Molybdenum disulfide (MoS2) is the most widely studied transition metal dichalcogenide (TMDC) material, in part because it is a natural crystal present in the earth, thus making it abundant and easily accessible. Geological MoS2 has been used in various studies that look at incorporating MoS2 into devices for nanoelectronics and optoelectronics. However, variations in the electronic properties of a single MoS2 surface are known to exist due to defects that are intrinsic to natural MoS2. This work reports the presence of bismuth impurities in MoS2 with concentrations high enough to be detected by X-ray photoelectron spectroscopy (XPS). These concentrations are further corroborated with inductively coupled plasma optical emission spectroscopy (ICP-OES). Localization of these bismuth clusters is shown using XPS-mapping, and the cluster size is determined to be on the order of tens of microns. This work provides important insights into the nature of impurities that are known to exist in MoS2. Keywords: Geological MoS2, Impurities, Bismuth, X-ray photoelectron spectroscopy concentrations are higher than ~0.1%, which is the typical detection limit of XPS [19]. The chemical state of these Bi impurities is determined. Estimates of the impurity size and distribution across the MoS2 surface are also reported.
Material and MethodsGeological MoS2 crystal (Graphene Supermarket[20]) was cleaned by mechanical exfoliation with scotch tape which removed the top most layers of MoS2, leaving a freshly exposed crystal surface. These samples were then loaded into ultra-high vacuum (UHV) for Xray photoelectron spectroscopy (XPS) in less than 30 minutes. XPS spectra were acquired using Al K X-rays (1468.7 eV) at a pass energy of 26 eV in a PHI VersaProbe III system. This XPS tool is also equipped with a scanning X-ray induced (SXI) secondary electron imaging feature for accurate point selection in the micrometer range, and a variety of X-ray spot sizes ranging from 9 to 200 m. Spectra of geological MoS2 from another vendor (SPI Supplies [21]) are shown in Supplementary Material to confirm that Bi is detected from more than one material source, but all XPS analyses shown in the main text are of MoS2 from Graphene Supermarket.XPS mapping was performed by selecting a random area of the crystal and through the SXI imaging mode, setting up an array of points that are 100 m apart horizontally and vertically. The Mo 3d and S 2p spectra were taken at each of these points using an X-ray beam spot size of 100 m. The points analyzed were within an 800 m x 800 m area, for a total of 81 spots checked. These spectra were batch processed using the PHI MultiPak software in order to identify which of the 81 points had Bi peaks present from XPS.A particle/cluster size check of the bismuth impurities was achieved by centering the Xray spot on a Bi impurity, and without moving the sample, analyzing the same spot using different X-ray beam spot sizes: 9 m, 15 m, 20 m, 50 m, 100 m, and 200 m. All XPS peak fitting in this work to obtain areas of ...