Laser diagnostics of nanoscale dielectric films on absorbing substrate by differential reflectivity and ellipsometry

The differential reflection characteristics for ultrathin inhomogeneous dielectric film on absorbing substrate are investigated in the long-wavelength approximation. The obtained first-order expressions for differential reflectivity and changes in the ellipsometric angles caused by ultrathin layer are of immediate interest to the solution of the inverse problem. The method to determine the averaged values (not the realistic profile) of refractive index for inhomogeneous nanometric films are shown. The novel possibilities for determining the dielectric constant and thickness of nanoscale homogeneous films by the differential ellipsometric and reflectivity measurements are developed, and a simple method to estimate whether the nanometric film is homogeneous or not is also discussed.     

Optical diagnostics of nanoscale dielectric layers on interference films by polarization-dependent differential reflectivity

The small change in the reflectance (differential reflectance) of s- or p-polarized light from an interference film as a result of the deposition of a nanoscale insulating layer on it is investigated theoretically. Analytical relations describing the contribution of nanoscale layers to the reflectance from an interference film as function of film thickness are obtained in the long-wavelength approximation. It is shown that the utilization of interference films in reflection diagnostics through differential measurements allows a significant enhancement of the sensitivity of these techniques and also opens up new possibilities for resolving the inverse problem of determining simultaneously the optical constant and thickness of nanoscale dielectric layers.     

椭偏光散射分析类金刚石薄膜的散射特性

 基于光学薄膜反射椭偏法的测量原理,对光学薄膜散射椭偏特性进行了研究。给出了光学薄膜散射逆问题的解决方法,并对不同脉冲频率下采用脉冲真空电弧离子镀技术沉积的类金刚石薄膜的散射特性进行了研究。分析了光学薄膜界面的相关特性以及膜层中局部缺陷对散射光椭偏特性的影响。结果表明:随着脉冲频率的增加,所沉积的类金刚石薄膜的相关性变差,且薄膜中的局部缺陷引起的体散射越明显。     

Optical study of BST films combining ellipsometry and reflectivity

Optical properties of plasma laser-deposited Ba_0.75Sr_0.25TiO₃ (BST) thin films have been investigated using variable angle spectroscopic ellipsometry (VASE) and near-normal spectroscopic reflectivity (NNSR) within a broad spectral range at room temperature. The samples prepared under various deposition conditions and the Si substrate coated with the structure SiO₂/TiO_x/Pt were measured. The X-ray diffraction, atomic force microscopy and alpha step measurement were used for characterization of the samples. A special attention was paid to study sample texture. Both sets of experimental data (VASE and NNSR) were fitted simultaneously to obtain the optical constants (e.g. complex refractive index) and thicknesses of the films. For modeling of the experimental data in the range of transparency the Cauchy and Urbach formulas were used. The direct fit procedure and the Cody-Lorentz model were applied around and below absorption edge. In the entire spectral range the reflectivity spectra were analyzed by Kramers-Kronig analysis. The data around the absorption edge were fitted using the single-wavelength method and the absorption edge features were found up about 3.5 eV. The platinum-coated Si substrate data were fitted as a semi-infinite medium using the Drude and Lorentz oscillators model. The structure model for optical characterization of the sample included not only the BST layers and substrate but also the intermix and surface roughness layers to achieve good agreement with experimental data. The substrate structure was modeled by a simple bulk with surface roughness.     

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利用在线椭偏仪对非晶碳氢膜进行了光学常数、沉积率和刻蚀率的测量。在无直流负偏压或偏压较小时,薄膜呈现聚合物结构,折射率和消光系数较小;当增加直流负偏压时,薄膜的折射率和消光系数显著提高,所成膜为硬质非晶碳氢膜。在以CH4作为气源进行沉积时,随着偏压的增加,沉积率先升高再降低,在偏压为-100V时,沉积率为最大。H2/N2(30%N2)的混合气体的刻蚀率要比单独用H2作为刻蚀气体的刻蚀率要大。对于CH4/N2(30%N2),在偏压从0V增加到300V过程中,在大约50V时,基底上的薄膜有一个从沉积到刻蚀的转化过程。     

Infrared reflectivity and dielectric permeability of ultra-thin Cu and Al films

In this report we present an experimental investigation of the reflectivity (R) and the dielectric permeability () for Cu and Al ultra-thin films ranging in thickness from a few monolayers to 12 nm at infrared and visible wavelengths. The metal films were prepared by RF-sputtering on SiO₂ (glass) and Si substrates. IR reflectivity was measured at 9.2 μm, while was measured with the help of laser ellipsometer at a wavelength of 632.8 nm. Two types of oscillations on R(d) and (d) were discovered for two thickness regions determined by the critical thickness value d*. Oscillations at d<d* with periods near 0.3 nm for Al and Cu films were observed on R(d) and (d) due to quantum sized effects (QSEs). At d>d* (thickness between 6–12 nm) we discover a new type of strong oscillation of R(d) and (d) with an oscillating period of 0.2 nm. For thickness larger than 12 nm all the oscillations tend to disappear and R and behave almost as their volume values. A possible explanation for the appearance of these two kinds of oscillations is based on the introduction of the critical film thickness d*.     

Reflection characterization of anisotropic ultrathin dielectric films on absorbing isotropic substrates

The reflection of linearly polarized light from an ultrathin anisotropic dielectric film on isotropic absorbing substrate is investigated analytically in the long-wavelength limit. All analytical results are correlated with the numerical solution of the anisotropic reflection problem on the basis of rigorous electromagnetic theory. Simple analytical approach developed in this work not only gives a physical insight into the reflection problem but also provides a way of estimating the necessary experimental accuracy for optical diagnostics by reflection characteristics. It is shown that obtained expressions are of immediate interest for determining the parameters of anisotropic surface layers. Innovative possibilities for optical diagnostics of anisotropic properties of ultrathin dielectric layers upon absorbing materials are discussed.     

Evaluation of probe lasers employed in optical diagnostics for phase transformation of thin films during excimer laser crystallization

The stability and reliability of probe laser is an important factor affecting the inspection of the phase transformation process of Si thin films during excimer laser crystallization using in-situ time-resolved optical measurements. The changes in 2D intensity profile, peak power density, and beam wander of the commonly used helium–neon (He–Ne) and diode laser are investigated experimentally. It is found that the peak power density of He–Ne laser is higher than that of diode laser, while the total power of He–Ne laser is lower than that of diode laser. Although the instability in the peak power density of He–Ne laser will increase with increasing the operation time, the beam stability of He–Ne laser is better than that of diode laser. For long-time operation (>24 h) of optical measurements, the diode laser is a good candidate of probe laser. Conversely, the diode laser is suitable for the short-time operation (<24 h) of optical measurements because the beam-wander is higher than that of He–Ne laser.     

Inverse relationships for ellipsometry of uniaxially anisotropic nanoscale dielectric films on isotropic materials

The possibilities of determining the optical parameters of uniaxially anisotropic non-absorbing ultrathin films on the basis of ellipsometric parameters are analyzed in the framework of a long-wavelength approximation. It is shown that the special convenience of this analytical approach lies in the fact that it enables to find out the situations where it is possible to decouple the optical constants and the thickness (to provide correlation-free measurements) of an anisotropic ultrathin film. The accuracy of the obtained formulas for determining the parameters of ultrathin films is estimated by computer simulation of the reflection problem on the basis of the exact electromagnetic theory for anisotropic layered systems.     

Albumin adsorption on oxide thin films studied by spectroscopic ellipsometry

Thin films of tantalum, niobium, zirconium and titanium oxides were deposited by reactive magnetron sputtering and their wettability and surface energy, optical properties, roughness, chemical composition and microstructure were characterized using contact angle measurements, spectroscopic ellipsometry, profilometry, X-ray photoelectron spectroscopy and X-ray diffraction, respectively. The purpose of the work was to correlate the surface properties of the films to the Bovine Serum Albumin (BSA) adsorption, as a first step into the development of an initial in vitro test of the films biocompatibility, based on standardized protein adsorption essays. The films were immersed into BSA solutions with different protein concentrations and protein adsorption was monitored in situ by dynamic ellipsometry; the adsorption-rate was dependent on the solution concentration and the immersion time. The overall BSA adsorption was studied in situ using spectroscopic ellipsometry and it was found to be influenced by the wettability of the films; larger BSA adsorption occurred on the more hydrophobic surface, the ZrO₂ film. On the Ta₂O₅, Nb₂O₅ and TiO₂ films, hydrophilic surfaces, the overall BSA adsorption increased with the surface roughness or the polar component of the surface energy.     

AlN:Cr thin films synthesized by pulsed laser deposition: Studies by X-ray diffraction and spectroscopic ellipsometry

The structure and optical properties of AlN thin films doped with Cr atoms were studied by X-ray diffractometry, Fourier transform infrared spectroscopy and spectroscopic ellipsometry analyses. The films were synthesized by pulsed laser deposition from an AlN:Cr (10% Cr) target onto Si(1 0 0) wafers in vacuum at residual pressure of 10⁻³ Pa or in nitrogen at a dynamic pressure of 0.1 Pa. The study of the XRD patterns revealed that both phases co-existed in the synthesized films and that the amorphous one was prevalent. Two different amorphous matrices, i.e. two types of chemical bond arrangements, were found in films deposited at 0.1 Pa N₂. By difference, deposition in vacuum resulted in the coexistence of hexagonal and cubic crystallites embedded into an amorphous matrix. The introduction of Cr atoms into the AlN lattice causes a broadening of the IR spectrum along with the shift toward higher wavenumbers of the characteristic Al-N bands at 2351 cm⁻¹ and 665 cm⁻¹, respectively. This was related to the generation of a compressive stress inside films. In comparison to the optical constants of pure AlN films, the synthesized AlN:Cr films exhibited a smaller refractive index and showed a weak absorption throughout the 300-800 nm spectral region, characteristic to amorphous AlN structure.     

A study of the optical properties of titanium oxide films prepared by dc reactive magnetron sputtering

TiO₂ thin films were deposited on the glass substrates by dc reactive magnetron sputtering technique at different sputtering pressures (2 × 10⁻³ to 2 × 10⁻² mbar). The films prepared at low pressures have an anatase phase, and the films prepared at high pressures have an amorphous phase. The optical properties were studied by measuring the transmittance and the ellipsometric spectra. The optical constants of the films in the visible range were obtained by fitting the transmittance combined with the ellipsometry measurements using the classical model with one oscillator. The refractive index of the films decreases from 2.5 until 2.1 as the sputtering pressure increases from 2 × 10⁻³ to 2 × 10⁻² mbar. The films prepared at the pressure higher than 6 × 10⁻³ mbar show a volume inhomogeneity. This volume inhomogeneity has been calculated by fitting the transmittance and the ellipsometric spectra. The volume inhomogeneity of the film prepared at the highest sputtering pressure is about 10%. Although the films prepared at high pressures show a large volume inhomogeneity, they have low extinction coefficients. It is suggested that the anatase phase results in more light scattering than amorphous phase does, and then a high extinction coefficient.     

X-ray and neutron studies of nanoscale atomic diffusion in thin films and multilayers

In the present work we review some X-ray and neutron based techniques capable of measuring diffusion lengths in thin films with an accuracy of a fraction of a nanometer. The techniques have been used for studying both self-diffusion of the constituent species in a thin film, as well as interdiffusion at the interfaces in multilayers. The high accuracy of the techniques in depth profiling of an element or a specific isotope makes very low diffusivities ∼10⁻²³ m²/s, amenable to measurements, and allows one to study the subtle effects of factors like internal stresses or structural relaxation on self-diffusion in compositionally homogeneous films. Depth selectivity of X-ray standing wave technique in multilayers makes it possible to distinguish between diffusion at the two types of the interfaces, namely A-on-B and B-on-A, in a single multilayer structure.     

Preparation and characterization of transparent NiO thin films deposited by spray pyrolysis technique

Nickel oxide thin films were successfully fabricated with various deposition time (t_d = 5, 10, and 15 min) on glass substrates using spray pyrolysis technique. The deposited films undergo thermal treatment at 350 °C for various annealing time (t_a = 0, 15, 30 and 60 min). In this study, the effect of t_d and t_a on film thickness was observed and their influence on structural, morphological and optical properties were investigated. The films deposited with t_d = 5 min showed amorphous structure while the films grown at higher deposition time became partially crystallized with preferred growth along (1 1 1) direction. Heat treatment carried out in air allowed us to tune the polycrystalline structure and the diffraction intensity at preferred peak increases with the increase in t_a which is a consequence of better crystallinity. This was reflected in the AFM micrographs of the films which suggested that the thermal annealing (or increasing t_a) facilitates the process of grain-growth, and improves the crystalline microstructure. The optical transmission of the films was found to vary with t_d and t_a and thus film thickness. The thinner films show higher transparency in the UV–vis spectral region. The optical band gap was blue-shifted from 3.35 eV to 3.51 eV depending on t_a. The effect of t_a on the various optical constants of the NiO films has also been discussed.     

Ellipsometry investigation of the effects of annealing temperature on the optical properties of indium tin oxide thin films studied by Drude-Lorentz model

Float glass substrates covered by high quality ITO thin films (Balzers) were subjected for an hour to single thermal treatments at different temperature between 100 °C and 600 °C. In order to study the electric and optical properties of both annealed and not annealed ITO-covered float glasses, ellipsometry, spectrophotometry, impedance analysis, and X-ray measurements were performed. Moreover, variable angle spectroscopic ellipsometry provides relevant information on the electronic and optical properties of the samples. ITO film is modeled as a dense lower layer and a surface roughness layer. The estimated optical density for ITO and the optical density of the surface roughness ITO layer increases with the annealing temperature. In the near-IR range, the extinction coefficient decreases while the maximum of the absorption in the near UV range shift towards low photon energy as the annealing temperature increases. Spectrophotometry was used to estimate the optical band-gap energy of the samples. The thermal annealing changes strongly the structural and optical properties of ITO thin films, because during the thermal processes, the ITO thin film absorbs oxygen from air. This oxygen absorption decreases the oxygen vacancies therefore the defect densities in the crystalline structure of the ITO thin films also decrease, as confirmed both by ellipsometry and X-ray measurements.     

Superhydrophobic and transparent ZnO thin films synthesized by spray pyrolysis technique

Superhydrophobic and transparent zinc oxide (ZnO) thin films were deposited by a simple and cost effective spray pyrolysis technique (SPT) onto the glass substrates at 723 K from an aqueous zinc acetate precursor solution. The solution concentration was varied from 0.1 to 0.4 M and its effect on structural, morphological, wetting and optical properties of ZnO thin films was studied. The synthesized films were found to be polycrystalline, with preferential growth along c-axis. A slight improvement in the crystallite size and texture coefficient is observed as the concentration of the solution is increased. SEM micrographs show the uniform distribution of spherical grains of about 60-80 nm grain size. The films were specular and highly transparent with average transmittance of about 85%. The spectrum shows sharp absorption band edge at 381 nm, corresponding to optical gap of 3.25 eV. The samples of texture coefficient less than 90% and roughness less than 75 nm are hydrophobic and above these values they become superhydrophobic in nature. The hydrophobicity coupled with high transmittance is of great importance in commercial application such as transparent self-cleaning surfaces, anti-fog, anti-snow, fluid microchips and microreactors.     

Influence of sputter-etching of substrate on the microstructural and optical properties of ZnO films deposited by RF magnetron sputtering

ZnO films were prepared using radio frequency magnetron sputtering on Si(1 1 1) substrates that were sputter-etched for different times ranging from 10 to 30 min. As the sputter-etching time of the substrate increases, both the size of ZnO grains and the root-mean-square (RMS) roughness decrease while the thickness of the ZnO films shows no obvious change. Meanwhile, the crystallinity and c-axis orientation are improved by increasing the sputter-etching time of the substrate. The major peaks at 99 and 438 cm⁻¹ are observed in Raman spectra of all prepared films and are identified as E₂(low) and E₂(high) modes, respectively. The Raman peak at 583 cm⁻¹ appears only in the films whose substrates were sputter-etched for 20 min and is assigned to E₁(LO) mode. Typical ZnO infrared vibration peak located at 410 cm⁻¹ is found in all FTIR spectra and is attributed to E₁(TO) phonon mode. The shoulder at about 382 cm⁻¹ appearing in the films whose substrates were sputter-etched for shorter time (10-20 min) originates from A₁(TO) phonon mode. The results of photoluminescence (PL) spectra reveal that the optical band gap (Eg) of the ZnO films increases from 3.10 eV to 3.23 eV with the increase of the sputter-etching time of the substrate.     

Determination of refractive index profiles of gradient optical waveguides by ellipsometry

Ag⁺-Na⁺ and K⁺-Na⁺ ion-exchanged optical waveguides in soda-lime glass are characterised by ellipsometry. Refractive index profiles of the waveguides are calculated from ellipsometric multiple angle of incidence data using the Newton-Kantorovitch type iterative procedure and compared with those reconstructed by inverse WKB method. It is demonstrated that such continuous profiles with relatively small index gradient (of the order of 0.1 and 0.01), extending to few micrometers in depth, can be determined by ellipsometric measurements. A good agreement is found between results obtained by ellipsometry and by the inverse WKB method at depths above 500–600 nm, while there is a difference in the subsurface region, where ellipsometry is more sensitive to the quality of the surface. The profiles obtained by the two methods are consistent if the surface thin layer is etched.     

Electronic and optical properties in ZnO:Ga thin films induced by substrate stress

The effects of biaxial stress in ZnO:Ga thin films on different substrates, e.g., sapphire(0001), quartz, Si(001), and glass have been investigated by X-ray diffraction, atomic force microscopy, and electrical transport and ellipsometric measurements. A strong dependence of orientation, crystallite size, transport, and electronic properties upon the substrate-induced stress has been found. The structural properties indicate that a tensile stress exists in epitaxial ZnO:Ga films grown on sapphire, Si, and quartz, while a compressive stress appears in films grown on glass. The resistivity of the films decreased with increasing biaxial stress, which is inversely proportional to the product of the carrier concentration and Hall mobility. The refractive index n was found to decrease with increasing biaxial stress, while the optical band gap E₀ increased with stress. These behaviors are attributed to lattice contraction and the increase in the carrier concentration that is induced by the stress. Our experimental data suggest that the mechanism of substrate-induced stress is important for understanding the properties of ZnO:Ga thin films and for the fabrication of devices which use these materials.     

Correlation of optical and microstructural properties of Gd2O3 thin films through phase-modulated ellipsometry and multi-mode atomic force microscopy

Gadolinium oxide thin films have been prepared by electron beam evaporation with different reactive oxygen pressures at low ambient substrate temperature. These thin films have been analyzed with phase-modulated spectroscopic ellipsometry and multi-mode atomic force microscopy (AFM). The distinct influences of oxygen pressure on surface topographies, microstructures and refractive indices of the thin films have been observed from the results of these advanced measurements. Both these techniques have displayed very strong co-relationships in the characterisation results acquired through respective modes of measurements and data analysis. Unequivocally, these two techniques indicated an optimum value of the oxygen pressure leading to best optical and structural properties of such a novel optical coating material.