The mechanism of amine formation on Si(100) activated with chlorine atoms

Finstad, Casey C.; Thorsness, Adam G.; Muscat, Anthony J.

doi:10.1016/j.susc.2006.05.023

Cited by 24 publications

(49 citation statements)

References 64 publications

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“…Yet, some reactivity remains, and the factors that control this remaining reactivity are only poorly understood. In a paper in this issue, Finstad and co-workers show how Cl-terminated and H-terminated Si(0 0 1) surfaces show very different reactivity toward NH 3 , and investigate the chemical and structural factors that control the reactivity [4]. Their results help to provide new insights into how monoatomic ''passivating'' species control the reactivity of semiconductor surfaces.…”

mentioning

confidence: 99%

Passivation and activation: How do monovalent atoms modify the reactivity of silicon surfaces?

Hamers

2006

Surface Science

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confidence: 99%

Passivation and activation: How do monovalent atoms modify the reactivity of silicon surfaces?

Hamers

2006

Surface Science

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“…Early work examined adsorption and dissociation of gas phase ammonia on clean, reconstructed Si(100) 2x1 [11][12][13][14][15][16][17] or Si(111) 7x7 [14,[18][19][20] surfaces; only recently has the attention been placed on ammonia reactions with passivated surfaces, such as H-terminated silicon surfaces. Examples of work involving modified Si surfaces include the stepwise NH 3 vapor dissociation on H-terminated Si(111) surfaces, [21] and ammonia/amine reactions on Cl-terminated Si (100) and Si(111) surfaces using both vapor [22][23][24] and wet chemical [24][25][26][27] conditions. In this work, new questions arise, highlighting the need for fundamental understanding of the reaction mechanisms.…”

Section: Introductionmentioning

confidence: 99%

“…Because the Si-F bond is surrounded by a ring of six Si-H bonds, this is an excellent model surface to compare the relative reactivity of amines with Si-F and Si-H surface groups. On the premise that Si-F reacts faster than Si-H with amines, [23] yet less readily than Si-Cl (halogen reactivity increases with increasing atomic number), this model surface is ideal to study reactions with the isolated Si-F groups.…”

Section: Introductionmentioning

confidence: 99%

Ammonia modification of oxide-free Si(111) surfaces

et al. 2016

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Amination of surfaces is useful in a variety of fields, ranging from device manufacturing to biological applications. Previous studies of ammonia reaction on silicon surfaces have concentrated on vapor phase rather than wet chemical processes, and mostly on clean Si surfaces. In this work, the interaction of liquid and vapor-phase ammonia is examined on three types of oxide-free surfaces-passivated by hydrogen, fluorine (1/3 monolayer) or chlorine-combining infrared absorption spectroscopy, X-ray photoelectron spectroscopy and first-principles calculations. The resulting chemical composition highly depends on the starting surface; there is a stronger reaction on both F-and Cl-terminated than on the H-terminated Si surfaces, as evidenced by the formation of Si-NH 2. Side reactions can also occur, such as solvent reaction with surfaces, formation of ammonium salt by-products (in the case of 0.2 M ammonia in dioxane solution), and nitridation of silicon (in the case of neat and gas phase ammonia reactions for instance). Unexpectedly, there is formation of Si-H bonds on hydrogen-free Cl-terminated Si(111) surfaces in all cases, whether vapor phase of neat liquid ammonia is used. First principles modeling of this complex system suggests that step edge surface defects may play a key role in enabling the reaction under certain circumstances, despite the endothermic nature for Si-H bond formation.

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“…However, a few previous studies have reported that endothermic chemisorption can occur under certain conditions. 9,10 In dissociative chemisorption of a diatomic molecule AB, for example, the adsorption energy E ad can often be estimated as the sum of the formation energy of two newly established adsorbate-surface bonds, E AS and E BS , less the energy needed to break the molecular bond E AB . If E AB is larger than E AS or E BS , the bond cleavage and the formation of two new bonds must take place simultaneously for exothermic chemisorption.…”

Section: Introductionmentioning

confidence: 99%

Adsorption and abstraction reactions of HCl on a single Si(100) dangling bond

Chang

Chien

et al. 2011

Phys. Rev. B

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On a Si(100)-(2x1) surface with abundant dangling bonds, reaction of HCl molecules at room temperature is dominated by exothermic dissociative adsorption of H and Cl on two adjacent dangling bonds. This co-adsorption reaction is blocked for an isolated dangling bond, yet surprisingly endothermic H or Cl abstractive adsorption occurs, as observed by in situ scanning tunneling microscopy. On an isolated dimer dangling bond pair, co-adsorption of H and Cl is common as expected, but adsorption of a pair of abstracted Cl or H from two HCl molecules also occurs. These results, complemented by theoretical calculations, indicate that dissociative adsorption and abstractive reaction of a multi-atom gas molecule can be initiated at a single DB by forming an intermediate adsorption state.

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The mechanism of amine formation on Si(100) activated with chlorine atoms

Cited by 24 publications

References 64 publications

Passivation and activation: How do monovalent atoms modify the reactivity of silicon surfaces?

Passivation and activation: How do monovalent atoms modify the reactivity of silicon surfaces?

Ammonia modification of oxide-free Si(111) surfaces

Adsorption and abstraction reactions of HCl on a single Si(100) dangling bond

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