Fabrication and characterization of plasma polymer thin films from monoterpene alcohols for applications in organic electronics and biotechnology

After more than twenty years of basic and applied research, the use of nanotechnology in the design and manufacture of nanoscale materials is rapidly increasing, particularly in commercial applications that span from electronics across renewable energy areas, and biomedical devices. Novel polymers are attracting significant attention for they promise to provide a low−cost high−performance alternative to existing materials. Furthermore, these polymers have the potential to overcome limitations imposed by currently available materials thus enabling the development of new technologies and applications that are currently beyond our reach. This work focuses on the development of a range of new low−cost environmentally−friendly polymer materials for applications in areas of organic (flexible) electronics, optics, and biomaterials. The choice of the monomer reflects the environmentally−conscious focus of this project. Terpinen−4−ol is a major constituent of Australian grown Melaleuca alternifolia (tea tree) oil, attributed with the oil's antimicrobial and anti−inflammatory properties. Plasma polymerisation was chosen as a deposition technique for it requires minimal use of harmful chemicals and produces no hazardous by−products. Polymer thin films were fabricated under varied process conditions to attain materials with distinct physico−chemical, optoelectrical, biological and degradation characteristics. The resultant materials, named polyterpenol, were extensively characterised using a number of well−accepted and novel techniques, and their fundamental properties were defined. Polyterpenol films were demonstrated to be hydrocarbon rich, with variable content of oxygen moieties, primarily in the form of hydroxyl and carboxyl functionalities. The level of preservation of original monomer functionality was shown to be strongly dependent on the deposition energy, with higher applied power increasing the molecular fragmentation and substrate temperature. Polyterpenol water contact angle contact angle increased from 62.7° for the 10 W samples to 76.3° for the films deposited at 100 W. Polymers were determined to resist solubilisation by water, due to the extensive intermolecular and intramolecular hydrogen bonds present, and other solvents commonly employed in electronics and biomedical processing. Independent of deposition power, the surface topography of the polymers was shown to be smooth (Rq <0.5 nm), uniform and defect free. Hardness of polyterpenol coatings increased from 0.33 GPa for 10 W to 0.51 GPa for 100 W (at 500 μN load). Coatings deposited at higher input RF powers showed less mechanical deformation during nanoscratch testing, with no considerable damage, cracking or delamination observed. Independent of the substrate, the quality of film adhesion improved with RF power, suggesting these coatings are likely to be more stable and less susceptible to wear. Independent of fabrication conditions, polyterpenol thin films were optically transparent, with refractive index approximating that of glass. Refractive index increased slightly with deposition power, from 1.54 (10 W) to 1.56 (100 W) at 500 nm. The optical band gap values declined with increasing power, from 2.95 eV to 2.64 eV, placing the material within the range for semiconductors. Introduction of iodine impurity reduced the band gap of polyterpenol, from 2.8 eV to 1.64 eV, by extending the density of states more into the visible region of the electromagnetic spectrum. Doping decreased the transparency and increased the refractive index from 1.54 to 1.70 (at 500 nm). At optical frequencies, the real part of permittivity (k) was determined to be between 2.34 and 2.65, indicating a potential low-k material. These permittivity values were confirmed at microwave frequencies, where permittivity increased with input RF energy – from 2.32 to 2.53 (at 10 GHz ) and from 2.65 to 2.83 (at 20 GHz). At low frequencies, the dielectric constant was determined from current−voltage characteristics of Al−polyterpenol−Al devices. At frequencies below 100 kHz, the dielectric constant varied with RF power, from 3.86 to 4.42 at 1 kHz. For all samples, the resistivity was in order of 10⁸−10⁹ _m (at 6 V), confirming the insulating nature of polyterpenol material. In situ iodine doping was demonstrated to increase the conductivity of polyterpenol, from 5.05 × 10⁻⁸ S/cm to 1.20 × 10⁻⁶ S/cm (at 20 V). Exposed to ambient conditions over extended period of time, polyterpenol thin films were demonstrated to be optically, physically and chemically stable. The bulk of ageing occurred within first 150 h after deposition and was attributed to oxidation and volumetric relaxation. Thermal ageing studies indicated thermal stability increased for the films manufactured at higher RF powers, with degradation onset temperature associated with weight loss shifting from 150 ºC to 205 ºC for 10 W and 100 W polyterpenol, respectively. Annealing the films to 405 °C resulted in full dissociation of the polymer, with minimal residue. Given the outcomes of the fundamental characterisation, a number of potential applications for polyterpenol have been identified. Flexibility, tunable permittivity and loss tangent properties of polyterpenol suggest the material can be used as an insulating layer in plastic electronics. Implementation of polyterpenol as a surface modification of the gate insulator in pentacene-based Field Effect Transistor resulted in significant improvements, shifting the threshold voltage from + 20 V to –3 V, enhancing the effective mobility from 0.012 to 0.021 cm²/Vs, and improving the switching property of the device from 10⁷ to 10⁴. Polyterpenol was demonstrated to have a hole transport electron blocking property, with potential applications in many organic devices, such as organic light emitting diodes. Encapsulation of biomedical devices is also proposed, given that under favourable conditions, the original chemical and biological functionality of terpinen−4−ol molecule can be preserved. Films deposited at low RF power were shown to successfully prevent adhesion and retention of several important human pathogens, including P. aeruginosa, S. aureus, and S. epidermidis, whereas films deposited at higher RF power promoted bacterial cell adhesion and biofilm formation. Preliminary investigations into in vitro biocompatibility of polyterpenol demonstrated the coating to be non−toxic for several types of eukaryotic cells, including Balb/c mice macrophage and human monocyte type (HTP−1 non-adherent) cells. Applied to magnesium substrates, polyterpenol encapsulating layer significantly slowed down in vitro biodegradation of the metal, thus increasing the viability and growth of HTP−1 cells. Recently, applied to varied nanostructured titanium surfaces, polyterpenol thin films successfully reduced attachment, growth, and viability of P. aeruginosa and S. aureus.

Hydrothermal synthesis and characterization of CaSO4 pseudomicrorods

Calcium sulphate (CaSO4) pseudomicrorods have been synthesized by alow-temperature hydrothermal method using CaSO4 powder as a precursor and hexadecylamine as a surfactant at 180 degrees C for at different intervals of time. The powder X-ray diffraction pattern indicates that the as-formed pseudomicrorods are of orthorhombic phase with lattice parameters a = 7.0023(4) angstrom, b = 6.9939(5) angstrom and c = 6.2434(4) angstrom. Scanning electron microscopy images show that the pseudomicrorods have diameters of about 0.2-2.5 mm and lengths of about 2-10 mm. Fourier transform infrared spectroscopy shows a strong doublet near 609 and 681 cm(-1) arising from nu(4) (SO42) bending vibrations. The strongest band observed at 1132 cm(-1) is associated with nu(3) (SO42-) stretching vibrations. The band near 420-450 cm(-1) is attributed to nu(2) (SO42-) bending vibrations. The Raman spectrum exhibits an intense peak at 1008 cm(-1) associated with the SO42- mode. The photoluminescence spectrum exhibits UV bands (330, 350 nm), strong green bands (402, 436 nm) and weak blue bands (503 nm). A widening of the optical band gap was observed as the particle size decreased.

Synthesis and Characterization of a Class of Donor-Acceptor Conjugated Molecules: Experiments and Theoretical Calculations

A class of conjugated molecules containing donor (thiophene) and acceptor (malononitrile) is synthesized by Knoevenagel condensation reaction between 2-(2,6-dimethy1-4H-pyran-4-ylidene) malononitrile and thiophene carbaldehyde containing two and three thiophene units. The resulting molecules are characterized by H-1 and C-13 NMR. We have performed UV-vis absorption, fluorescence, and cyclic voltammetry measurements on these materials. The spectroscopic and electrochemical measurements proved beyond doubt that these materials possess lowexcitation gap and are suitable for being an active material in various electronic devices. We have also performed electronic structure calculations using density functional theory (DFT) and INDO/SCI methods to characterize the ground and excited states of this class of molecules. These donor-acceptor molecules show a strong charge transfercharacter that increases with the increase in the number of thiophene rings coupled to the malononitrile acceptor moiety. We have also calculated the pi-coherence length, Stoke's shift, and effect of solvents on excited states for this class of molecules, Our theoretical values agree well with experimental results.

A silicon micromachined photonic band gap cell, characteristics and an application

A novel PBG cell based on micromachining of Silicon using wet anisotropic etching has been considered. Since this is based on etching of the Silicon substrate, it is amenable to fabrication with standard Silicon processes and integration with millimeter wave circuits. We characterize this kind of PBG cell by full wave simulations using a time domain code. For the purpose of characterization, the scenario of a 50 ohm microstrip line placed on a Silicon substrate which is anisotropically etched to create patterns with sloping walls is considered. This is shown to produce the well known PBG response of stop bands in certain frequency bands. We look at the variation in the transmission coefficient (S-21) response as the number of periods, length based average fill factor and depth of micromachining are varied. One application of a low pass filter has been proposed and simulated results are given.

Synthesis,characterization and photoluminescence properties of CaSiO3 :Dy3+ nanophosphors

CaSiO3 : Dy3+ (1-5 mol. %) nanophosphors were synthesized by a simple low-temperature solution combustion method. Powder X-ray diffraction patterns revealed that the phosphors are crystalline and can be indexed to a monoclinic phase. Scanning electron micrographs exhibited faceted plates and angular crystals of different sizes with a porous nature. Photoluminescence properties of the Dy3+-doped CaSiO3 phosphors were observed and analyzed. Emission peaks at 483, 573 and 610 nm corresponding to Dy3+ were assigned as F-4(9/2)-> H-6(15/2), F-4(9/2) -> H-6(13/2) and F-4(9/2) -> H-6(11/2) transitions, respectively, and dominated by the Dy3+ F-4(9/2) -> H-6(13/2) hyperfine transition. Experimental results revealed that the luminescence intensity was affected by both heat treatment and the concentration of Dy3+ (1-5 mol. %) in the CaSiO3 host. Optimal luminescence conditions were achieved when the concentration of Dy3+ was 2 mol. %. UV-visible absorption features an intense band at 240 nm, which corresponds to an O-Si ligand-to-metal charge transfer band in the SiO32- group. The optical energy band gap for the undoped sample was found to be 5.45 eV, whereas in Dy3+-doped phosphors it varies in the range 5.49-5.65 eV. The optical energy gap widens with increase of Dy3+ ion dopant.

Synthesis, characterization and photoluminescence properties of Gd2O3:Eu3+ nanophosphors prepared by solution combustion method

Gd2O3:Eu3+ (0.5-8.0 mol%) nanophosphors have been prepared by low temperature solution combustion method using metal nitrates as oxidizers and oxalyl dihydrazide (ODH) as a fuel. The phosphors are well characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and photoluminescence (PL) techniques. PXRD patterns of as-formed and calcined (800 degrees C, 3 h) Gd2O3 powders exhibit monoclinic phase with mean crystallite sizes ranging from 20 to 50 nm. Eu3+ doping changes the structure from monoclinic to mixed phase of monoclinic and cubic. SEM micrographs shows the products are foamy, agglomerated and fluffy in nature due to the large amount of gases liberated during combustion reaction. Upon 254 nm excitation the photoluminescence of the Gd2O3:Eu3+ particles show red emission at 611 nm corresponding to D-5(0)-> F-7(2) transition. It is observed that PL intensity increases with calcination temperature. This might be attributed to better crystallization and eliminates the defects, which serve as centers of non-radiative relaxation for nanomaterials. It is observed that the optical energy gap (E-g) is widened with increase Eu3+ content. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis, characterization and photoluminescence properties of CaSiO3: Eu3+ red phosphor

CaSiO3:Eu3+ (1-5 mol%) red emitting phosphors have been synthesized by a low-temperature solution combustion method. The phosphors have been well characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and optical spectroscopy. PXRD patterns reveal monoclinic CaSiO3 phase can be obtained at 900 degrees C. The SEM micrographs show the crystallites with irregular shape, mostly angular. Upon 254 nm excitation, the phosphor show characteristic fluorescence D-5(0) -> F-7(J) (J = 0, 1, 2, 3, 4) of the Eu3+ ions. The electronic transition located at 614 nm corresponding to D-5(0) -> F-7(2) of Eu3+ ions, which is stronger than the magnetic dipole transition located at 593 nm corresponding to D-5(0) -> F-7(1) of Eu3+ ions. Different pathways involved in emission process have been studied. Concentration quenching has been observed for Eu3+ concentration >4 mol%. UV-visible absorption shows an intense band at 240 nm in undoped and 270 nm in Eu3+ doped CaSiO3 which is attributed to oxygen to silicon (O-Si) ligand-to-metal charge-transfer (LMCT) band in the SiO32- group. The optical energy band gap is widened with increase of Eu3+ ion dopant. (C) 2010 Elsevier B.V. All rights reserved.

Ultrasonic spray pyrolysis of CZTS solar cell absorber layers and characterization studies

CZTS (Copper Zinc Tin Sulphide) is a wide band gap quartnery chalcopyrite which has a band gap of about 1.45 eV and an absorption coefficient of 10(4) cm(-1); thus making it an ideal material to be used as an absorber layer in solar cells. Ultrasonic Spray Pyrolysis is a deposition technique, where the solution is atomized ultrasonically, thereby giving a fine mist having a narrow size distribution which can be used for uniform coatings on substrates. An Ultrasonic Spray Pyrolysis equipment was developed and CZTS absorber layers were successfully grown with this technique on soda lime glass substrates using aqueous solutions. Substrate temperatures ranging from 523 K to 723 K were used to deposit the CZTS layers and these films were characterized using SEM, EDAX and XRD. It was observed that the film crystallized in the kesterite structure and the best crystallites were obtained at 613 K. It was observed that the grain size progressively increased with temperature. The optical band gap of the material was obtained as 1.54 eV.

Electrical characterization of surface defects in GaSb created by hydrogen plasma

Using steady state and transient capacitance measurements, the electrical characteristics of a defect layer on the surface of bulk GaSb created during the hydrogen plasma treatment is presented. The trap density, activation energies, and the thickness of the defect layer have been calculated. The trap densities are comparable in magnitude to the carrier concentration. The defects introduce multiple energy levels in the band gap. Typical defect layer thicknesses range from a few angstroms to a fraction of a micron. © 1995 American Institute of Physics.

Combustion synthesis, characterization and Raman studies of ZnO nanopowders

Spherical shaped ZnO nanopowders (14-50 nm) were synthesized by a low temperature solution combustion method in a short time <5 min. Rietveld analysis show that ZnO has hexagonal wurtzite structure with lattice constants a = 3.2511(1) angstrom, c = 5.2076(2) angstrom, unit cell volume (V) = 47.66(5) (angstrom)(3) and belongs to space group P63mc. SEM micrographs reveal that the particles are spherical in shape and the powders contained several voids and pores. TEM results also confirm spherical shape, with average particle size of 14-50 nm. The values are consistent with the grain sizes measured from Scherrer's method and Williamson-Hall (W-H) plots. A broad UV-vis absorption spectrum was observed at similar to 375 nm which is a characteristic band for the wurtzite hexagonal pure ZnO. The optical energy band gap of 3.24 eV was observed for nanopowder which is slightly lower than that of the bulk ZnO (3.37 eV). The observed Raman peaks at 438 and 588 cm(-1) were attributed to the E(2) (high) and E(1) (LO) modes respectively. The broad band at 564 cm(-1) is due to disorder-activated Raman scattering for the A(1) mode. These bands are associated with the first-order Raman active modes of the ZnO phase. The weak bands observed in the range 750-1000 cm(-1) are due to small defects. (C) 2011 Elsevier B.V. All rights reserved.

Optical, electrical and structural characterization of ZnO:Al thin films prepared by a low cost sol-gel method

ZnO:Al thin films were prepared on glass and silicon substrates by the sol-gel spin coating method. The x-ray diffraction (XRD) results showed that a polycrystalline phase with a hexagonal structure appeared after annealing at 400 degrees C for 1 h. The transmittance increased from 91 to about 93% from pure ZnO films to ZnO film doped with 1 wt% Al and then decreased for 2 wt% Al. The optical band gap energy increased as the doping concentration was increased from 0.5 wt% to 1 wt% Al. The metal oxide semiconductor (MOS) capacitors were fabricated using ZnO films deposited on silicon (100) substrates and electrical properties such as current versus voltage (I-V) and capacitance versus voltage (C-V) characteristics were studied. The electrical resistivity decreased and the leakage current increased with an increase of annealing temperature. The dielectric constant was found to be 3.12 measured at 1 MHz. The dissipation value for the film annealed at 300 degrees C was found to be 3.1 at 5 V. (C) 2011 Elsevier Ltd. All rights reserved.

Structural characterization, EPR and thermoluminescence properties of Cd-1 (-) xNixSiO3 nanocrystalline phosphors

Cd-1 - xNixSiO3 (x = 1-7 mol%) nanophosphors have been prepared for the first time by the combustion method using oxylyldihydrizide as a fuel. Powder X-ray diffraction results confirm the formation of monoclinic phase. Scanning electron micrographs show that Ni2+ influences the porosity of samples. The optical energy gap is widened with increase of Ni2+ ion dopant. The electron paramagnetic resonance spectrum of Ni2+ ions in CdSiO3 exhibits a symmetric absorption at g = 2.343 and the site symmetry around Ni2+ ions is predominantly octahedral. The number of spins participating in resonance (N) and the paramagnetic susceptibility (chi) has been evaluated. The thermoluminescence intensity is found to increase up to similar to 20 min ultra-violet exposure and thereafter, decrease with further increase of ultra-violet dose. The kinetic parameters such as activation energy (E), frequency factor (s)and order of kinetics was estimated using glow peak shape method and the results are discussed. (c) 2012 Elsevier Ltd. All rights reserved.

CdSiO3:Pr3+ nanophosphor: Synthesis, characterization and thermoluminescence studies

A series of Pr3+ (1-9 mol%) doped CdSiO3 nanophosphors have been prepared for the first time by a low temperature solution combustion method using oxalyldihydrizide (ODH) as a fuel. The final product was characterized by Powder X-ray diffraction (PXRD), Fourier Transform Infrared Spectroscopy (FTIR), scanning electron microscopy (SEM), and UV-Vis spectroscopy. The average crystallite size was calculated using Debye-Scherrer's formula and Williamson-Hall (W-H) plots and found to be in the range 31-37 nm. The optical energy band gap (E-g) of undoped for Pr3+ doped samples were estimated from Tauc relation which varies from 5.15-5.36 eV. Thermoluminescence (TL) properties of Pr3+ doped CdSiO3 nanophosphor has been investigated using gamma-irradiation in the dose range 1-6 kGy at a heating rate of 5 degrees C s(-1). The phosphor shows a well resolved glow peak at similar to 171 degrees C along with shouldered peak at 223 degrees C in the higher temperature side. It is observed that TL intensity increase with increase of Pr3+ concentration. Further, the TL intensity at 171 degrees C is found to be increase linearly with increase in gamma-dose which is highly useful in radiation dosimetry. The kinetic parameters such as activation energy (E), frequency factor (s) and order of kinetics was estimated by Luschiks method and the results are discussed. (c) 2012 Elsevier B.V. All rights reserved.

Deposition and characterization of pure and Cd doped SnO2 thin films by the nebulizer spray pyrolysis (NSP) technique

Pure and cadmium doped tin oxide thin films were deposited on glass substrates from aqueous solution of cadmium acetate, tin (IV) chloride and sodium hydroxide by the nebulizer spray pyrolysis (NSP) technique. X-ray diffraction reveals that all films have tetragonal crystalline structure with preferential orientation along (200) plane. On application of the Scherrer formula, it is found that the maximum size of grains is 67 nm. Scanning electron microscopy shows that the grains are of rod and spherical in shape. Energy dispersive X-ray analysis reveals the average ratio of the atomic percentage of pure and Cd doped SnO2 films. The electrical resistivity is found to be 10(2) Omega cm at higher temperature (170 degrees C) and 10(3) Omega cm at lower temperature (30 degrees C). Optical band gap energy was determined from transmittance and absorbance data obtained from UV-vis spectra. Optical studies reveal that the band gap energy decreases from 3.90 eV to 3.52 eV due to the addition of Cd as dopant with different concentrations.

Fabrication and characterization of sub 100 nm period polymer gratings for photonics applications

We report on the fabrication of polymethylmethacrylate (PMMA) nanogratings on silicon (Si) and glass substrates using electron beam lithography technique. Various aspects of proximity corrections using Monte Carlo simulation have been discussed. The fabrication process parameters such as proximity gap of exposure, exposure dosage and developing conditions have been optimized for high-density PMMA nanogratings structure on Si and glass substrates. Electron beam exposure is adjusted in such a way that PMMA acts as a negative tone resist and at the same time resolution loss due to proximity effect is minimum. Both reflection and transmission-type, nanometre period gratings have been fabricated and their diffraction characteristics are evaluated.