Spectroscopic Ellipsometric Measurements Research Articles

Study of reactive electron beam deposited tantalum penta oxide thin films with spectroscopic ellipsometry and atomic force microscopy

The optical and surface morphological properties of thin films are profoundly influenced by the deposition technique and the various process parameters employed. In present work, several tantalum penta oxide thin films have been fabricated using reactive electron beam evaporation at varying oxygen (O2) pressures, ranging from 3 × 10−3 Pa to 8 × 10−2 Pa. Refractive index, extinction coefficient, and voids in thin film microstructure were determined through the analysis of spectroscopic ellipsometric measurements. The refractive index, which exhibits a decreasing trend, varies between 1.859 and 2.067, with the exception being the lowest O2 pressure. The variation has been explained in terms of varying oxygen content and voids in the thin films. The extinction coefficient exhibits a decreasing trend due to the increasing oxidation of tantalum, except at O2 pressure of 8 × 10−2 Pa. Increase in the extinction coefficient at this pressure could be due to porous film microstructure, resulting in dominant light scattering. Variation of film density which is similar to that of refractive index, has been attributed to the varying oxidation of tantalum (Ta) and film porosity. Surface root mean square (rms) roughness, correlation length and Hurst parameter, have been derived from suitable analysis of atomic force microscopy measurements. Variations of correlation length and rms roughness have been explained in terms of varying surface shadowing effects and oxidation of Ta with varying O2 pressure.

Interferometric Imaging Ellipsometer for Characterizing the Physical Parameters of a Grown Oxide Layer

Interferometric and ellipsometric techniques are widely used in object characterization, investigation and testing. Both techniques are crucial for industrial sectors in manufacturing and production. In this work, an interferometric imaging ellipsometry method has been developed to measure the ellipsometric parameters Ψ, Δ and thickness t of native oxide layer formed on a copper thin film at wide angle of incidence 57.8–80.2º instantaneously. In this system, Michelson interferometer is illuminated with 45° polarized laser beam of 30 mm diameter. The produced fringes are split by a polarizing beam splitter (PBS) into p- and s- polarization fringes. The interferograms are captured separately by two CCD sensors at the reference and the measurement states without moving any parts in the optical system for each state. The detected p- and s- interferograms are analyzed using ImageJ software for mathematically calculating the values of Ψ, Δ and t of the oxide layer grown on copper thin film surface. The proposed method avoids the offset errors and the probable misalignment resulting from the beam and the optical components. In addition, it gathers the information of the interference pattern with the state of polarization of light for accurate, precise and real time contrast images. The oxide layer thickness is determined under controlled environment with high accuracy and low uncertainty. The results obtained by the proposed technique are consistent with the spectroscopic ellipsometer measurements.

Effect of substrate temperature on the near-infrared shielding properties of WO3-x thin films deposited by RF magnetron sputtering

Near-infrared (NIR) shielding materials emerge as potential candidates for energy conservation applications. In this work, tungsten oxide (WO3-x, 0 < x < 1) thin films were deposited on soda-lime glass substrate by RF magnetron sputtering at various substrate temperatures and NIR shielding properties of the films were studied. Structural, morphological and compositional properties of the films were also investigated. Optical constants, thickness and roughness of the films were extracted from spectroscopic ellipsometric (SE) measurements. The correlativity of SE with UV–Vis–NIR spectrophotometry, cross-sectional field emission scanning electron microscopy and atomic force microscopy was investigated. Of all the films, WO3-x thin films deposited at 500 °C showed the lowest NIR transmittance of about 23% with the highest visible transmittance of above 70% corresponding to a Tvis/Tsol ratio of 1.35 and NIR shielding value of 75%. WO3-x coated soda lime glass shows better NIR shielding performance compared to commercial soda lime glass in the thermal shielding test. The underlying reason for NIR absorption is the presence of oxygen vacancies which promote formation of W5+ ions and the resultant combined effects of polaron absorption and surface plasmon resonance. This work is significant in utilizing a facile technique for developing undoped WO3-x thin films for efficient NIR shielding applications.

Spectrally Selective Solar Absorber Coating of W/WAlSiN/SiON/SiO2 with Enhanced Absorption through Gradation of Optical Constants: Validation by Simulation

The properties of spectrally selective solar absorber coatings can be fine-tuned by varying the thickness and composition of the individual layers. We have deposited individual layers of WAlSiN, SiON, and SiO2 of thicknesses ~940, 445, and 400 nm, respectively, for measuring the refractive indices and extinction coefficients using spectroscopic ellipsometer measurements. Appropriate dispersion models were used for curve fitting of Ψ and Δ for individual and multilayer stacks in obtaining the optical constants. The W/WAlSiN/SiON/SiO2 solar absorber exhibits a high solar absorptance of 0.955 and low thermal emissivity of 0.10. The refractive indices and extinction coefficients of different layers in the multilayer stack decrease from the substrate to the top anti-reflection layer. The graded refractive index of the individual layers in the multilayer stack enhances the solar absorption. In the tandem absorber, WAlSiN is the main absorbing layer, whereas SiON and SiO2 act as anti-reflection layers. A commercial simulation tool was used to generate the theoretical reflectance spectra using the optical constants are in well accordance with the experimental data. We have attempted to understand the gradation in refractive indices of the multilayer stack and the physics behind it by computational simulation method in explaining the achieved optical properties. In brief, the novelty of the present work is in designing the solar absorber coating based on computational simulation and ellipsometry measurements of individual layers and multilayer stack in achieving a high solar selectivity. The superior optical properties of W/WAlSiN/SiON/SiO2 makes it a potential candidate for spectrally selective solar absorber coatings.

A Rational Fabrication Method for Low Switching-Temperature VO2.

Due to its remarkable switching effect in electrical and optical properties, VO is a promising material for several applications. However, the stoichiometry control of multivalent vanadium oxides, especially with a rational deposition technique, is still challenging. Here, we propose and optimize a simple fabrication method for VO rich layers by the oxidation of metallic vanadium in atmospheric air. It was shown that a sufficiently broad annealing time window of 3.0–3.5 h can be obtained at an optimal oxidation temperature of 400 °C. The presence of VO was detected by selected area diffraction in a transmission electron microscope. According to the temperature dependent electrical measurements, the resistance contrast (R30 °C/R100 °C) varied between 44 and 68, whereas the optical switching was confirmed using in situ spectroscopic ellipsometric measurement by monitoring the complex refractive indices. The obtained phase transition temperature, both for the electrical resistance and for the ellipsometric angles, was found to be 49 ± 7 °C, i.e., significantly lower than that of the bulk VO2 of 68 ± 6 °C.

Solution-based hafnium oxide thin films as potential antireflection coating for silicon solar cells

Hafnium oxide (HfO2) thin films were formed by spin coating deposition and annealed in ambient air. Following the molarity optimization of hafnium content in the solution, effect of spin coating and thermal processes on the antireflection properties were analyzed. Characterizations were carried out by spectrophotometer, X-ray diffraction, spectroscopic ellipsometer and scanning electron microscopy measurements. Post deposition annealing temperatures range from 500 to 1000 °C. Annealing led the crystallinity of the films above 500 °C and possess monoclinic phase. Average reflectivity of 11.32% was achieved with 71.36 nm HfO2 film after annealing at 700 °C. Ellipsometer measurements reveals refractive index of such a film as 1.934 at 600 nm. Average reflectance increases when annealing temperature is over 700 °C mainly due to the increase of refractive index which is recorded as 2.05 after annealing at 800 °C. Fresnel equations, transfer matrix method and PC1D simulations were carried out for reflectance spectra approximations. The experimental results and the theoretical data were relatively comparable. Spin coating HfO2 thin films are found promising as an antireflection layer for solar cells.

Optical properties of ultrathin ZnO films fabricated by atomic layer deposition

Ultrathin zinc oxide (ZnO) films with thickness down to several nanometers have been fabricated by atomic layer deposition. The chemical composition, surface morphology, crystalline structure, optical properties and photoluminescence characteristics of the ZnO films with various thicknesses were investigated. The X-ray photoelectric spectroscopy illustrates that the deposited films are uniformly distributed with zinc and oxygen atoms. Spectroscopic ellipsometric measurements reveal that both the refractive index and extinction coefficient decrease monotonically as the thickness of the film decreases. The thickness of the ZnO films obtained via ellipsometry is consistent with X-ray reflectivity measurements. The excitonic emission peak of the photoluminescence spectrum shifts to higher energies when the film thickness decreases to a few nanometers. This blueshift phenomenon is consistent with the expansion of the fundamental optical bandgap determined from ellipsometry, which could be well described by the effective mass model using physically meaningful parameters. The results obtained in this study could provide guidance to the design and optimization of optoelectronic devices based on ultrathin ZnO films.

Effect of crystallinity on thermal atomic layer etching of hafnium oxide, zirconium oxide, and hafnium zirconium oxide

Thermal atomic layer etching (ALE) can be achieved using sequential, self-limiting fluorination and ligand-exchange reactions. Previous studies have demonstrated thermal ALE of amorphous HfO2 and ZrO2 ALD films. This study explored the differences between thermal ALE of amorphous and polycrystalline films of hafnium oxide, zirconium oxide, and hafnium zirconium oxide on silicon wafers. HF, XeF2, or SF4 were used as the fluorination reactants. Titanium tetrachloride or dimethylaluminum chloride (DMAC) was employed as the metal precursor for ligand exchange. The spectroscopic ellipsometric measurements revealed that the amorphous films had much higher etch rates per cycle than the crystalline films regardless of the fluorination reactants or metal precursors for ligand exchange. The differences were most pronounced for HfO2. Using HF and TiCl4 as the reactants at 250 °C, the etch rates were 0.36 Å/cycle for amorphous HfO2 and 0.02 Å/cycle for crystalline HfO2. In comparison, the etch rates were 0.61 Å/cycle for amorphous ZrO2 and 0.26 Å/cycle for crystalline ZrO2. The etch rates were 0.35 Å/cycle for amorphous HfZrO4 and 0.04 Å/cycle for crystalline HfZrO4. When HF and DMAC were used as the reactants, the etch rates were higher than with HF and TiCl4 for every material. Using HF and DMAC as the reactants at 250 °C, the etch rates were 0.68 Å/cycle for amorphous HfO2 and 0.08 Å/cycle for crystalline HfO2. In comparison, the etch rates were 1.11 Å/cycle for amorphous ZrO2 and 0.82 Å/cycle for crystalline ZrO2. The etch rates were 0.69 Å/cycle for amorphous HfZrO4 and 0.16 Å/cycle for crystalline HfZrO4. SF4 as the fluorination reactant resulted in higher etch rates than for HF when using TiCl4 as the metal precursor for ligand exchange. XeF2 as the fluorination reactant resulted in even higher etch rates than for SF4. The differences in the etch rate with the fluorination reactant can be partially attributed to differences in thermochemistry for fluorination by HF, SF4, and XeF2. The differences in etch rates between amorphous and crystalline films may be caused by the greater degree of fluorination and subsequent ligand-exchange reaction for the amorphous films. The amorphous films have a lower density and may be able to better accommodate the large volume expansion upon fluorination.

Optical Characterization of Non-Stoichiometric Silicon Nitride Films Exhibiting Combined Defects

The study was devoted to optical characterization of non-stoichiometric silicon nitride films prepared by reactive magnetron sputtering in argon-nitrogen atmosphere onto cold (unheated) substrates. It was found that these films exhibit the combination of three defects: optical inhomogeneity (refractive index profile across the films), uniaxial anisotropy with the optical axis perpendicular to the boundaries and random roughness of the upper boundaries. The influence of the uniaxial anisotropy was included into the corresponding formulae of the optical quantities using the matrix formalism and the approximation of the inhomogeneous layer by a multilayer system consisting of large number thin homogeneous layers. The random roughness was described using the scalar diffraction theory. The processing of the experimental data was performed using the multi-sample modification of the least-squares method, in which experimental data of several samples differing in thickness were processed simultaneously. The dielectric response of the silicon nitride films was modeled using the modification of the universal dispersion model, which takes into account absorption processes corresponding to valence-to-conduction band electron transitions, excitonic effects and Urbach tail. The spectroscopic reflectometric and ellipsometric measurements were supplemented by measuring the uniformity of the samples using imaging spectroscopic reflectometry.

Effect of balanced and unbalanced magnetron sputtering processes on the properties of SnO2 thin films

A comparative study has been carried on the role of balanced magnetron (BM) and unbalanced magnetron (UBM) sputtering processes on the properties of SnO2 thin films. The oxygen partial pressure, substrate temperature and deposition pressure were kept 20%, 700 °C and 30 mTorr, respectively and the applied RF power varied in the range of 150–250 W. It is observed that the UBM deposition causes significant effect on the structural, electrical and optical properties of SnO2 thin films than BM as evidenced by X-ray diffraction, C-V, Spectroscopic Ellipsometer and Photoluminescence measurements. The value of band gap (Eg) of the films deposited at 150 W in UBM is found as Eg = 3.83 eV which is much higher than the value of Eg = 3.69 eV as observed in BM sputtering indicating that UBM sputtering results in good crystalline quality. Further, the C-V measurements of SnO2 thin films deposited using UBM at high power 250 W show hysteresis with large flat band shift indicating that these thin films can be used for the fabrication of memory device. The observed results have been attributed to different mechanisms which exist simultaneously under unbalanced magnetron sputtering due to ion bombardment of growing SnO2 thin film by energetic Ar+ ions.

Tb3+-doped WO3 thin films: A potential candidate in white light emitting devices

Good crystalline, highly ordered, highly transparent and efficient luminescent Tb3+-doped tungsten oxide (WO3) thin films are fabricated using Radio Frequency (RF) magnetron sputtering technique. XRD analysis shows that the prepared films are in monoclinic phase showing crystal growth along a-axis. Micro-Raman spectra also support the formation of monoclinic crystalline WO3 phase in the prepared thin films. Morphological studies reveal a porous nature for heavily Tb3+-doped WO3 films. Prepared films are very close to the chemical stoichiometry of WO3 and the added impurity Tb exists mainly in +3 oxidation state. The fabricated thin films show better transparency particularly in the visible region. The calculated band gap energy values are in the range of 3.08–3.24 eV. Thickness and optical constants of the prepared films are calculated using spectroscopic ellipsometric measurements. Low values of extinction coefficient also support better transparency of the deposited films in the visible region. Tb3+-doped WO3films exhibit strong blue, green and red emissions under UV excitation which suggest the possibility of using these luminescent films in white light emitting devices. The experimental value of decay time constants corresponds to intense green emission (546 nm) shows a slight increase with increase in Tb3+ concentration.

Investigation of valence electron excitation and plasmonic enhancement in sputter grown NMZO thin films: For energy harvesting applications

We report a novel approach of sputter-stimulated plasmonic generation in Na-doped MgZnO (NMZO) thin films. Sputtering of material during film growth by utilizing secondary direct-coupled ion-source present in dual-ion beam sputtering system leads to the generation of nanoclusters of its constituent elements due to different sputtering-out rates of various elements present in the films. The authentication of plasmonic generation in NMZO is conducted as follows a) identification of plasmonic signature in electron energy loss spectra obtained by ultraviolet photoelectron spectroscopy measurement, b) valence bulk, valence surface, and particle plasmon resonance energy calculations are performed, and each plasmon peak is indexed with corresponding plasmon energy peak of different nanoclusters, and c) spectroscopic ellipsometric measurement is deployed to verify plasmonic behavior by investigating different optical properties. Additionally, incorporation of the plasmonic feature along with alkali metals plays a crucial role in the improvement of the performance of solar cells. Therefore, plasmon enhanced NMZO as a backscattering layer in between CIGSe/back contact is probed to ascertain the additional benefits of 1) Na incorporation into the absorber layer as a result of the Na diffusion from the NMZO layer, and 2) improvement in the morphology of the CIGSe thin film with the incorporation of NMZO layer in between the back-contact and CIGSe. The diffusion of Na into the absorber layer is probed by deploying secondary ion mass spectroscopy measurements, and improvement in the morphology of CIGSe with the incorporation of NMZO layer between the back-contact/absorber is investigated using field-emission scanning electron microscope analysis.

Structural and Optical Properties of Amorphous Al2O3 Thin Film Deposited by Atomic Layer Deposition

Aluminum oxide (Al2O3) amorphous structure with short-range order and long-range disorder has presented promising applications in optical and optoelectronic devices. In this paper, the Al2O3 films with different thickness were prepared by atomic layer deposition (ALD) technology at 200°C in order to achieve amorphous structure. X-ray diffraction (XRD) and energy dispersive spectrum (EDS) results indicated that the Al2O3 films were amorphous structure and stable O/Al ratio. The surface topography investigated by atomic force microscopy (AFM) showed that the samples were smooth and crack-free. Spectroscopic ellipsometer (SE) measurements were operated to investigate the effect of thickness on the structure and optical properties of films with Tauc-Lorentz model. It is found that the band gap exhibits a steady value ~2.3 eV by the UV-VIS transmittance method, but the T-L model was ~3.0 eV. The refractive index and extinction coefficient are related to the variation of thickness and the samples surface quality of amorphous network structure in the thin films. The outstanding optoelectronic properties and facile fabrication of Al2O3 films amorphous structure can be extended to other similar oxides, which could display wide applications in various engineering and industrial fields.

Cu(II) and Ni(II) 4-cyanobenzoate complexes with nicotinamide: Synthesis, spectral, structural and optical characterization and thermal behavior

Two new copper(II) and nickel(II) complexes [M(NCC6H4COO)2(C6H6N2O)2(H2O)2] (where M:Cu and Ni) have been synthesized and characterized by elemental analysis, FT-IR and UV–Vis spectroscopy, spectroscopic ellipsometer (SE), X-ray crystallography, thermal analysis and molar conductivity. X-ray measurements showed that both of the complexes crystallized in triclinic system with the space group P-1. The isostructure complexes have distorted octahedral geometry around the metal atom center. In both of the crystal structures, the metal atoms are coordinated by two nitrogen atoms from two different nicotinamide ligands, two carboxyl oxygen atoms from two different 4-cyanobenzoate anions and two oxygen atoms from two different water molecules. From the linear absorption spectra and spectroscopic ellipsometer measurements, it was observed that these complexes showed different optical behaviors.

Critical dimension metrology of a plasmonic photonic crystal based on Mueller matrix ellipsometry and the reduced Rayleigh equation.

A computationally efficient algorithm based on the reduced Rayleigh equation, combined with an optimization scheme, is used to accurately retrieve the morphological parameters of a two-dimensional plasmonic photonic crystal from angle-resolved spectroscopic Mueller matrix ellipsometric measurements. The numerical method is successfully tested against experimental data and gives morphological parameters consistent with SEM and AFM measurements.

Area-Selective Atomic Layer Deposition Using an Inductively Coupled Plasma Polymerized Fluorocarbon Layer: A Case Study for Metal Oxides

Area-selective atomic layer deposition (AS-ALD) has attracted immense attention in recent years for self-aligned accurate pattern placement with subnanometer thickness control. Here, we demonstrate a methodology to achieve AS-ALD by using inductively couple plasma (ICP) grown fluorocarbon polymer film as hydrophobic blocking layer for selective deposition. Our approach has been tested for metal-oxide materials including ZnO, Al2O3, and HfO2. Contact angle, X-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometer, and scanning electron microscopy (SEM) measurements were performed to investigate the blocking ability of plasma polymerized fluorocarbon layers against ALD-grown metal-oxide films. A considerable growth inhibition for ZnO has been observed on fluorocarbon coated Si(100) surfaces, while the same polymerized surface caused a relatively slow nucleation for HfO2 films. No growth selectivity was obtained for Al2O3 films, displaying almost the same nucleation behavior on Si and fluorocarbon ...

Determination of the Bimetallic Layers’ Film Thicknesses by Phase Detection of SPR Prism Coupler

In this paper, the phase detection method is demonstrated to determine the film thicknesses of bimetallic layers by surface plasmon resonance (SPR) prism coupler. It was proposed and developed by matching the experimental results to the theoretical curves of the phase difference with different angles of incidence. The results of both of the two metallic film thicknesses obtained by our method coincide well with the measurement results of atomic force microscope (AFM) and spectroscopic ellipsometer (SE) measurement. Both theoretical analysis and experimental results indicate that the method proposed is stable and reliable, and feasible to be used to determine the film thickness of bimetallic layers directly with nanometer order resolution.

Lanthanide-Assisted Deposition of Strongly Electro-optic PZT Thin Films on Silicon: Toward Integrated Active Nanophotonic Devices.

The electro-optical properties of lead zirconate titanate (PZT) thin films depend strongly on the quality and crystallographic orientation of the thin films. We demonstrate a novel method to grow highly textured PZT thin films on silicon using the chemical solution deposition (CSD) process. We report the use of ultrathin (5-15 nm) lanthanide (La, Pr, Nd, Sm) based intermediate layers for obtaining preferentially (100) oriented PZT thin films. X-ray diffraction measurements indicate preferentially oriented intermediate Ln2O2CO3 layers providing an excellent lattice match with the PZT thin films grown on top. The XRD and scanning electron microscopy measurements reveal that the annealed layers are dense, uniform, crack-free and highly oriented (>99.8%) without apparent defects or secondary phases. The EDX and HRTEM characterization confirm that the template layers act as an efficient diffusion barrier and form a sharp interface between the substrate and the PZT. The electrical measurements indicate a dielectric constant of ∼650, low dielectric loss of ∼0.02, coercive field of 70 kV/cm, remnant polarization of 25 μC/cm(2), and large breakdown electric field of 1000 kV/cm. Finally, the effective electro-optic coefficients of the films are estimated with a spectroscopic ellipsometer measurement, considering the electric field induced variations in the phase reflectance ratio. The electro-optic measurements reveal excellent linear effective pockels coefficients of 110 to 240 pm/V, which makes the CSD deposited PZT thin film an ideal candidate for Si-based active integrated nanophotonic devices.

Radio frequency sputtered Al:ZnO-Ag transparent conductor: A plasmonic nanostructure with enhanced optical and electrical properties

Optimization of metal-based transparent conductors (MTCs) made of silver and aluminium-doped zinc oxide (AZO) prepared by radio-frequency (r.f.) sputtering has been carried out through tuning of metal film properties. The influence of morphology and related plasmonic features of AZO/Ag/AZO MTCs on their optical and electrical performance is demonstrated and it is shown that the nominal thickness of the silver layer itself is not the most crucial value determining the MTC performance. The MTC performance has been optimized by a search of deposition conditions ensuring fractal-type metal layer formation up to a certain coalescence state that enables full gaining from silver optical properties, including its plasmonic features. For 150 W- and 200 W-deposited silver, MTCs with maximum transmittance as high as 83.6% have been obtained. These coatings have a figure of merit as good as 0.01 Ω−1 and a remarkably wide spectral transparency region: transmittance higher than 70% down to 1200 nm for 200W-samples. Modelling of the MTC coatings is proposed additionally, based on variable angle spectroscopic ellipsometric measurements, which takes into account the variation of the optical properties of silver when deposited in various conditions and embedded in a semiconductor stack.

Optical properties of cubic-phase Cu2GeSe4 single crystal

We report optical properties of bulk Cu2GeSe4 single crystal. X-ray powder diffraction measurement shows that this ternary compound forms in the cubic crystal structure and its lattice parameter is 5.5815(3) Å. Spectroscopic ellipsometric measurements are performed from 1.0 to 8.5 eV with the crystal at room temperature. Dielectric function ε = ε1 + iε2, complex refractive index N = n + ik, normal incidence reflectivity R, and absorption coefficients α of Cu2GeSe4 are obtained by modeling the ellipsometric data. The vibrational properties of Cu2GeSe4 are characterized by Raman scattering spectroscopy. The data show four major optical structures whose spectral positions are accurately determined by analyzing the spectra with multiple Gaussian-Lorentzian mixed line profiles.