Atomic Layer Deposition of Pt Thin Films Using Dimethyl (N,N-Dimethyl-3-Butene-1-Amine-N) Platinum and O₂ Reactant

Abstract

Pt thin films, using the Pt precursor, dimethyl­(N,N-dimethyl-3-butene-1-amine-N)­platinum (DDAP, C8H19NPt), were deposited by atomic layer deposition (ALD). The growth characteristics of the Pt thin films were systemically investigated. A saturated growth rate was obtained with an increase in precursor and reactant pulse times, revealing the nature of the ALD self-limiting process. The growth rate increased with increasing deposition temperature and finally became saturated above 280 °C, showing a high growth rate of 0.85 Å/cycle. The short incubation time for Pt nucleation promoted the growth characteristics, which can be favorable for catalytic applications. The high reactivity and small adsorbate size produced the relatively high growth rate of the Pt thin films deposited with the DDAP precursor. A very low resistivity, close to the value of bulk Pt, was obtained for all Pt thin films deposited at various temperatures. The low resistivity was due to the similar crystalline structure and very high purity of the Pt thin films at all deposition temperatures explored in this study. In addition, Pt thin films were also deposited on a high-aspect-ratio substrate and showed good uniformity and step coverage, with a constant work function, which can be promising for electrode applications. Synthesis of Pt films by ALD using the DDAP Pt precursor and O2 is a noteworthy approach for obtaining films with a high growth rate and low resistivity.

Ultralow Loading (Single‐Atom and Clusters) of the Pt Catalyst by Atomic Layer Deposition Using Dimethyl ((3,4‐η) N,N‐dimethyl‐3‐butene‐1‐amine‐N) Platinum (DDAP) on the High‐Surface‐Area Substrate for Hydrogen Evolution Reaction

“…recently reported a GPC of 0.085 nm with DDAP precursor. [ 30 ] Therefore, the current Pt precursor indicated a better/faster growth kinetics (surface reactivity) compared to the others. However, the overall ALD process conditions (like vapor pressure and size of the Pt precursor molecule, deposition temperature, reactant, shape, and size of the reactor, working pressure, etc.)…”

“…[ 22,23,25 ] The preparation of the hierarchically porous NC–CC substrate is already reported, and in the current investigation, we followed the same procedure. [ 22,24 ] ALD of Pt has been investigated by several authors, [ 26–30 ] however, the majority of the reports uses trimethyl (methylcyclopentadienyl) platinum [IV] (MeCpPtMe 3 ) as the Pt precursor, and oxygen as the reactant. [ 27,28 ] Further, depending on the type of reactants (O 2 , air, and O 2 –H 2 mixture), the deposition temperature varies from 200 to 300 °C.…”

Direct Integration of Strained‐Pt Catalysts into Proton‐Exchange‐Membrane Fuel Cells with Atomic Layer Deposition

“…Among the many strategies in this line, one can enhance ECA by further increasing the ratio of surface platinum atoms that are catalytically active, for example, by optimizing catalyst geometry, especially given that ALD can be utilized to synthesize atomic scale catalyst down to single‐atom active sites. [ 73,74 ] With innovations on ALD chemicals, especially the Pt ALD precursors, [ 75,76 ] and deeper understanding and innovation of ALD deposition processes, [ 77,78 ] ORR activity normalized by mass or cost are expected to be improved further.…”

Synthesis and Characterization of Ni-Pt Alloy Thin Films Prepared by Supercritical Fluid Chemical Deposition Technique

“…Lee et al reported that the highest growth rate for Pt thin films occurred in the temperature range 280 °C to 340 °C. At higher temperatures, the Pt precursor typically is more exothermic, which is enhanced the chemisorption between precursor and converting agent on surface-active sites of the substrate, resulting in a fast growth rate [ 47 ]. Battiston et al reported that the starting temperatures for Pt film deposition should be at least 240 °C and they divided the deposition temperatures range 240–300 °C in the presence of oxygen and 280–440 °C in the water vapor.…”