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Bulk single crystals of WTe2 were grown by the self-flux method and characterized by X-ray diffraction, polarized micro-Raman spectroscopy, and optical microscopy. All methods revealed a high crystalline quality, thus demonstrating the advantages of the growth method used as a starting base for the synthesis of high-quality 2D materials. In each main scattering configuration, we recorded a series of Raman spectra in different sample orientations achieved by rotating the sample around the incident laser beam. In addition to the well-established case of excitation along the c crystal axis, we also applied laser excitation along the a and b axes. Thus, scattering configurations were also realized in the XZ and YZ polarization planes, for which no comparative literature data have yet been established. In these experiments, two new Raman-active phonons with B2 symmetry and frequencies of 89 cm-1 and 122 cm-1 were identified. The obtained experimental data enabled us to derive the magnitude ratios of all three tensor elements of the A1 modes and to find their phase differences.
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Raman spectroscopy allows for the unambiguous identification of materials through the inelastic scattering of light. This technique has a great many uses in various aspects of society from academic, scientific, and industry. This paper explores a specific type of Raman spectrometer called a spatial heterodyne Raman spectrometer (SHRSy), which is a variation of an interferometric spectrometer. It utilizes a Michelson interferometer and replaces the mirrors with gratings that transform it from a time-domain spectrometer to a spatial-domain spectrometer, allowing for the entirety of the spectrum to be captured at once. This study specifically tests a half-inch two-grating monolithic SHRS (½-in. 2g-mSHRS), which has a weight of <60 g and a size of 2.2 × 2.2 × 1.3 cm. To do this we excite a variety of organic liquids with a 532 nm neodymium-doped yttrium aluminum garnet (Nd:YAG) pulsed laser, using an excitation energy of 6.5 mJ/pulse and distance of 3 m in conjunction with an intensified charge-coupled device camera. This is the first time that the SHRS has been used for investigating polarized Raman spectra of liquids. We discuss and contrast the instrumental properties such as resolution, spectral range, étendue, and field of view with previously tested mSHRS to give context to the instrument's performance.
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Chiral materials possess broken inversion and mirror symmetry and show great potential in the application of next-generation optic, electronic, and spintronic devices. Two-dimensional (2D) chiral crystals have planar chirality, which is nonsuperimposable on their 2D enantiomers by any rotation about the axis perpendicular to the substrate. The degree of freedom to construct vertical stacking of 2D monolayer enantiomers offers the possibility of chiral manipulation for designed properties by creating multilayers with either a racemic or enantiomerically pure stacking order. However, the rapid recognition of the relative proportion of two enantiomers becomes demanding due to the complexity of stacking orders of 2D chiral crystals. Here, we report the unambiguous identification of racemic and enantiomerically pure stackings for layered ReSe2 and ReS2 using circular polarized Raman spectroscopy. The chiral Raman response is successfully manipulated by the enantiomer proportion, and the stacking orders of multilayer ReSe2 and ReS2 can be completely clarified with the help of second harmonic generation and scanning transmission electron microscopy measurements. Finally, we trained an artificial intelligent Spectra Classification Assistant to predict the chirality and the complete crystallographic structures of multilayer ReSe2 from a single circular polarized Raman spectrum with the accuracy reaching 0.9417 ± 0.0059.
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We have investigated the impact of obesity on the structural organization, morpho-mechanical properties of collagen fibers from rat tail tendon fascicles (RTTFs). Polarized Raman microspectroscopy showed that the collagen bands 855, 875, 938, and 960 cm-1 as well as those 1631 and 1660 cm-1 were affected by diet. Mechanical properties exhibited an increase in the yield strength from control (CTRL) to high fat (HF) diet (9.60 ± 1.71 and 13.09 ± 1.81 MPa) (p < 0.01) and ultimate tensile strength (13.12 ± 2.37 and 18.32 ± 2.83 MPa) (p < 0.05) with no significant change in the Young's Modulus. During mechanical, the band at 875 cm-1 exhibited the most relevant frequency shift (2 cm-1). The intensity of those at 855, 875, and 938 cm-1 in HF collagen displayed a comparable response to mechanical stress as compared to CTRL collagen with no significant diet-related changes in the Full Width at Half Maximum. Second harmonic generation technique revealed i) similar fiber straightness (0.963 ± 0.004 and 0.965 ± 0.003) and ii) significant changes in fibers diameter (1.48 ± 0.07 and 1.52 ± 0.08 µm) (p < 0.05) and length (22.06 ± 2.38 and 29.00 ± 3.76 µm) (p < 0.001) between CTRL and HF diet, respectively. The quantification of advanced glycation end products (AGEs) revealed an increase in both carboxymethyl-lysine and total fluorescence AGEs from CTRL to HF RTTFs.
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Colágeno , Cauda , Ratos , Animais , Colágeno/química , Obesidade/etiologia , Dieta Hiperlipídica/efeitos adversos , Tendões/fisiologia , Resistência à TraçãoRESUMO
Helicity-dependent Raman spectra of an isolated, chiral, single-wall carbon nanotube (SWNT) are reported using circularly polarized light. A polar plot of polarized Raman intensity for the radial breathing mode (RBM), which is excited by left-handed or right-handed circularly polarized light, shows asymmetric angle dependence relative to the nanotube axis direction, which reflects the axial chirality of a SWNT. The asymmetry in the polar plot of the RBM can be analyzed by a complex Raman tensor. The complex phase of each component of the Raman tensor has a maximum at chiral angle θ = 15° of a SWNT which is between two achiral SWNTs, that is, zigzag (θ = 0°) and armchair (θ = 30°) SWNTs. Considering the interaction between the chiral SWNT and the circularly polarized light, we discuss the origin of the complex phases excited by the opposite helicity of the circularly polarized light.
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Current clinical methods of bone health assessment depend to a great extent on bone mineral density (BMD) measurements. However, these methods only act as a proxy for bone strength and are often only carried out after the fracture occurs. Besides BMD, composition and tissue-level mechanical properties are expected to affect the whole bone's strength and toughness. While the elastic properties of the bone extracellular matrix (ECM) have been extensively investigated over the past two decades, there is still limited knowledge of the yield properties and their relationship to composition and architecture. In the present study, morphological, compositional and micropillar compression bone data was collected from patients who underwent hip arthroplasty. Femoral neck samples from 42 patients were collected together with anonymous clinical information about age, sex and primary diagnosis (coxarthrosis or hip fracture). The femoral neck cortex from the inferomedial region was analyzed in a site-matched manner using a combination of micromechanical testing (nanoindentation, micropillar compression) together with micro-CT and quantitative polarized Raman spectroscopy for both morphological and compositional characterization. Mechanical properties, as well as the sample-level mineral density, were constant over age. Only compositional properties demonstrate weak dependence on patient age: decreasing mineral to matrix ratio (p = 0.02, R2 = 0.13, 2.6 % per decade) and increasing amide I sub-peak ratio Iâ¼1660/Iâ¼1683 (p = 0.04, R2 = 0.11, 1.5 % per decade). The patient's sex and diagnosis did not seem to influence investigated bone properties. A clear zonal dependence between interstitial and osteonal cortical zones was observed for compositional and elastic bone properties (p < 0.0001). Site-matched microscale analysis confirmed that all investigated mechanical properties except yield strain demonstrate a positive correlation with the mineral fraction of bone. The output database is the first to integrate the experimentally assessed microscale yield properties, local tissue composition and morphology with the available patient clinical information. The final dataset was used for bone fracture risk prediction in-silico through the principal component analysis and the Naïve Bayes classification algorithm. The analysis showed that the mineral to matrix ratio, indentation hardness and micropillar yield stress are the most relevant parameters for bone fracture risk prediction at 70 % model accuracy (0.71 AUC). Due to the low number of samples, further studies to build a universal fracture prediction algorithm are anticipated with the higher number of patients (N > 200). The proposed classification algorithm together with the output dataset of bone tissue properties can be used for the future comparison of existing methods to evaluate bone quality as well as to form a better understanding of the mechanisms through which bone tissue is affected by aging or disease.
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The application of two-dimensional materials has been expanded by introducing the twisted bilayer (TBL) system. However, the landscape of the interlayer interaction in hetero-TBLs has not yet been fully understood, while that in homo-TBLs has been extensively studied, with the dependence on the twist angle between the constituent layers. Here, we present detailed analyses on the interlayer interaction that depends on the twist angle in WSe2/MoSe2 hetero-TBL via Raman and photoluminescence studies combined with first-principles calculation. We observe interlayer vibrational modes, moiré phonons, and the interlayer excitonic states that evolve with the twist angle and identify different regimes with distinct characteristics of such features. Moreover, the interlayer excitons that appear strong in the hetero-TBLs with twist angles near 0° or 60° have different energies and photoluminescence excitation spectra for the two cases, which results from different electronic structures and carrier relaxation dynamics. These results would enable a better understanding of the interlayer interaction in hetero-TBLs.
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Monitoring of extracellular matrix (ECM) microstructure is essential in studying structure-associated cellular processes, improving cellular function, and for ensuring sufficient mechanical integrity in engineered tissues. This paper describes a novel method to study the microscale alignment of the matrix in engineered tissue scaffolds (ETS) that are usually composed of a variety of biomacromolecules derived by cells. First, a trained loading function was derived from Raman spectra of highly aligned native tissue via principal component analysis (PCA), where prominent changes associated with specific Raman bands (e.g., 1444, 1465, 1605, 1627-1660, and 1665-1689 cm-1) were detected with respect to the polarization angle. These changes were mainly caused by the aligned matrix of many compounds within the tissue relative to the laser polarization, including proteins, lipids, and carbohydrates. Hence this trained function was applied to quantify the alignment within ETS of various matrix components derived by cells. Furthermore, a simple metric called Amplitude Alignment Metric (AAM) was derived to correlate the orientation dependence of polarized Raman spectra of ETS to the degree of matrix alignment. It was found that the AAM was significantly higher in anisotropic ETS than isotropic ones. The PRS method revealed a lower p-value for distinguishing the alignment between these two types of ETS as compared to the microscopic method for detecting fluorescent-labeled protein matrices at a similar microscopic scale. These results indicate that the anisotropy of a complex matrix in engineered tissue can be assessed at the microscopic scale using a PRS-based simple metric, which is superior to the traditional microscopic method. This PRS-based method can serve as a complementary tool for the design and assessment of engineered tissues that mimic the native matrix organizational microstructures.
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Engenharia Tecidual , Alicerces Teciduais , Análise Espectral Raman/instrumentação , Análise Espectral Raman/métodos , Engenharia Tecidual/métodos , MicroscopiaRESUMO
Optical anisotropy, which is quantified by birefringence (Δn) and linear dichroism (Δk), can significantly modulate the angle-resolved polarized Raman spectroscopy (ARPRS) response of anisotropic layered materials (ALMs) by external interference. This work studies the separate modulation of birefringence on the ARPRS response and the intrinsic response by selecting transparent birefringent crystal α-MoO3 as an excellent platform. It is found that there are several anomalous ARPRS responses in α-MoO3 that cannot be reproduced by the real Raman tensor widely used in non-absorbing materials; however, they can be well explained by considering the birefringence-induced Raman selection rules. Moreover, the systematic thickness-dependent study indicates that birefringence modulates the ARPRS response to render an interference pattern; however, the amplitude of modulation is considerably lower than that by linear dichroism as occurred in black phosphorous. This weak modulation brings convenience to the crystal orientation determination of transparent ALMs. Combining the atomic vibrational pattern and bond polarizability model, the intrinsic ARPRS response of α-MoO3 is analyzed, giving the physical origins of the Raman anisotropy. This study employs α-MoO3 as an example, although it is generally applicable to all transparent birefringent ALMs.
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One-dimensional (1D) conducting materials are of great interest as potential building blocks for integrated nanocircuits. Ternary 1D transition-metal chalcogenides, consisting of M6X6 wires with intercalated A atoms (M = Mo or W; X = S, Se, or Te; A = alkali or rare metals, etc.), have attracted much attention due to their 1D metallic behavior, superconductivity, and mechanical flexibility. However, the conventional solid-state reaction usually produces micrometer-scale bulk crystals, limiting their potential use as nanoscale conductors. Here we demonstrate a versatile method to fabricate indium (In)-intercalated W6Te6 (In-W6Te6) bundles with a nanoscale thickness. We first prepared micrometer-long, crystalline bundles of van der Waals W6Te6 wires using chemical vapor deposition and intercalated In into the crystal via a vapor-phase reaction. Atomic-resolution electron microscopy revealed that In atoms were surrounded by three adjacent W6Te6 wires. First-principles calculations suggested that their wire-by-wire stacking can transform through postgrowth intercalation. Individual In-W6Te6 bundles exhibited metallic behavior, as theoretically predicted. We further identified the vibrational modes by combining polarized Raman spectroscopy and nonresonant Raman calculations.
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2H-1T' MoTe2 van der Waals heterostructures (vdWHs) have promising applications in optoelectronics due to a seamlessly homogeneous semiconductor-metal coupled interface. However, the existing methods to fabricate such vdWHs involved complicated steps that may deteriorate the interfacial coupling and are also lacking precise thickness control capability. Here, a one-step growth method was developed to controllably grow bilayer 2H-1T' MoTe2 vdWHs in the small growth window overlapped for both phases. Atomic-resolution low-voltage transmission electron microscopy shows the distinct moiré patterns in the bilayer vdWHs, revealing the epitaxial nature of the top 2H phase with the lattice parameters regulated by the underneath 1T' phase. Such epitaxially stacked bilayer vdWHs modulate the interlayer coupling by resonating their vibration modes, as unveiled by the angle-resolved polarized Raman spectroscopy and first-principles calculations.
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Ultrafast photonics has become an interdisciplinary topic of great consequence due to the spectacular progress of compact and efficient ultrafast pulse generation. Wide spectrum bandwidth is the key element for ultrafast pulse generation due to the Fourier transform limitation. Herein, monoclinic Nb2GeTe4, an emerging class of ternary narrow-gap semiconductors, was used as a real saturable absorber (SA), which manifests superior wide-range optical absorption. The crystallization form and growth mechanism of Nb2GeTe4 were revealed by a thermodynamic phase diagram. Furthermore, the Nb2GeTe4-SA showed reliable saturation intensity and larger modulation depth, ascribed to a built-in electric field driven by the asymmetric crystal architecture confirmed via X-ray diffraction, polarized Raman spectra, and scanning transmission electron microscopy. Based on the Nb2GeTe4-SA, femtosecond mode-locked operation with good overall performance was achieved by a properly designed ring cavity. These results suggest that Nb2GeTe4 shows great promise for ultrafast photonic applications and arouse interests in exploring the intriguing properties of the ternary van der Waals material family.
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Atomic-layered materials, such as high-quality bismuth oxychalcogenides, which are composed of oppositely charged alternate layers grown using chemical vapor deposition, have attracted considerable attention. Their physical properties are well-suited for high-speed, low-power-consumption optoelectronic devices, and the rapid determination of their crystallographic characteristics is crucial for scalability and integration. In this study, we introduce how the crystallographic structure and quality of such materials can be projected through Raman spectroscopy analysis. Frequency modes at â¼55, â¼78, â¼360, and â¼434 cm-1 were detected, bearing out theoretical calculations from the literature. The low-frequency modes positioned at 55 and 78 cm-1 were activated by structural defects, such as grain boundaries and O-rich edges in the Bi2O2Se crystals, accompanied by sensitivity to the excitation energy. Furthermore, the line defects at â¼55 cm-1 exhibited a strong 2-fold polarization dependence, similar to graphene/graphite edges. Our results can help illuminate the mechanism for activating the Raman-active mode from the infrared active mode by defects, as well as the electronic structures of these two-dimensional layered materials. We also suggest that the nanoscale width line defects in Bi2O2Se can be visualized using Raman spectroscopy.
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The organization of proteins is an important determinant of functionality in soft tissues. However, such organization is difficult to monitor over time in soft tissue with complex compositions. Here, we establish a method to determine the alignment of proteins in soft tissues of varying composition by polarized Raman spectroscopy (PRS). Unlike most conventional microscopy methods, PRS leverages non-destructive, label-free sample preparation. PRS data from highly aligned muscle layers were utilized to derive a weighting function for aligned proteins via principal component analysis (PCA). This trained weighting function was used as a master loading function to calculate a principal component score (PC1 Score) as a function of polarized angle for tendon, dermis, hypodermis, and fabricated collagen gels. Since the PC1 Score calculated at arbitrary angles was insufficient to determine level of alignment, we developed an Amplitude Alignment Metric by fitting a sine function to PC1 Score with respect to polarized angle. We found that our PRS-based Amplitude Alignment Metric can be used as an indicator of level of protein alignment in soft tissues in a non-destructive manner with label-free preparation and has similar discriminatory capacity among isotropic and anisotropic samples compared to microscopy-based image processing method. This PRS method does not require a priori knowledge of sample orientation nor composition and appears insensitive to changes in protein composition among different tissues. The Amplitude Alignment Metric introduced here could enable convenient and adaptable evaluation of protein alignment in soft tissues of varying protein and cell composition. STATEMENT OF SIGNIFICANCE: Polarized Raman spectroscopy (PRS) has been used to characterize the of organization of soft tissues. However, most of the reported applications of PRS have been on collagen-rich tissues and reliant on intensities of collagen-related vibrations. This work describes a PRS method via a multivariate analysis to characterize alignment in soft tissues composed of varying proteins. Of note, the highly aligned muscle layer of mouse skin was used to train a master function then applied to other soft tissue samples, and the degree of anisotropy in the PRS response was evaluated to obtain the level of alignment in tissues. We have demonstrated that this method supports convenient and adaptable evaluation of protein alignment in soft tissues of varying protein and cell composition.
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Colágeno , Análise Espectral Raman , Animais , Anisotropia , Géis , Camundongos , TendõesRESUMO
The family of group IV-VI monochalcogenides has an atomically puckered layered structure, and their atomic bond configuration suggests the possibility for the realization of various polymorphs. Here, we report the synthesis of the first hexagonal polymorph from the family of group IV-VI monochalcogenides, which is conventionally orthorhombic. Recently predicted four-atomic-thick hexagonal GeSe, so-called γ-GeSe, is synthesized and clearly identified by complementary structural characterizations, including elemental analysis, electron diffraction, high-resolution transmission electron microscopy imaging, and polarized Raman spectroscopy. The electrical and optical measurements indicate that synthesized γ-GeSe exhibits high electrical conductivity of 3 × 105 S/m, which is comparable to those of other two-dimensional layered semimetallic crystals. Moreover, γ-GeSe can be directly grown on h-BN substrates, demonstrating a bottom-up approach for constructing vertical van der Waals heterostructures incorporating γ-GeSe. The newly identified crystal symmetry of γ-GeSe warrants further studies on various physical properties of γ-GeSe.
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Van der Waals epitaxy on the surface of two-dimensional (2D) layered crystals has gained significant research interest for the assembly of well-ordered nanostructures and fabrication of vertical heterostructures based on 2D crystals. Although van der Waals epitaxial assembly on the hexagonal phase of transition metal dichalcogenides (TMDCs) has been relatively well characterized, a comparable study on the distorted octahedral phase (1T' or Td) of TMDCs is largely lacking. Here, we investigate the assembly behavior of one-dimensional (1D) AgCN microwires on various distorted TMDC crystals, namely 1T'-MoTe2, Td-WTe2, and 1T'-ReS2. The unidirectional alignment of AgCN chains is observed on these crystals, reflecting the symmetry of underlying distorted TMDCs. Polarized Raman spectroscopy and transmission electron microscopy directly confirm that AgCN chains display the remarkable alignment behavior along the distorted chain directions of underlying TMDCs. The observed unidirectional assembly behavior can be attributed to the favorable adsorption configurations of 1D chains along the substrate distortion, which is supported by our theoretical calculations and observation of similar assembly behavior from different cyanide chains. The aligned AgCN microwires can be harnessed as facile markers to identify polymorphs and crystal orientations of TMDCs.
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We performed polarized Raman spectroscopy on mechanically exfoliated few-layer MoTe2 samples and observed both 1T' and Td phases at room temperature. Few-layer 1T' and Td MoTe2 exhibited a significant difference especially in interlayer vibration modes, from which the interlayer coupling strengths were extracted using the linear chain model: strong in-plane anisotropy was observed in both phases. Furthermore, temperature-dependent Raman measurements revealed a peculiar phase transition behavior in few-layer 1T' MoTe2. In contrast to bulk 1T' MoTe2 crystals, where the phase transition to the Td phase occurs at â¼250 K, the temperature-driven phase transition to the Td phase is increasingly suppressed as the thickness is reduced, and the transition and the critical temperature varied dramatically from sample to sample even for the same thickness. Raman spectra of intermediate phases that correspond to neither 1T' nor Td phase with different interlayer vibration modes were observed, which suggests that several metastable phases exist with similar total energies.
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Bone is a natural composite possessing outstanding mechanical properties combined with a lightweight design. The key feature contributing to this unusual combination of properties is the bone hierarchical organization ranging from the nano- to the macro-scale. Bone anisotropic mechanical properties from two orthogonal planes (along and perpendicular to the main bone axis) have already been widely studied. In this work, we demonstrate the dependence of the microscale compressive mechanical properties on the angle between loading direction and the mineralized collagen fibril orientation in the range between 0° and 82°. For this, we calibrated polarized Raman spectroscopy for quantitative collagen fibril orientation determination and validated the method using widely used techniques (small angle X-ray scattering, micro-computed tomography). We then performed compression tests on bovine cortical bone micropillars with known mineralized collagen fibril angles. A strong dependence of the compressive micromechanical properties of bone on the fibril orientation was found with a high degree of anisotropy for both the elastic modulus (Ea/Et=3.80) and the yield stress (σay/σty=2.54). Moreover, the post-yield behavior was found to depend on the MCF orientation with a transition between softening to hardening behavior at approximately 50°. The combination of methods described in this work allows to reliably determine structure-property relationships of bone at the microscale, which may be used as a measure of bone quality.
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Osso Cortical , Análise Espectral Raman , Animais , Osso e Ossos , Bovinos , Módulo de Elasticidade , Estresse Mecânico , Microtomografia por Raio-XRESUMO
The vibrational modes in organic/inorganic layered perovskites are of fundamental importance for their optoelectronic properties. The hierarchical architecture of the Ruddlesden-Popper phase of these materials allows for distinct directionality of the vibrational modes with respect to the main axes of the pseudocubic lattice in the octahedral plane. Here, we study the directionality of the fundamental phonon modes in single exfoliated Ruddlesden-Popper perovskite flakes with polarized Raman spectroscopy at ultralow frequencies. A wealth of Raman bands is distinguished in the range from 15 to 150 cm-1 (2-15 meV), whose features depend on the organic cation species, on temperature, and on the direction of the linear polarization of the incident light. By controlling the angle of the linear polarization of the excitation laser with respect to the in-plane axes of the octahedral layer, we gain detailed information on the symmetry of the vibrational modes. The choice of two different organic moieties, phenethylammonium (PEA) and butylammonium (BA), allows us to discern the influence of the linker molecules, evidencing strong anisotropy of the vibrations for the (PEA)2PbBr4 samples. Temperature-dependent Raman measurements reveal that the broad phonon bands observed at room temperature consist of a series of sharp modes and that such mode splitting strongly differs for the different organic moieties and vibrational bands. Softer molecules such as BA result in lower vibrational frequencies and splitting into fewer modes, while more rigid molecules such as PEA lead to higher frequency oscillations and larger number of Raman peaks at low temperature. Interestingly, in distinct bands the number of peaks in the Raman bands is doubled for the rigid PEA compared to the soft BA linkers. Our work shows that the coupling to specific vibrational modes can be controlled by the incident light polarization and choice of the organic moiety, which could be exploited for tailoring exciton-phonon interaction, and for optical switching of the optoelectronic properties of such 2D layered materials.
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Strong in-plane anisotropy of atomic layer and thin-film black phosphorus (P) offers new device perspectives and stimulates increasing interest and explorations, where precisely determining the black P crystal orientation and anisotropic axes is a necessity. Here, we demonstrate that the crystal orientation and intrinsic in-plane optical anisotropy of black P crystals in a broad thickness range (from â¼5 to â¼300 nm) can be directly and precisely determined, by polarized reflectance measurement alone, in visible range. Combining experiments with modeling of optical anisotropy and multilayer interference effects, we elucidate the underlying principles and validate these measurements. The polarized reflectance method is not only easy to implement but also deterministic, nondestructive, and effective for both on-substrate and suspended black P atomic layers and thin films.