A brief introduction reviews the changes that have occurred in semiconductor wafer processing, which, coupled with developments in X ray Photoelectron Spectroscopy, XPS, instrumentation, have led to XPS becoming a primary materials analysis tool in this industry. Three specific examples illustrating the use of XPS and Angle resolved XPS, ARXPS, are then presented. These are nitridation processing of high k gate material (HfO2 based); the monitoring of Al content and chemistry in a 10A TiAlN film (a metal gate add on process to high k); and deposition of diamond-like amorphous C films (a candidate for hard mask applications in DRAM, NAND flash, and NOR flash memories).
Chemical vapor deposition allows the preparation of few-layer films of MoTe2 in three distinct structural phases depending on the growth quench temperature: 2H, 1T', and 1T. We present experimental and computed Raman spectra for each of the phases and utilize transport measurements to explore the properties of the 1T MoTe2 phase. Density functional theory modeling predicts a (semi-)metallic character. Our experimental 1T films affirm the former, show facile μA-scale source-drain currents, and increase in conductivity with temperature, different from the 1T' phase. Variation of the growth method allows the formation of hybrid films of mixed phases that exhibit susceptibility to gating and significantly increased conductivity.
We report on experimental demonstration of single- and few-layer chemical vapor deposited (CVD) molybdenum disulfide (MoS2) nanomechanical resonators by employing a scalable transfer-print method. CVD MoS2 crystals are released from their growth substrates (with well-preserved, uniform crystal quality) by a water-assisted lift-off technique, and suspended over pre-patterned arrays of microtrenches through an all-dry, aligned transfer process. We measure device performance from the resulting single- and few-layer drumhead resonators (1-2 μm in diameter), showing fundamental resonance frequencies (f0) up to ~80 MHz, and figures-of-merit (f0×Q) up to ~2.4×1010 Hz. We quantify the uniformity of resonance performance in arrays of devices, and show that 250 °C thermal annealing can enhance the performance and uniformity.
Growth by chemical vapor deposition (CVD) leads to multilayer WS2 of very high quality, based on high-resolution angle-resolved photoemission spectroscopy. The experimental valence band electronic structure is considered to be in good agreement with that obtained from density functional theory calculations. We find the spin-orbit splitting at the K¯ point to be 420 ± 20 meV with a hole effective mass of −0.35 ± 0.02 me for the upper spin-orbit component (the branch closer to the Fermi level) and −0.43 ± 0.07 me for the lower spin-orbit component. As predicted by theory, a thickness-dependent increase of bandwidth is observed at the top of the valence band, in the region of the Brillouin zone center. The top of the valence band of the CVD-prepared films exhibits a substantial binding energy, consistent with n-type behavior, and in agreement with transistor characteristics acquired using devices incorporating the same WS2 material.
The growth of micron-scale single-layer MoS2 islands is seeded and distributed at high fidelity by means of a regular array of micron-scale holes that extend through the oxide layer of a 300 nm SiO2/Si substrate. Low coverages exhibit individual sub-micron MoS2 islands directly adjacent to the seed positions. At moderate coverage the seed holes are encircled by merged MoS2 islands, whose overall shape and internal grain boundaries reveal coalescence out of several initial crystallites. Seeded islands are strictly monolayer in height, non-overlapping and they offer high photoluminescence as well as conventional Raman signatures.
Transition metal dichalcogenides (TMDs) have emerged as a new class of two-dimensional materials that are promising for electronics and photonics. To date, optoelectronic measurements in these materials have shown the conventional behavior expected from photoconductors such as a linear or sublinear dependence of the photocurrent on light intensity. Here, we report the observation of a new regime of operation where the photocurrent depends superlinearly on light intensity. We use spatially resolved photocurrent measurements on devices consisting of CVD-grown monolayers of TMD alloys spanning MoS2 to MoSe2 to show the photoconductive nature of the photoresponse, with the photocurrent dominated by recombination and field-induced carrier separation in the channel. Time-dependent photoconductivity measurements show the presence of persistent photoconductivity for the S-rich alloys, while photocurrent measurements at fixed wavelength for devices of different alloy compositions show a systematic decrease of the responsivity with increasing Se content associated with increased linearity of the current-voltage characteristics. A model based on the presence of different types of recombination centers is presented to explain the origin of the superlinear dependence on light intensity, which emerges when the nonequilibrium occupancy of initially empty fast recombination centers becomes comparable to that of slow recombination centers.
We demonstrate bandgap tuning of a single-layer MoS2 film on SiO2/Si via substitution of its sulfur atoms by selenium through a process of gentle sputtering, exposure to a selenium precursor, and annealing. We characterize the substitution process both for S/S and S/Se replacement. Photoluminescence and, in the latter case, X-ray photoelectron spectroscopy provide direct evidence of optical band gap shift and selenium incorporation, respectively. We discuss our experimental observations, including the limit of the achievable bandgap shift, in terms of the role of stress in the film as elucidated by computational studies, based on density functional theory. The resultant films are stable in vacuum, but deteriorate under optical excitation in air.
MoS2(1-x) Se2x single-layer films are prepared using a mixture of organic selenium and sulfur precursors as well as a solid molybdenum source. The direct bandgaps are found to scale nearly linearly with composition in the range of 1.87 eV (pure single-layer MoS2 ) to 1.55 eV (pure single-layer MoSe2 ) permitting straightforward bandgap engineering.
An Mo2S3 monolayer grown on copper coexists with well-known MoS2 patches and triangular islands. Imaging by scanning tunneling microscopy after exposure to anthraquinone shows the new structure to be far more active in adsorption, permitting even the formation of a compressed adsorbate layer before other surface areas, including the supposedly reactive brim areas of MoS2 islands, capture this adsorbate.