Reflectance Anisotropy Spectroscopy Research Articles

The relevance of structural variability in the time-domain for computational reflection anisotropy spectroscopy at solid–liquid interfaces

In electrochemistry, reactions and charge-transfer are to a large extent determined by the atomistic structure of the solid–liquid interface. Yet due to the presence of the liquid electrolyte, many surface-science methods cannot be applied here. Hence, the exact microscopic structure that is present under operating conditions often remains unknown. Reflection anisotropy spectroscopy (RAS) is one of the few techniques that allow for an in operando investigation of the structure of solid–liquid interfaces. However, an interpretation of RAS data on the atomistic scale can only be obtained by comparison to computational spectroscopy. While the number of computational RAS studies related to electrochemical systems is currently still limited, those studies so far have not taken into account the dynamic nature of the solid–liquid interface. In this work, we investigate the temporal evolution of the spectroscopic response of the Au(110) missing row reconstruction in contact with water by combining ab initio molecular dynamics with computational spectroscopy. Our results show significant changes in the time evolution of the RA spectra, in particular providing an explanation for the typically observed differences in intensity when comparing theory and experiment. Moreover, these findings point to the importance of structural surface/interface variability while at the same time emphasising the potential of RAS for probing these dynamic interfaces.

Creation and plasmon anisotropy spectroscopy of wedge-shaped gold nanoclusters conditioned by GaAs(001) surface

Wedge-shaped nanoclusters of gold (Au2Ga) are fabricated by high-temperature annealing of a gold nanofilm deposited onto (001) surface of p-doped GaAs crystal with a very thin overlayer of natural oxide. The data of diagnostics confirm the presence in prepared Au/p-GaAs(001) structures of the wedge-shaped Au-intermetallic nanoclusters elongated in [110] direction at GaAs surface. A crystallographic model of the wedge-shaped Au (Au2Ga) nanoclusters conditioned by GaAs(001) surface is discussed in relation with their physicochemical nature. Anisotropic plasmons localized on equally oriented Au-based nanoclusters are detected optically with the reflectance anisotropy spectroscopy and investigated thoroughly with the spectroscopy of polarized light reflection. It is proved experimentally and theoretically that the inhomogeneously broadened infrared spectral peak at the energy about 1.1 eV is associated with plasmons polarized along the wedge-shaped clusters in [110] crystal direction. Another peak - at the energy approximately of 1.8 eV - is due to plasmons having orthogonal polarization in direction [11¯0].

Identification and control of crystalline nuclei facets imparting to the breaking of symmetry selection rules of optical phonon modes in GaP/Si (001)

The complex interfacial structural issues associated with hetero-polar epitaxial integration of GaP on Si(001) are resolved by improving the kinetics of gallium and phosphorous adatoms during the initial nucleation process. This is achieved through the use of Raman spectroscopy as a feedback mechanism. The peak intensity ratio of forbidden (transverse optical)-to-allowed (longitudinal optical) phonons of GaP under unpolarized Raman scattering is contemplated as an initial guide to ascertain the relative density of defect-mediated non-(001) GaP facets. The azimuthal-angle dependent polarized Raman spectroscopy is then applied to identify and quantify the nucleation of higher-index non-(001) ({111} and {112}) faceted islands in the nucleation layer and their propagation in the overgrown structures. The nucleation of GaP adatoms on the Silicon surface at ∼525 °C leads to a smooth surface and substantially suppresses the defect-mediated facets. The optimal mobility and controlled adsorption of adatoms of Ga and P on the substrate surface under intermediate nucleation kinetics foster the charge-neutral interface, and hence the defect-suppressed two-dimensional layer growth of GaP. The proposed Raman spectroscopy methodology emerges as a rapid and economical alternative to existing in situ reflection anisotropy spectroscopy and high-resolution transmission electron microscopy techniques for structural identification. This method of growth optimization can also be applied to other III-V polar semiconductors to achieve high-quality and efficient monolithic integration of devices on existing Si technology.

In Situ Monitoring of the Al(110)‐[EMImCl] : AlCl3 Interface by Reflection Anisotropy Spectroscopy

AbstractRecently, Al‐batteries (AlBs) have become promising candidates for post‐lithium batteries, with [EMImCl] : AlCl3 (1 : 1.5) as the most commonly used electrolyte. However, progress in the development of AlBs is currently hindered by the lack of understanding of its solid‐electrolyte interface. Monitoring the structure of this interface under operational conditions by complementary spectroscopy could help to identify and overcome bottlenecks of the system. Reflection anisotropy spectroscopy (RAS), an optical in situ technique, provides access to physical and chemical properties of electrochemical interfaces on an atomistic level. Herein, we report the first example of RAS as an in situ characterization technique for non‐aqueous battery systems, investigating an Al(110)‐based model system. During chemical pre‐treatment in [EMImCl] : AlCl3, the Al(110) surface passivation film is modified. The oxide film is partially etched while an inhomogeneous passivation layer forms, increasing the surface roughness. Upon electrochemical cycling, applied potential‐dependent oscillations of the anisotropy are observed and demonstrate the applicability of RAS to monitor phenomena such as plating/stripping and surface passivation in real‐time.

Understanding growth‐faulted GaAsBi samples by Reflectance Anisotropy Spectroscopy.

Reflectance Anisotropy Spectroscopy (RAS) has been recently applied to Molecular Beam Epitaxy (MBE) of GaAsBi alloys. The presence of the voluminous Bi atoms induces strain in the crystal lattice, modifying the substrate symmetry of the centrosymmetric GaAs(001) and then producing clear signatures in the anisotropy spectra of the GaAsBi layers. In particular, the amplitude of the characteristic structure measured below 2.5 eV has been shown to be directly related to the Bi concentration, while the sign has a meaningful correlation to the strain conditions present in the sample. In this paper, we extend the application of RAS to “faulted” GaAsBi samples, i.e. samples that after growth result not satisfactory for research because of problems or errors risen during the complex deposition process (wrong growth temperature, excess or deficiency of Bi flux, formation of dislocations, etc.). We demonstrate that also in these cases RAS offers a useful characterization of the sample, possibly (if RAS runs during the deposition) singling out the occurrence of faults eventuality, and thus validating its potential applicability to an all‐optical real time monitoring of the deposition process.This article is protected by copyright. All rights reserved.

Reflectance anisotropies of polycrystalline Ce[formula omitted] Gd[formula omitted] O[formula omitted]/ Si[formula omitted] interfaces

Ce1−xGdxO2−x/2 thin films were deposited by spin coating on oxidized Si(001) substrates. Two strain regimes are observed by μ− Raman spectroscopy: for x< 0.1 the films are tensile strained, whereas a strain component of the wave number shift of −71.2x cm−1 compensates with a 32.6x cm−1 bond component for x> 0.1. Reflectance anisotropy spectroscopy (RAS) measurements were carried out on these films in which interface-related optical anisotropies signatures appearing in the 1.5 eV to 3.6 eV photon energy range are found dependent on the incorporation of Gd in the lattice. To explain the observed RAS signatures with a complex reflectance three-phase model, we resorted to spectroscopic ellipsometry (SE) to retrieve the interface optical anisotropies (IOA) related to the changes in refractive index, <Δn>, between interface formed by both the oxidized Si(001) and polycrystalline CeO2:Gd films, and to assess the CeO2 energy gap variation from 3.2 to 2.8 eV in the 0 <x< 0.4 composition range. This study renders the combination of RAS, Raman, and SE versatile tools to optimize the growth parameters during the fabrication of devices based on polycrystalline CeO2 on a quantitative basis.

Exploring the range of applicability of anisotropic optical detection in axially coordinated supramolecular structures

Ensuring the highest accuracy in determining the molecular assembling and the preservation of the chemical and physical properties of the molecules during the growth of organic layers requires a real-time monitoring of film formation. In this respect, optical techniques are preferred since they result in minimum organic film damage. Among these techniques, Reflectance Anisotropy Spectroscopy (RAS) proved to be the one with the highest sensitivity due to the development of intrinsic anisotropies in the optical response of molecular films, where molecular packing is driven by Van der Waals interactions. Recently, we proposed an original strategy to enable the growth of organic films via molecular self-assembly through highly directional coordination bonds. Herein, we consider a straightforward supramolecular structure employing axial bonds, based on the 1:1 assembly of a CoII porphyrin (CoTPP) and a linear ligand (DPNDI). This system is characterized by a rather isotropic structure that might, in principle, result in a weak RAS signal. Therefore, in the present work, we critically assess the range of applicability of such a spectroscopy. A number of other surface science techniques, including Low Energy Electron Diffraction (LEED), photoemission spectroscopies (PES and IPES) and Atomic Force Microscopy (AFM) is employed to fully characterize the axially coordinated molecular film.

Chiral Porphyrin Assemblies Investigated by a Modified Reflectance Anisotropy Spectroscopy Spectrometer.

Reflectance anisotropy spectroscopy (RAS) has been largely used to investigate organic compounds: Langmuir-Blodgett and Langmuir-Schaeffer layers, the organic molecular beam epitaxy growth in situ and in real time, thin and ultrathin organic films exposed to volatiles, in ultra-high vacuum (UHV), in controlled atmosphere and even in liquid. In all these cases, porphyrins and porphyrin-related compounds have often been used, taking advantage of the peculiar characteristics of RAS with respect to other techniques. The technical modification of a RAS spectrometer (CD-RAS: circular dichroism RAS) allows us to investigate the circular dichroism of samples instead of the normally studied linear dichroism: CD-RAS measures (in transmission mode) the anisotropy of the optical properties of a sample under right and left circularly polarized light. Although commercial spectrometers exist to measure the circular dichroism of substances, the "open structure" of this new spectrometer and its higher flexibility in design makes it possible to couple it with UHV systems or other experimental configurations. The importance of chirality in the development of organic materials (from solutions to the solid state, as thin layers deposited-in liquid or in vacuum-on transparent substrates) could open interesting possibilities to a development in the investigation of the chirality of organic and biological layers. In this manuscript, after the detailed explanation of the CD-RAS technique, some calibration tests with chiral porphyrin assemblies in solution or deposited in solid film are reported to demonstrate the quality of the results, comparing curves obtained with CD-RAS and a commercial spectrometer.

Experimental and Computational Aspects of Electrochemical Reflection Anisotropy Spectroscopy: A Review

AbstractElectrode/electrolyte interfaces play a crucial role in many electrochemical energy conversion and storage technologies. Hence, a deep understanding of the interfacial structure, energetic alignment and processes is of high relevance and has triggered the development of a number of in situ and operando techniques. One approach for gaining information about the change in surface chemistry and structure on an atomic scale is reflection anisotropy spectroscopy (RAS). This review presents and discusses the continuing effort to develop RAS as an in situ optical probe for solid‐liquid interfaces under applied potentials. Experimental and computational basic principles are presented and key challenges of electrochemical RAS are highlighted. Furthermore, we exemplarily demonstrate the potential of the method for spectroelectrochemistry, focusing on indium phosphide‐ and gold‐aqueous electrolyte interfaces as exemplary case studies, and outline research directions for battery systems.

Fourier Transform Infrared Reflection Anisotropy Spectroscopy of Semiconductor Crystals and Structures: Development and Application in the Mid-Infrared.

A new method of reflection anisotropy spectroscopy (RAS) with increased mid-IR efficiency owing to the use of a Fourier transform infrared (FT-IR) spectrometer has been developed. An optical setup was implemented using a photoelastic modulator (PEM) to modulate the direction of linear polarization of the probe beam originating from the Michelson interferometer. An original measurement algorithm was proposed to eliminate the influence of spectral inhomogeneity of the PEM efficiency on the obtained spectra using appropriate calibration. It was shown that to preserve the sign of the RAS signal, it is necessary to use a specialized procedure for phase correction of the interferogram registered by the FT-IR spectrometer. In the visible range, good agreement was confirmed between the obtained reflection anisotropy (RA) spectra of a semiconductor crystal and the results of independent measurements using a conventional diffraction-grating spectrometer-based setup. The RA spectrum of a III-V semiconductor heterostructure in the mid-infrared range (λ up to 8 µm) is demonstrated. Application of the developed FT-IR RAS method to layered black phosphorus has enabled characterization of anisotropic interband transitions in this graphene-like semiconductor crystal.

Chemical modification of the GaP(0 0 1) surface electric field with sulfide solutions

The surface electric field in GaP(001) passivated with aqueous and alcoholic sulfide solutions is studied by reflectance anisotropy spectroscopy using data on the surface chemical and electronic structure obtained by synchrotron-radiation X-ray photoelectron spectroscopy. Treatment of n-GaP(001) surface with a sulfide solution decreases the surface electric field depending on sulfide solution composition. In particular, passivation with the solution of ammonium sulfide in 2-propyl alcohol turns the total surface electric field almost to zero, while passivation with the aqueous ammonium sulfide solution reduces the surface electric field in a lesser extent. On the other hand, sulfide treatment of p-GaP(001) surface enhances the surface electric field dramatically and this enhancement is nearly independent of the sulfide solution composition. Such changes in the surface electric field can be related to the modification of the dipole associated with chemical bonds in the passivating layer.

Reflectance anisotropy spectroscopy (RAS) for in-situ identification of roughness morphologies evolving during reactive ion etching (RIE)

When using reactive ion etching (RIE) as a semiconductor processing tool, techniques to recognize upcoming roughness and to identify the roughness morphologies at the etch front in-situ and in real-time can significantly increase yield and thus productivity of the technological processes. Here, reflectance anisotropy spectroscopy (RAS) is applied in combination with sophisticated statistical data analyses to recognize or even define the possible roughness morphologies on RIE-etched monocrystalline substrates in real time. We exemplarily use GaSb, but our approach will also work for other III/V semiconductors and even silicon, as long as the material is monocrystalline. In the first step of the evaluation of RAS spectra, principal component analysis (PCA) and linear discriminant analysis (LDA) are performed. The algorithms are capable of calculating eigenvectors that produce the maximum variance from the spectroscopic data, thus allowing for a reduction of dimensionality of the dataset and for a distinction of different roughness morphologies. In a second step, consulting a base of earlier RAS data from former own samples, such results can be employed to identify the current surface morphology based on its spectra in-situ and in real-time.

Optical Anisotropy of Porphyrin Nanocrystals Modified by the Electrochemical Dissolution.

Reflectance anisotropy spectroscopy (RAS) coupled to an electrochemical cell represents a powerful tool to correlate changes in the surface optical anisotropy to changes in the electrochemical currents related to electrochemical reactions. The high sensitivity of RAS in the range of the absorption bands of organic systems, such as porphyrins, allows us to directly correlate the variations of the optical anisotropy signal to modifications in the solid-state aggregation of the porphyrin molecules. By combining in situ RAS to electrochemical techniques, we studied the case of vacuum-deposited porphyrin nanocrystals, which have been recently observed dissolving through electrochemical oxidation in diluted sulfuric acid. Specifically, we could identify the first stages of the morphological modifications of the nanocrystals, which we could attribute to the single-electron transfers involved in the oxidation reaction; in this sense, the simultaneous variation of the optical anisotropy with the electron transfer acts as a precursor of the dissolution process of porphyrin nanocrystals.

Probing the correlation between morphology and optical anisotropy in ZnTPP films grown at different temperatures

Films of tetraphenylporphyrins (TPP) have been recently investigated for their ability in protecting graphite electrode surfaces from degradation. The effectiveness of the protection depends on both the molecule–substrate and molecule–molecule interactions, which determine the type of film growth and its morphology. For instance, meso-tetraphenyl porphyrin-Zn(II) (ZnTPP) arranges differently depending on the substrate, conditions used for deposition and post-growth treatments. Since many parameters influence film morphology and strategies to reach an efficient protective coverage, here we investigate the role of the substrate temperature in determining morphological variations in thick ZnTPP films. ZnTPP molecules were sublimated by an organic molecular beam epitaxy (OMBE) system on a highly oriented pyrolytic graphite (HOPG) substrate, controlled in temperature by a variable temperature cryostat. The film morphology was characterized by atomic force microscopy (AFM), whereas the type of growth by reflectance anisotropy spectroscopy (RAS), which is highly sensitive to the orientation and type of arrangement of molecules on the substrate; changes in the film valence electronic structure were monitored in situ by UV photoemission spectroscopy (UPS). The comparison between AFM and RAS investigations clearly correlates a ZnTPP film morphology to the characteristic optical signal, both influenced by temperature conditions and diffusivity of molecules on the substrate.

Reactive Ion Etching (RIE) Induced Surface Roughness Precisely Monitored In-Situ and in Real Time by Reflectance Anisotropy Spectroscopy (RAS) in Combination with Principle Component Analysis (PCA)

Reactive ion etching (RIE) of group IV or III/V semiconductors is an important step in many lithographic processes in semiconductor technology. Typically, surface roughness is undesired, but more and more applications arise where rough surfaces are used as functional quasi-layers. Either to avoid roughness or to precisely define it, in situ monitoring and control of the state of the etch front is desirable to increase yield. As we already know, reflectance anisotropy spectroscopy (RAS) or RAS equipment might be used to monitor the state of the etch front, to determine the current etch depth in situ precisely with accuracies of as good as some lattice constants only, and to identify roughness morphologies, the latter in combination with principle component analysis (PCA) and linear discriminant analysis (LDA). In cases where only one specific morphology with different characteristic parameters is under consideration, PCA suffices for monitoring, although the task is even harder. The PCA-RAS combination allows for distinguishing states of the etch front, which differ by a couple of minutes of etch duration only.

Sensing Sub‐Surface Strain in GaAsBi(001) Surfaces by Reflectance Anisotropy Spectroscopy

Reflectance anisotropy spectroscopy (RAS) is applied to study the reconstructed GaAsBi(001) surfaces at room temperature. Arsenic‐capped GaAsBi samples with 7% Bi concentration are grown by molecular beam epitaxy (MBE) in nearly matched conditions on a proper buffer layer and annealed in ultra‐high vacuum (UHV). Low energy electron diffraction (LEED) shows that, following the As decapping, a 2 × 3/1 × 3 phase (Bi‐rich) is obtained after annealing the sample at 400 °C, while subsequent annealing at 450 °C yields a deterioration of the surface order. RAS spectra measured in situ allow to definitely confirm that the characteristic Bi‐dependent anisotropy measured below 2.5 eV has not a true surface origin, although being connected to the surface: it is related to the strain of the directional bonds between Bi atoms existing at the surface and below the surface. This result has a twofold significance: it recommends that previous attributions to the surface of RAS anisotropy features in III–V semiconductors should be in some cases revisited; for the future, it shows that RAS is suitable to characterize 2D‐layered materials, and to investigate the consequences of strain in the electronic properties of low‐dimensional systems.

MOCVD surface preparation of V-groove Si for III-V growth

V-groove nanopatterning of Si substrates has recently demonstrated promise for achieving high-quality III-V-on-Si epitaxy while providing a lower-cost processing route than chemo-mechanical polishing to produce epi-ready planar wafers. A key factor in determining the crystalline quality of III-V buffer layers is the Si surface structure and its chemical composition. Unlike planar Si surfaces, the surfaces of V-grooves prior to growth have not been studied in detail. Here, we study the surface of V-groove Si prepared for GaP nucleation via X-ray photoelectron spectroscopy and low-energy electron diffraction. We identify several pretreatments, using both 830°C and 1000°C annealing under an As background pressure, as being suitable for deoxidizing and cleaning the V-groove Si surface. The V-groove Si was found to behave similarly to reference Si(0 0 1) and Si(1 1 1) planar samples, demonstrating that in situ techniques such as reflection anisotropy spectroscopy can be used on reference samples to infer the state of the V-groove surface, and indicating that the extensive research on planar Si surfaces can be directly applied to V-grooves.

Adsorbate‐Induced Modifications in the Optical Response of the Si(553)–Au Surface

The conductivity of substrate‐supported metallic nanowires can be adjusted, e.g., by strain or adsorbates. In this article, the effect of atomic hydrogen and toluene‐3,4‐dithiol (TDT) adsorption on the quasi‐1D structures of the Si(553)‐(5 × 2)–Au reconstruction is investigated. Reflectance anisotropy spectroscopy (RAS) and infrared ellipsometry reveal optical signatures of the surface. Spectral modifications related to the adsorbate exposure suggest the activation of adsorption‐induced interband transitions. Density functional theory (DFT) calculations reproduce the spectral modifications and explain their origin. Preferential adsorption on sites located at the step edges of the structure occurs independent of the type of adsorbate and induces a charge transfer between electronic states related to the step edges and the Au dimer rows. This charge redistribution modifies the electronic structure close to the Fermi level, enhances the dimerization of the Au chains, and strongly influences the low‐energy region of the RAS spectra. While previous studies employed atomic H as a chief adsorbate, it is shown here that even molecular H deeply modifies the Si(553)–Au optical response. Structural modification of Au–Si(553) by H and TDT adsorbates as suggested from recent ab initio calculations are verified.

Reflectance anisotropy spectroscopy of strain-engineered GaAsBi alloys

In this paper, we present results obtained by an optical technique, namely, reflectance anisotropy spectroscopy (RAS), applied to a series of GaAs1−xBix samples grown by molecular beam epitaxy (MBE) under different strain conditions with the increasing concentration of Bi, up to the higher value of about 7%. The epitaxial buffer layers for the growing GaAs1−xBix layer were prepared with either a compressive strain (as it is commonly done) or a tensile strain: The latter case has been proven to be a strategy that allows us to obtain a better crystalline quality [Tisbi et al., Phys. Rev. Appl. 14, 014028 (2020)]. A characteristic, well defined anisotropy signal below 2.5 eV is demonstrated to be connected to the presence of Bi and, in particular, to the strain produced in the sub-surface region by the voluminous Bi atoms. The amplitude of this signal directly relates to the Bi quantity, while its sign gives information about the local clustering/ordering of Bi atoms in the grown sample. We conclude that the detailed interpretation of RAS signatures and the knowledge of their origin offer the opportunity to utilize this technique to follow in real time the GaAsBi growth either in MBE or in metal organic vapor phase epitaxy processes.

The interfacial structure of InP(100) in contact with HCl and H2SO4 studied by reflection anisotropy spectroscopy.

Indium phosphide and derived compound semiconductors are materials often involved in high-efficiency solar water splitting due to their versatile opto-electronic properties. Surface corrosion, however, typically deteriorates the performance of photoelectrochemical solar cells based on this material class. It has been reported that (photo)electrochemical surface functionalisation protects the surface by combining etching and controlled corrosion. Nevertheless, the overall involved process is not fully understood. Therefore, access to the electrochemical interface structure under operando conditions is crucial for a more detailed understanding. One approach for gaining structural insight is the use of operando reflection anisotropy spectroscopy. This technique allows the time-resolved investigation of the interfacial structure while applying potentials in the electrolyte. In this study, p-doped InP(100) surfaces are cycled between anodic and cathodic potentials in two different electrolytes, hydrochloric acid and sulphuric acid. For low, 10 mM electrolyte concentrations, we observe a reversible processes related to the reduction of a surface oxide phase in the cathodic potential range which is reformed near open-circuit potentials. Higher concentrations of 0.5 N, however, already lead to initial surface corrosion.