Adsorption chemistry of cyanogen iodide on silicon ()

Rajasekar, P.; Kadossov, E.; Watt, Tyler; Materer, Nicholas F.

doi:10.1016/s0039-6028(02)01956-8

Cited by 11 publications

(74 citation statements)

References 27 publications

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“…10,11 Assuming that the reaction pathways shown in Figure 4 are followed experimentally, some tentative conclusions can be inferred. The initial dative bonded end-on adsorption structure (XCN1) is expected to form via a barrierless transition state.…”

Section: Resultsmentioning

confidence: 98%

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Adsorption and Decomposition Pathways of Cyanogen Halides on Si(100)−(2×1)

2003

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The adsorption and surface reactions of ICN, BrCN, and ClCN on the Si(100)-(2×1) surface are studied using ab initio quantum calculations on single-and triple-dimer silicon clusters. These cyanogen halides can physisorb into an end-on molecular species that is bound through the N to the Si cluster via a dative bond. The adsorption energy of this dative bonded species is found to depend on the cluster size. This species can further react to form a side-on intermediate by reacting across the Si-dimer bond or can lose the halide group and form an adsorbed CN species. The adsorbed CN group can have N-bonded and C-bonded orientations, with the C-bonded configuration having the lowest energy. The side-on intermediate can react to an additional intermediate species in which the halide-carbon bond is broken and the C end of the CN group inserts into the Si-dimer bond. An adsorbed CN group can subsequently form from this insertion species. Once the reaction proceeds from the dative bonded species, no significant barriers are present and the lowest energy structure is predicted to form in agreement with experimental studies.

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Section: Resultsmentioning

confidence: 98%

“…Thus, for both pathways, the lowest energy structure is expected to form in agreement with experimental studies. 10,11 …”

Section: Discussionmentioning

confidence: 99%

Adsorption and Decomposition Pathways of Cyanogen Halides on Si(100)−(2×1)

2003

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“…This type of molecular adsorption processes was also noted in other CN-containing molecules reacting with the silicon surface. [11][12][13][14][15][16]36,37 The predicted adsorption energy is 10.1 kcal/mol, suggesting that the interaction is moderately strong. The predicted bond lengths in Table 1 show that the C-C bond distance is 1.346 Å, which is close to a C(sp)-C(sp) single bond distance, 1.38 Å 38 (a C(sp)dC(sp) double bond is known to be 1.28 Å).…”

Section: A1 Single-dimer Model Calculationsmentioning

confidence: 99%

Adsorption and Reaction of C₂N₂ on Si(100)-2 × 1: A Computational Study with Single- and Double-Dimer Cluster Models

Wang

Lin

2004

J. Phys. Chem. B

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The adsorption and decomposition of C 2 N 2 on the Si(100)-2 × 1 surface have been calculated by the hybrid density functional B3LYP method with Si 9 H 12 and Si 15 H 16 as single-and double-dimer models, respectively. The result of our single-dimer surface model calculation shows that the surface reaction started from a single N atom of C 2 N 2 molecularly adsorbed on one silicon atom of the dimer. From the result of bond distance changes and vibrational frequency analysis, this process occurs by direct interaction of the CtN group with a silicon dangling bond. Two different reaction paths follow; the first path occurs by the adjoined carbon atom adsorption producing four-member-ring product -Si-N-C-(CN)Si-, similar to the HCN molecule adsorbing sideway on this surface. The other path occurs by the adsorption of the second nitrogen atom with another Si atom producing a six-member-ring product, -Si-N-C-C-N-Si-. The mechanisms for the decomposition of these adsorbates have been elucidated. The result of our calculation with the double-dimer surface model reveals that the reaction barriers are somewhat lower than single-dimer system for either CC or CN bond-breaking processes but with a similar trend. The predicted stabilities of various surface species from physisorbed C 2 N 2 to chemisorbed CN radicals and silicon nitride and silicon carbide are consistent with the results of our previous studies using HREELS, XPS, UPS, and TPD methods as well as with others' data for similar reactions of CN-containing species with the Si(100)-2 × 1 surface. The predicted result for adsorption of two C 2 N 2 based on both surface models indicates a significant decrease in the adsorption energy for the second C 2 N 2 molecule.

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13] However, most experimental and theoretical reports are on the adsorption of CN-containing molecules on the transition metal surfaces; [1][2][3][4][5][6] there are few experimental and theoretical reports about CN-containing molecule adsorption on semiconductor Si surface. [7][8][9][10][11][12][13] The interaction of CN-containing species with Si surfaces is not only fundamentally interesting [7][8][9] but also practically relvant to the chemical vapor deposition (CVD) of CN x films, 14 particularly SiCN x films which have been demonstrated to exhibit crystalline texture. 15 Lin et al 10 studied the adsorption and decomposition of HCN on Si (100)-(2×1) by using density functional theory calculation on the Si 9 H 12 model dimer clusters.…”

Section: Introductionmentioning

confidence: 99%

“…10 Recently, Materer et al studied the adsorption, and decomposition of cyanogen halides (XCN, X = Cl, Br, I) on Si (100) surface by X-Ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and temperature programmed desorption (TPD) spectroscopy. 11,12 For submonolayer exposure, XPS indicates that the CN triple bond of XCN remains intact upon adsorption at 100 K. The UPS spectrum contains two peaks assigned to the π-electrons in the CN triple bond. And, Materer et al 13 also studied that the adsorption and surface reactions of ICN on Si (100)-(2×1) by ab initio quantum calculation on model dimer clusters.…”

Section: Introductionmentioning

confidence: 99%

ADSORPTION AND DECOMPOSITION OF ClCN ON Si (100)-(2×1) SURFACE: A DENSITY FUNCTIONAL THEORY STUDY

Zhang

et al. 2004

J. Theor. Comput. Chem.

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The adsorption and decomposition of ClCN on Si (100)-(2×1) surface is studied by using density functional theory and the cluster model method. The Si 9 H 12 dimer cluster is used to simulate the surface. The present calculations show that ClCN may be adsorbed molecularly without a barrier onto the surface with both linear (L1) and parallel (S1) modes. L1 can isomerize to S1 with a small barrier of 5.6 kcal/mol. Both ClCN and ClNC end-on adsorbates were found to dissociate readily to produce Cl and CN species, which was in excellent agreement with the experiment.

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Adsorption chemistry of cyanogen iodide on silicon ()

Cited by 11 publications

References 27 publications

Adsorption and Decomposition Pathways of Cyanogen Halides on Si(100)−(2×1)

Adsorption and Decomposition Pathways of Cyanogen Halides on Si(100)−(2×1)

Adsorption and Reaction of C₂N₂ on Si(100)-2 × 1: A Computational Study with Single- and Double-Dimer Cluster Models

ADSORPTION AND DECOMPOSITION OF ClCN ON Si (100)-(2×1) SURFACE: A DENSITY FUNCTIONAL THEORY STUDY

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Adsorption chemistry of cyanogen iodide on silicon ()

Cited by 11 publications

References 27 publications

Adsorption and Decomposition Pathways of Cyanogen Halides on Si(100)−(2×1)

Adsorption and Decomposition Pathways of Cyanogen Halides on Si(100)−(2×1)

Adsorption and Reaction of C2N2 on Si(100)-2 × 1: A Computational Study with Single- and Double-Dimer Cluster Models

ADSORPTION AND DECOMPOSITION OF ClCN ON Si (100)-(2×1) SURFACE: A DENSITY FUNCTIONAL THEORY STUDY

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Adsorption and Reaction of C₂N₂ on Si(100)-2 × 1: A Computational Study with Single- and Double-Dimer Cluster Models