Composition Of Ultrathin Films Research Articles

Composition of ultrathin binary polymer brushes by thermogravimetry-gas chromatography-mass spectrometry.

In the present paper, a reliable and rugged thermogravimetry-gas chromatography-mass spectrometry (TGA-GC-MS) method was developed to determine the composition of ultrathin films consisting of binary blends of functional polystyrene (PS) and polymethylmethacrylate (PMMA) grafted to a silicon wafer. A general methodology will be given to address the composition determination problem for binary or even multicomponent polymer brush systems using the PS/PMMA-based samples as a paradigmatic example. In this respect, several distinct tailor-made materials were developed to ensure reliable calibration and validation stages. The analytical method was tested on unknown samples to follow the composition evolution in PS/PMMA brushes during the grafting reaction. A preferential grafting of the PMMA was revealed in full agreement with its preferential interaction with the SiO2 polar surface.

Synthesis of Transition Metal Dichalcogenide WSe2thin Films By Atomic Layer Deposition

Two-dimensional layered transition metal dichalcogenides, such as MoS2, WSe2 and MoSe2 have received a lot of attention recently due to their promising unique thermal, mechanical, electrical, optical properties. Tungsten Diselenide (WSe2), one of the transition metal dichalcogenides of interest for 2-D electronic systems, exhibits not only good thermal stability and high melting point, but also excellent optical and electrical properties. WSe2 is a semiconductor with a bandgap which could be used for the fabrication of solar cells and LEDs of various colors [1, 2]. Many techniques have been developed for synthesis of WSe2 films on different substrates in recent years, such as sold state reaction, elctrodepositon, RF-magnetron sputtering, electrodepostion, pulsed laser depostion, chemical vapor depositon. However, there are very few references that report atomic layer deposition (ALD) results of WSe2 films. This technique exhibits self-limiting surface reactions, which means accidental overdosing of precursors does not result in increased film deposition on the substrate surface. This self-terminating character is able to accurately control thickness and composition of ultra thin films and achieves uniformity, conformality and even monolayers of transition metal dichalcogenides. Here we report on a large-area synthesis of WSe2 films on native oxide covered and hydroxyl terminated Si substrates by using the Savannah 100 ALD system from Ultratech/Cambridge Nanotech. Tungsten hexacarbonyl (W(CO)6) and (trimethylsilyl) selenide ((Me3Si)2Se) are employed as the chemical ALD precursors for Tungsten and selenium, respectively. Generally 20 sccm N2 was used as a carrier gas for the precursors. The growth temperature was set at 275, 300 and 325oC. The crystal structure and chemical composition of WSe2 films were identified by using X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDS). The film morphology was characterized by field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). The optical property was analyzed by Raman spectroscopy and photoluminescence (PL) spectroscopy. The strong Raman scattering of in-plane E1 2g and out-of-plane A1g vibration modes, and the dominant PL of direct transition from Kc to Kv and indirect transition from Λc to Γv with absence of Kc to Γv are typical optical spectra of layered WSe2. The reduction of out-of-plane vibration mode and the absence of PL from indirect transition provide the evidence of fewer layer WSe2.

Effects of surface pretreatments on interface structure during formation of ultra-thin yttrium silicate dielectric films on silicon

X-ray photoelectron spectroscopy (XPS) and medium energy ion scattering (MEIS) are used to determine chemical bonding and composition of ultra-thin films of mixed yttrium, silicon, and oxygen, formed by oxidation of metal on clean and pre-treated silicon. XPS and MEIS analyses indicate that oxidation of yttrium on bare silicon results in a fully oxidized film with a significant fraction of Y–O–Si bonding. The mixed Y–O–Si structure results from the relatively rapid reaction between Y and the Si substrate to form yttrium silicide, followed by oxidation. The effect of various silicon pretreatments, including in situ oxidation and nitridation, on bulk and interface film composition are also examined. Transmission electron microscopy (TEM) of 40 Å thick films indicates that the yttrium silicate films are amorphous with uniform contrast throughout the layer. MEIS shows evidence for a graded metal concentration in the dielectric near the silicon interface, with uniform oxygen concentration (consistent with full oxidation) throughout the film. Angle resolved XPS (ARXPS) shows no significant signal related to Si +4, as would be expected from a substantial SiO 2 interface layer. Capacitance–voltage analysis demonstrates that a ∼10 Å equivalent oxide thickness can be achieved. The effects of ultra-thin silicon oxide, nitrided-oxide and nitrided silicon interfaces on silicon consumption during the oxidation of yttrium are investigated. When yttrium is deposited on a thin (∼10 Å) SiO 2 film and oxidized, a yttrium silicate film is formed with bonding and composition similar to films formed on bare silicon. However, when the interface is a thin nitride, the silicon consumption rate is significantly reduced, and the resulting film composition is closer to Y 2O 3. The consumption of the silicon substrate by metal is shown to occur during oxidation and during vacuum annealing of yttrium on silicon. The relatively rapid formation of metal–silicon bonds suggests that metal–silicon structures may also be important reactive intermediates in silicon/dielectric interface formation reactions during chemical vapor deposition. In addition to thermodynamic stability, understanding the relative rates of elementary reaction steps in film formation is critical to control composition and structure at the dielectric/Si interface.

Surface alloying and pinhole formation in ultra-thin [formula omitted] films

Relatively mild annealing sometimes produces unexpectedly large changes in surface composition of ultra-thin films. We report results of a scanning tunnelling microscopy study of such annealing in an Fe Cu(100) system. Copper appears in the surface region after a short 490 K anneal. We specifically exclude the possibility of bulk interdiffusion and conclude that this surface copper comes from the substrate through microscopic pinholes. Our primary finding is that the balance of surface free energies which strongly prefers Cu/Fe/Cu over Fe Cu is the main driving force for pinhole formation and copper segregation. Furthermore, we report a significant surface alloying in this otherwise almost immiscible system.