Low Temperature Chemical Vapor Deposition of Titanium Nitride Thin Films with Hydrazine and Tetrakis(dimethylamido)titanium

Amato‐Wierda, Carmela; Norton, Edward T.; Wierda, Derk A.

doi:10.1149/1.1390924

Cited by 8 publications

(3 citation statements)

References 23 publications

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“…The long-term goal of our research is to explore new nitrogen source compounds that can be used to grow metal nitride phases by chemical vapor deposition techniques. While ammonia is by far the most widely used nitrogen source compound in film growth, the high stability of ammonia and concomitant high film deposition temperatures has led to increasing consideration of alternative nitrogen source compounds in the past several years within the context of GaN and TiN film growth. ,− Hydrazine and alkylhydrazines have been the focus of most of the effort; however, nitrogen heterocycles such as those described herein are potentially useful source compounds. , …”

Section: Discussionmentioning

confidence: 99%

Early Transition Metal Complexes Containing 1,2,4-Triazolato and Tetrazolato Ligands: Synthesis, Structure, and Molecular Orbital Studies

Yélamos

et al. 2001

Inorg. Chem.

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Several early transition metal complexes bearing 1,2,4-triazolato and tetrazolato ligands have been prepared by reaction of the pyrazolato complexes Ti(tBu(2)pz)(4-x)Cl(x) (tBu(2)pz = 3,5-di-tert-butylpyrazolato; x = 1, 2) and M(tBu(2)pz)(5-x)Cl(x) (M = Nb, Ta: x = 2, 3) with the sodium or potassium salts derived from 1,2,4-triazoles and tetrazoles. The X-ray structure analysis of Ti(tBu(2)pz)(2)(Me(2)C(2)N(3))(2) shows eta(2)-coordination of the 1,2,4-triazolato ligands, while in Ti(tBu(2)pz)(3)(C(2)H(2)N(3)) and Nb(tBu(2)pz)(3)(Me(2)C(2)N(3))(2) the analogous groups are joined in a eta(1)-fashion in the solid-state structure. Solution NMR studies at different temperatures suggest transition states involving eta(2)-1,2,4-triazolato ligands for the complexes containing eta(1)-1,2,4-triazolato ligands in the solid state. X-ray crystal structures of analogous tetrazolato complexes Ti(tBu(2)pz)(3)(PhCN(4)) and Nb(tBu(2)pz)(3)(PhCN(4))(2) show eta(1)-coordination of the 2-nitrogen atoms of the tetrazolato ligands. Molecular orbital calculations have been carried out on several model titanium complexes and provide detailed insight into the bonding between early transition metal centers and 1,2,4-triazolato and tetrazolato ligands. The eta(2)-coordination mode of 1,2,4-triazolato and tetrazolato ligands is predicted to be more stable than the eta(1)-coordination mode by 13.8-5.2 kcal/mol.

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Section: Discussionmentioning

confidence: 99%

Early Transition Metal Complexes Containing 1,2,4-Triazolato and Tetrazolato Ligands: Synthesis, Structure, and Molecular Orbital Studies

Yélamos

et al. 2001

Inorg. Chem.

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“…6,7 Physical vapor deposition (PVD) suffers indeed from a poor step coverage and chemical vapor deposition (CVD) requires high temperatures processing. [8][9][10][11][12] Reversely, ALD provides an accurate control of the thickness and it allows to grow highly-conformal layers with a high quality at relatively low temperatures. 13 The surface chemical reaction involved during the ALD process can either be thermally activated by heating the reactor or it can be activated by generating a plasma in the chamber (plasma-enhanced ALD, PE-ALD).…”

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confidence: 99%

Highly-Conformal TiN Thin Films Grown by Thermal and Plasma-Enhanced Atomic Layer Deposition

Assaud

Pitzschel

Hanbücken

et al. 2014

ECS J. Solid State Sci. Technol.

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Atomic layer deposition (ALD) was used to synthesize highly-conformal titanium nitride thin films using both thermal activation at 250 • C and plasma activation at 200 • C. Tetrakisdimethylaminotitanium (TDMAT) and ammonia have been utilized as precursors. The evolutions of the thickness and the roughness of the films with the number of ALD cycles have been monitored by spectroscopic ellipsometry and atomic force microscopy, respectively. A slight difference has been observed between thermal and plasma-enhanced ALD TiN films. The chemical composition of the resulting layers for the two activation modes has been investigated by X-ray photoelectron spectroscopy. It indicates a partial oxidation of the film and it shows that the oxide content depends on the activation method and varies with the deposition temperature. The studies of both morphology and crystalline structure carried out by electron microscopy and X-ray diffraction have revealed homogeneous and polycrystalline films for the two activation processes. Electrical measurements have shown that the films grown by plasma-activation exhibit a higher conductivity. Finally, the TiN films were grown on high aspect ratio templates such as anodic aluminum oxide membranes. It demonstrates that highly-conformal TiN thin films can even be obtained by plasma-assisted process within such narrow three-dimensional nanostructures. That was unexpected.

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“…The process uses low-temperature cracking of hydrazine to form nitrogen radicals that react with metal-bearing substrates to form nitride films. Also, hydrazine has been used as a precursor along with tetrakis (dimethylamido) titanium (TDMAT) for the low-temperature chemical vapor deposition of TiN thin films between 50 and 200 °C at 10 Torr, with growth rates between 5 and 35 nm/min. , Likewise, a novel hydrazide sol−gel process has been developed to synthesize nanocrystalline titanium nitride, which involves the reaction of titanium isopropoxide with anhydrous hydrazine in the presence of anhydrous acetonitrile to yield a solid precursor. Fully crystallized, single phase TiN is detected by X-ray diffraction at a temperature of 800 °C …”

Section: Introductionmentioning

confidence: 99%

Stardust's Hydrazine (N₂H₄) Fuel: A Potential Contaminant for the Formation of Titanium Nitride (Osbornite)

2007

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Low Temperature Chemical Vapor Deposition of Titanium Nitride Thin Films with Hydrazine and Tetrakis(dimethylamido)titanium

Cited by 8 publications

References 23 publications

Early Transition Metal Complexes Containing 1,2,4-Triazolato and Tetrazolato Ligands: Synthesis, Structure, and Molecular Orbital Studies

Early Transition Metal Complexes Containing 1,2,4-Triazolato and Tetrazolato Ligands: Synthesis, Structure, and Molecular Orbital Studies

Highly-Conformal TiN Thin Films Grown by Thermal and Plasma-Enhanced Atomic Layer Deposition

Stardust's Hydrazine (N₂H₄) Fuel: A Potential Contaminant for the Formation of Titanium Nitride (Osbornite)

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Low Temperature Chemical Vapor Deposition of Titanium Nitride Thin Films with Hydrazine and Tetrakis(dimethylamido)titanium

Cited by 8 publications

References 23 publications

Early Transition Metal Complexes Containing 1,2,4-Triazolato and Tetrazolato Ligands: Synthesis, Structure, and Molecular Orbital Studies

Early Transition Metal Complexes Containing 1,2,4-Triazolato and Tetrazolato Ligands: Synthesis, Structure, and Molecular Orbital Studies

Highly-Conformal TiN Thin Films Grown by Thermal and Plasma-Enhanced Atomic Layer Deposition

Stardust's Hydrazine (N2H4) Fuel: A Potential Contaminant for the Formation of Titanium Nitride (Osbornite)

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Stardust's Hydrazine (N₂H₄) Fuel: A Potential Contaminant for the Formation of Titanium Nitride (Osbornite)