Electron‐beam‐induced decomposition of trimethylamine on Si(100)‐2 × 1

Davies, Brian M.; Craig, J.H.

doi:10.1002/sia.1642

Cited by 9 publications

(10 citation statements)

References 22 publications

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“…Thus, XPS and MS results collectively support the idea that dehydrogenation is the major chemical transformation that accompanies electron irradiation of molecularly adsorbed 1,2-DAP . Hydrogen has also been observed as the dominant gas phase product when surface bound amines , and organic films, including alkanes and self-assembled monolayers, − are irradiated by incident electrons ranging in energies from 5 eV to 2 keV.…”

Section: Discussionmentioning

confidence: 99%

Growth and Microstructure of Nanoscale Amorphous Carbon Nitride Films Deposited by Electron Beam Irradiation of 1,2-Diaminopropane

2009

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The deposition and microstructure of nanoscale nitrogen containing carbon films produced by irradiating adsorbed 1,2-diaminopropane (1,2-DAP) molecules with >40 eV electrons has been studied. The growth rate of films deposited in the presence of a constant partial pressure of 1,2-DAP was directly proportional to the flux of both precursor 1,2-DAP molecules and the incident electrons, consistent with an electron beam induced deposition (EBID) process. Deposited films were highly textured and weakly adhered to the polycrystalline Au substrate. Complementary information on the electron stimulated decomposition of the precursor and the accompanying film growth was obtained from experiments performed under ultrahigh vacuum (UHV) on nanometer scale thick films of 1,2-DAP. Results from these UHV studies were consistent with the idea that decomposition was initiated by secondary electrons, produced by the interaction of the primary electron beam with the adsorbate layer and the substrate. Reactions of these low energy secondary electrons with adsorbed 1,2-DAP molecules were responsible for dehydrogenation as well as film growth. For prolonged electron exposures nitrile species were produced, supporting the idea that changes in the film’s microstructure and chemical composition were due to the effects of C−H and N−H, rather than C−C or C−N, bond cleavage. Collectively, our results indicate that EBID initially leads to the formation of a hydrogenated carbon nitride (a:C−N(H)) film. Further electron stimulated dehydrogenation ultimately yields an amorphous carbon−nitride film (a:C−N).

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Section: Discussionmentioning

confidence: 99%

Growth and Microstructure of Nanoscale Amorphous Carbon Nitride Films Deposited by Electron Beam Irradiation of 1,2-Diaminopropane

2009

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“…Adsorption and decomposition of alkylamines on Si(100) have been studied previously. − The Si(100) surface consists of rows of dimers, a result of thermodynamically stable (2 × 1) reconstruction. These dimers buckle to further stabilize the surface.…”

Section: Introductionmentioning

confidence: 99%

“…As a result, silicon dimers acquire a zwitterionic character, with the “buckled-down” silicon atom more positively charged than the “buckled-up” atom. Species containing lone pairs (such as amines) can dissociatively adsorb on the Si(100) surface. − This process is known to start with a nucleophilic attack of the buckled-down Si atom by the lone pair on nitrogen. The tetra-coordinated nitrogen (N 4C ) of this molecularly adsorbed state returns readily to its previous tri-coordination through dissociation.…”

Section: Introductionmentioning

confidence: 99%

“…Species containing lone pairs (such as amines) can dissociatively adsorb on the Si(100) surface. [46][47][48][49][50][51] This process is known to start with a nucleophilic attack of the buckled-down Si atom by the lone pair on nitrogen. The tetra-coordinated nitrogen (N 4C ) of this molecularly adsorbed state returns readily to its previous tri-coordination through dissociation.…”

Section: Introductionmentioning

confidence: 99%

“…In some cases, however, the reaction does not proceed past this local N 4C well due to kinetic restrictions, such as in the case of trimethylamine. [46][47][48][49] In this study, a combination of infrared spectroscopy and density functional methods is used to discuss the first steps of adsorption of TDMAT on Si(100). First, we discuss the possibilities for adsorption and dissociation on a single dimer based on theoretical methods, comparing our results to previous theoretical studies of amines on the same surface.…”

Section: Introductionmentioning

confidence: 99%

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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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Towards a comprehensive understanding of the Si(100)-2×1 surface termination through hydrogen passivation using methylamine and methanol: a theoretical approach

et al. 2018

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Electron‐beam‐induced decomposition of trimethylamine on Si(100)‐2 × 1

Cited by 9 publications

References 22 publications

Growth and Microstructure of Nanoscale Amorphous Carbon Nitride Films Deposited by Electron Beam Irradiation of 1,2-Diaminopropane

Growth and Microstructure of Nanoscale Amorphous Carbon Nitride Films Deposited by Electron Beam Irradiation of 1,2-Diaminopropane

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

Towards a comprehensive understanding of the Si(100)-2×1 surface termination through hydrogen passivation using methylamine and methanol: a theoretical approach

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