Intermolecular Interactions in Self-Assembly Process of Sodium Dodecyl Sulfate by Vertically Polarized Raman Spectra

Molecular self-assembly is extremely important in many fields, but the characterization of their corresponding intermolecular interactions is still lacking. The C-H stretching Raman band can reflect the hydrophobic interactions during the self-assembly process of sodium dodecyl sulfate （SDS） in aqueous solutions. However, the Raman spectra in this region are seriously overlapped by the OH stretching band of water. In this work, vertically polarized Raman spectra were used to improve the detection sensitivity of spectra of C-H region for the first time. The spectral results showed that the first critical micelle concentration and the second critical micelle concentration of SDS in water were 8.5 and 69 mmol/L, respectively, which were consistent with the results given by surface tension measurements. Because of the high sensitivity of vertically polarized Raman spectra, the critical micelle concentration of SDS in a relatively high concentration of salt solution could be obtained in our experiment. The two critical concentrations of SDS in 100 mmol/L NaCl solution were recorded to be 1.8 and 16.5 mmol/L, respectively. Through comparing the spectra and surface tension of SDS in water and in NaCl solution, the self-assembly process in bulk phase and at interface were discussed. The interactions among salt ions, SDS and water molecules were also analyzed. These results demonstrated the vertically polarized Raman spectra could be employed to study the self-assembly process of SDS in water.

Lattice deformation in epitaxial Fe3O4 films on MgO substrates studied by polarized Raman spectroscopy

The lattice structures of epitaxial Fe3O4 films deposited on MgO were studied systematically using polarized Raman spectroscopy as a function of film thickness,where interesting phenomena were observed.Firstly,the spectral conflict to the Raman selection rules(RSRs)was observed under cross-sectional configuration,which can be attributed to the tetragonal deformation in the growth direction due to the lattice mismatch between Fe3O4 and MgO.Secondly,the blue shift and broadening of Raman peaks evidenced the decrease of the tensile strain in Fe3O4 films with decreasing thickness.Thirdly,distinct from the other Raman modes,the lowest T2g mode exhibited asymmetric lineshape,which can be interpreted using the spatial correlation model.The increased correlation length introduced in the model can well explain the enhanced peak asymmetry feature with decreasing thickness.These results provide useful information for understanding the lattice structure of epitaxial Fe3O4 film.

Understanding angle-resolved polarized Raman scattering from black phosphorus at normal and oblique laser incidences

The selection rule for angle-resolved polarized Raman(ARPR)intensity of phonons from standard grouptheoretical method in isotropic materials would break down in anisotropic layered materials(ALMs)due to birefringence and linear dichroism effects.The two effects result in depth-dependent polarization and intensity of incident laser and scattered signal inside ALMs and thus make a challenge to predict ARPR intensity at any laser incidence direction.Herein,taking in-plane anisotropic black phosphorus as a prototype,we developed a so-called birefringence-linear-dichroism(BLD)model to quantitatively understand its ARPR intensity at both normal and oblique laser incidences by the same set of real Raman tensors for certain laser excitation.No fitting parameter is needed,once the birefringence and linear dichroism effects are considered with the complex refractive indexes.An approach was proposed to experimentally determine real Raman tensor and complex refractive indexes,respectively,from the relative Raman intensity along its principle axes and incident-angle resolved reflectivity by Fresnel’s law.The results suggest that the previously reported ARPR intensity of ultrathin ALM flakes deposited on a multilayered substrate at normal laser incidence can be also understood based on the BLD model by considering the depth-dependent polarization and intensity of incident laser and scattered Raman signal induced by both birefringence and linear dichroism effects within ALM flakes and the interference effects in the multilayered structures,which are dependent on the excitation wavelength,thickness of ALM flakes and dielectric layers of the substrate.This work can be generally applicable to any opaque anisotropic crystals,offering a promising route to predict and manipulate the polarized behaviors of related phonons.

Different angle-resolved polarization configurations of Raman spectroscopy: A case on the basal and edge plane of two-dimensional materials

Angle-resolved polarized Raman（ARPR） spectroscopy can be utilized to assign the Raman modes based on crystal symmetry and Raman selection rules and also to characterize the crystallographic orientation of anisotropic materials.However, polarized Raman measurements can be implemented by several different configurations and thus lead to different results. In this work, we systematically analyze three typical polarization configurations： 1） to change the polarization of the incident laser, 2） to rotate the sample, and 3） to set a half-wave plate in the common optical path of incident laser and scattered Raman signal to simultaneously vary their polarization directions. We provide a general approach of polarization analysis on the Raman intensity under the three polarization configurations and demonstrate that the latter two cases are equivalent to each other. Because the basal plane of highly ordered pyrolytic graphite（HOPG） exhibits isotropic feature and its edge plane is highly anisotropic, HOPG can be treated as a modelling system to study ARPR spectroscopy of twodimensional materials on their basal and edge planes. Therefore, we verify the ARPR behaviors of HOPG on its basal and edge planes at three different polarization configurations. The orientation direction of HOPG edge plane can be accurately determined by the angle-resolved polarization-dependent G mode intensity without rotating sample, which shows potential application for orientation determination of other anisotropic and vertically standing two-dimensional materials and other materials.

Polarization Raman spectra of graphene nanoribbons

The on-surface synthesis method allows the fabrication of atomically precise narrow graphene nanoribbons(GNRs),which bears great potential in electronic applications.Here,we synthesize armchair graphene nanoribbons(AGNRs)and chevron-type graphene nanoribbons(CGNRs)array on a vicinal Au(111112)surface using 10,10′-dibromo-9,9′-bianthracene(DBBA)and 6,12-dibromochrysene(DBCh)as precursors,respectively.This process creates spatially wellaligned GNRs,as characterized by scanning tunneling microscopy.AGNRs show strong Raman linear polarizability for application in optical modulation devices.Different from the distinct polarization of AGNRs,only weak polarization exists in CGNRs polarized Raman spectrum,which suggests that the presence of the zigzag boundary in the nanoribbon attenuates the polarization rate as an important factor affecting the polarization.We analyze the Raman activation mode of CGNRs using the peak polarization to expand the application of the polarization Raman spectroscopy in nanoarray analysis.

Hundred-watt-level linearly polarized tunable Raman random fiber laser

A high power linearly polarized tunable Raman random fiber laser（RFL） was studied theoretically and experimentally. The parameters required for the system design were obtained through numerical simulation, based on which a hundred-watt-level linearly polarized tunable RFL was successfully demonstrated. The central wavelength can be continuously tuned from 1113.76 to 1137.44 nm, and the output power exceeds 100 W for all of the lasing wavelengths with the polarization extinction ratio（PER） exceeding 20 d B at the maximum output power.Besides, the linewidth, spectral evolution, and temporal dynamics of a specified wavelength（1124.72 nm） were investigated in detail. Moreover, the theoretical results and the experimental results fit well. To the best of our knowledge, this is the first time for a hundred-watt-level linearly polarized tunable RFL ever reported.

Visualization of Ferroelectric Domains in Thin Films of Molecular Materials Using Confocal Micro-Raman Spectroscopy

Ferroelectrics are an important class of functional materials.Among all their unique properties,the study of their ferroelectric domains and domain walls is of great interest due to their importance in ferroelectric applications.There are many methods to characterize ferroelectric domains,namely,scanning probe microscopy,optical microscopy,electron microscopy,etc.Currently,newly emerged molecular ferroelectrics are attracting much attention from chemists,physicists and researchers in material sciences due to their structural flexibility,light mass,simple fabrication,etc.However,for the characterization of molecular ferroelectric domains,most conventional methods require either a complicated preparation process or direct contact between physical probes and material surfaces,limiting the development of molecular ferroelectric materials.In this report,we have demonstrated that confocal micro-Raman spectroscopy,as a nondestructive and noncontact in-situ method,is very suitable for studying the ferroelectric polarization and structures of domains in molecular ferroelectrics.Taking recently reported molecular ferroelectric trimethylchloromethyl ammonium trichlorocadmium(II)(TMCM-CdCl_(3))as an example,the non-180°domains have been characterized and visualized at different temperatures.Such a simple and extendable method requires minimum sample preparation,which would further benefit the research of molecular ferroelectric domain engineering and promote the miniaturization and integration of molecular ferroelectric films.

Identification of vibrational mode symmetry and phonon anharmonicity in SbCrSe_(3)single crystal using Raman spectroscopy

Developing an understanding of the physics underlying vibrational phonon modes,which are strongly related to thermal transport,has attracted significant research interest.Herein,we report the successful synthesis of bulk SbCrSe_(3)single crystal and its thermal transport property over the temperature range from 2 to 300 K.Using angle-resolved polarized Raman spectroscopy(ARPRS)and group theory calculation,the vibrational symmetry of each observed Raman mode in the cleaved(001)crystal plane of SbCrSe_(3)is identified for the first time,and then further verified through firstprinciples calculations.The ARPRS results of some Raman modes(e.g.,Ag2~64 cm-1 and Ag 7~185 cm-1)can be adopted to determine the crystalline orientation.More importantly,the temperature dependence of the lattice thermal conductivity(κL)is revealed to be more accurately depicted by the three-phonon scattering processes throughout the measured temperature range,substantiated by in-situ Raman spectroscopy analysis and the model-predictedκL.These results reveal the fundamental physics of thermal transport for SbCrSe_(3)from a completely new perspective and should thus ignite research interest in the thermal properties of other lowdimensional materials using the same strategy.

On the Mitigation of Polarization Dependency of Distributed Raman Amplifier Gain by Transmission Fiber PMD

We show theoretically and experimentally that Raman PDG can be formulated as a function of the pump light DOP and the transmission fiber PMD. Raman PDG is sufficiently reduced thanks to the inevitable fiber PMD.

Unravelling the anisotropic light-matter interaction in strainengineered trihalide MoCl_(3)

Layered trihalides exhibit distinctive band structures and physical properties due to the sixfold coordinated 3d or 4d transition metal site and partially occupied d orbitals,holding great potential in condensed matter physics and advanced electronic applications.Prior research focused on trihalides with highly symmetric honeycomb-like structures,such as CrI3 andα-RuCl_(3),while the role of crystal anisotropy in trihalides remains elusive.In particular,the trihalide MoCl_(3) manifests strong in-plane crystal anisotropy with the largest difference in Mo–Mo interatomic distances.Research on such material is imperative to address the lack of investigations on the effect of anisotropy on the properties of trihalides.Herein,we demonstrated the anisotropy of MoCl_(3) through polarized Raman spectroscopy and further tuned the phonon frequency via strain engineering.We showed the Raman intensity exhibits twofold symmetry under parallel configuration and fourfold symmetry under perpendicular configuration with changing the polarization angle of incident light.Furthermore,we found that the phonon frequencies of MoCl_(3) decrease gradually and linearly with applying uniaxial tensile strain along the axis of symmetry in the MoCl_(3) crystal,while those frequencies increase with uniaxial tensile strain applied perpendicularly.Our results shed light on the manipulation of anisotropic light-matter interactions via strain engineering,and lay a foundation for further exploration of the anisotropy of trihalides and the modulation of their electronic,optical,and magnetic properties.

Highly-anisotropic optical and electrical properties in layered SnSe

Anisotropic materials are of considerable interest because of their unique combination of polarization- or direction-dependent electrical, optical, and thermoelectric properties. Low-symmetry two-dimensional （2D） materials formed by van der Waals stacking of covalently bonded atomic layers are inherently anisotropic. Layered SnSe exhibits a low degree of lattice symmetry, with a distorted NaC1 structure and an in-plane anisotropy. Here we report a systematic study of the in-plane anisotropic properties in layered SnSe, using angle-resolved Raman scattering, optical absorption, and electrical transport studies. The optical and electrical characterization was direction-dependent, and successfully identified the crystalline orientation in the layered SnSe. Furthermore, the dependence of Raman-intensity anisotropy on the SnSe flake thickness and the excitation wavelength were investigated by both experiments and theoretical calculations. Finally, the electrical transport studies demonstrated that few-layer SnSe field- effect transistors （FETs） have a large anisotropic ratio of carrier mobility （N 5.8） bet- ween the armchair and zigzag directions, which is a record high value reported for 2D anisotropic materials. The highly-anisotropic properties of layered SnSe indicate considerable promise for anisotropic optics, electronics, and optoelectronics.

Layered material GeSe and vertical GeSe/MoS2 p-n heterojunctions

GroupqV monochalcogenides are emerging as a new class of layered materials beyond graphene, transition metal dichalcogenides （TMDCs）, and black phosphorus （BP）. In this paper, we report experimental and theoretical investigations of the band structure and transport properties of GeSe and its heterostructures. We find that GeSe exhibits a markedly anisotropic electronic transport, with maximum conductance along the armchair direction. Density functional theory calculations reveal that the effective mass is 2.7 times larger along the zigzag direction than the armchair direction; this mass anisotropy explains the observed anisotropic conductance. The crystallographic orientation of GeSe is confirmed by angle- resolved polarized Raman measurements, which are further supported by calculated Raman tensors for the orthorhombic structure. Novel GeSeflVIoS2 p-n heterojunctions are fabricated, combining the natural p-type doping in GeSe and n-type doping in MoS2. The temperature dependence of the measured junction current reveals that GeSe and MoS2 have a type-II band alignment with a conduction band offset of N 0.234 eV. The anisotropic conductance of GeSe may enable the development of new electronic and optoelectronic devices, such as high-efficiency thermoelectric devices and plasmonic devices with resonance frequency continuously tunable through light polarization direction. The unique GeSe/MoS2 p-n junctions with type-II alignment may become essential building blocks of vertical tunneling field-effect transistors for low-power applications. The novel p-type layered material GeSe can also be combined with n-type TMDCs to form heterogeneous complementary metal oxide semiconductor （CMOS） circuits.

Impact of polarization mode dispersion and nonlinearities on 2-channel DWDM chaotic communication systems

This paper has designed 2-channel dense wavelength division multiplexing （DWDM） chaotic sys- tem at the frequencies of 193.1 and 193,2THz, respec- tively. The optical chaotic signals were produced by using the semiconductor laser that is numerically modeled by employing laser rate equations. These two channels were multiplexed and then propagated through single mode optical fiber （SMF） of 80kin length with dispersion compensating fiber of 16 km length. Erbium doped fiber amplifier （EDFA） was used to compensate the power losses in the SMF. In lhis paper, we investigated the effects of polarization mode dispersion （PMD） and nonlinearities especially stimulated Raman scattering （SRS） on 2 channel DWDM chaotic communication system by varying the length of the SMF and value of differential group delay （DGD）.