Surface-enhanced Raman spectroscopy chips based on two-dimensional materials beyond graphene

Surface-enhanced Raman spectroscopy (SERS) based on two-dimensional (2D) materials has attracted great attention over the past decade.Compared with metallic materials,which enhance Raman signals via the surface plasmon effect,2D materials integrated on silicon substrates are ideal for use in the fabrication of plasmon-free SERS chips,with the advantages of outstanding fluorescence quenching capability,excellent biomolecular compatibility,tunable Fermi levels,and potentially low-cost material preparation.Moreover,recent studies have shown that the limits of detection of 2D-material-based SERS may be comparable with those of metallic substrates,which has aroused significant research interest.In this review,we comprehensively summarize the advances in SERS chips based on 2D materials.As several excellent reviews of graphene-enhanced Raman spectroscopy have been published in the past decade,here,we focus only on 2D materials beyond graphene,i.e.,transition metal dichalcogenides,black phosphorus,hexagonal boron nitride,2D titanium carbide or nitride,and their heterostructures.We hope that this paper can serve as a useful reference for researchers specializing in 2D materials,spectroscopy,and diverse applications related to chemical and biological sensing.     

Optical and electrical properties of two-dimensional anisotropic materials

Two-dimensional(2D) anisotropic materials, such as B-P, B-As, GeSe, GeAs, ReSe2, KP15 and their hybrid systems, exhibit unique crystal structures and extraordinary anisotropy. This review presents a comprehensive comparison of various 2D anisotropic crystals as well as relevant FETs and photodetectors, especially on their particular anisotropy in optical and electrical properties. First, the structure of typical 2D anisotropic crystal as well as the analysis of structural anisotropy is provided. Then, recent researches on anisotropic Raman spectra are reviewed. Particularly, a brief measurement principle of Raman spectra under three typical polarized measurement configurations is introduced. Finally, recent progress on the electrical and photoelectrical properties of FETs and polarization-sensitive photodetectors based on 2D anisotropic materials is summarized for the comparison between different 2D anisotropic materials. Beyond the high response speed, sensitivity and on/off ratio, these 2D anisotropic crystals exhibit highly conduction ratio and dichroic ratio which can be applied in terms of polarization sensors, polarization spectroscopy imaging, optical radar and remote sensing.     

Lattice vibration and Raman scattering of two-dimensional van der Waals heterostructure

Research on two-dimensional(2D) materials and related van der Waals heterostructures(vdWHs) is intense and remains one of the leading topics in condensed matter physics.Lattice vibrations or phonons of a vdWH provide rich information,such as lattice structure,phonon dispersion,electronic band structure and electron–phonon coupling.Here,we provide a mini review on the lattice vibrations in vdWHs probed by Raman spectroscopy.First,we introduced different kinds of vdWHs,including their structures,properties and potential applications.Second,we discussed interlayer and intralayer phonon in twist multilayer graphene and MoS2.The frequencies of interlayer and intralayer modes can be reproduced by linear chain model(LCM)and phonon folding induced by periodical moiré potentials,respectively.Then,we extended LCM to vdWHs formed by distinct 2D materials,such as MoS2/graphene and hBN/WS2 heterostructures.We further demonstrated how to calculate Raman intensity of interlayer modes in vdWHs by interlayer polarizability model.     

Highly In‐Plane Optical and Electrical Anisotropy of 2D Germanium Arsenide

Anisotropic 2D materials exhibit unique optical, electrical, and thermoelectric properties that open up possibilities for diverse angle‐dependent devices. However, the explored anisotropic 2D materials are very limited and the methods to identify the crystal orientations and to study the in‐plane anisotropy are in the initial stage. Here azimuth‐dependent reflectance difference microscopy (ADRDM), angle‐resolved Raman spectra, and electrical transport measurements are used to systematically characterize the influence of the anisotropic structure on in‐plane optical and electrical anisotropy of 2D GeAs, a novel group IV–V semiconductor. It is proved that ADRDM offers a way to quickly identify the crystal orientations and also to directly characterize the in‐plane optical anisotropy of layered GeAs. The anisotropic electrical transport behavior of few‐layer GeAs field‐effect transistors is further measured and the anisotropic ratio of the mobility is as high as 4.6, which is higher than the other 2D anisotropic materials such as black phosphorus. The dependence of the Raman intensity anisotropy on the sample thickness, excitation wavelength, and polarization configuration is investigated both experimentally and theoretically. These data will be useful for designing new high‐performance devices and the results suggest a general methodology for characterizing the in‐plane anisotropy of low‐symmetry 2D materials.     

用于真空在线测量的离轴非球面结构反射差分光谱仪设计与实现

基于旋转补偿器的反射差分光谱(RC-RDS)技术是 具有亚单层光学灵敏度的高精度表面表征方法,其全光谱快 速测量性能,特别适合在线检测。为满足真空在线测量的应用需求,综合考虑使用空间、工 作距离、光束 直径、光谱宽度和通光率等限制因素,提出了基于离轴抛物(OAP)反射镜的光学测头设 计方案,构建的测试样机 实现了有效工作距离大于50cm、光斑直径小于6.5mm和光谱范围涵盖280～825nm等性能。实验研究了超高 真空环境Cu(110) 样品在退火处理中的RDS,仪器详细记录了信号随温度的演 变过 程,测量精度优于3×10－4,表明新方案满足真空环境下表面 高灵敏光学测试的需求。     

Direct Growth of Germanene at Interfaces between Van der Waals Materials and Ag(111)

Germanene, a 2D honeycomb germanium crystal, is grown at graphene/Ag(111) and hexagonal boron nitride (h-BN)/Ag(111) interfaces by segregating germanium atoms. A simple annealing process in N₂ or H₂/Ar at ambient pressure leads to the formation of germanene, indicating that an ultrahigh-vacuum condition is not necessary. The grown germanene is stable in air and uniform over the entire area covered with a van der Waals (vdW) material. As an important finding, it is necessary to use a vdW material as a cap layer for the present germanene growth method since the use of an Al₂O₃ cap layer results in no germanene formation. The present study also proves that Raman spectroscopy in air is a powerful tool for characterizing germanene at the interfaces, which is concluded by multiple analyses including first-principles density functional theory calculations. The direct growth of h-BN-capped germanene on Ag(111), which is demonstrated in the present study, is considered to be a promising technique for the fabrication of future germanene-based electronic devices.     

3D Aluminum Hybrid Plasmonic Nanostructures with Large Areas of Dense Hot Spots and Long‐Term Stability

Plasmonic materials possessing dense hot spots with high field enhancement over a large area are highly desirable for ultrasensitive biochemical sensing and efficient solar energy conversion; particularly those based on low‐cost noncoinage metals with high natural abundance are of considerable practical significance. Here, 3D aluminum hybrid nanostructures (3D‐Al‐HNSs) with high density of plasmonic hot spots across a large scale are fabricated via a highly efficient and scalable nonlithographic method, i.e., millisecond‐laser‐direct‐writing in liquid nitrogen. The nanosized alumina interlayer induces intense and dual plasmonic resonance couplings between adjacent Al nanoparticles with bimodal size distribution within each of the hybrid assemblies, leading to remarkably elevated localized electric fields (or hot spots) accessible to the analytes or reactants. The 3D‐stacked nanostructure substantially raises the hot spot density, giving rise to plasmon‐enhanced light harvesting from deep UV to the visible, strong enhancement of Raman signals, and a very low limit of detection outperforming reported Al nanostructures, and even comparable to the noble metals. Combined with the long‐term stability and good reproducibility, the 3D‐Al‐HNSs hold promise as a robust low‐cost plasmonic material for applications in plasmon‐enhanced spectroscopic sensing and light harvesting.     

Influence of hydrogen dilution and substrate temperature on growth of nanocrystalline hydrogenated silicon carbide films deposited by RF sputtering

Hydrogenated nanocrystalline silicon carbide (nc-SiC: H) thin films were prepared by radiofrequency magnetron sputtering. Deposition was effectuated in plasma of Argon and Hydrogen mixture with several proportions (30-80% H₂) and at different substrate temperatures (ambient, 500 °C). The films microstructure was studied by means of FTIR and Raman spectroscopy. These two techniques helped us to have an idea on the composition of our samples and the existing species. A comparative study of the obtained results has allowed us to make conclusions about the role of both hydrogen dilution and substrate temperature on deposition of layers with good parameters in terms of crystallinity and optical properties. These observations were correlated with those obtained by diffraction and high-resolution TEM.     

2D MXenes as a Promising Candidate for Surface Enhanced Raman Spectroscopy: State of the Art,Recent Trends,and Future Prospects

Surface-enhanced enhanced Raman spectroscopy (SERS) has emerged as a powerful analytical technique for ultrasensitive and label-free detection of chemical species, with numerous applications in various fields. Recently, 2D MXenes, have evoked substantial intrigue as promising substrates for SERS. Hence, a comprehensive understanding of the developments in the Raman effect and the mechanisms involved in SERS is highly crucial. The review reflects the advances, working principle, and dual mechanisms, including SERS's electromagnetic and chemical mechanisms. Noble metal nanostructures are highly prioritized as SERS substrates owing to their excellent sensitivity. However, due to certain disadvantages that they pose, metal-free SERS substrates with exceptional tunable properties are extensively researched in the current days. The combination of 2D MXenes and nanostructures can be effective in producing enhanced SERS signals. SERS performance of different MXene-based materials is emphasized. The performance of this combination is credited to their large surface-to-volume ratio, good electrical conductivity, and surface-terminated functionalities. The recent advancements in MXenes and MXenes-based heterostructures driven SERS sensing concerning the structural design of the material, its performance, and the mechanisms are studied. Finally, a detailed conclusion is provided with the challenges and future perspectives for designing 2D materials for efficient SERS sensors.     

Combined use of three-dimensional X-ray diffraction imaging and micro-Raman spectroscopy for the non-destructive evaluation of plasma arc induced damage on silicon wafers

The practicality of plasma etching, combined with low temperature and directional process capabilities make it an integral part of the IC manufacturing process. A significant cause of damage to wafers during plasma processing is arcing damage. Plasma arcing damage results in large pits and non-uniformities on the wafer surface which can lead to wafer breakage and high yield losses.Thus a non-destructive wafer damage metrology is crucial to the understanding of wafer failure mechanisms. We report on the successful use of a combined suite of non-destructive metrology techniques to locate the arc damage sites and examine the physical processes which have occurred as a result of the damage. These consist of 3D X-ray diffraction imaging (3D-XRDI), micro-Raman spectroscopy (μRS), and scanning electron microscopy (SEM).In the case of the two examples examined in this study the plasma induced damage on the wafer surface appears as regions of damage ranging from 100 μm to 1000 μm in diameter. 3D-XRDI shows that the strain fields propagate out from the damage site in all directions, with the damage penetrating up to ? of the way through the substrate. K-means clustering and false colouring algorithms are used to highlight the regions of interest in 3D-XRDI, and to enhance the analysis process. Sectioning of the 3D images has enabled non-destructive imaging of the internal damage in the samples at any location. Micro-Raman spectroscopy results indicate the presence of both crystalline and amorphous silicon. Strain measurements at the damage site show tensile strains as high as 500 MPa in certain situations, with strain levels increasing from the surface towards the bottom of the dislocation cell structures, which can be distinguished in the synchrotron X-ray topographs. 3D-XRDI and μRS results are in close correlation, proving the potential for 3D-XRDI as non-contact, non-destructive metrology particularly suited to these problems.     

In-situ monitoring of InP(100) and GaP(100) interfaces and characterization with RDS at 20 K

MOVPE-preparation of highly ordered InP(100) and GaP(100) surfaces was monitored with in-situ reflectance difference spectroscopy (RDS). Specific ordered P-terminated and ordered cation-terminated surface reconstructions were identified with specific structured RD spectra with the highest peaks. After contamination-free transfer of the samples to UHV, RDS measurements were performed also at 20 K. The experimental RD spectrum for the In-terminated, (2×4) reconstructed InP(100) surface shows a remarkable similarity to a recently published theoretical spectrum, whereas there is only moderate similarity between the experimental RD spectrum for the (2×4) reconstructed Ga-terminated GaP(100) surface and a recently proposed theoretical spectrum.