Preparation and properties of UV-curable di-functional sulfur-containing thioacrylate and thiourethane acrylate monomers with high refractive indices

We synthesized UV-curable di-functional sulfur-containing thioacrylate and thiourethane acrylate with high refractive indices. The structures of monomers were confirmed by nuclear magnetic resonance spectroscopy (NMR) and Fourier transform infrared spectroscopy (FT-IR). The formulation of UV-curable coating film was prepared by thioacrylate monomer, thiourethane acrylate monomer, α-hydroxy-α-methylpropiophenone as the photoinitiator, and bisphenol A epoxy acrylate as the oligomer. The cured coating films were investigated using thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), Taber abraser tests, transmittance, and refractive index. The value of refractive index for all coating films increased after UV-curing. Transparent, photocurable coating films with high abrasion resistance were prepared. The monomers showed high refractive index. The refractive indices of synthesized monomers (thioacrylate and thiourethane acrylate monomer) are 1.623 and 1.577, respectively.     

Effects of the chirality and functionality of monomers on the holographic gratings formed in photosensitive films

Photosensitive holographic polymer films were fabricated. Instead of liquid crystals, a nonreactive high‐refractive‐index diphenyl sulfide was mixed with several monomers and an initiator for the preparation of the holographic grating films. To investigate the formation of periodic arrays of the photosensitive refractive‐index modulation films and the effects of the chirality and functionality of monomers on the diffraction efficiency, chiral monomeric (?)‐bornyl acrylate, (+)‐bornyl acrylate, and the racemate (±)‐bornyl acrylate were synthesized and copolymerized with various multifunctional monomers. A reasonable schematic of the photosensitive polymerization mechanism was proposed. The effects of the multifunctional monomers, initiator concentrations, and feed monomer concentrations on the diffraction efficiencies were investigated. The morphologies of the polymer matrices were studied with scanning electron microscopy. Pictures of real light diffraction patterns with 15 grating points were obtained. In comparison with those described in the literature, the diffraction efficiency obtained in this investigation was relatively high. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2246–2254, 2003     

Synthesis and characterization of Co and Ga co-doped ZnO thin films as an electrode for dye sensitized solar cells

Using a time efficient and cost effective approach so called sol‒gel dip coating route, we deposited thin films of ZnO and 1% Co & (0%, 0.5%, 1%, and 1.5%) Ga co-doped ZnO on the fluorine doped tin oxide substrates. All the films exhibited hexagonal wurtzite structure. X-rays study revealed that crystallite size increased with increase of doping. Optical parameters like absorbance, transmittance, refractive index, band gap, extinction coefficient and dielectric constants were measured using UV–Vis spectroscopy and it has been noticed that doping resulted in reduction of band gap. It has also been observed that, the films prepared with 1% Co & 1% Ga co-doped ZnO have comparatively smaller band gap and thus have high refractive index and high transmittance in visible region. The calculation of different electrically important factors for instance, high current density, small open circuit voltage, efficiency and fill factor revealed that co-doped ZnO with 1% Co and 1% Ga has relatively high efficiency of 2.43% and thus shows the potential of this composition as an electrode for solar cell devices.     

Preparation and characterization of high refractive index thin films of TiO2/epoxy resin nanocomposites

By using sol–gel method, amorphous titania was introduced into epoxy matrix to prepare a series of high refractive index TiO₂/epoxy resin nanocomposite films. To increase the refractive index of the hybrid films, triethoxysilane‐capped trimercaptothioethylamine (TCTMTEA), a new kind of high refractive index coupling agent was synthesized from trimercaptothioethylamine (TMTEA). In the experiment, TCTMTEA acted as the solidification agent together with TMTEA except being used as the coupling agent. The hybrid films have been characterized via FTIR, AFM, DSC, TGA, etc. The experimental results showed that the amorphous TiO₂ had been dispersed uniformly in the organic polymer matrix with the size smaller than 100 nm in each sample. More importantly, the refractive index of this kind of materials can be continuously adjusted from 1.61 to 1.797 with the content of TiO₂ increasing from 0% to 65% in mass, and the continuously adjusted refractive index is very important for the applications in optical antirefractive films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1631–1636, 2006     

Alteration of the refractive index of polyacrylate and poly(styrene-<Emphasis Type="Italic">co</Emphasis>-acrylate) films via molecular structure modification

The alteration in the refractive index (RI) of the polyacrylate and poly(styrene-co-acrylate) films was performed in order to produce a gradient index in the polymeric RI profiles. Such gradient is imperative especially in realizing the fabrication of the polymeric multilayer optical filters and the graded-refractive-index polymeric-based antireflection films. In this study, the highest RI obtained is 1.528 with the poly(styrene-co-acrylate) film which consists of 25 wt% of styrene (Sty), 70 wt% of butyl acrylate (BA) and 5 wt% of acrylic acid, with 8 wt% of divinyl benzene (DVB) which can be utilized to alter the flexibility or the hardness of the polymeric materials. Replacing Sty with methyl methacrylate (MMA) in the copolymer without DVB gives the lowest RI of 1.472 and a difference of RI of 0.056. The Sty copolymer system that contains 8 wt% of DVB has been identified to be one of the effective factors, which yields a refractive index of approximately 0.040 higher than that obtained from the PMMA copolymer system when the same amount of DVB was used. The incorporation of the DVB up to 8.5 wt% has resulted in an increase of the refractive index of approximately 0.013 in the poly(MMA-co-BA-co-AA) copolymer. The refractive index of the polyacrylate copolymer film does not change significantly with the increasing amount of up to 7 % of TMVS in both acidic and alkaline environment. The difference of the refractive index of the film under both mediums is in the order of 10^?3.     

Optical Scattering from Nanostructured Glass Surfaces

Nanostructured glass surfaces enable new and innovative applications for glass substrates. These nanostructures enable trapping as well as extraction of light. They affect the propagation of light such that it scatters and is trapped or extracted based on the index of the propagation media. The diffusive scattering component as opposed to the specular component is what enables the trapping and extraction. Often smooth surfaces are required for growing semiconductor thin films. Scattering sites beneath these surfaces can significantly enhance the optical performance of these films. Example devices utilizing these substrates include organic light-emitting diodes (OLED) displays, OLED lighting components, and microelectromechanical systems reflective displays. We demonstrate methods to fabricate these substrates using nanoparticle deposition processes. Important parameters of these nanoparticles and their agglomerates include both size and refractive index. We characterize these substrates using atomic force microscopy and scanning electron microscopy microscopy, and we simulate their optical properties using optical scattering models.     

Holographic Gratings in Photosensitive Acrylic Polymers with High Refractive Index Diphenyl Sulfide

To investigate the effects of polymer matrices on the diffraction efficiency of holographic grating, a series of chiral compounds of bornyl acrylate (BA), bornyl methacrylate (BMA), and their enantiomers derived from borneol were synthesized. Instead of conventional liquid crystals, in this investigation we used a high refractive index diphenyl sulfide (DS, n ²⁰ _D=1.6327) mixed with initiators, bornyl acrylate, bornyl methacrylate, and multifunctional monomers to prepare the photosensitive holographic grating films. Membranes having a large refractive index difference (n) between the cured grating arrays and revealing high diffraction efficiency (DE) were created by using the compositions. The dynamic formation of the holographic grating and the dependence of the diffracting efficiency on laser exposure time and intensity were carried out. It was found that the intensity of the writing laser may affect the polymerization rate leading to various results of holographic grating. Bragg grating and Raman–Nath grating depending on the incident writing angles were all obtained. We also investigated the plural recording function of the photosensitive films, the morphologies of the polymer matrices, and laser light grating through the holographic grating membranes. Thermogravimetric analyses of the photosensitive membranes were also estimated.     

Optical and structural properties of amorphous SexTe100-x aligned nanorods

In the present work, we report studies on optical and structural phenomenon in as-deposited thin films composed of aligned nanorods of amorphous Se_xTe_100-x (x = 3, 6, 9, and 12). In structural studies, field emission scanning electron microscopic (FESEM) images suggest that these thin films contain high yield of aligned nanorods. These nanorods show a completely amorphous nature, which is verified by X-ray diffraction patterns of these thin films. Optical studies include the measurement of spectral dependence of absorption, reflection, and transmission of these thin films, respectively. On the basis of optical absorption data, a direct optical band gap is observed. This observation of a direct optical band gap in these nanorods is interesting as chalcogenides normally show an indirect band gap, and due to this reason, these materials could not become very popular for semiconducting devices. Therefore, this is an important report and will open up new directions for the application of these materials in semiconducting devices. The value of this optical band gap is found to decrease with the increase in selenium (Se) concentration. The reflection and absorption data are employed to estimate the values of optical constants (extinction coefficient (k) and refractive index (n)). From the spectral dependence of these optical constants, it is found that the values of refractive index (n) increase, whereas the values of extinction coefficient (k) decrease with the increase in photon energy. The real and imaginary parts of dielectric constants calculated with the values of extinction coefficient (k) and refractive index (n), are found to vary with photon energy and dopant concentration.     

A correlation between the microstructure and optical properties of hydrogenated amorphous carbon films prepared by RF magnetron sputtering

Comparative and systematic studies of the effect of the radiofrequency (RF) bias on the microstructure and the optical properties of hydrogenated amorphous carbon (a-C:H) have been carried out on films deposited by RF magnetron sputtering under different RF power varying from 10 to 250 W applied to the graphite target, leading to a negative bias voltage at the target in the range of −60 to −600 V.A combination of infrared (IR) absorption experiments, which give information about the local microstructure (i.e. C–C and C–H bonding), and optical transmission measurements in the UV-visible and near IR, from which we determined the optical gap E₀₄ and the refractive index n, are applied to fully characterize the samples in their as-deposited state. The results show first that the films deposited at low RF power (i.e. low negative bias) exhibit a more open microstructure (polymeric character) with a lower density than those deposited at high RF power (i.e. high negative bias). They also indicate that the total bonded H content as well as the sp³/sp² ratio of carbon atoms bonded to H decrease with increasing RF power leading to the formation of higher proportions of C-sp² sites. The same tendency is observed for the optical gap E₀₄. On the contrary, the refractive index increases with increasing RF power, suggesting the densification of the films in going to a higher RF power.     

Influences of Mn doping on the microstructural,semiconducting, and optoelectronic properties of HgO nanostructure films

Mn-doped HgO nanostructured thin films (Hg_1-xMn_xO) have been prepared using electron beam evaporation technique on Corning glass (1022) substrate at room temperature with different concentrations x = 0, 0.015, 0.05, 0.1, 0.15, and 0.2. The microstructural, morphological, semiconducting, and optoelectronic properties of the films have been investigated. The X-ray diffraction spectra suggest a hexagonal wurtzite type structure with lattice parameters decreased with increasing Mn content. It was found that the average particle size of the films decreases with increasing Mn doping which is confirmed by FE-SEM and AFM micrographs. The optical band gap of the investigated Mn-doped HgO nanocrystalline films is determined from the absorption coefficient and found to increase with the increase of Mn concentration which is attributed to the sp-d exchange interaction and/or the quantum confinement effect. The refractive index and extinction coefficient of the Mn-doped HgO films are also reported. The refractive index dispersion n(λ) is analyzed by single-effective-oscillator dispersion model proposed by the Wemple–DiDomenico (WDD). The oscillator parameters were estimated. The obtained dispersion values are suitable for the design of optoelectronic devices.     

A highly branched polythiourethane acrylate used for UV-curable high antireflection coatings

A series of highly branched polythiourethane acrylates (BPTUAs) were prepared through the double thiol-ene click reaction of thiol-endcapped difunctional thiourethane as an oligomer A₂ (Oligo-TU) with trimethylolpropane tri(thioglycolate ethylene glycol acrylate) (TMPTTA) as a trifunctional monomer B₃ in different ratios. The Oligo-TU was synthesized via the addition reactions of 2,4-toulene diisocyanate with 1,4-butanediol, and further with 4,4′-thiobisbenzenethiol. The TMPTTA was synthesized by the thiol-ene click reaction of trimethylolpropane tri(thioglycolate) (TMPTT) with an excess of ethylene glycol diacrylate. For comparison, a tetrafunctional thiourethane acrylate (TUA) was also synthesized. Finally, the obtained BPTUA and TUA were further modified with 2-mercaptobenzothiazole, 2-mercaptothiazoline and mercapto-5-methyl-thiadiazole, respectively, to form highly branched polyfunctional thiazole-based acrylates BPTUA-TAs and TUA-TAs. The molecular structures were confirmed by FT-IR and ¹H NMR analyses. The number average molecular weights and their polydispersity were determined by GPC spectroscopy. The UV irradiation using a medium pressure mercury lamp was applied to prepare the optical films in the presence of a photoinitiator. The refractive indices of UV-cured films were measured using a He-Ne laser at 632.8 nm. The results showed that both BPTUA and TUA films possess the similar refractive indices in the range of 1.592–1.604. However, the higher refractive indices in the range of 1.603–1.620 with BPTUA-TA films than 1.601–1.609 of TUA-TA films were obtained. All samples showed the high pencil hardness and impact resistance, as well good flexibility.     

Characterization of Optical Thin Films by Spectroscopic Ellipsometry

Spectroscopic ellipsometry was used to rapidly and nonde- structively characterize ion-plated SiO₂ and Ta₂O₅ films on glass substrates as a function of temperature. The analysis provided the density (as a function of depth) and optical properties of the films. The SiO₂ film had a higher refractive index than is typical for thermally grown SiO₂. This was attributed to compaction of the film during the deposition process. Similarly, the ion-plated Ta₂O₅ film had the high refractive index characteristic of a high-density film. The films were not affected strongly by temperature during heating >100°C.     

Towards facile fabrication of photonics components from inorganic and hybrid sol-gel films. Preparation and optical properties characterization

New trends towards development of integrated optics and miniaturization of photonic devices require fabrication of miniaturized photonic components. Fabrication of waveguiding films with designed optical properties is a fundamental process for production of planar integrated devices.We report here preparation of thin layers based on TiO₂ precursor (TET – titanium(IV) ethoxide) and SiO₂ precursors, namely inorganic (TEOS – tetraethyl orthosilicate) or organically modified (GLYMO ? 3-glycidoxypropyltrimethoxysilane) as candidates for potential application in the planar integrated circuits.The thin layers were deposited on soda-lime glass substrates using the sol-gel method and dip-coating technique and processed at relatively low temperature (up to 300 °C). Several parameters e.g. a) the type of SiO₂ precursor, b) the presence of complexing agent for TET and c) heat treatment temperature were tested for their influence on thickness and refractive index of the obtained films.Furthermore, a few series of sol-gel films activated with luminescent dye (Rhodamine B) was fabricated. The influence of the above-listed parameters on luminescent properties of the films was characterized because of lack of systematic study in the literature in this aspect. Moreover, a spectrum of the light at the output of a chosen luminescent dye-doped waveguiding film excited by laser source was investigated.In addition, the subject of our investigations were films prepared at 200 °C with various amounts of TET and organically modified SiO₂ precursor in concentration range not presented before. Their optical properties such as homogeneity and values of optical band gap of TiO₂ clusters were explored. For selected samples the waveguide properties including the optical losses were evaluated. For the first time, hybrid films with presented composition and refractive index in range of 1.59–1.71 were used for patterning by nanoimprint technique allowing for reproduction of periodic structures, which may serve for example as grating couplers or DFB (distributed feedback) resonators.     

Effect of doped niobium pentoxide on structure and properties of hafnium oxide films deposited by ion beam assisted deposition

Hafnium oxide is widely used in optical coating materials because of its high refractive index, broad band gap, high laser damage threshold and its high transparency in the wavelength range from ultraviolet to middle infrared (0.20–12 μm). However, hafnium oxide has some defects such as strong crystallinity and poor surface quality, which results in enhanced absorption and reflection of light wave and limits its application in optical field. As a pentoxide with high transparency and excellent optical properties in the wavelength range from ultraviolet to mid-infrared(0.35–9 μm), the doping of niobium pentoxide can effectively improve the surface quality and optical properties of the films. Mixed films with different chemical compositions were prepared by ion beam assisted deposition, and the microstructure, crystallinity, surface quality, optical properties and mechanical properties of the mixed films with different chemical compositions were investigated. The doping of niobium pentoxide inhibits the crystallization of hafnium oxide, optimizes the surface quality of the films, and improves the refractive index and mechanical properties of mixed films, effectively broadens the application of hafnium oxide in the field of optical films.     

高介电HfO_xN_y薄膜的制备及其光学性能研究

采用直流反应磁控溅射方法,在硅衬底制备了高介电HfOxNy薄膜。用椭偏仪研究了后期退火处理对薄膜光学性质的影响,结果表明,薄膜的折射率随退火温度的升高而增加,这主要是由于高温退火导致薄膜内部缺陷减少,使得薄膜松散的内部结构变得更加致密;薄膜的消光系数随退火温度的升高而降低,这是由于因为退火后薄膜内的缺陷减少。光学禁带宽度随退火温度的升高而增加,这是由于退火过程中薄膜中N含量的减少而导致。     

Characterization of antireflective coatings on poly(methyl methacrylate) substrate by different process parameters

The high/low refractive index organic/inorganic antireflective (AR) hybrid polymers were formed using the sol–gel process, in which TiO₂/2‐hydroxyethyl methacrylate (2‐HEMA) (high refractive index hybrid polymer) and SiO₂/2‐HEMA (low refractive index hybrid polymer) two‐layer thin films were formed on a hard coating deposited poly(methyl methacrylate) (HC‐PMMA) substrate by both spin coating and dip coating. The relationship between the process parameters and the optical properties, thickness, porosity, surface morphology, and adhesion was determined. The results show that the reflectance of the two‐layer thin films on HC‐PMMA substrate is less than 0.21% (λ = 550 nm), with good adhesion (5B) and a hardness of up to 4H. In addition, the thickness, porosity, and roughness of the films affect refractive index and the antireflection properties of the AR two‐layered thin film. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Optical dispersion analysis of template assisted 1D-ZnO nanorods for optoelectronic applications

Morphology and size play crucial influential roles in semiconductor nanotechnology. Capping agents have been adopted in this study for controlled fabrication of symmetrical zinc oxide (ZnO) nanostructures, with a preferred orientation and agglomeration inhibition. Elongated one-dimensional (1D) ZnO nanorods were successfully synthesised in a simple two-step process. X-ray diffraction (XRD) revealed high crystalline films with a preferred (002) plane orientation. Ethylene glycol (EG) surfactant was found to produce substantial effect on both the morphology and crystallinity as relatively small uniform nanorods with crocked ends were observed from morphological analysis. All the synthesised ZnO films depicted optical transmittance of over 50% in the visible range and a strong absorption peak in the UV proximity, at 380 nm. An evaluation of the optical parameters calculated from the measured transmittance indicated that surfactants can be used to modify the refractive index, real and imaginary dielectric constants of ZnO nanorods, to optimize the performance of optoelectronic devices.     

氮化硅薄膜生长随时间演化过程及其特性研究

氮化硅SiN_x薄膜凭借介电常数高和稳定性好的特点而被广泛应用于光电器件中,但薄膜的厚度对器件的性能有重要影响。针对此问题采用等离子体化学气相沉积技术,以高纯NH₃、N₂和SiH₄为反应气体,优化其他沉积参数,通过改变沉积时间来生长SiN_x薄膜。用X射线衍射谱(XRD),紫外-可见光光谱(UV-VIS)、傅里叶变换红外光谱(FTIR)和扫描电镜(SEM)对薄膜结构进行表征,详细研究了沉积时间与薄膜厚度的关系以及沉积时间对薄膜性能的影响。试验结果表明:所制备的样品为非晶SiN_x薄膜结构,薄膜厚度随沉积时间均匀增加;薄膜折射率随沉积时间的增加而增大,光学带隙基本不随时间变化。SEM测试结果表明,随着沉积时间增加,薄膜致密性与均匀性越来越好,氧含量也越来越少,说明薄膜致密性提高可以有效阻挡O原子进入薄膜,阻止后氧化现象的发生。     

Preparation and characterization of Al-doped ZnO piezoelectric thin films grown by pulsed laser deposition

Undoped and Al-doped ZnO (AZO) thin films (Al: 3, 5 at%) using a series of high quality ceramic targets have been deposited at 450 ºC onto glass substrates using PLD method. The used source was a KrF excimer laser (248 nm, 25 ns, 2 J/cm²). The study of the obtained thin films has been accomplished using X-ray diffraction (XRD), M-lines spectroscopy and Rutherford backscattering spectroscopy (RBS). XRD patterns have shown that the films crystallize in a hexagonal wurtzite type structure with a highly c-axis preferred (002) orientation, and the grain sizes decrease from 37 to 25 nm with increasing Al doping. The optical waveguiding properties of the films were characterized by means of the prism-coupling method. The distinct M-lines of the guided transverse magnetic (TM) and transverse electric (TE) modes of the ZnO films waveguide have been observed. The M-lines device has allowed determination of the accurate values of refractive index and thickness of the studied ZnO and AZO thin films. An evaluation of experimental uncertainty and calculation of the precision of the refractive index and thickness were developed on ZnO films. The RBS results agree with XRD and m-lines spectroscopy measurements.     

Optical properties,thermal stability,and forming region of high refractive index La2O3–TiO2–Nb2O5 glasses

The high refractive index La₂O₃–TiO₂–Nb₂O₅ glasses were prepared by containerless processing, and the glass‐forming region was determined. The refractive index showed the range from 2.20 to 2.32, and the values were much higher than those of most optical glasses. The completely miscible 30LaO_3/2–(70?x)TiO₂–xNbO_5/2 (0 ≤ x ≤70) system was fabricated to study the compositional dependence of refractive index and optical transmittance. The crucial determinants of the refractive index of oxide glasses, oxygen molar volume, and electronic polarizability of oxygen ions were calculated. The principle of additivity of glass properties was suitable for the calculation of refractive index between glass and compositional oxides. All the glasses were colorless and transparent in the visible to 6.5 μm middle infrared (MIR) region. These results are useful for designing new optical glasses with high refractive index and low wavelength dispersion in wide optical window.