Combination Of Spectroscopic Ellipsometry Research Articles

Origins and cavity-based regulation of optical anisotropy of α-MoO3 crystal

Orthogonal α-MoO3 is one of the most common and air-stable compounds of molybdenum, holding the merits of wide bandgap, van der Waals (vdW) structure, biaxial symmetry and recently discovered hyperbolic topological transitions, which has drawn significant attention in developing novel nanophotonic and optoelectronic devices. Herein the broadband optical anisotropy, one of the most fundamental physical characteristics of α-MoO3 crystal, was systematically investigated using a combination of spectroscopic ellipsometry (SE) and reflectance difference spectroscopy (RDS). The centimeter-level high-quality α-MoO3 crystal was grown by modified physical vapor deposition. The optical refractive indices along three crystalline axes were precisely determined by SE in the broad spectral range (400–1600 nm), and then the in-plane and out-plane birefringence was analyzed. Both the intrinsic and resonant cavity modulated optical anisotropy of α-MoO3 was studied by polarization-resolved RDS, from which we find the physical origins of linear dichroism are dominated by electronical transitions along the c-axis. Furthermore, the external photonic cavity of SiO2 enables enhanced sensitivity to view electronical transitions and a high modulation ratio of optical anisotropy reached 30, which provides new opportunities to tune optical anisotropy for polarized photonic devices. Our results can help understand the physical origin of the highly optical anisotropy of α-MoO3 and establish an effective metrological tool to study other types of vdW crystals.

Investigation of SARS-CoV-2 nucleocapsid protein interaction with a specific antibody by combined spectroscopic ellipsometry and quartz crystal microbalance with dissipation

Detailed evaluations of the antigen and antibody interaction rate and strength of the immune complex formed are very important for medical and bioanalytical applications. These data are crucial for the development of sensitive and fast immunosensors suitable for continuous measurements. Therefore, combined spectroscopic ellipsometry (SE) and quartz crystal microbalance with dissipation (QCM-D) technique (SE/QCM-D) was used for the evaluation: (i)of covalent immobilization of SARS-CoV-2 nucleocapsid protein (SCoV2-N) on QCM-D sensor disc modified by self-assembled monolayer based on 11-mercaptoundecanoic acid and (ii)interaction of immobilized SCoV2-N with specific polyclonal anti-SCoV2-N antibodies followed by immune complex formation process. The results show that the SCoV2-N monolayer is rigid due to the low energy dissipation registered during the QCM-D measurement. In contrast, the anti-SCoV2-N layer produced after interaction with the immobilized SCoV2-N formed a soft and viscous layer. It was determined, that the sparse distribution of SCoV2-N on the surface affected the spatial arrangement of the antibody during the formation of immune complexes. The hinge-mediated flexibility of the antibody Fab fragments allows them to reach the more distantly located SCoV2-N and establish a bivalent binding between proteins in the formed SCoV2-N/anti-SCoV2-N complex. It was noted that the SE/QCM-D method can provide more precise quantitative information about the flexibility and conformational changes of antibody during the formation of the immune complex on the surface over time.

Spectroscopic Ellipsometry and Quartz Crystal Microbalance with Dissipation for the Assessment of Polymer Layers and for the Application in Biosensing.

Polymers represent materials that are applied in almost all areas of modern life, therefore, the characterization of polymer layers using different methods is of great importance. In this review, the main attention is dedicated to the non-invasive and label-free optical and acoustic methods, namely spectroscopic ellipsometry (SE) and quartz crystal microbalance with dissipation (QCM-D). The specific advantages of these techniques applied for in situ monitoring of polymer layer formation and characterization, biomolecule immobilization, and registration of specific interactions were summarized and discussed. In addition, the exceptional benefits and future perspectives of combined spectroscopic ellipsometry and QCM-D (SE/QCM-D) in one measurement are overviewed. Recent advances in the discussed area allow us to conclude that especially significant breakthroughs are foreseen in the complementary application of both QCM-D and SE techniques for the investigation of polymer structure and assessment of the interaction between biomolecules such as antigens and antibodies, receptors and ligands, and complementary DNA strands.

Characterization on Percolation of Nanostructured Silver Films by the Topological Properties of Spectroscopic Ellipsometric Parameter Trajectories

Silver (Ag) films with different nanostructures were prepared by electron beam evaporation and characterized by spectroscopic ellipsometry in combination with X-ray diffraction and field emission s...

Broadband and comparative third-order nonlinearities in reduced graphene oxide with CVD graphene

Abstract We successfully fabricated 2D thin film by dispersing reduced graphene oxide into the PVA matrix and experimentally determined the third-order nonlinearity of reduced graphene oxide in the visible region of the spectrum (450–750 nm) by the combination of spectroscopic ellipsometry and femtosecond pump and probe spectroscopy. The utilization of chemical vapor deposition (CVD) graphene increases in nanophotonics technologies owing to the high tunability superior to noble metals. However, their scalable application is limited due to high-temperature, high-cost fabrication techniques, and complicated transfer procedures. Here, reduced graphene oxide is proposed to be a promising nominee, with relatively simple and low-cost fabrication techniques. Comparable nonlinearity to that of CVD graphene, and identical tunability that π conjugation electronic transitions dominates their nonlinear response, demonstrated that reduced graphene oxide is a viable alternative. The third-order susceptibility in the visible region reveals their substantial behavior to wavelength and pulse width of light in nonlinear state, which propels the movement of manipulating light at the nanoscale over broad wavelength.

Brillouin zone center phonon modes in ZnGa2O4

Infrared-active lattice mode properties of melt-grown high-quality single bulk crystals of ZnGa2O4 are investigated by combined spectroscopic ellipsometry and density functional theory computation analysis. The normal spinel structure crystals are measured by spectroscopic ellipsometry at room temperature in the range of 100 cm–1–1200 cm–1. The complex-valued dielectric function is determined from a wavenumber-by-wavenumber approach, which is then analyzed by the four-parameter semi-quantum model dielectric function approach augmented by impurity mode contributions. We determine four infrared-active transverse and longitudinal optical mode pairs, five localized impurity mode pairs, and the high frequency dielectric constant. All four infrared-active transverse and longitudinal optical mode pairs are in excellent agreement with results from our density functional theory computations. With the Lyddane–Sachs–Teller relationship, we determine the static dielectric constant, which agrees well with electrical capacitance measurements performed on similarly grown samples. We also provide calculated parameters for all Raman-active and for all silent modes and, thereby, provide a complete set of all symmetry predicted Brillouin zone center modes.

Initial Growth and Crystallization Onset of Plasma Enhanced-Atomic Layer Deposited ZnO

Direct plasma enhanced-atomic layer deposition (PE-ALD) is adopted for the growth of ZnO on c-Si with native oxide at room temperature. The initial stages of growth both in terms of thickness evolution and crystallization onset are followed ex-situ by a combination of spectroscopic ellipsometry and X-ray based techniques (diffraction, reflectivity, and fluorescence). Differently from the growth mode usually reported for thermal ALD ZnO (i.e., substrate-inhibited island growth), the effect of plasma surface activation resulted in a substrate-enhanced island growth. A transient region of accelerated island formation was found within the first 2 nm of deposition, resulting in the growth of amorphous ZnO as witnessed with grazing incidence X-ray diffraction. After the islands coalesced and a continuous layer formed, the first crystallites were found to grow, starting the layer-by-layer growth mode. High-temperature ALD ZnO layers were also investigated in terms of crystallization onset, showing that layers are amorphous up to a thickness of 3 nm, irrespective of the deposition temperature and growth orientation.

Changes in surface morphology of helium-induced tungsten nanostructure during high-temperature annealing

Abstract When exposed to high-flux helium plasmas, tungsten is known to develop a surface nanostructure called tungsten fuzz. Although there exists a consensus for the general mechanisms that lead to this nanostructure, a number of questions regarding its formation have yet to be addressed. One common approach to investigate helium-tungsten interactions is thermal desorption spectroscopy (TDS), as TDS can offer insight into the trapping of helium in tungsten that ultimate drives the nanostructure growth. However, during TDS, the surface morphology of the tungsten nanostructure can change dramatically at temperatures substantially lower than those required to fully desorb the trapped helium. For a comprehensive interpretation of TDS spectra, the helium release from trapping sites should be disentangled from complications that may arise from the changing surface morphology. In this work, we characterize the effects of high-temperature annealing on the surface morphology of tungsten nanostructure during TDS. Six ITER-grade W samples were exposed to helium plasma under identical conditions (a He ion fluence Φ i = 8.6 × 10 24 m − 2 , ion energy of 90 eV, and sample temperature of 1123 K) to generate similar surface nanostructures on each sample. Samples were then annealed at various temperatures for different durations to determine the impact of annealing temperature and duration on the surface nanostructure. During annealing, TDS spectra of the He release rate were obtained using a quadrupole mass spectrometer, yielding He release peaks near 373 K and 1123 K. Changes to the surface morphology were observed on samples annealed at temperatures as low as 1173 K, using a combination of spectroscopic ellipsometry and helium ion microscopy with focused ion beam profiling.

Optical and magneto-optical properties of GdxFe(100-x) thin films close to the compensation point

Unlike ferromagnetic materials, ferrimagnetic metals have recently received considerable attention due to their bulk perpendicular magnetic anisotropy, low net magnetization and tunable magnetic properties. This makes them perfect candidates for the research of recently discovered spin-torque related phenomena. Among other ferrimagnetic metals, GdFe has an advantage in relatively large magnetic moments in both sublattices and tunability of compensation point above the room temperature by small changes in its composition. We present a systematic study of optical and magneto-optical properties of amorphous GdxFe(100-x) thin films of various compositions (x = 18.3, 20.0, 24.7, 26.7) prepared by DC sputtering on thermally oxidized SiO2 substrates. A combination of spectroscopic ellipsometry and magneto-optical spectroscopy in the photon energy range from 1.5 to 5.5 eV with advanced theoretical models allowed us to deduce the spectral dependence of complete permittivity tensors across the compensation point. Such information is important for further optical detection of spin related phenomena driven by vicinity of compensation point in nanostructures containing GdFe.

Diagnostic of graphene on Ge(100)/Si(100) in a 200 mm wafer Si technology environment by spectroscopic ellipsometry/reflectometry

Comprehensive diagnostics is a prerequisite for the application of graphene in semiconductor technologies. Here, the authors present long-term investigations of graphene on 200-mm Ge(100)/Si(100) wafers under clean room environmental conditions. Diagnostic of graphene was performed by a fast and nondestructive metrology method based on the combination of spectroscopic ellipsometry and reflectometry (SE/R), realized within a wafer optical metrology tool. A robust procedure for unambiguous thickness monitoring of a multilayer film stack, including graphene, interface layer GeOx underneath graphene, and surface roughness is developed and applied for process control. The authors found a relationship between the quality of graphene and the growth of GeOx beneath graphene. Enhanced oxidation of Ge beneath graphene was registered as a long-term process. SE/R measurements were validated and complemented using atomic force microscopy, scanning electron microscopy, Raman spectroscopy, and secondary ion mass spectrometry. This comparative study shows a high potential for optical metrology of graphene deposited on Ge/Si structures, due to its great sensitivity, repeatability, and flexibility, realized in a nondestructive way.

Combination of spectroscopic ellipsometry and spectroscopic reflectometry with including light scattering in the optical characterization of randomly rough silicon surfaces covered by native oxide layers

A combined method of spectroscopic ellipsometry and spectroscopic reflectometry is employed for the optical characterization of randomly rough surfaces of silicon single crystal covered with very thin native oxide layers within spectral range 197–1240 nm (1.0–6.3 eV). It is shown that random roughness of the samples of this system exhibits a wide interval of spatial frequencies so that the Rayleigh–Rice theory, scalar diffraction theory for coherent light and scalar diffraction theory with including light scattering must be used to achieve good fits of experimental data. The ellipsometric data are compatible with the Rayleigh–Rice theory within the entire spectral range while the reflectometric data must be processed separately within two sub-ranges using two different theoretical approaches. In one of the sub-ranges the combination of Rayleigh–Rice theory and scalar diffraction theory for coherent light is utilized for obtaining good fits of the corresponding experimental data of reflectance. Within the latter sub-range the scalar diffraction theory including the influence of light scattering on reflectance enables us to achieve good fits. Further, it is shown that using this combined method the values of basic roughness parameters, i.e. the rms values of heights, autocorrelation lengths and rms values of slopes of roughness irregularities, can be determined together with thickness values of the native oxide layers. A comparison of the results achieved optically with those determined by atomic force microscopy is performed. The assessment of efficiency of spectroscopic ellipsometry and spectroscopic reflectometry in characterizing random roughness with the wide interval of spatial frequencies is also presented.

Origin of quasilocal plasmons in Nb-substituted EuTiO3

Doped perovskite oxides are promising ``material building blocks'' for achieving tunable and intrinsically low-loss plasmonic features in the visible- to near-infrared range, which are unlikely to obtain from conventional plasmonic materials. Here, using a combination of spectroscopic ellipsometry, soft x-ray absorption, x-ray photoemission, and ultraviolet photoemission spectroscopic measurements we observe an unconventional tunable low-loss quasilocal plasmon in the IR energy (1 eV) range in the Nb-substituted perovskite oxide $\mathrm{EuTi}{\mathrm{O}}_{3}$ ($\mathrm{EuT}{\mathrm{i}}_{1\ensuremath{-}x}\mathrm{N}{\mathrm{b}}_{x}{\mathrm{O}}_{3}$). This low-loss plasmon oscillation is formed by many-body interactions, an interplay of quasifree ${d}^{1}$ electrons and hybridizations of Eu 4f-Ti $3d$ and O 2p-Ti $3d$. We find that the Nb substitution at Ti site modifies the $\mathrm{Ti}{\mathrm{O}}_{6}$ octahedral tilting and, consequently, alters the electronic structure. Our study reveals the importance of charge, orbital, and lattice to generate plasmons in $\mathrm{EuT}{\mathrm{i}}_{1\ensuremath{-}x}\mathrm{N}{\mathrm{b}}_{x}{\mathrm{O}}_{3}$.

Electronic structure of La2/3Sr1/3MnO3 : Interplay of oxygen octahedra rotations and epitaxial strain

Influence of epitaxial strain and oxygen octahedra rotations on electronic structure of ${\mathrm{La}}_{2/3}{\mathrm{Sr}}_{1/3}{\mathrm{MnO}}_{3}$ ultrathin films was systematically studied. The investigated films were grown by pulsed laser deposition on four different substrates: cubic (001)-oriented ${\mathrm{LaAlO}}_{3}$, (001) ${({\mathrm{LaAlO}}_{3})}_{1/3}{({\mathrm{Sr}}_{2}{\mathrm{AlTaO}}_{6})}_{2/3}$, (001) ${\mathrm{SrTiO}}_{3}$, and orthorhombic (110) ${\mathrm{DyScO}}_{3}$, providing a broad range of induced epitaxial strains. Magnetic properties were found to deteriorate with increasing value of the epitaxial strain, as expected due to unit cell distortion increasingly deviating from the bulk and effect of the magnetically inert layer. A combination of spectroscopic ellipsometry and magneto-optical Kerr effect spectroscopy was used to determine spectra of the diagonal and off-diagonal elements of permittivity tensor. The off-diagonal elements at room temperature confirmed the presence of two previously reported electronic transitions in the spectra of all films. Moreover they revealed another electronic transition around 4.3 eV only in the spectra of films grown under compressive strain. We proposed classification of this transition as a crystal field paramagnetic Mn ${t}_{2g}\ensuremath{\rightarrow}{e}_{g}$ transition. Ab initio calculations were employed to distinguish between the potential influence of oxygen octahedra rotations and distortions. The ab initio calculations indicated a negligible influence of oxygen octahedra rotations on magneto-optical properties of ${\mathrm{La}}_{2/3}{\mathrm{Sr}}_{1/3}{\mathrm{MnO}}_{3}$. They further supported the proposed classification of the additional electronic transition, showing a key role of strain in controlling the electronic structure of ultrathin perovskite films.

Functionalizing gold with single strand DNA: novel insight into optical properties via combined spectroscopic ellipsometry and nanolithography measurements.

We have studied the self-assembly of 22-base oligonucleotides bound by a short alkyl thiol linker (C6-ssDNA) on flat Au films. The self-assembled monolayer (SAM) was modified by addition of a spacer (mercaptohexanol, MCH). Molecular depositions were monitored in situ by spectroscopic ellipsometry (SE). SAMs were characterized in a liquid environment by coupling SE (difference spectra method) with Atomic Force Microscope (AFM) measurements. We exploited the biofilm thickness obtained by AFM nanolithography and imaging to solve the refractive index/thickness correlation in optical measurements on ultrathin molecular layers. The combined SE/AFM analysis provided reliable estimates of the thickness and the refractive index of the biofilm in the NIR region (650-1300 nm) and revealed new aspects of DNA molecular organization: exposure to MCH leads to an increase of both film thickness and refractive index, which points to a reorganization of C6-ssDNA film. We show that the contribution of the thiol/Au interface has to be included in the optical model to obtain a more reliable determination of the refractive index of the biofilm in a liquid. The careful, correlative characterization of the mixed C6-ssDNA/MCH SAM represents a key step towards the optimization of a robust detection scheme based on helix-helix hybridization.

(TiO2)1–x(TaON)x Solid Solution for Band Engineering of Anatase TiO2

Band engineering of anatase TiO2 was achieved by means of an anatase (TiO2)1–x(TaON)x (TTON) solid solution. Epitaxial thin films of TTON (0.1 ≤ x ≤ 0.9) were synthesized by nitrogen plasma-assisted pulsed laser deposition on (LaAlO3)0.3(SrAl0.5Ta0.5O3)0.7 substrates. Epitaxial growth of anatase TTON was confirmed by X-ray diffraction. The lattice constants of the TTON thin films increased with TaON content in accordance with Vegard’s law, indicating formation of a complete solid solution. The bandgaps, band alignment, and refractive indices of the TTON thin films were investigated by combination of spectroscopic ellipsometry and X-ray photoelectron spectroscopy. The bandgap of the anatase TTON systematically decreased with increasing x, mainly because of an upward shift in the valence band maximum caused by broadening of the valence band as a result of hybridization of the shallow N 2p orbital. The position of the conduction band minimum was rather insensitive to chemical composition, which makes the ban...

Polycrystalline La1-xSrxMnO3 films on silicon: Influence of post-Deposition annealing on structural, (Magneto-)Optical, and (Magneto-)Electrical properties

The integration of La1-xSrxMnO3 (LSMO) thin film technology into established industrial silicon processes is regarded as challenging due to lattice mismatch, thermal expansion, and chemical reactions at the interface of LSMO and silicon. In this work, we investigated the physical properties of thin La0.73Sr0.27MnO3 films deposited by magnetron sputtering on silicon without a lattice matching buffer layer. The influence of a post-deposition annealing treatment on the structural, (magneto-)optical, and (magneto-)electrical properties was investigated by a variety of techniques. Using Rutherford backscattering spectroscopy, atomic force microscopy, Raman spectroscopy, and X-ray diffraction we could show that the thin films exhibit a polycrystalline, rhombohedral structure after a post-deposition annealing of at least 700°C. The dielectric tensor in the spectral range from 1.7eV to 5eV determined from spectroscopic ellipsometry in combination with magneto-optical Kerr effect spectroscopy was found to be comparable to that of lattice matched films on single crystal substrates reported in literature [1]. The values of the metal-isolator transition temperature and temperature-dependent resistivities also reflect a high degree of crystalline quality of the thermally treated films.

Anisotropic optical constants, birefringence, and dichroism of wurtzite GaN between 0.6 eV and 6 eV

We report the room-temperature anisotropic dielectric functions (DFs), refractive indices, and absorption coefficients as well as birefringence and dichroism of wurtzite GaN in the spectral range between 0.6 eV and 6 eV. They have been determined by combined spectroscopic ellipsometry, optical retardation, and transmission measurements on a series of m- and c-plane bulk substrates prepared from crystals grown by hydride vapor phase epitaxy. The accuracy of the derived DFs is estimated by investigation of the role of mosaicity-related crystal imperfections, self-consistency test based on a Kramers-Kronig analysis, and examination of the influence of kind of overlayer. We also briefly discuss optical properties of a highly defective near-surface layer of GaN crystals introduced by their mechanical polishing.

Modeling and in Situ Probing of Surface Reactions in Atomic Layer Deposition.

Atomic layer deposition (ALD) has matured into a preeminent thin film deposition technique by offering a highly scalable and economic route to integrate chemically dissimilar materials with excellent thickness control down to the subnanometer regime. Contrary to its extensive applications, a quantitative and comprehensive understanding of the reaction processes seems intangible. Complex and manifold reaction pathways are possible, which are strongly affected by the surface chemical state. Here, we report a combined modeling and experimental approach utilizing ReaxFF reactive force field simulation and in situ real-time spectroscopic ellipsometry to gain insights into the ALD process of Al2O3 from trimethylaluminum and water on hydrogenated and oxidized Ge(100) surfaces. We deciphered the origin for the different peculiarities during initial ALD cycles for the deposition on both surfaces. While the simulations predicted a nucleation delay for hydrogenated Ge(100), a self-cleaning effect was discovered on oxidized Ge(100) surfaces and resulted in an intermixed Al2O3/GeOx layer that effectively suppressed oxygen diffusion into Ge. In situ spectroscopic ellipsometry in combination with ex situ atomic force microscopy and X-ray photoelectron spectroscopy confirmed these simulation results. Electrical impedance characterizations evidenced the critical role of the intermixed Al2O3/GeOx layer to achieve electrically well-behaved dielectric/Ge interfaces with low interface trap density. The combined approach can be generalized to comprehend the deposition and reaction kinetics of other ALD precursors and surface chemistry, which offers a path toward a theory-aided rational design of ALD processes at a molecular level.

Enhancing Carrier Mobilities in Organic Thin-Film Transistors Through Morphological Changes at the Semiconductor/Dielectric Interface Using Supercritical Carbon Dioxide Processing.

Charge-carrier mobilities in poly(3-hexylthiophene) (P3HT) organic thin-film transistors (OTFTs) increase 5-fold when OTFTs composed of P3HT films on trichloro (1H, 1H, 2H, 2H-perfluorooctyl) silane (FTS) monolayers supported on SiO2 dielectric substrates (P3HT/FTS/SiO2/Si) are subjected to supercritical carbon dioxide (scCO2) processing. In contrast, carrier mobilities in P3HT/octadecyltrichlorosilane (OTS)/SiO2 OTFTs processed using scCO2 are comparable to mobilities measured in as-cast P3HT/OTS/SiO2/Si devices. Topographical images of the free and buried interfaces of P3HT films reveal that scCO2 selectively alters the P3HT morphology near the buried P3HT/FTS-SiO2 interface; identical processing has negligible effects at the P3HT/OTS-SiO2 interface. A combination of spectroscopic ellipsometry and grazing-incidence X-ray diffraction experiments indicate insignificant change in the orientation distribution of the intermolecular π-π stacking direction of P3HT/FTS with scCO2 processing. The improved mobilities are instead correlated with enhanced in-plane orientation of the conjugated chain backbone of P3HT after scCO2 annealing. These findings suggest a strong dependence of polymer processing on the nature of polymer/substrate interface and the important role of backbone orientation toward dictating charge transport of OTFTs.

Ellipsometric and reflectometric characterization of thin films exhibiting thickness non-uniformity and boundary roughness

In this paper epitaxial ZnSe thin films prepared by molecular beam epitaxy onto GaAs single crystal substrates exhibiting two defects, i.e. boundary roughness and thickness non-uniformity, are optically characterized using a combination of spectroscopic ellipsometry and near-normal spectroscopic reflectometry. The influence of boundary roughness is included into optical quantity formulae by the combination of the scalar diffraction theory and Rayleigh–Rice theory. Very thin overalyers modelled by rough thin films with identically rough boundaries are taken into account on the upper boundaries of the ZnSe thin films. Two approximations are used to express the local reflection coefficient of the rough ZnSe thin films covered with the overlayers within combination of both the theories. Thickness non-uniformity is incorporated by means of averaging the elements of the unnormalized Mueller matrices. The universal dispersion model of the optical constants of the ZnSe thin films based on parametrization of the joint density of electronic states is used. The spectral dependencies of the optical constants of the ZnSe thin films are determined within the wide spectral range (0.12–8.7eV). Moreover, the mean thickness of the ZnSe thin films and thickness of overlayers are determined together with the other structural parameters characterizing the defects. The values of roughness parameters, determined by the optical method, are verified by a comparison with results achieved by atomic force microscopy. It is also shown that the approximations of the local reflection coefficient presented are usable for processing the experimental data.