on PDLC films with the bipolar nematic director configuration in the droplets, where the film transmittance, microscopic structure, and birefringence of the polymer matrix were studied. It is shown that the orientational ordering of bipolar nematic droplets, introducing the main contribution to the ability of stretched PDLC film to polarize the transmitted light, is strongly dependent upon initial droplet shape and the elastic properties of the polymer matrix. The 'anomalous' nematic director orientation is also observed in a portion of elongated droplets where the axes of bipolar configurations do not coincide with the major axes of the droplet cavities due to the presence of inclusions at the cavity walls. The effect of alternation of droplet size and shape upon stretching and the influence of optical anisotropy of the polymer matrix on film transmittance are analysed. On the basis of the results obtained, simple criteria for optimization of main PDLC polarizer performance are formulated.     

Tuning the optical properties of mesoporous TiO2 films by nanoscale engineering

The optical properties of spin-coated titanium dioxide films have been tuned by introducing mesoscale pores into the inorganic matrix. Differently sized pores were templated using Pluronic triblock copolymers as surfactants in the sol-gel precursor solutions and adjusted by varying the process parameters, such as the polymer concentration, annealing temperature, and time. The change in refractive index observed for different mesoporous anatase films annealed at 350, 400, or 450 °C directly correlates with changes in the pore size. Additionally, the index of refraction is influenced by the film thickness and the density of pores within the films. The band gap of these films is blue-shifted, presumably due to stress the introduction of pores exerts on the inorganic matrix. This study focused on elucidating the effect different templating materials (Pluronic F127 and P123) have on the pore size of the final mesoporous titania film and on understanding the relation of varying the polymer concentration (taking P123 as an example) in the sol-gel solution to the pore density and size in the resultant titania film. Titania thin film samples or corresponding titanium dioxide powders were characterized by X-ray diffraction, cross-section transmission electron microscopy, nitrogen adsorption, ellipsometery, UV/vis spectrometry, and other techniques to understand the interplay between mesoporosity and optical properties.     

Facile route to Zn-based II-VI semiconductor spheres, hollow spheres, and core/shell nanocrystals and their optical properties

A convenient chemical conversion method that allows the direct preparation of nanocrystalline ZnE (E = O, S, Se) semiconductor spheres and hollow spheres as well as their core/shell structures is reported. By using monodisperse ZnO nanospheres as a starting reactant and in situ template, ZnS, ZnSe solid and hollow nanospheres, and ZnO/ZnS and ZnO/ZnSe core/shell nanostructures have been obtained through an ultrasound-assisted solution-phase conversion process. The formation mechanism of these nanocrystals is connected with the sonochemical effect of ultrasound irradiation. The photoluminescence and electrogenerated chemiluminescence properties of the as-prepared nanocrystals were investigated.     

Tetrazine-functionalized and vertically-aligned mesoporous silica films with electrochemical activity and fluorescence properties

In spite of their attractive physico-chemical properties making them very promising in the field of functional molecular materials, s-tetrazine derivatives remain underexploited in practical devices mainly because their immobilization in a stable form maintaining all their features is still challenging. Here, we show that combining a ‘click chemistry azide/alkyne’ approach with an electrochemically-assisted self-assembly (EASA) method, which is likely to generate azide-functionalized and vertically-aligned mesoporous silica films, and further derivatization of the ordered mesoporous material with propargyl–tetrazine via a soft Huisgen coupling reaction, enable one to reach this goal. The resulting tetrazine-functionalized films formed onto transparent indium–tin oxide (ITO) electrodes exhibit well-defined voltammetric signals, with peak currents proportional to the functionalization level and stable upon multiple potential scanning, as well as effective fluorescence properties as evidenced from fluorescence spectra with maximum emission at 555–560 nm.