Transition metal dichalcogenides (TMDs) have been a core constituent of 2D material research throughout the last decade. Over this time, research focus has progressively shifted from synthesis and fundamental investigations, to exploring their properties for applied research such as electrochemical applications and integration in electrical devices. Due to the rapid pace of development, priority is often given to application-oriented aspects while careful characterisation and analysis of the TMD materials themselves is occasionally neglected. This can be particularly evident for characterisations involving X-ray photoelectron spectroscopy (XPS), where measurement, peak-fitting, and analysis can be complex and nuanced endeavours requiring specific expertise. To improve the availability and accessibility of reference information, here we present a detailed peak-fitted XPS analysis of ten transition metal chalcogenides. The materials were synthesised as large-area thin-films on SiO2 using direct chalcogenisation of pre-deposited metal films. Alongside XPS, the Raman spectra with several excitation wavelengths for each material are also provided. These complementary characterisation methods can provide a more complete understanding of the composition and quality of the material. As material stability is a crucial factor when considering applications, the in-air thermal stability of the TMDs was investigated after several annealing points up to 400 °C. This delivers a trend of evolving XPS and Raman spectra for each material which improves interpretation of their spectra while also indicating their ambient thermal limits. This provides an accessible library and set of guidelines to characterise, compare, and discuss TMD XPS and Raman spectra.
Defects in planar and vertically oriented nanographitic structures (NGSs) synthesized by plasma enhanced chemical vapor deposition (PECVD) has been investigated using Raman and X-ray photoelectron spectroscopy. While Raman spectra reveal the dominance of vacancy and boundary type defects respectively in vertical and planar NGSs, XPS provides additional information on vacancy related defect peaks at C 1s spectrum that originate from non-conjugated carbon atoms in hexagonal lattice. Although an excellent correlation prevails between these two techniques, our results show that estimation of surfa…
Two-dimensional (2D) transition metal dichalcogenide (TMD) nanosheets exhibit remarkable electronic and optical properties. The 2D features, sizable bandgaps, and recent advances in the synthesis, characterization, and device fabrication of the representative MoS$_2$, WS$_2$, WSe$_2$, and MoSe$_2$ TMDs make TMDs very attractive in nanoelectronics and optoelectronics. Similar to graphite and graphene, the atoms within each layer in 2D TMDs are joined together by covalent bonds, while van der Waals interactions keep the layers together. This makes the physical and chemical properties of 2D TMDs …
Tungsten ditelluride (WTe2), a layered transition-metal dichalcogenide (TMD), has recently demonstrated an extremely large magnetoresistance effect, which is unique among TMDs. This fascinating feature seems to be correlated with its special electronic structure. Here, we report the observation of 6 Raman peaks corresponding to the A_2^4, A_1^9, A_1^8, A_1^6, A_1^5 and A_1^2 phonons, from the 33 Raman-active modes predicted for WTe2. This provides direct evidence to distinguish the space group of WTe2 from that of other TMDs. Moreover, the Raman evolution of WTe2 from bulk to monolayer is clea…
Layered inorganic materials, such as the transition metal dichalcogenides (TMDs), have attracted much attention due to their exceptional electronic and optical properties. Reliable synthesis and characterization of these materials must be developed if these properties are to be exploited. Herein, we present low-frequency Raman analysis of MoS2, MoSe2, WSe2 and WS2 grown by chemical vapour deposition (CVD). Raman spectra are acquired over large areas allowing changes in the position and intensity of the shear and layer-breathing modes to be visualized in maps. This allows detailed characterizat…
Transition-metal dichalcogenide (TMD) semiconductors have been widely studied due to their distinctive electronic and optical properties. The property of TMD flakes is a function of its thickness, or layer number (N). How to determine N of ultrathin TMDs materials is of primary importance for fundamental study and practical applications. Raman mode intensity from substrates has been used to identify N of intrinsic and defective multilayer graphenes up to N=100. However, such analysis is not applicable for ultrathin TMD flakes due to the lack of a unified complex refractive index ($\tilde{n}$) …
Janus transition metal dichalcogenides (TMDs) lose the horizontal mirror symmetry of ordinary TMDs, leading to the emergence of additional features, such as native piezoelectricity, Rashba effect, and enhanced catalytic activity. While Raman spectroscopy is an essential nondestructive, phase- and composition-sensitive tool to monitor the synthesis of materials, a comprehensive study of the Raman spectrum of Janus monolayers is still missing. Here, we discuss the Raman spectra of WSSe and MoSSe measured at room and cryogenic temperatures, near and off resonance. By combining polarization-resolv…
Typical Raman spectra of transition metal dichalcogenides (TMDs) display two prominent peaks, E2g and A1g, that are well separated from each other. We find that these modes are degenerate in bulk WSe2 yielding one single Raman peak. As the dimensionality is lowered, the observed peak splits in two as a result of broken degeneracy. In contrast to our experimental findings, our phonon dispersion calculations reveal that these modes remain degenerate independent of the number of layers. Interestingly, for minuscule biaxial strain the degeneracy is preserved but once the crystal symmetry is broken…
Electronic structure near Fermi level of Pr2CoFeO6 (at 300 K) was investigated by X-ray photoemission spectroscopy (XPS) technique. All three cations, i.e., Pr, Co and Fe were found to be trivalent in nature. XPS analysis also suggested the system to be insulating in nature. Moreover, Raman spectroscopy study indicated the random distribution of the B-site ions (Co/Fe) triggered by same charge states. In temperature-dependent Raman study, the relative heights of the two observed phonon modes exhibited anomalous behaviour near magnetic transition temperature TN~270 K, thus indicating towards in…
Ferroelectric oxides interfaced with transition metal dichalcogenides (TMDCs) offer a promising route toward ferroelectric-based devices due to lack of dangling bonds on the TMDC surface leading to a high-quality and abrupt ferroelectric/TMDC interface. In this work, the thermal stability of this interface is explored by first depositing hafnium zirconium oxide (HZO) directly on geological MoS2 and as-grown WSe2, followed by sequential annealing in ultra-high vacuum (UHV) over a range of temperatures (400-800 °C), and examining the interface through X-ray photoelectron spectroscopy (XPS). We s…
The transition-metal dichalcogenides (TMD) MoS2 and WS2 show remarkable electromechanical properties. Strain modifies the direct band gap into an indirect one, and substantial strain even induces an semiconductor-metal transition. Providing strain through mechanical contacts is difficult for TMD monolayers, but state-of-the-art for TMD nanotubes. We show using density-functional theory that similar electromechanical properties as in monolayer and bulk TMDs are found for large diameter TMD single- (SWNT) and multi-walled nanotubes (MWNTs). The semiconductor-metal transition occurs at elongation…
Laser-assisted chemical modification is demonstrated on ultra-thin transition-metal dichalcogenides (TMDs), locally replacing selenium by sulfur atoms. The photo-conversion process takes place in a controlled reactive gas environment and the heterogeneous reaction rates are monitored via in situ real-time Raman and photoluminescence spectroscopies. The spatially localized photo-conversion resulted in a heterogeneous TMD structure, with chemically distinct domains, where the initial high crystalline quality of the film is not affected during the process. This has been further confirmed via tran…
Atomically thin materials such as graphene and semiconducting transition metal dichalcogenides (TMDCs) have attracted extensive interest in recent years, motivating investigation into multiple properties. In this work, we demonstrate a refined version of the optothermal Raman technique to measure the thermal transport properties of two TMDC materials, MoS2 and MoSe2, in single-layer (1L) and bi-layer (2L) forms. This new version incorporates two crucial improvements over previous implementations. First, we utilize more direct measurements of the optical absorption of the suspended samples unde…
Transition metal dichalcogenides (TMDs) have recently attracted attention due to their interesting electronic and optical properties. Fabrication of these materials in a reliable and facile method is important for future applications, as are methods to characterize material quality. Here we present the chemical vapor deposition of MoSe2 monolayer and few layer crystals. These results show the practicality of using chemical vapor deposition to reliably fabricate these materials. Low frequency Raman spectra and mapping of shear and layer breathing modes of MoSe2 are presented for the first time.…
A simple, non-invasive method using Raman spectroscopy for the estimation of the thickness of graphene layers grown epitaxially on silicon carbide (SiC) is presented, enabling simultaneous determination of thickness, grain size and disorder using the spectra. The attenuation of the substrate Raman signal due to the graphene overlayer is found to be dependent on the graphene film thickness deduced from X-ray photoelectron spectroscopy and transmission electron microscopy of the surfaces. We explain this dependence using an absorbing overlayer model. This method can be used for mapping graphene …
The tiny Ag diffusion to MgCNi3 has been prepared by solid states reaction. Its structure was characterized by X-ray diffractometer (XRD). The results show that a small mount of Ag substitute for Ni sites, and much of Ag are in vacancy sites of the MgCNi3. We have further studied the surface properties of Ag-MgCNi3 using Raman scattering spectra, and X-ray photoemission spectra (XPS). Raman spectroscopy shows that the Ag-MgCNi3 has a special Raman peak around 842.1 cm-1 compared to that of C. The superconductor transition temperature (about 6.6 K) of Ag-MgCNi3 was lower than that of pure MgCNi…
Transition metal dichalcogenides (TMDs) are layered materials which show excellent potential for nanoelectronic and optoelectronic applications. However, as many of the exciting features of these materials are controlled by the anharmonic effects, a proper understanding of the phonon properties and anharmonicity associated with these materials is essential for the proposed applications to be realized. We present here a comprehensive study on the phonon properties of two different TMDs; viz., MoS2 and MoTe2, as a function of temperature, laser excitations, and polarization, as well as flake-thi…
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, namel…
The growth of transition metal dichalcogenide (TMDC) alloys provides an opportunity to experimentally access information elucidating how optical properties change with gradual substitutions in the lattice compared with their pure compositions. In this work, we performed growths of alloyed crystals with stoichiometric compositions between pure forms of NbSe2 and WSe2, followed by an optical analysis of those alloys by utilizing Raman spectroscopy and spectroscopic ellipsometry.
Thickness-dependent degradation and optical access in epitaxial 2H-MoTe2 protected by metallic capping layers
University of Lodz（罗兹大学）；University of Warsaw（华沙大学）；Military University of Technology（军事理工大学）；Polish Academy of Sciences, Institute of Physics（波兰科学院物理研究所）；Ensemble3 Centre of Excellence（卓越中心 Ensemble3）
Great achievements have been made in alloying of two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDs), which can allow tunable band gaps for practical applications in optoelectronic devices. However, telluride-based TMDs alloys were less studied due to the difficulties of sample synthesis. Here, in this work we report the large-area synthesis of 2D MoTexSe2-x alloy films with controllable Te composition by a modified alkali metal halides assisted chemical vapor deposition method. The as-prepared films have millimeter-scale transverse size. Raman spectra experiments combi…
Understanding thermal transport in layered transition metal dichalcogenide (TMD) crystals is crucial for a myriad of applications exploiting these materials. Despite significant efforts, several basic thermal transport properties of TMDs are currently not well understood. Here, we present a combined experimental-theoretical study of the intrinsic lattice thermal conductivity of the representative TMD MoSe$_2$, focusing on the effect of material thickness and the material's environment. We use Raman thermometry measurements on suspended crystals, where we identify and eliminate crucial artefact…
Atomically thin materials such as graphene and semiconducting transition metal dichalcogenides have attracted extensive interest in recent years, motivating investigation into multiple properties. In this work, we used the opto thermal Raman technique to measure the thermal transport properties of a popular TMDC material WSe$_2$, in single atomic layer, bilayer, and trilayer forms.
Intense light-matter interactions and unique structural and electrical properties make Van der Waals heterostructures composed by Graphene (Gr) and monolayer transition metal dichalcogenides (TMD) promising building blocks for tunnelling transistors, flexible electronics, as well as optoelectronic devices, including photodetectors, photovoltaics and quantum light emitting devices (QLEDs), bright and narrow-line emitters using minimal amounts of active absorber material. The performance of such devices is critically ruled by interlayer interactions which are still poorly understood in many resp…
Group-10 transition metal dichalcogenides (TMDs) are rising in prominence within the highly innovative field of 2D materials. While PtS2 has been investigated for potential electronic applications, due to its high charge-carrier mobility and strong layer-dependent bandgap, it has proven to be one of the more difficult TMDs to synthesise. In contrast to most TMDs, Pt has a significantly more stable monosulfide, the non-layered PtS. The existence of two stable platinum sulfides, sometimes within the same sample, has resulted in much confusion between the materials in the literature. Neither of t…
Two-dimensional materials (2DM) have attracted much interest due to their distinct optical, electronic, and catalytic properties. These properties can be by tuned a range of methods including substitutional doping or, as recently demonstrated, by surface functionalization with single atoms, increasing even further 2DM portfolio. Here we theoretically and experimentally describe the coordination reaction between MoS$_2$ monolayers with 3d transition metals (TMs), exploring the nature and the trend of MoS$_2$-TMs interaction. Density Functional Theory calculations, X-Ray Photoelectron Spectrosco…
Twisted 2D bilayer materials are created by artificial stacking of two monolayer crystal networks of 2D materials with a desired twisting angle $θ$. The material forms a moiré superlattice due to the periodicity of both top and bottom layer crystal structure. The optical properties are modified by lattice reconstruction and phonon renormalization, which makes optical spectroscopy an ideal characterization tool to study novel physics phenomena. Here, we report a Raman investigation on a full period of the twisted bilayer (tB) WSe$_2$ moiré superlattice (\textit i.e. 0° $\leq θ\leq$ 60°). We obs…
Since double resonance Raman (DRR) spectra are laser-energy dependent, the first-principles calculations of DRR for two-dimensional materials are challenging. Here, the DRR spectrum of monolayer MoTe$_2$ is calculated by home-made program, in which we combine {\em ab-initio} density-functional-theory calculations with the electron-phonon Wannier (EPW) method. Within the fourth-order perturbation theory, we are able to quantify not only the electron-photon matrix elements within the dipole approximation, but also the electron-phonon matrix elements using the Wannier functions. The reasonable ag…
Metal and magnetic overlayers alter the surface of the topological insulator (TI) bismuth selenide (Bi$_2$Se$_3$) through proximity effects but also by changing the composition and chemical structure of the Bi$_2$Se$_3$ sub-surface. The interface between Bi$_2$Se$_3$ and Mn metal or manganese selenide was explored using x-ray photoelectron spectroscopy (XPS) revealing chemical and electronic changes at the interface. Depositing Mn metal on Bi$_2$Se$_3$ without an external source of Se shows unexpected bonding within the Mn layer due to Mn-Se bonding as Se diffuses out of the Bi$_2$Se$_3$ layer…
The transition metal ions doped with TiO2 films are of magnetic properties at room temperatures and have stimulated many scientists to study other properties. The Co-TiO2 sandwich composite films have been recently grown on glass and silicon substrates by using alternately radio frequency reactive and direct current magnetron sputtering. The microstructural properties of these films were characterized with Raman spectra and X-ray photoemission spectra (XPS). It shows an anatase TiO2 containing Co nano-layer. Optical absorption spectra have red shift with Co nano-layer increasing, which origina…
In view of their immensely intriguing properties, two dimensional materials are being intensely researched in search of novel phenomena and diverse application interests, however, studies on the realization of nanocomposites in the application-worthy thin-film platform are rare. Here we have grown MoS2-hBN composite thin films on different substrates by the pulsed laser deposition technique and made comparative studies with the pristine MoS2 and hBN films. The Raman, XPS and HRTEM confirm the concomitant presence of both the 1T (conducting) and 2H (semiconducting) polymorphs of MoS2 in the com…
Nano-engineered surface enhanced Raman spectroscopy substrates for probing tissue-material interactions
MIT（麻省理工学院）；University of Wyoming（怀俄明大学）；Brigham and Women's Hospital（布莱根和妇女医院）；Harvard Medical School（哈佛医学院）；Ragon Institute of MGH, MIT and Harvard（MGH、麻省理工学院和哈佛拉贡研究所）；Jameel Clinic for AI & Healthcare, MIT（麻省理工学院贾米尔人工智能与医疗诊所）
The structural polymorphism in transition metal dichalcogenides (TMDs) provides exciting opportunities for developing advanced electronics. For example, MoTe$_2$ crystallizes in the 2H semiconducting phase at ambient temperature and pressure, but transitions into the 1T$^\prime$ semimetallic phase at high temperatures. Alloying MoTe$_2$ with WTe$_2$ reduces the energy barrier between these two phases, while also allowing access to the T$_d$ Weyl semimetal phase. The MoWTe$_2$ alloy system is therefore promising for developing phase change memory technology. However, achieving this goal necessi…
Transition metal dichalcogenides (TMDs) are a class of widely studied 2D layered materials which exist in various polymorphs. The 1T' phase of MoTe2 is of prime importance as it has been reported to show quantum spin hall (QSH) behavior with a fairly large band-gap of ~ 60 meV, in contrast to most QSH materials known. It is noteworthy that though the monolayer 1T'-MoTe2 was initially predicted to show the QSH behavior, recent theoretical studies claim that the few-layered counterparts also exhibit higher order topological behavior. Besides, 1T'-MoTe2 also undergoes a hysteretic phase transitio…
We demonstrate a method to induce tensile and compressive strain into two-dimensional transition metal dichalcogenide (TMDC) MoS$_{2}$ via the deposition of stressed thin films to encapsulate exfoliated flakes. With this technique we can directly engineer MoS$_{2}$ strain magnitude by changing deposited thin film stress, therefore allowing variable strain to be applied on a flake-to-flake level. These thin film stressors are analogous to SiN$_{x}$ based stressors implemented in industrial CMOS processes to enhance Si mobility, suggesting that our concept is highly scalable and may be applied f…
A study on the NO2 gas sorption ability of amorphous Ge33Se67 coated quartz crystal microbalance (QCM) is presented. The thin films have been characterized before and after sorption/desorption processes of NO2 by energy-dispersive X-ray spectroscopy (EDS), grazing angle X-ray diffraction (GAXRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and atom force microscopy (AFM) measurements. These studies indicated that physisorption occurs when NO2 gas molecules are introduced into the chalcogenide film and the thin film composition or structure do not change. The mass loading due to …
Transition metal dichalcogenides (TMDCs) have emerged as a new two dimensional materials field since the monolayer and few-layer limits show different properties when compared to each other and to their respective bulk materials. For example, in some cases when the bulk material is exfoliated down to a monolayer, an indirect-to-direct band gap in the visible range is observed. The number of layers $N$ ($N$ even or odd) drives changes in space group symmetry that are reflected in the optical properties. The understanding of the space group symmetry as a function of the number of layers is there…
Here we report mid infrared (mid-IR) photothermal response of multi layer MoS2 thin film grown on crystalline (p-type silicon and c-axis oriented single crystal sapphire) and amorphous substrates (Si/SiO2 and Si/SiN) by pulsed laser deposition (PLD) technique. The photothermal response of the MoS2 films was measured as changes in the resistance of MoS2 films when irradiated with mid IR (7 to 8.2 μm) source. We show that it is possible to enhance the temperature coefficient of resistance (TCR) of the MoS2 thin film by controlling the interface through proper choice of substrate and growth condi…
Van der Waals heterostuctures, made from stacks of two-dimensional materials, exhibit unique light-matter interactions and are promising for novel optoelectronic devices. The performance of such devices is governed by near-field coupling through, e.g., interlayer charge and/or energy transfer. New concepts and experimental methodologies are needed to properly describe two-dimensional heterointerfaces. Here, we report on interlayer charge and energy transfer in atomically thin metal (graphene)/semiconductor (transition metal dichalcogenide (TMD, here MoSe$_2$)) heterostructures using a combinat…
Pseudo-one dimensional (pseudo-1D) materials are a new-class of materials where atoms are arranged in chain like structures in two-dimensions (2D). Examples include recently discovered black phosphorus, ReS2 and ReSe2 from transition metal dichalcogenides, TiS3 and ZrS3 from transition metal trichalcogenides and most recently GaTe. The presence of structural anisotropy impacts their physical properties and leads to direction dependent light-matter interactions, dichroic optical responses, high mobility channels, and anisotropic thermal conduction. Despite the numerous reports on the vapor phas…
Optoelectronic devices based on graphene and other two-dimensional (2D) materials, such as transition metal dichalcogenides (TMDs) are the focus of wide research interest. The characterization these emerging atomically thin materials and devices strongly relies on a set of measurements involving both optical and electronic instrumentation ranging from scanning photocurrent mapping to Raman and photoluminescence (PL) spectroscopy. Furthermore, proof-of-concept devices are usually fabricated from micro-meter size flakes, requiring microscopy techniques to characterize them. Current state-of-the-…
Platinum diselenide (PtSe${_2}$) is a two-dimensional (2D) material with outstanding electronic and piezoresistive properties. The material can be grown at low temperatures in a scalable manner which makes it extremely appealing for many potential electronics, photonics, and sensing applications. Here, we investigate the nanocrystalline structure of different PtSe${_2}$ thin films grown by thermally assisted conversion (TAC) and correlate them with their electronic and piezoresistive properties. We use scanning transmission electron microscopy for structural analysis, X-ray photoelectron spect…
Growth of $>$100 $μ$m thick diamond layer adherent on aluminium nitride is presented in this work. While thick films failed to adhere on untreated AlN films, hydrogen/nitrogen plasma treated AlN films retained the thick diamond layers. Clear differences in zeta potential measurement confirms the surface modification due to hydrogen/nitrogen plasma treatment. Areal Raman maps showed an increase in non-diamond carbon in the initial layers of diamond grown on pre-treated AlN. The presence of non-diamond carbon has minimal effect on the interface between diamond and AlN. The surfaces studied with …
In this study we investigated the sorption ability of Ge20Se80 thin films applied as active layers of quartz crystal microbalance (QCM) for NO2 gas sensing. To identify the chalcogenide system appropriate for gas sensing, we provided data for the packing fraction of a number of chalcogenide systems and discussed their suitability. We performed Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and atom force microscopy (AFM) measurements on the thin films both before and after gas absorption, which showed that the introduced gas molecules interact electrostatically with the chalcogen a…
Wide and ultrawide-bandgap semiconductors lie at the heart of next-generation high-power, high-frequency electronics. Here, we report the growth of ultrawide-bandgap boron nitride (BN) thin films on wide-bandgap gallium nitride (GaN) by pulsed laser deposition. Comprehensive spectroscopic (core level and valence band XPS, FTIR, Raman) and microscopic (AFM and STEM) characterizations confirm the growth of BN thin films on GaN. Optically, we observed that BN/GaN heterostructure is second-harmonic generation active. Moreover, we fabricated the BN/GaN heterostructure-based Schottky diode that demo…
Kusachiite (copper bismuth oxide) is one of the most promising photocathode materials for high solar-to-hydrogen production efficiency. Here we attempt to synthesize phase pure copper bismuth oxide (CuBi2O4) nanopowders using a facile solid-state reaction technique, subsequently sintered at 750 0C for 4 h in air. These CuBi2O4 (CBO) powders have been further sequentially ball-milled (SBM) up to 25 h to elucidate the milling duration effect on the optical bandgap of the ball-milled CuBi2O4 (SBM-CBO). The X-ray diffractometry (XRD), Raman, X-ray Photoelectron spectroscopy (XPS), and UV-VIS-NIR D…
Monolayer tungsten disulfide ($WS_2$) has recently attracted large interest as a promising material for advanced electronic and optoelectronic devices such as photodetectors, modulators, and sensors. Since these devices can be integrated in a silicon (Si) chip via back-end-of-line (BEOL) processes, the stability of monolayer $WS_2$ in BEOL fabrication conditions should be studied. In this work, the thermal stability of monolayer single-crystal $WS_2$ at typical BEOL conditions is investigated; namely (i) heating temperature of $300$ $^\circ C$, (ii) pressures in the medium- ($10^{-3}$ mbar) an…
