Silane Activation by Ti(NMe2)4 and NH3 during Chemical Vapor Deposition of Ti−Si−N Films

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

doi:10.1021/cm990174j

Cited by 7 publications

(9 citation statements)

References 43 publications

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“…2 Due to the importance of TDMAT, the reaction of organotitanium compounds in the gas phase has been studied both theoretically 5,22,34,35 and experimentally. 20,24,28,[36][37][38][39][40] Another important focus of applied research involved has been on the reaction of TDMAT with different substrates such as metals, nitrides, and silica. 20,21,[23][24][25][26][27]29,38,[41][42][43] However, in spite of the importance of the interaction of TDMAT with the technologically relevant Si(100) surface, studies of the system TDMATSi(100) are very scarce.…”

Section: Introductionmentioning

confidence: 99%

Chemistry of Diffusion Barrier Film Formation: Adsorption and Dissociation of Tetrakis(dimethylamino)titanium on Si(100)-2 × 1

Rodríguez‐Reyes

Teplyakov

2007

J. Phys. Chem. C

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Tetrakis(dimethylamino)titanium (TDMAT) is one of the most prominent precursors for deposition of thin diffusion barrier films onto semiconductor substrates for microelectronic applications. Adsorption and dissociation of this compound on a Si(100)-2 × 1 surface is studied by a combination of density functional calculations and infrared spectroscopy. Our computational investigation suggests that initial interaction occurs through the nucleophilic attack of a surface silicon atom by the lone pair of nitrogen. This molecularly adsorbed state (where the N atom attached to the surface is tetra-coordinated) is found to be a local minimum, and further transformation leads to the dissociation through scission of either the N-Ti or the N-C bond. Dissociation of TDMAT is permitted kinetically if it occurs through the scission of the N-Ti bond, while scission of an N-C bond is kinetically hindered despite the thermodynamic stability of the structure produced. In view of its amine-like behavior upon adsorption, TDMAT was expected to be molecularly adsorbed at cryogenic temperatures but dissociated at room temperature. These two facts are confirmed by infrared spectroscopy. Dissociation pathways involving two neighboring Si-Si dimers of the Si(100)-2 × 1 surface were considered as well, and the formation of an interdimer N-Ti bridge is found to be energetically possible. The elucidation of the mechanism of TDMAT adsorption holds the promise of a better understanding of the initial steps of thin film growth.

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Section: Introductionmentioning

confidence: 99%

Chemistry of Diffusion Barrier Film Formation: Adsorption and Dissociation of Tetrakis(dimethylamino)titanium on Si(100)-2 × 1

Rodríguez‐Reyes

Teplyakov

2007

J. Phys. Chem. C

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“…In particular, previous results from our group demonstrated that gas-phase chemistry during CVD of titanium silicon nitride (Ti−Si−N) from tetrakis(dimethylamido)titanium (TDMAT or Ti(N(CH 3 ) 2 ) 4 ), NH 3 , and SiH 4 is critical. Most importantly, it was established that TDMAT activates silane in the presence of ammonia at 723 K . The amount of silane activation is dependent upon the relative amounts of TDMAT and ammonia.…”

Section: Introductionmentioning

confidence: 99%

Kinetic and Mechanistic Studies of the Thermal Decomposition of Ti(N(CH₃)₂)₄ during Chemical Vapor Deposition by in Situ Molecular Beam Mass Spectrometry

Norton

Amato‐Wierda

2001

Chem. Mater.

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Various aspects of the kinetics and mechanism occurring during the gas-phase thermal decomposition of Ti(N(CH 3 ) 2 ) 4 , tetrakis(dimethylamido)titanium, have been determined by in situ molecular beam mass spectrometry coupled to a chemical vapor deposition reactor. The rate of Ti(N(CH 3 ) 2 ) 4 decomposition was measured between 333 and 583 K. The rate constants increase with reactor surface area to volume ratio (S/V), particularly above 530 K (S/V ) 0.118 mm -1 ), which indicates a change in mechanism at higher temperatures. For S/V ) 0.118 mm -1 , the Arrhenius parameters between 300 and 530 K are E a ) 16 ( 2 kJ mol -1 and A ) 32 ( 4 s -1 . For the high-temperature regime above 530 K, E a ) 166 ( 16 kJ mol -1 and A ) (1.6 ( 0.2) × 10 16 s -1 . These parameters are consistent with the following mechanistic interpretation for Ti(N(CH 3 ) 2 ) 4 decomposition: activated adsorption to the walls at low temperatures, followed by gas-phase unimolecular decomposition in combination with some surface process at higher temperatures. Mass spectral evidence supports β-hydride elimination and metallacycle formation as the TDMAT decomposition pathways.

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“…19 Silicon titanium nitride coatings or layers are prepared mainly by chemical vapor deposition (CVD). 20,21 These silicon titanium nitride powders and layers are typically produced in dense forms, which can be used as structural and/or wear-resistant materials due to their high hardness and creep resistance. 22 Our interest is to develop new micro-and mesoporous nonoxide materials with high surface area accessible for applications in heterogeneous catalysis.…”

Section: Introductionmentioning

confidence: 99%

Ammonothermal Synthesis of a Mesoporous Si−Ti−N Composite Material from a Single-Source Precursor

et al. 2005

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The preparation and structure of the novel compound bis(dimethylamino)silylamino-µ-bis[(dimethylamino)silylimino]titanium {Ti[NHSi(NMe 2 ) 3 ] 2 [µ-NSi(NMe 2 ) 3 ]} 2 , 1, are reported. Ammonolysis of compound 1 in an autoclave at 160 °C gave a mesoporous silicon titanium imide powder, 2, with a high surface area and narrow pore size distribution. A mesoporous Si-Ti-N composite material was obtained after pyrolysis of powder 2 under NH 3 flow at 1000 °C. The BET surface area is 163 m 2 g -1 , and the average pore diameter is 71 Å. The influence of the pyrolysis temperature on the porosity of the product is also discussed on the basis of FTIR and nitrogen physisorption analyses.

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Silane Activation by Ti(NMe₂)₄ and NH₃ during Chemical Vapor Deposition of Ti−Si−N Films

Cited by 7 publications

References 43 publications

Chemistry of Diffusion Barrier Film Formation: Adsorption and Dissociation of Tetrakis(dimethylamino)titanium on Si(100)-2 × 1

Chemistry of Diffusion Barrier Film Formation: Adsorption and Dissociation of Tetrakis(dimethylamino)titanium on Si(100)-2 × 1

Kinetic and Mechanistic Studies of the Thermal Decomposition of Ti(N(CH₃)₂)₄ during Chemical Vapor Deposition by in Situ Molecular Beam Mass Spectrometry

Ammonothermal Synthesis of a Mesoporous Si−Ti−N Composite Material from a Single-Source Precursor

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Silane Activation by Ti(NMe2)4 and NH3 during Chemical Vapor Deposition of Ti−Si−N Films

Cited by 7 publications

References 43 publications

Chemistry of Diffusion Barrier Film Formation: Adsorption and Dissociation of Tetrakis(dimethylamino)titanium on Si(100)-2 × 1

Chemistry of Diffusion Barrier Film Formation: Adsorption and Dissociation of Tetrakis(dimethylamino)titanium on Si(100)-2 × 1

Kinetic and Mechanistic Studies of the Thermal Decomposition of Ti(N(CH3)2)4 during Chemical Vapor Deposition by in Situ Molecular Beam Mass Spectrometry

Ammonothermal Synthesis of a Mesoporous Si−Ti−N Composite Material from a Single-Source Precursor

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Silane Activation by Ti(NMe₂)₄ and NH₃ during Chemical Vapor Deposition of Ti−Si−N Films

Kinetic and Mechanistic Studies of the Thermal Decomposition of Ti(N(CH₃)₂)₄ during Chemical Vapor Deposition by in Situ Molecular Beam Mass Spectrometry