Titanium nitride films for barrier applications produced by rapid thermal CVD and subsequent in-situ annealing

Leutenecker, R.; Fröschle, B.; Cao-Minh, U.; Ramm, Peter

doi:10.1016/0040-6090(95)06898-8

Cited by 21 publications

(13 citation statements)

References 4 publications

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“…2. Although the deposition temperature of TiN film was very low, the chlorine content in this TiN film was substantially lower (below 0.5 at.%) than that in the films grown by other CVD methods which contained 2-14 at.% of Cl [11][12][13] (14 at.% at 300 • C, 5.7 at.% at 500 • C, 2 at.% at 600 • C, < 2 at.% at 630 • C). The reason was that in the ALD system, the self-limiting reaction by the separated introduction of each reactant and purge gas causes the complete surface reaction during deposition which results in the very low contents of impurities.…”

Section: Resultsmentioning

confidence: 74%

TiN Diffusion Barrier Grown by Atomic Layer Deposition Method for Cu Metallization

Uhm

Jeon

2001

Jpn. J. Appl. Phys.

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The effects on the impurity content, microstructure, resistivity and barrier characteristics of TiN film deposited by an atomic layer deposition (ALD) method have been evaluated. The TiN films were deposited on Si(100) substrates at 450 • C using the reactant gases TiCl 4 and NH 3 . The chemical and physical properties of ALD TiN thin films were measured. The TiN films had a randomly-oriented columnar grain microstructure. The chlorine content in the films was below the detection limit of Auger electron spectroscopy (< 0.5 at.%) due to the complete surface reaction by self-limiting reaction in ALD method. This low Cl content in film induced a low film resistivity of 120 µ cm. The barrier properties of this ALD films were tested by the etch-pit method. The result showed a retardation of the interdiffusion between Cu and Si in samples annealed for one hour at temperatures up to 450 • C.

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Section: Resultsmentioning

confidence: 74%

TiN Diffusion Barrier Grown by Atomic Layer Deposition Method for Cu Metallization

Uhm

Jeon

2001

Jpn. J. Appl. Phys.

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“…6,7 Therefore, CVD has received much attention for these applications because it offers superior conformality, as well as the ability to cover larger areas. 4,8 The two most extensively used thermal CVD precursor systems are: (i) the inorganic halide, TiCl 4 and ammonia; 3,7,[9][10] or (ii) the organometallic compounds, tetrakis(dimethylamido)titanium (TDMAT) or tetrakis-(diethylamido)titanium (TDEAT) and ammonia. [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] The first system requires temperatures too high (500-700°C) for most device applications, and the films are contaminated with unacceptable levels of chlorine.…”

Section: Introductionmentioning

confidence: 99%

Chemical vapor deposition of titanium nitride thin films from tetrakis(dimethylamido)titanium and hydrazine as a coreactant

Amato‐Wierda

Wierda

2000

J. Mater. Res.

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Hydrazine was used as a coreactant with tetrakis(dimethylamido)titanium for the low-temperature chemical vapor deposition of TiN between 50 and 200°C. The TiN film-growth rates ranged from 5 to 45 nm/min. Ti:N ratios of approximately 1:1 were achieved. The films contain between 2 and 25 at.% carbon, as well as up to 36 at.% oxygen resulting from diffusion after air exposure. The resistivity of these films is approximately 10 4 ⍀ cm. Annealing the films in ammonia enhances their crystallinity. The best TiN films were produced at 200°C from a 2.7% hydrazine-ammonia mixture. The Ti:N ratio of these films is approximately 1:1, and they contain no carbon or oxygen. These films exhibit the highest growth rates observed.

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“…One plausible cause for such distinct behavior could be segregation of impurities at interfaces. For low temperature CVD processes, chlorine contamination is a concern [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] , which stems from the widely used metal chloride as a precursor in CVD reactions (e.g. TiCl 4 is the most widely used inorganic precursor employed in the CVD of titanium-containing materials (TiN, TiC, TiO 2 , Ti(C,N)) [22]).…”

mentioning

confidence: 99%

“…TiCl 4 is the most widely used inorganic precursor employed in the CVD of titanium-containing materials (TiN, TiC, TiO 2 , Ti(C,N)) [22]). However, most authors have reported that chlorine is incorporated into the lattice [4,5,7,[9][10][11]13,19,23], rather than to interfaces and no direct evidence has been provided. Therefore, APT is performed on Ti(C,N) and Zr(C,N) coatings to explore if segregation is occurring at GBs and discuss which effect this segregation could have on the mechanical properties of these coatings.…”

mentioning

confidence: 99%

“…Chlorine contamination related to CVD processes, using metal chloride precursors, is well known and documented for Low Temperature (LT) CVD processes; like Plasma Assisted (PA) [4][5][6][7][8][9][10][11][12][13]23,34] and Low Pressure (LP) CVD [12,[14][15][16][17][18][19][20][21]. However, its effects on MT-CVD process are underestimated or overlooked, given that chlorine content decreases considerably with higher temperatures and at MT-CVD temperature deposition range (700~950°C) the Cl concentration is very low.…”

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confidence: 99%

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Atom Probe Tomography investigations on grain boundary segregation in polycrystalline Ti(C,N) and Zr(C,N) CVD coatings

et al. 2019

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Atom Probe Tomography (APT) was used to obtain a direct evidence of Chlorine segregation and Cobalt diffusion at the grain boundaries (GBs) of polycrystalline coatings deposited by moderate temperature chemical vapor deposition (MT-CVD) on a WC-Co cemented carbide substrate. Reasons behind segregations are discussed, and its effects are correlated to the micromechanical properties of Ti(C,N) and Zr(C,N). It is concluded that chlorine segregation is a relevant factor for explaining the low cohesive strength at the GBs of Ti(C,N) leading to intergranular failure during micro-compression testing, while its absence in Zr(C,N) along with Co diffusion contribute to grain boundary strengthening.

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Titanium nitride films for barrier applications produced by rapid thermal CVD and subsequent in-situ annealing

Cited by 21 publications

References 4 publications

TiN Diffusion Barrier Grown by Atomic Layer Deposition Method for Cu Metallization

TiN Diffusion Barrier Grown by Atomic Layer Deposition Method for Cu Metallization

Chemical vapor deposition of titanium nitride thin films from tetrakis(dimethylamido)titanium and hydrazine as a coreactant

Atom Probe Tomography investigations on grain boundary segregation in polycrystalline Ti(C,N) and Zr(C,N) CVD coatings

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