Electrodeposited MoxSyOz/Ni Tribological Coatings.

Deposition of molybdenum disulfide (MoS2) coatings using physical vapor deposition (PVD) and mechanical burnishing has been widely assessed for solid lubricants in space applications but still suffers from line-of-sight constraints on complex geometries. Here, we highlight one of the first demonstrations of electrodeposited MoxSyOz and MoxSyOz/Ni thin-film coatings from aqueous solutions of ammonium tetrathiomolybdate for solid lubricant applications and their remarkable ability to provide low coefficients of friction and high wear resistance. Characterization of the coating morphology shows amorphous microstructures with a high oxygen content and cracking upon drying. Even so, electrodeposited MoxSyOz can achieve low steady-state coefficients of friction (µ ∼ 0.05-0.06) and wear rates (2.6 × 10-7 mm3/(N m)) approaching those of physical vapor deposited coatings (2.3 × 10-7 mm3/(N m)). Additionally, we show that adding dopants such as nickel increased the wear rate (7.5 × 10-7 mm3/(N m)) and initial coefficient of friction (µi = 0.23) due to compositional modifications such as dramatic sub-stoichiometry (S/Mo ∼ 1) and expression of a NiOx surface layer, although doping did reduce the degree of cracking upon drying.

Comparison of Orientation Mapping in SEM and TEM.

Multiple experimental configurations for performing nanoscale orientation mapping are compared to determine their fidelity to the true microstructure of a sample. Transmission Kikuchi diffraction (TKD) experiments in a scanning electron microscope (SEM) and nanobeam diffraction (NBD) experiments in a transmission electron microscope (TEM) were performed on thin electrodeposited hard Au films with two different microstructures. The Au samples either had a grain size that is >50 or <20 nm. The same regions of the samples were measured with TKD apparatuses at 30 kV in an SEM with detectors in the horizontal and vertical configurations and in the TEM at 300 kV. Under the proper conditions, we demonstrate that all three configurations can produce data of equivalent quality. Each method has strengths and challenges associated with its application and representation of the true microstructure. The conditions needed to obtain high-quality data for each acquisition method and the challenges associated with each are discussed.

PtRu nanofilm formation by electrochemical atomic layer deposition (E-ALD).

The high CO tolerance of PtRu electrocatalysis, compared with pure Pt and other Pt-based alloys, makes it interesting as an anode material in proton exchange membrane fuel cells (PEMFC) and direct methanol fuel cells (DMFC). This report describes the formation of bimetallic PtRu nanofilms using the electrochemical form of atomic layer deposition (E-ALD). Metal nanofilm formation using E-ALD is facilitated by use of surface-limited redox replacement (SLRR), where an atomic layer (AL) of a sacrificial metal is first formed by UPD. The AL is then spontaneously exchanged for a more noble metal at the open-circuit potential (OCP). In the present study, PtRu nanofilms were formed using SLRR for Pt and Ru, and Pb UPD was used to form the sacrificial layers. The PtRu E-ALD cycle consisted of Pb UPD at -0.19 V, followed by replacement using Pt(IV) ions at OCP, rinsing with blank, then Pb UPD at -0.19 V, followed by replacement using Ru(III) ions at OCP. PtRu nanofilm thickness was controlled by the number of times the cycle was repeated. PtRu nanofilms with atomic proportions of 70/30, 82/18, and 50/50 Pt/Ru were formed on Au on glass slides using related E-ALD cycles. The charge for Pb UPD and changes in the OCP during replacement were monitored during the deposition process. The PtRu films were then characterized by CO adsorption and electrooxidation to determine their overpotentials. The 50/50 PtRu nanofilms displayed the lowest CO electrooxidation overpotentials as well as the highest currents, compared with the other alloy compositions, pure Pt, and pure Ru. In addition, CO electrooxidation studies of the terminating AL on the 50/50 PtRu nanostructured alloy were investigated by deposition of one or two SLRR of Pt, Ru, or PtRu on top.

Electrodeposition of CuInSe2 (CIS) via electrochemical atomic layer deposition (E-ALD).

The growth of stoichiometric CuInSe(2) (CIS) on Au substrates using electrochemical atomic layer deposition (E-ALD) is reported here. Parameters for a ternary E-ALD cycle were investigated and included potentials, step sequence, solution compositions and timing. CIS was also grown by combining cycles for two binary compounds, InSe and Cu(2)Se, using a superlattice sequence. The formation, composition, and crystal structure of each are discussed. Stoichiometric CIS samples were formed using the superlattice sequence by performing 25 periods, each consisting of 3 cycles of InSe and 1 cycle of Cu(2)Se. The deposits were grown using 0.14, -0.7, and -0.65 V for Cu, In, and Se precursor solutions, respectively. XRD patterns displayed peaks consistent with the chalcopyrite phase of CIS, for the as-deposited samples, with the (112) reflection as the most prominent. AFM images of deposits suggested conformal deposition, when compared with corresponding image of the Au on glass substrate.

Preliminary studies in the electrodeposition of PbSe/PbTe superlattice thin films via electrochemical atomic layer deposition (ALD).

This paper concerns the electrochemical growth of compound semiconductor thin film superlattice structures using electrochemical atomic layer deposition (ALD). Electrochemical ALD is the electrochemical analogue of atomic layer epitaxy (ALE) and ALD, methods based on nanofilm formation an atomic layer at a time, using surface-limited reactions. Underpotential deposition (UPD) is a type of electrochemical surfaced-limited reaction used in the present studies for the formation of PbSe/PbTe superlattices via electrochemical ALD. PbSe/PbTe thin-film superlattices with modulation wavelengths (periods) of 4.2 and 7.0 nm are reported here. These films were characterized using electron probe microanalysis, X- ray diffraction, atomic force microscopy (AFM), and infrared reflection absorption measurements. The 4.2 nm period superlattice was grown after deposition of 10 PbSe cycles, as a prelayer, resulting in an overall composition of PbSe0.52Te0.48. The 7.0 nm period superlattice was grown after deposition of 100 PbTe cycle prelayer, resulting for an overall composition of PbSe0.44Te0.56. The primary Bragg diffraction peak position, 2theta, for the 4.2 superlattice was consistent with the average (111) angles for PbSe and PbTe. First-order satellite peaks, as well as a second, were observed, indicating a high-quality superlattice film. For the 7.0 nm superlattice, Bragg peaks for both the (200) and (111) planes of the PbSe/PbTe superlattice were observed, with satellite peaks shifted 1 degrees closer to the (111), consistent with the larger period of the superlattice. AFM suggested conformal superlattice growth on the Au on glass substrate. Band gaps for the 4.2 and 7.0 nm period superlattices were measured as 0.48 and 0.38 eV, respectively.