UV-curable ZnS/polymer nanocomposite for replication of micron and submicron features

In view of the wide interest in high refractive index polymers for microreplication, study was made of UV-curable high refractive index nanocomposite material for microreplication purposes. The refractive index of the nanocomposite was tailored through the addition of surface-modified ZnS nanoparticles to commercial ORMOCOMP^® inorganic–organic hybrid polymer. The refractive index of ORMOCOMP^® was increased linearly from 1.514 (620 nm) to 1.645 (620 nm) by embedding of the nanoparticles (18.6 V%). The nanocomposite showed excellent transparency (T = 89–92%), and increase in the nanoparticle loading shifted the absorption edge from 380 nm to 420 nm. Low scattering of transmitted light (determined by UV–VIS–NIR spectrophotometry) and high dispersion of ZnS (determined by scanning electron microscopy with energy dispersive X-ray spectrometry and transmission electron microscopy) indicated low aggregation of the ZnS nanoparticles. Finally, the nanocomposite was applied to micromolding in capillaries to replicate micrometer-size channels (8 μm × 1.5 μm) with Bragg gratings (period 520 nm and depth 400 nm) on top of the channels. Based on the AFM results the MIMIC molding method was found to be suitable for the replication of microchannels into nanocomposite material.     

Characterization of photoactive polymer thin films using transmission spectrum

There are many different methods applied to obtain the optical constants of thin films using transmission spectrum, none of them applied to photoactive polymer thin films. The aim of this work is to find the suitable method for routine measurements of photoactive polymer thin films. In order to achieve this goal, different methods are applied to simulated thin films of known optical constants to compare their accuracies, hence choosing the most suitable method for studying the photoactive polymer thin films. It is found that the fitting methods are not suitable for photoactive polymer thin films while numerical solution of two independent transmission measurements is suitable for such films, so poly methy1 methacrylate (PMMA) films doped with different concentrations of photoactive unit Disperse Red 1 (DSR1) are characterized using this method. The refractive index of PMMA doped with 0.2% of DSR1 (1 g PMMA, 2 mg DSR1) is found to be 1.534 with error 0.656% at λ = 630 nm. It is also found that the refractive index of photoactive polymer thin films increases linearly with increasing photoactive unit up to concentration 0.25%.     

Third-order optical nonlinearities in anatase and rutile TiO2 thin films

Titanium dioxide (TiO₂) films have been fabricated on fused quartz and Si(001) substrates by pulsed laser deposition technique and the single-phase anatase and rutile films were obtained under the optimal conditions. The surface images and optical transmission spectra were investigated by scanning electron microscopy and double beam spectrophotometer, respectively. The values of optical band-gap and linear refractive index of the anatase and rutile films were determined. The optical nonlinearities of the films were measured by Z-scan method using a femtosecond laser (50 fs) at the wavelength of 800 nm. Through the open-aperture and closed-aperture Z-scan measurements, the real and imaginary parts of the third-order nonlinear optical susceptibility were calculated and the results show that the anatase phase TiO₂ films exhibit larger nonlinear refractive effects compared with rutile phase. The figure of merit, T, defined by T = βλ/n₂, was calculated to be 0.8 for anatase films, meeting the requirement of T < 1 and showing potential applications in all-optical switching devices.     

Overview about the optical properties and mechanical stress of different dielectric thin films produced by reactive-low-voltage-ion-plating

Thin films of Ta₂O₅, Nb₂O₅, and HfO₂ were deposited by reactive-low-voltage-ion-plating (RLVIP) on unheated glass and silicon substrates. The film thickness was about 200 nm. Optical properties as well as mechanical film stress of these layers were investigated in dependence of various deposition parameters, i.e. arc current and oxygen partial pressure. For an arc current in the range between 40 and 50 A and an oxygen partial pressure of at least 11 · 10^− 4 mbar good results were obtained. The refractive index and film thickness were calculated from spectrophotometric transmission data using the Swanepoel theory. For example at 550 nm wavelength the refractive index for thin RLVIP-Nb₂O₅-films was found to be n₅₅₀ = 2.40. The optical absorption was obtained by photo-thermal deflection spectrometry. For the investigated materials absorption coefficients in the range of k = 5 · 10^− 4 at 515 nm wavelength were measured. The mechanical film stress was determined by measuring the difference in bending of silicon substrates before and after the deposition process. For dense films, i.e. no water vapour sorption on atmosphere, the mechanical film stress was always compressive with values of some hundred MPa. In case of films deposited with higher arc currents (I_arc > 60A) and lower oxygen pressure (< 15 · 10^− 4 mbar) the influence of a post deposition heat treatment at 350 °C for 4 h on air was also investigated. For these films the properties could clearly be improved by such treatment. However, by using lower arc currents and higher oxygen partial pressure during the ion plating process, immediately dense and environmental stable films with good optical as well as mechanical properties could be achieved without post deposition heat treatment. All the results obtained will be presented in graphs and diagrams.     

Size-dependent optical and dielectric properties of nanocrystalline ZnS thin films synthesized via rf-magnetron sputtering technique

Nanocrystalline ZnS thin films have been synthesized by radio frequency magnetron sputtering technique on glass and Si substrates at a substrate temperature 300 K. X-ray diffraction and selected area electron diffraction studies confirmed the formation of nanocrystalline cubic phase of ZnS in the films, although the target material was hexagonal ZnS. The particle size, calculated from the XRD patterns of the thin films was found in the range 2.06-4.86 nm. TEM micrographs of the thin films revealed the manifestation of ZnS nanoparticles with sizes in the range 3.00-5.83 nm. UV-vis-NIR spectrophotometric measurements showed that the films were highly transparent (∼90%) in the wavelength range 400-2600 nm with a blue shift of the absorption edge. The direct allowed bandgaps have been calculated and they lie in the range 3.89-4.44 eV. The particle size, calculated from the shift of direct bandgap, due to quantum confinement effect lying in the range 3.23-5.60 nm, well support the TEM results. The room temperature photoluminescence spectra of the films showed two peaks centered around 315 and 450 nm. We assigned the first peak due to bandgap transitions while the latter was due to sulfur vacancy in the films. The composition analysis by energy dispersive X-rays also supported the existence of sulfur deficiency in the films. The dielectric property study showed high dielectric constant (85-100) at a higher frequency (>5 kHz).     

High refractive index films of ZnS/PVP nanocomposite by in situ thermolysis

A simple and rapid process for deposition of high refractive index films of ZnS/PVP nanocomposite (NC) is described. Precursor films are dip-coated on glass/quartz substrates from methanolic solution of polyvinylpyrrolidone (PVP) containing Zn⁺²–thiourea (TU) complex. ZnS/PVP nanocomposite films are produced by heating the solid precursor at 200°C for 10 min in air. Heat treatment converts the Zn⁺²–TU complex to ZnS by thermolysis in situ PVP. The transmission spectra of the films (typically 700 nm thickness) in the wavelength range of 200–1000 nm showed an absorption edge near 300 nm due to ZnS nanoparticles and high transmission of 97% beyond 400 nm. ZnS nanoparticles are uniformly dispersed in PVP matrix having sizes of about 3–4 nm. For ZnS loading of 45% by weight, the refractive index of ZnS/PVP is 1.65 which is in between that of PVP (1.48) and ZnS (2.36). Fourier Transform Infrared (FTIR) spectroscopy of the composite showed that there is a strong interaction between ZnS nanocrystals and PVP. The root mean square (RMS) roughness of the films is about 3 nm as determined by atomic force microscope (AFM).     

Deposition of silicon nitride thin films by hot-wire CVD at 100 °C and 250 °C

Silicon nitride thin films for use as passivation layers in solar cells and organic electronics or as gate dielectrics in thin-film transistors were deposited by the Hot-wire chemical vapor deposition technique at a high deposition rate (1-3 ?/s) and at low substrate temperature. Films were deposited using NH₃/SiH₄ flow rate ratios between 1 and 70 and substrate temperatures of 100 °C and 250 °C. For NH₃/SiH₄ ratios between 40 and 70, highly transparent (T ~ 90%), dense films (2.56-2.74 g/cm³) with good dielectric properties and refractive index between 1.93 and 2.08 were deposited on glass substrates. Etch rates in BHF of 2.7 ?/s and < 0.5 ?/s were obtained for films deposited at 100 °C and 250 °C, respectively. Films deposited at both substrate temperatures showed electrical conductivity ~ 10^− 14 Ω^− 1 cm^− 1 and breakdown fields > 10 MV cm^− 1.     

Poly (vinyl alcohol) thin film filled with CdSe–ZnS quantum dots: Fabrication,characterization and optical properties

A transparent poly (vinyl alcohol) (PVA) nanocomposite thin film (30–50 nm) reinforced with core/shell cadmium selenide (CdSe)/zinc sulfide (ZnS) quantum dots (QDs) was fabricated by a drop-casting method. A narrow peak at ～556 nm observed in the UV–vis spectrum indicates the uniformly dispersed QDs in the PVA matrix. FT-IR analysis indicates the interaction between the QDs and the polymer matrix. Both PVA and PVA-QDs nanocomposite thin films show polarized light dependent absorption properties with several different absorption peaks. As compared to the only fluorescent emission peak at 574 nm of QDs, the pure PVA and PVA-DDs nanocomposites show an excitation wavelength dependent fluorescent emission property.     

High-index low-loss gallium phosphide thin films fabricated by radio frequency magnetron sputtering

High-index low-loss Gallium Phosphide thin films for visible light have been produced by radio frequency magnetron sputtering in an argon environment. This broadens the high refractive index limit of transparent optical materials using a physical deposition process. Energy-dispersive x-ray analysis and spectroscopic ellipsometry were used to characterize the stoichiometry and optical properties. A post-deposition high-temperature anneal was found to be necessary to restore the proper stoichiometric ratio and to reduce the absorption. The annealing conditions were optimized by an in-situ fiber-optic transmission spectrum monitoring system. The films exhibit a high refractive index (N = 3.23) and a low extinction coefficient (K = 0.029) at 633 nm. Such high index GaP films have broad applications in nanophotonic device designs.     

Effect of substrate temperature on the optical parameters of thermally evaporated Ge-Se-Te thin films

Thin films of Ge₁₀Se_90 − xTe_x (x = 0, 10, 20, 30, 40, 50) glassy alloys were deposited at three substrate temperatures (303 K, 363 K and 423 K) using conventional thermal evaporation technique at base pressure of ~ 10^− 4 Pa. X-ray diffraction results show that films deposited at 303 K are of amorphous nature while films deposited at 363 K and 423 K are of polycrystalline nature. The optical parameters, refractive index and optical gap have been derived from the transmission spectra (using UV-Vis-NIR spectrophotometer) of the thin films in the spectral region 400-1500 nm. This has been observed that refractive index values remain almost constant while the optical gap is found to decrease considerably with the increase of substrate temperature. The decrease in optical gap is explained on the basis of change in nature of films, from amorphous to polycrystalline state, with the increase of substrate temperature. The optical gap has also been observed to decrease with the increase of Te content.     

Highly conductive and transparent carbon nanotube composite thin films deposited on polyethylene terephthalate solution dipping

In this letter we present highly conductive and transparent thin films of single-walled carbon nanotubes (SWCNT) and conductive polymer composite deposited on polyethylene terephthalate film substrates by solution dipping. The initial results show that 66 Ω/? sheet resistance can be achieved with 80% transmission at the wavelength of 550 nm. This result is much superior to the performances of the pure SWCNT thin films deposited using the same technique. The improvement is attributed to the increase of effective electric conductive tube-tube junctions in the CNT network.     

The effect of annealing on structural, electrical and optical properties of nanostructured ZnS/Ag/ZnS films

In this paper a ZnS/Ag/ZnS (ZAZ) nano-multilayer structure is designed theoretically and optimum thicknesses of ZnS and Ag layers are calculated at 35 and 17 nm, respectively. Several conductive transparent ZAZ nano-multilayer films are deposited on a glass substrate at room temperature by thermal evaporation method. Changes in the electrical, structural, and optical properties of samples are investigated with respect to annealing in air at different temperatures. High-quality nano-multilayer films with the sheet resistance of 8 Ω/sq and the optical transmittance of 83% at 200 °C annealing temperature are obtained. The figure of merit is applied on the ZAZ films and their performance as transparent conductive electrodes are determined.     

Low-temperature processing of transparent conductive indium tin oxide nanocomposites using polyvinyl derivatives

We report on the influence of additives on the electrical, optical, morphological and mechanical properties of transparent conductive indium tin oxide (In₂O₃:Sn; ITO) nanoparticle films by the use of polymers as matrix material. Key issues to fabricate layers suitable for use in electronic device applications are presented. Polyvinyl derivatives polyvinyl acetate, polyvinyl alcohol (PVA) and polyvinyl butyral were applied and their suitability to form transparent conductive ITO nanocomposite coatings at a maximum process temperature of 130 °C was investigated. A low-temperature treatment with UV-light has been developed to provide the possibility of curing ITO thin films deposited on substrates which do not withstand high process temperatures. Compared to best pure ITO layers (0.2 Ω^− 1 cm^− 1), the ITO-PVA nanocomposite coatings show a conductance value of 4.1 Ω^− 1 cm^− 1 and 5.9 Ω^− 1 cm^− 1 after reducing in forming gas. Sheet resistance of ca. 1200 Ω/□ with coexistent transmittance of 85% at 550 nm for a layer thickness of about 1.45 μm was achieved. The conductance enhancement is a consequence of nanoparticulate ITO network densification due to the acting shrinkage forces caused by the polymer matrix during film drying and additionally UV-induced crosslinking of PVA.     

Characterization of (Al, Si)N films deposited by balanced magnetron sputtering

Hard and transparent nanocomposite (Al, Si)N films are attractive for optical applications. In this paper, experimental results will be reported on nanocomposite (Al, Si)N films prepared by balanced magnetron sputtering. Microstructure and properties of the films were systematically characterized as a function of Si content of the films. It is shown that the (Al, Si)N films are transparent and exhibit no absorption in a wide range of wavelengths from ~ 0.3 to ~ 9 µm, i.e. from ultraviolet to mid-infrared region. Maximum hardness exceeding 25 GPa has been obtained when the Si content of the films is above 25 at.% and the microstructure of the films undergoes a transformation from nanocrystalline to amorphous states. It is demonstrated that the microstructure detail of the films is different, as compared with that of the films prepared by using unbalanced magnetron sputtering, and the reasons for this discrepancy is discussed.     

Thermally stable transparent conducting and highly infrared reflective Ga-doped ZnO thin films by metal organic chemical vapor deposition

Highly transparent conductive Ga-doped ZnO (GZO) thin films have been prepared on glass substrates by metal organic chemical vapor deposition. The effect of Ga doping on the structural, electrical and optical properties of GZO films has been systematically investigated. Under the optimum Ga doping concentration (∼4.9 at.%), c-axis textured GZO film with the lowest resistivity of 3.6 × 10⁻⁴ Ω cm and high visible transmittance of 90% has been achieved. The film also exhibits low transmittance (<1% at 2500 nm) and high reflectance (>70% at 2500 nm) to the infrared radiation. Furthermore, our developed GZO thin film can well retain the highly transparent conductive performance in oxidation ambient at elevated temperature (up to 500 °C).     

Preparation and properties of cross-linked zirconia nanoparticle films on polycarbonate

Highly-crystalline zirconia (ZrO₂) nanoparticle was functionalized with 3-(N-aminoethyl) aminopropyltrimethoxysilane (AAPTMS) and dispersed in water at primary particle size level under basic condition (pH 13-14). The aqueous ZrO₂ nanoparticle dispersion was cast on a polycarbonate substrate with 1,4-butanediol digylcidyl ether as a cross-linker. Nanoparticle films with as high as 81 wt.% of ZrO₂ were obtained through heating the cast dispersion at 120 °C, which are highly transparent. The refractive index ranges from 1.70 to 1.77 at wavelength of 632 nm with the decrease of the amount of AAPTMS attached to ZrO₂ nanoparticles. Nanoindentation tests show that the hardness of the film reaches 1.7 GPa. In addition, both punched tape abrasion and nanoscratch tests reveal that the films exhibit prominent scratch resistant performance.     

Optical properties of swift ion beam irradiated CdTe thin films

This paper reports the effect of swift (80 MeV) oxygen (O⁺⁶) ion irradiation on the optical properties of CdTe thin films grown by conventional thermal evaporation on glass substrates. The films are found to be slightly Te-rich in composition and irradiation results no change in the elemental composition. The optical constants such as refractive index (n), absorption coefficient (α) and the optical band gap energy show significant variation in their values with increase in ion fluence. Upon irradiation the band gap energy decreased from a value of 1.53 eV to 1.46 eV whereas the refractive index (n) increased from 2.38 to 3.12 at λ = 850 nm. The photoluminescence spectrum shows high density of native defects whose density strongly depends on the ion fluence. Both analyses indicate considerable defect production after swift ion beam irradiation.     

Fabrication of conducting poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) thin films by ultrasonic spray-assisted mist deposition method

Transparent conducting polymer, poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) thin films were fabricated by a vapor-deposition technique, ultrasonic spray-assisted mist deposition method. The thickness was well controlled from 40 to 600 nm, keeping reasonable conductivity of 300-450 S/cm. The films with thickness less than 180 nm have high (> 80%) transmission over a wide (270-800 nm) spectral region. In addition, formation of ring-dot electrode pattern with a hard-mask was demonstrated, achieving lithography-less patterning. The results encourage that this deposition method is developed as an actual process technology of transparent electrodes in devices.     

The effect of nitrogen on the properties of zinc nitride thin films and their conversion into p-ZnO:N films

Zinc nitride thin films were deposited by magnetron sputtering using ZnN target in plasma containing either N₂ or Ar gases. The rf-power was 100 W and the pressure was 5 mTorr. The properties of the films were examined with thermal treatments up to 550 °C in N₂ and O₂ environments. Films deposited in Ar plasma were opaque and conductive (ρ ∼ 10^− 1 to 10^− 2 Ω cm, N_D ∼ 10¹⁸ to 10²⁰ cm^− 3) due to excess of Zn in the structure. After annealing at 400 °C, the films became more stoichiometric, Zn₃N₂, and transparent, but further annealing up to 550 °C deteriorated the electrical properties. Films deposited in N₂ plasma were transparent but very resistive even after annealing. Both types of films were converted into p-type ZnO upon oxidation at 400 °C. All thermally treated zinc nitride films exhibited a shoulder in transmittance at around 345 nm which was more profound for the Ar-deposited films and particularly for the oxidized films. Zinc nitride has been found to be a wide band gap material which makes it a potential candidate for transparent optoelectronic devices.     

Effect of tellurium addition on the optical and physical properties of germanium selenide glassy semiconductors

Thin films of the glasses Ge₁₀ Se_90−x Te_x (0 ≤ x ≥ 40) have been prepared by melt quenching technique; thin films were evaporated at a pressure of ≈10⁻⁴ Pa. The optical absorption behavior of these thin films was studied from the reflection and transmission spectrum in the spectral range 200-1200 nm. The optical constants i.e optical band gap (E_opt), absorption coefficient, refractive index (n) are calculated. The optical band gap has been estimated using Tauc extrapolation and found to decrease with Te content. The Dispersion of refractive index has been studied in terms of Wemple - Di Domenico model. The value of static refraction index has been found to increase with Te content. The distribution of the possible chemical bonds has been calculated. The obtained results were correlated with the character of the chemical bond for the prepared compositions through a study of parameters such as average heat of atomization (Hs), the cohesive energies of the bonds (CE), The mean bond energy <E> and average coordination number (m).