Low temperature thermal ALD TaNx and TiNx films from anhydrous N2H4

Wolf, Steven; Breeden, Michael; Kwak, Iljo; Park, Jun H.; Kavrik, Mahmut Sami; Naik, Mehul; Álvarez, Daniel; Spiegelman, Jeffrey; Kummel, Andrew C.

doi:10.1016/j.apsusc.2018.07.153

Cited by 11 publications

(9 citation statements)

References 31 publications

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“…Resistance to wear and friction and resistance to corrosion make them very important compounds in applications for protective coatings of structures, which are generally made of steel, cutting tools, and reconstruction of worn parts. Likewise, these compounds have excellent electrical and thermal conductivity, high chemical stability, low diffusion, and adequate adherence [3][4][5][6][7]. For all these properties that have made nitride materials of vital importance, great efforts have been devoted to the study of transition metal nitrides to find hard and resistant materials that meet the growing demand that has been generated in recent decades in various applications, as 2 of 15 already mentioned [8,9].…”

Section: Introductionmentioning

confidence: 99%

Growth Mechanisms of TaN Thin Films Produced by DC Magnetron Sputtering on 304 Steel Substrates and Their Influence on the Corrosion Resistance

et al. 2022

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In this work, thin films of TaN were synthesized on 304 steel substrates using the reactive DC sputtering technique from a tantalum target in a nitrogen/argon atmosphere. All synthesis parameters such as gas ratio, pressure, gas flow, and substrate distance, among others, were fixed except the applied power of the source for different deposited coatings. The effect of the target power on the formation of the resulting phases and the microstructural and morphological characteristics was studied using XRD and AFM techniques, respectively, in order to understand the growth mechanisms. Phase, line profile, texture, and residual stress analysis were carried out from the X-ray diffraction patterns obtained. Atomic force microscopy analysis allowed us to obtain values for surface grain size and roughness which were related to growth mechanisms in accordance with XRD results. Results obtained showed a strong correlation between the growth energy with the crystallinity of the samples and the formation of the possible phases since the increase in the growth power caused the samples to evolve from an amorphous structure to a cubic monocrystalline structure. For all produced samples, the δ-TaN phase was observed despite the low N2 content used in the process (since for low N2 content it was expected to be possible to obtain films with α-Ta or hexagonal ε-TaN crystalline structure). In order to determine the corrosion resistance of the coatings, electrochemical impedance spectroscopy and polarization resistance were employed in the Tafel region. The results obtained through this evaluation showed a direct relationship between the power used and the improvement of the properties against corrosion for specific grain size values.

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Section: Introductionmentioning

confidence: 99%

Growth Mechanisms of TaN Thin Films Produced by DC Magnetron Sputtering on 304 Steel Substrates and Their Influence on the Corrosion Resistance

et al. 2022

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“…As an example, TiN thin films have been successfully deposited via ALD using TiCl 4 and pure NH 3 as the precursors. Several studies have also reported superior qualities of thin films, such as low electrical resistance and good crystallinity, via ALD [24,25]. However, halide contamination commonly found in thin films affects the device reliability, and the hydrogen halide generated as a byproduct may damage not only the underlying layer but also the ALD reactor and its piping system [26,27].…”

Section: Introductionmentioning

confidence: 99%

Adsorption of Titanium Halides on Nitride and Oxide Surfaces during Atomic Layer Deposition: A DFT Study

Park

Jang

et al. 2020

Coatings

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Various processes based on atomic layer deposition (ALD) have been reported for growing Ti-based thin films such as TiN and TiO2. To improve the uniformity and conformity of thin films grown via ALD, fundamental understanding of the precursor–substrate surface reactions is required. Herein, we present a density functional theory (DFT) study of the initial nucleation process of some titanium halide precursors (TiCl4, TiBr4, and TiI4) on Si surfaces having –OH or –NH2 functional groups. We consider the most favorable adsorption site in the reaction between the precursor and functional group of the surface, based on the thermodynamics and kinetics of the reaction. Sequential dissociation reaction mechanisms of halide ligands were systematically investigated. The exothermicity of the dissociative adsorption was found to be in the order of: TiI4 > TiBr4 > TiCl4. In addition, the precursors were observed to be more exothermic and show higher reaction rate constant when adsorbed on the –OH–terminated surface than on the –NH2–terminated surface. These observations reveal the selectivity of deposition by surface functional groups.

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“…A fraction of Ti within the lattice of 1:2 and 1:1 Zr-to-Ti samples had a BE of 456 eV, a value corresponding to that of metallic Ti(IV) 3 N 4 . In contrast, in Zr 3d XPS spectra (Figure S8b) of these samples, a broad, coalesced peak consisting of peaks from Zr(IV) 3 N 4 , oxynitrides, and oxides can be observed, ,, suggesting that Zr ions are preferentially reacting in air to form the electrically insulating materials. We note that N 1s and O 1s spectra of all samples show multiple peaks, suggesting that, indeed, the surface is composed of complex mixtures of metal oxides, oxynitrides, and nitrides (Figures S8c,d).…”

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confidence: 97%

“…Recently, we have demonstrated the capability to control the atomic ratio of Ti and Al within mixed metal nitride films synthesized via plasma-enhanced atomic layer deposition (PE-ALD) where the TiN component exhibits strong metallic behavior that may render films suitable as candidate electrodes . Indeed, others have also exploited PE-ALD to synthesize various metal nitrides at relatively mild temperatures ( e.g., , Zr x N y at 150–300 °C, − Co x N y at 100–150 °C, Ti x N y at 250–300 °C, , Ta x N y at 230–300 °C , ). We build upon these findings to incorporate various amounts of Zr within the TiN lattice and examine the valence state of Zr as a function of composition.…”

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confidence: 99%

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Stabilization of Low Valent Zirconium Nitrides in Titanium Nitride via Plasma-Enhanced Atomic Layer Deposition and Assessment of Electrochemical Properties

Noh

Jeon

Martinson

et al. 2020

ACS Appl. Energy Mater.

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The increasing awareness of metal nitrides as feasible electrocatalysts in numerous energy-relevant transformations motivates greater synthetic control of mixed metal nitride compositions and their valence states. We report plasma-enhanced atomic layer deposition of titanium zirconium nitride, with an emphasis on the experimental parameters that influence the valence states of the two metal ions. We further examined the consequence of various ratios of Ti and Zr on the electrochemically active surface areas (ECSAs). Films with a Zr-to-Ti ratio of 1:2 or 1:1 yielded the highest ECSA; deviation from these values led to a large fraction of electrically insulating or semiconducting titanium or zirconium oxynitrides/oxides. The systematic examination establishes a fundamental structure–property relationship critical to assessing the electrochemical/electrocatalytic properties of metal nitrides.

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Low temperature thermal ALD TaNx and TiNx films from anhydrous N2H4

Cited by 11 publications

References 31 publications

Growth Mechanisms of TaN Thin Films Produced by DC Magnetron Sputtering on 304 Steel Substrates and Their Influence on the Corrosion Resistance

Growth Mechanisms of TaN Thin Films Produced by DC Magnetron Sputtering on 304 Steel Substrates and Their Influence on the Corrosion Resistance

Adsorption of Titanium Halides on Nitride and Oxide Surfaces during Atomic Layer Deposition: A DFT Study

Stabilization of Low Valent Zirconium Nitrides in Titanium Nitride via Plasma-Enhanced Atomic Layer Deposition and Assessment of Electrochemical Properties

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