Synthesis and characterization of HfO2 and ZrO2 thin films deposited by plasma assisted reactive pulsed laser deposition at low temperature

A plasma assisted reactive pulsed laser deposition process was demonstrated for low-temperature deposition of thin hafnia (HfO₂) and zirconia (ZrO₂) films from metallic hafnium or zirconium with assistance of an oxygen plasma generated by electron cyclotron resonance microwave discharge. The structure and the interface of the deposited films on silicon were characterized by means of Fourier transform infrared spectroscopy, which reveals the monoclinic phases of HfO₂ and ZrO₂ in the films with no interfacial SiO_x layer between the oxide film and the Si substrate. The optical properties of the deposited films were investigated by measuring the refractive indexes and extinction coefficients with the aid of spectroscopic ellipsometry technique. The films deposited on fused silica plates show excellent transparency from the ultraviolet to near infrared with sharp ultraviolet absorption edges corresponding to direct band gap.     

Crystal structure and optical absorption investigations on β-In2S3 thin films

The crystal structure of annealed β-In₂S₃ thin films with different thickness was investigated by X-ray diffraction technique. Lattice parameters, crystallite size and microstrain were calculated. It was found that the lattice parameters are independent on film thickness, while annealing temperatures increase them. Crystallite sizes were increased with the increase of the film thickness and improved by annealing temperatures. In all cases, the microstrains were decreased gradually with the increase in both film thickness and annealing temperatures. Optical properties of β-In₂S₃ thin films were performed in the spectral range from 400 to 2500 nm to determine the optical constants (n and k), the high frequency dielectric constant, ε_∞, the lattice dielectric constant, ε_L, and the energy gap. The optical constants were found to be independent on film thickness in the range from 200 to 630 nm. The high frequency dielectric and lattice dielectric constants of the as-deposited film increased by annealing temperatures. The energy gap for the as-deposited In₂S₃ was found to be 2.60 eV and increased to 2.70 and 2.75 eV by annealing at 423 and 473 K for 1 h, respectively.     

Structural characterization and frequency response of sol–gel derived Bi3/2MgNb3/2O7 thin films

The Bi_3/2MgNb_3/2O₇ (BMN) thin films were prepared via a modified sol–gel process on glass substrates at various post-annealing temperatures. The crystalline structure, morphology and frequency response have been investigated systematically. The X-ray diffraction results indicated that the BMN thin films had different orientations depending on post-annealing temperature. Thin films annealed above 650 °C presented well crystallized cubic pyrochlore structure with (222) orientation, and (400) preferentially oriented were observed when they were annealed below 600 °C. The surface morphology images of the BMN thin films revealed different grain size and grain size distribution, and the average grain size increased from 28.3 to 37.0 nm as the post-annealing temperature increasing. The low frequency dielectric properties of the BMN thin films were closely correlated with the (222) orientation, which was favorable to enhanced dielectric constant and tunability. The high-frequency optical measurements revealed an average transmittance (T _av ) varying between 76.6 and 82.2 % and band gap energy (E _g ) ranging from 3.40 to 3.44 as a function of the temperature and the crystallite size. Thin film annealed at 700 °C possessed the best crystallinity and highest (222) orientation, and showed the best electrical properties, with a dielectric constant of 105 at 1 MHz, dielectric tunability of 25.8 %, and an average optical transmittance of 82.2 % in the visible range (400–800 nm), making it promising for optical/electronic tunable devices applications.     

Influence of the film thickness on structural and optical properties of CdTe thin films electrodeposited on stainless steel substrates

CdTe thin films of different thicknesses were deposited by electrodeposition on stainless steel substrates (SS). The dependence of structural and optical properties on film thickness was evaluated for thicknesses in the range 0.17–1.5 μm. When the film is very thin the crystallites lack preferred orientation, however, thicker films showed preference for (111) plane. The results show that structural parameters such as crystallite size, lattice constant, dislocation density and strain show a noticeable dependence on film thickness, however, the variation is significant only when the film thickness is below 0.8 μm. The films were successfully transferred on to glass substrates for optical studies. Optical parameter such as absorption coefficient (α), band gap (E_g), refractive index (n), extinction coefficient (k_e), real (?_r) and imaginary (?_i) parts of the dielectric constant were studied. The results indicate that all the optical parameters strongly depend on film thickness.     

Colloidal synthesis of Gd<Superscript>3+</Superscript> doped ZrO<Subscript>2</Subscript> based dielectrics and their structural and electrochemical property studies

Solution processed wide band gap dielectrics have nowadays started to receive renewed interest for practical application in semiconductor electronics. In this regard, undoped and gadolinium (Gd) doped zirconia (ZrO₂) nanocrystallites were colloidally processed and their potential for dielectric applications has been demonstrated. X-ray diffraction measurements revealed the effective crystallization of nanostructures and the successful substitution of Gd ions into the cubic ZrO₂ matrix. The particulate-like characteristics of undoped and Gd doped ZrO₂ nanostructures were examined through the electron microscopes, which hardly revealed any difference among them. The optical band gap of ZrO₂ nanostructures was determined to be around 4.64–4.80 eV from the absorbance measurements. The potential of Gd doped ZrO₂ nanostructures for dielectric functions were evaluated through electrochemical impedance spectroscopic measurements. The improved capacitance values estimated from the Nyquist plots suggests the potential of the investigated materials for low power and low voltage electronic applications.     

The chemical vapour deposition and characterization of ZrO2 films from organometallic compounds

ZrO₂ films were deposited on silicon substrates by oxygen-assisted decomposition of zirconium-β-diketonates at temperatures of 400–550°C. The deposits, fine-grained nearly stoichiometric monoclinic ZrO₂, were hard and showed strong adherence to the substrate. The films were characterized by transmission electron microscopy, X-ray diffraction and electron microprobe analysis and by measuring their dielectric and optical properties. The index of refraction was found to be 2.18, and the optical energy band gap was found to be 5.16 eV. The dielectric constant at 1 MHz was 17–18, and the dielectric strength varied between 1 × 10⁶ and 2.0 × 10⁶ V cm^?1. Capacitance-voltage measurements at 1 MHz indicated the presence of effective surface states with a concentration in the range (1.0?6.0) × 10¹¹cm^?2 for films deposited at temperatures above 500°C or for films deposited at 400–450°C and annealed at above 750°C. The flat-band voltages were between ?0.6 and + 0.2 V. The films showed satisfactory bias-temperature stability. The current-voltage characteristic followed an I ∝ V² dependence for negative bias and an I ∝ V^2.6 to I ∝ V^3.4 dependence for positive bias.     

Effects of dispersion and dissipation on the optical rotation and ellipticity of chiral sculptured thin films

The optical rotation and ellipticity spectra from a chiral sculptured thin film were calculated using the piecewise homogeneity approximation method and Bruggeman homogenization formalism. The effects of dispersion and dissipation on the spectra were investigated using experimental dielectric functions for bulk zirconia (ZrO₂) and titania (TiO₂). The results showed that, in the event of weak frequency dependence of the optical properties of the raw material, effects on the transmission optical activity spectra can be discounted.     

Advantages of transparent conducting oxide thin films with controlled permittivity for thin film photovoltaic solar cells

Our recent investigations have identified a pathway to produce transparent conducting oxide (TCO) films that demonstrate higher infrared transparency. The technique involves controlling the dielectric permittivity of the TCO film such that the electrical properties are maintained, but the plasma frequency (ω_p) is shifted to longer wavelength. This has the effect of reducing free-carrier absorption in the visible and near-infrared spectral region, thus producing a TCO film with higher optical transmission. The technique has been demonstrated for sputtered films of indium tin oxide by adding small amounts of ZrO₂ to a ceramic sputtering target, and for SnO₂:F films deposited by chemical vapor deposition using a metalorganic Zr source.     

Microstructure and electrical properties of Al2O3-ZrO2 composite films for gate dielectric applications

Al₂O₃-ZrO₂ composite films were fabricated on Si by ultrahigh vacuum electron-beam coevaporation. The crystallization temperature, surface morphology, structural characteristics and electrical properties of the annealed films are investigated. Our results indicate that the amorphous and mixed structure is maintained up to an annealing temperature of 900 °C, which is much higher than that of pure ZrO₂ film, and the interfacial oxide layer thickness does not increase after annealing at 900 °C. However, a portion of the Al₂O₃-ZrO₂ film becomes polycrystalline after 1000 °C annealing and interfacial broadening is observed. Possible explanations are given to explain our observations. A dielectric constant of 20.1 is calculated from the 900 °C-annealed ZrO₂-Al₂O₃ film based on high-frequency capacitance-voltage measurements. This dielectric characteristic shows an equivalent oxide thickness (EOT) as low as 1.94 nm. An extremely low leakage current density of ∼2×10⁻⁷ A/cm² at a gate voltage of 1 V and low interface state density are also observed in the dielectric film.     

Compositional effects on the optical properties of Gex Sb40−x Se60 thin films

Ge_x Sb_40−x Se₆₀ (x = 0, 2.42 and 23.41 at.%) thin chalcogenide films were deposited on glass and quartz substrates by the conventional thermal evaporation technique at 300 K. The chemical composition of the bulk material and as-deposited films were determined by energy dispersive analysis X-ray spectrometry (EDAX). X-ray diffraction pattern (XRD) of Ge_x Sb_40−x Se₆₀ (x = 0, 2.42 and 23.41 at.%) thin films indicates that they have amorphous structure. The optical transmission and reflection spectra were measured in the range of 500 to 2500 nm. The optical absorption coefficient spectra were studied for deposited samples. It is observed that the optical absorption edge shift to higher energy range, as the germanium content, x, increases in the film. The type of electronic transition, responsible for the optical properties, is indirect allowed transition. It is found that the optical band gap increases as the Ge content increases.The average coordination number (N_c) in Ge_x Sb_40−x Se₆₀ films increases, but the number of chalcogenide atoms remains constant. The number of Ge - Se bonds and the average bond energy of the system increase with the increase of the average coordination number. The optical band gap, E_g, increases with the increase of the average coordination number, (N_c). Also the energy gap, E₀₄, is discussed in terms of its relation to the chemical composition. The dispersion of the refractive index (n) is discussed in terms of the Single Oscillator Model (SOM) (Wimple - Didomenico model). The single oscillator energy (E₀), the dispersion energy (E_d) and the optical dielectric constant (?_∞) are also estimated.     

Dielectric properties of YSZ high-k thin films fabricated at low temperature by pulsed laser deposition

Yttria-stabilized zirconia (YSZ) films were deposited on Pt-coated silicon substrates and directly on n-type Si substrates, respectively, by pulsed laser deposition (PLD) technique using a YSZ (5 mol% Y₂O₃-stabilized ZrO₂) ceramic target. The YSZ films were deposited in 1.5×10⁻² Pa O₂ ambient at 300 °C and in situ post-annealed at 400 °C. X-ray diffraction (XRD) and differential thermal analysis measurements demonstrated that YSZ remained amorphous. The dielectric constant of amorphous YSZ was determined to be about 26.4 by measuring Pt/YSZ/Pt capacitor structure. The 6-nm-thick amorphous YSZ films with an equivalent oxide thickness (EOT) of 1.46 nm and a low leakage current of 7.58×10⁻⁵ A/cm² at 1 V gate voltage exhibit good electrical properties. YSZ thin films fabricated at low temperature 300 °C have satisfactory dielectric properties and could be a candidate of high-k gate dielectrics.     

The influence of preparation parameters on the deposition rate,density and optical properties of thin hydrogenated amorphous silicon films prepared by r.f. glow discharge

The computerization of the method by which the transmission data of thin hydrogenated amorphous silicon films on transparent substrates are calculated has made the manipulation of a large number of transmission spectra a practical possibility. A comparative study was carried out which demonstrates the effect of pressure, r.f. power and gas flow rate on the density ϱ, the refractive index n(λ), the dielectric constant ε_r, the optical absorption α(λ) and the optical gap E₀ of these films which were deposited from pure silane in a glow discharge system. The density of the films was determined by means of the well-known flotation technique using a ZnCl₂ solution as the flotation medium.     

Effects of Mg doping on structural, optical, and electrical properties of CuScO2(0001) epitaxial films

CuScO₂ thin films with different Mg concentrations were grown on a-plane sapphire substrates by combining the two-step deposition and post-annealing techniques using Cu₂(Sc_1−xMg_x)₂O_y [X = 0.01, 0.05, 0.10] targets. The effects of the Mg doping in the Sc-site on the structural, optical, and electrical properties of the films were investigated. A Mg-doped CuScO₂[3R](0001) epitaxial film was obtained at a Mg concentration of 1 at%. The slight increase in the a-axis lattice constant and the slight decrease in the c-axis lattice constant of the film were confirmed using two-dimensional X-ray reciprocal space mapping. No significant increase in optical absorption was observed in the film, and the energy gap for direct allowed transition was estimated at 3.7 eV. The film showed an increase in the electrical conductivity and carrier concentration and a decrease in the Hall mobility compared with those of the non-doped epitaxial film. The decrease in the overlap of Cu 3d orbitals due to the increase in the a-axis lattice constant is one cause of the decrease in the Hall mobility of the film. The temperature dependence of the electrical transport properties of the film exhibited semiconducting characteristics, and the activation energy estimated from the temperature dependence of the carrier concentration was 0.55 eV.     

Dielectric and tunable properties of Pb0.25BaxSr0.75−xTiO3 thin films fabricated by a modified sol-gel method

A modified sol-gel method was used to fabricate (Pb_0.25Ba_x Sr_0.75−x)TiO₃ (PBST) thin films with x = 0.05,0.1,0.15 and 0.2 on Pt/TiO₂/SiO₂/Si substrate. The structure, surface morphology, dielectric and tunable properties of PBST thin films were investigated as a function of barium content (x). X-ray diffraction and scanning electron microscopy analysis showed that we could get pure PBST perovskite phase and relative fine density thin films with smooth surface. It was found that the crystal lattice constant, grain size, room temperature dielectric constant, dielectric loss and tunability of Ba solutionizing PST thin films increased with the increase in Ba content. For (Pb_0.25Ba_0.2Sr_0.55)TiO₃ thin film, it had the highest dielectric constant of 1390 and the largest tunability of 80.6%. The figure of merit parameter reached a maximal value of 28.9 corresponding to the (Pb_0.25Ba_0.05 Sr_0.7)TiO₃ thin film, whose dielectric constant, dielectric loss and tunability measured at 1 MHz were 627, 0.024 and 69.4%, respectively.     

Optical and dielectric properties of double helix DNA thin films

In this work, the thin film of wheat DNA was deposited by spin-coating technique onto glass substrate, and the optical and dielectric properties of the double helix DNA thin film were investigated. The optical constants such as refractive index, extinction coefficient, dielectric constant, dissipation factor, relaxation time, and optical conductivity were determined from the measured transmittance spectra in the wavelength range 190–1100 nm. Meanwhile, the dispersion behavior of the refractive index was studied in terms of the single oscillator Wemple–DiDomenico (W–D) model, and the physical parameters of the average oscillator strength, average oscillator wavelength, average oscillator energy, the refractive index dispersion parameter and the dispersion energy were achieved. Furthermore, the optical band gap values were calculated by W–D model and Tauc model, respectively, and the values obtained from W–D model are in agreement with those determined from the Tauc model. The analysis of the optical absorption data indicates that the optical band gap E_g was indirect transitions. These results provide some useful references for the potential application of the DNA thin films in fiber optic, solar cell and optoelectronic devices.     

Optical and dielectric properties of poly(vinylacetate)/lead oxide composites

Composite films of poly(vinylacetate)/red lead oxide have been prepared by mixing the fine lead oxide particles into polyvinylacetate solution under ultrasonication followed by film casting technique. Structural, optical and dielectric properties have been performed to characterize these composites films and compared their properties to pure PVAc film. The changes in the structural of the prepared films were investigated by X-ray diffraction (XRD) and FT-IR spectra. It has been observed that the crystallinity of the composites films depends on the Pb-content. Optical spectra of the composites films showed direct allowed band gaps lying in the range of 5.0–4.6?eV which is lower than that of PVAc. Frequency and doping level dependence of dielectric constant (ε′), ac conductivity (σ_ac) and tangent loss (tanδ) have been measured. The values of ε′ were decreased with increasing in frequency, which indicates that the major contribution to the polarization comes from orientation polarization. The ac conductivity is more for doped PVAc than that of undoped PVAc. The experimental results show that ε′ and σ_ac increase with adding of lead oxide in PVAc. The controllable of optical and dielectric properties of the composite film will draw much attention for potential applications.     

Ion-based methods for optical thin film deposition

The optical properties of the dielectric oxide films SiO₂, Al₂O₃, TiO₂, ZrO₂, CeO₂ and Ta₂O₅ produced by ion-based techniques have been reviewed. The influence of ion bombardment during deposition is discussed in some detail and the various production techniques are described. Recent results on the deposition and properties of diamond-like carbon films are also reviewed. Finally, some examples of the practical applications of high quality dielectric oxide films are given.     

Role of high-k gate insulators for oxide thin film transistors

In conventional TFTs, SiO₂ or SiN_x have been used as gate insulators. But they could not induce the high on-current due to their low-capacitance. Since they have low-capacitance that originated from low dielectric constant, on-current of TFTs with low-k insulated are limited by low-capacitance. We have investigated high-k materials, such as HfO₂, ZrO₂ and modified structures for the use of gate insulators in oxide thin film transistors. ZrO₂ and HfO₂ are the most attractive materials with their superior properties, such as high breakdown field intensity (~ 15 MV/cm), high dielectric constant (~ 25), and the capability of room-temperature process. Since they have high-capacitance due to high dielectric constant, it can be easily expected to result in high on-current. In this work, we demonstrated the comparison of oxide thin film transistors with HfO₂, ZrO₂ and SiO₂ and the roles of gate insulators are analyzed. In the result, oxide thin film transistors with SiO₂, HfO₂ and ZrO₂ have on-currents of ~100 μA, ~500 μA, and ~3 mA, respectively. Especially oxide thin film transistor with ZrO₂ has larger on-current than oxide thin film transistor with HfO₂. The result means that ZrO₂ is more suitable than HfO₂ for the gate-dielectric material which can be fabricated at room temperature.     

Optical,DC and AC electrical investigations of 4-hydroxy coumarin molecule as an organic Schottky diode

The current–voltage (I–V) and optical characteristics of 4-hydroxy coumarin Schottky diode were investigated. The conventional methods related with device were used to extract the various diode parameters. From dielectric study low dielectric constant and loss was observed. From its optical study, an indirect allowed transition is shown by this compound. The optical band gap (E _g ) was found to be around 3.78 eV. The observed properties shown by this molecule give a bright opportunity to explore its application for different organic devices.     

Thin film fabrication of nano-porous 12CaO·7Al2O3 crystal and its conversion into transparent conductive films by light illumination

Thin film fabrication of crystalline 12CaO·7Al₂O₃ (C12A7) with zeolitic structure was examined, and their electrical and optical properties were measured. Polycrystalline thin films were prepared by post-annealing of amorphous films in oxygen atmosphere at temperatures above 800 °C. Choice of substrates was crucial for obtaining single-phase thin films. Although various oxide substrates (single crystals of Al₂O₃, Y-stabilized ZrO₂, MgO and silica glass) were examined, single-phase films were obtained only for MgO substrates and the other substrates reacted with the CaO component in the films during post-annealing. The optical band gap of C12A7 was evaluated to be 5.9 eV. Hydride ions were incorporated into the film by a thermal treatment in a hydrogen atmosphere at 1200 °C. The resulting transparent thin films were converted into transparent persistent electronic conductors exhibiting an electrical conductivity 6.2×10⁻¹ S cm⁻¹ at 300 K by ultraviolet light illumination. This is the first example of transparent conductive thin film in which conductive areas can be patterned directly by light.