Abstract
This contribution summarizes recent progress in the computational treatment of organic species deposited on silicon surfaces, with emphasis on the Si(100) surface. Representative theoretical studies of various organic species in contact with Si surfaces are surveyed, involving unsaturated hydrocarbons, amines, phosphines, and alcohols as adsorbates. The connection of the presented computational results to spectroscopic measurement is outlined in each individual case. The strengths and the limitations of a finite cluster model for simulating the Si substrate are discussed. Further, a comprehensive investigation of one specific system is presented, namely 1-propanol adsorbed on Si(001) -(2× 1). It is shown by density functional theory within periodic boundary conditions that 1-propanol in contact with Si(001) -(2× 1) initially occupies a metastable physisorbed state which turns into a stable chemisorbed ground state by dissociative hydrogen transfer. This fragmentation effect is confirmed by ab initio molecular dynamics at room temperature. The adsorbed organic layer induces further surface reconstruction. For the first time, the band structure of the 1-propanole/Si(001) film is determined. The tendency of the energy gap as a function of 1-propanole coverage indicates that the surface becomes increasingly insulating as the areal density of the organic adsorbate is enhanced
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Mui C, Wang GT, Bent SF, Musgrave CB (2001) Reactions of methylamines at the Si(100)-(2× 1) surface, J. Chem. Phys. 114: 10170–10180
Pike AR, Lie LH, Eagling RA, Ryder LC, Patole SN, Connolly BA, Horrocks BR, Houlton A (2002) DNA on silicon devices: On-chip synthsis, hybridization, and charge transfer, Angew. Chem. Int. Ed., 41: 615–617
Konecny R, Doren DJ (1998) Cycloaddition reactions of unsaturated hydrocarbons on the Si(100)-(2× 1) surface: theoretical predictions, Surf. Sci. 417: 169–188
Silvestrelli PL, Ancilotto F, Toigo F (2000) Adsorption of benzene on Si(100) from first principles, Phys. Rev. B 62: 1596–1599
Silvestrelli PL (2004) Adsorption of ethanol on Si(100) from first principles calculations, Surf. Sci. 552:17–26
Zhang L, Carman AJ, Casey SM (2003) Adsorption and thermal decomposition chemistry of 1-propanol and other primary alcohols on the Si(100) surface, J. Phys. Chem. B 107: 8424–8432
Carman A, Zhang L, Liswood JL, Casey SM (2003) Methylamine Adsorption on and Desorption from Si(100), J. Phys. Chem. B 107: 5491–5502
Waltenburg HN, Yates JT Jr (1995) Surface chemistry of silicon, Chem. Rev. 95: 1589–1673
Fazleev NG, Fry JL, Weiss AH (2004) Surface states and annihilation characteristics of positrons trapped at the (100) and (111) surfaces of silicon, Phys. Rev. B 70: 165309/1–17
Redondo A, Goddard WA III (1982) Electronic correlation and the silicon (100) surface: Buckling versus nonbuckling, J. Vac. Sci. Technol 21: 344–350, Paulus B (1998) Correlation calculations for the reconstruction of the Si(100) surface, Surf. Sci. 408: 195–202
Hamers RJ, Tromp RM, Demuth JE (1986) Scanning tunneling microscopy of silicon(001), Phys. Rev. B 34: 5343–5357
Monch W (2001) Semiconductor surfaces and interfaces, pp. 219–220 (Third Edition, Springer)
Takayanagi K, Tanishiro Y, Takahashi S, Takahashi M (1985) Structure analysis of silicon(111)-7× 7 reconstructed surface by transmission electron diffraction, Surf. Sci. 164: 367–392
Yates JT Jr (1991) Surface chemistry of silicon-the behaviour of dangling bonds, J. Phys.: Condens. Matter 3: S143–S156
Bozack MJ, Taylor PA, Choyke WJ, Yates JT (1986) Chemical activity of the carbon-carbon double bond on silicon surfaces, Surf. Sci. 177: L933–L937
Nishijima M, Yoshinobu J, Tsuda H, Onchi M (1987) The adsorption and thermal decomposition of acetylene on silicon(100) and vicinal silicon(100) 0ˆ, Surf. Sci. 192: 383–397
Yoshinobu J, Tsuda H, Onchi M, Nishijima M (1987) The adsorbed states of ethylene on silicon(100)c(4× 2), silicon(100)(2× 1), and vicinal silicon(100) 9ˆ: electron energy loss spectroscopy and low-energy electron diffraction studies, J. Chem. Phys. 87: 7332–7340
Taylor PA, Wallace RM, Cheng CC, Weinberg WH, Dresser MJ, Choyke WJ, Yates JT Jr (1992) Adsorption and decomposition of acetylene on silicon(100)-(2× 1), J. Am. Chem. Soc. 114: 6754–6760
Clemen L, Wallace RM, Taylor PA, Dresser MJ, Cheng CC, Choyke WJ, Weinberg WH, Yates JT Jr (1992) Adsorption and thermal behavior of ethylene on silicon(100)-(2× 1), Surf. Sci. 268: 205–216
Huang C, Widdra W, Weinberg WH (1994) Adsorption of ethylene on the Si(100)-(2× 1) surface, Surf. Sci. 315: L953–L958
Fisher AJ, Bloechl PE, Briggs GAD (1997) Hydrocarbon adsorption on Si(001): when does the Si dimer bond break?, Surf. Sci. 374: 298–305
Pan W, Zhu T, Yang W (1997) First-principles study of the structural and electronic properties of ethylene adsorption on Si(100)-(2× 1) surface, J. Chem. Phys. 107: 3981–3985
Hovis JS, Liu H, Hamers RJ (1998) Cycloaddition Chemistry of 1,3-Dienes on the Silicon(001) Surface: Competition between [4+2] and [2+2] Reactions, J. Phys. Chem. B 102: 6873–6879
Tepljakov AV, Kong MJ, Bent SF (1997) Vibrational Spectroscopic Studies of Diels-Alder Reactions with the Si(100)-2× 1 Surface as a Dienophile, J. Am. Chem. Soc. 119: 11100–11101; Tepljakov AV, Kong MJ, Bent SF (1998) Diels-Alder reactions of butadienes with the Si(100)-2× 1 surface as a dienophile: Vibrational spectroscopy, thermal desorption and near edge x-ray absorption fine structure studies, J. Chem. Phys. 108: 4599–4606
Konecny R, Doren DJ (1997) Theoretical Prediction of a Facile Diels-Alder Reaction on the Si(100)-2× 1 Surface, J. Am. Chem. Soc. 119: 11098–11099
Choi CH, Gordon MS (1999) Cycloaddition Reactions of 1, 3-Cyclohexadiene on the Silicon(001) Surface, J. Am. Chem. Soc. 121: 11311–11317
Shoemaker JR, Burggraf LW, Gordon MS (1999) SIMOMM: an integrated molecular orbital/molecular mechanics optimization scheme for surfaces, J. Phys. Chem. A 103: 3245–3251
Gokhale S, Trischberger P, Menzel D, Widdra W, Droege H, Steinrueck H-P, Birkenheuer U, Gutdeutsch U, Roesch N (1998) Electronic structure of benzene adsorbed on single-domain Si(001)-(2× 1): A combined experimental and theoretical study, J. Chem. Phys 108: 5554–5564; Birkenheuer U, Gutdeutsch U, Roesch N (1998) Geometrical structure of benzene absorbed on Si(001), Surf. Sci. 409: 213–228
Self KW, Pelzel RI, Owen JHG, Yan C, Widdra W, Weinberg WH (1998) Scanning tunneling microscopy study of benzene adsorption on Si(100)-(2× 1), J. Vac. Sci. Technol A 16: 1031–1036
Kong MJ, Teplyakow AV, Lyubovitsky JG, Bent SF (1998) NEXAFS studies of adsorption of benzene on Si(100)-2× 1, Surf. Sci. 411: 286–293
Borovsky B, Krueger M, Ganz E (1998) Metastable adsorption of benzene on the Si(001) surface, Phys. Rev. B 57, R4269–R4272
Lopinski GP, Moffat DJ, Wolkow RA (1998) Benzene/Si(100): metastable chemisorption and binding state conversion, Chem Phys Lett 282: 305–312; Lopinski GP, Fortier TM, Moffatt DJ, Wolkow RA, (1998) Multiple bonding geometries and binding state conversion of benzene/Si(100), J. Vac. Sci. Technol. A 16: 1037–1042; Wollow RA, Lopinski GP, Wolkow DJ, Moffat DJ (1998) Resolving organic molecule-silicon scanning tunneling microscopy features with molecular orbital methods, Surf. Sci. 416: L1107–L1113
Car R, Parrinello M (1985) Unified approach for molecular dynamics and density-functional theory, Phys. Rev. Lett. 55: 2471–2474
Cao X, Hamers RJ (2001) Silicon Surfaces as Electron Acceptors: Dative Bonding of Amines with Si(001) and Si(111) Surfaces J. Am. Chem. Soc 123: 10988–10996
Cao X, Hamers RJ (2002) Interactions of alkylamines with the silicon (001) surface, J. Vac. Sci. Tech. B 20, 1614–1619
Mui C, Han JH, Wang GT, Musgrave CB, Bent SF (2002) Proton Transfer Reactions on Semiconductor Surfaces, J. Am. Chem. Soc 124: 4027–4038
Carman A, Zhang L, Liswood JL, Casey SM (2003) Methylamine Adsorption on and Desorption from Si(100), J. Phys. Chem. B 107: 5491–5502
Björkvist M, Göthelid M, Grekh TM, Karlsson UO (1998) NH3 on Si(111)7× 7: Dissociation and surface reactions, Phys. Rev. B 57: 2327–2333
Wolkow R, Avouris P (1988) Atom-resolved surface chemistry using scanning tunneling microscopy, Phys. Rev. Lett 60: 1049–1052
Yu ML, Meyerson BS (1984) The adsorption of phosphine on silicon(100) and its effect on the coadsorption of silane, J. Vac. Sci. Technol. A 2: 446–449
Wang Y, Chen X, Hamers RJ (1994) Atomic-resolution study of overlayer formation and interfacial mixing in the interaction of phosphorus with Si(001), Phys. Rev. B 50: 4534–4547
Colaianni ML, Chen PJ, Yates JT, Jr (1994) Unique hydride chemistry on silicon-PH3 interaction with Si(100)-(2× 1), Vac. Sci. Technol. A 12: 2995–2998
Yu ML, Vitkavage DJ, Meyerson BS (1986) Doping reaction of PH3 and B2H6 with Si(001), J. Appl. Phys 59: 4032–4038
Kipp L, Bringans RD, Biegelsen DK, Northrup JE, Garcia A, Swartz LE (1995) Phosphine adsorption and decomposition on Si(100) 2× 1 studied by STM, Phys. Rev. B 52: 5843–5850
Hirose R, Sakamoto H (1999) Thermal desorption of surface phosphorus on Si(100) surfaces, Surf. Sci. Lett 430: L540–545
Maity N, Xia LQ, Engstrom JR (1995) Effect of PH3 on the dissociative chemisorption of SiH4 and Si2H6 on.Si(100): Implications on the growth on in situ doped Si thin films, Appl Phys Lett 66: 1909–1912
Yoo DS, Suemitsu M, Miyamoto N (1995) Hydrogen desorption process of Si(100)/PH3, J. Appl. Phys. 78: 4988
Wang Y, Bronikowski MJ, Hamers RJ (1994) An Atomically Resolved STM Study of the Interaction of Phosphine with the Silicon(001) Surface, J. Phys. Chem. 98: 5966–5973
Lin DS, Ku TS, Sheu TJ (1999) Thermal reactions of phosphine with Si(100): a combined photoemission and scanning-tunneling-microscopy study, Surf. Sci. 424: 7–18
Lin DS, Ku TS, Chen RP (2000) Interaction of phosphine with Si(100) from core-level photoemission and real-time scanning tunneling microscopy, Phys. Rev. B 61: 2799–2805
Shan J, Wang Y, Hamers RJ (1996) Adsorption and Dissociation of Phosphine on Si(001), J. Phys. Chem. 100: 4961–4969
Chen PJ, Colaianni ML, Wallace RM, Yates JT Jr (1991) Dissociative adsorption of PH3 on Si(111)-(7× 7): a high resolution electron energy loss spectroscopy study Surf. Sci. 244: 177–184
Bozso F, Avouris PH (1991) Adsorption of phosphorus on Si(111): Structure and chemical reactivity, Phys. Rev. B 43: 1847–1850
Cao PL, Lee LQ, Dai JJ, Zhou RH (1994) Adsorption and dissociation of PH3 on Si(100))2× 1 and Si(111)7× 7: Theoretical study, J. Phys: Condens Matter 6: 6103–6111
Miotto R, Srivastava GP, Miwa RH, Ferraz AC (2001) A comparative study of dissociative adsorption of NH3, PH3, and AsH3 on Si(001)-(2× 1), J. Chem. Phys. 114: 9549–9556
Becke AD (1993) Density-functional thermochemistry. III. The role of exact exchange, J. Chem. Phys. 98: 5648–5652
Bockstedte M, Kley A, Neugebaur J, Scheffler M (1997) Density-functional theory calculations for poly-atomic systems: electronic structure, static and elastic properties and ab initio molecular dynamics, Comput Phys. Commun. 107: 187–222
Perdew JP, Burke K, Ernzerhof M (1996) Generalized Gradient Approximation Made Simple, Phys. Rev. Lett. 77: 3865–3868
Troullier N, Martins JL (1991) Efficient pseudopotentials for plane-wave calculations, Phys. Rev. B 43: 1993–2006
Eng J, Raghavachari K, Struck LM, Chabal YJ, Bent BE, Flynn GW, Christman SB, Chaban EE, Williams GP, Radermacher K, Mantl S (1997) A vibrational study of ethanol adsorption on Si(100), J Chem Phys 106: 9889–9898; Casaletto MP, Zanoni R, Carbone M, Piancastelli MN, Aballe L, Weiss K, Horn K (2000) High-resolution photoemission study of ethanol on Si(100)2× 1, Surf. Sci. 447: 237–244
Casaletto MP, Zanoni R, Carbone M, Piancastelli MN, Aballe L, Weiss K, Horn K (2002) Methanol adsorption on Si(100)2× 1 investigated by high-resolution photoemis, Surf. Sci. 505: 251–259
Lu X, Zhang Q, Lin MC (2001) Adsorptions of Methanol, Formaldehyde and Formic Acid on the Si(100)-2× 1 Surface: A Theoretical Study, Phys. Chem. Chem. Phys. 3: 2156–2166
Kato T, Kang SY, Xu X, Yamabe T (2001) Possible Dissociative Adsorption of CH3OH and CH3NH2 on Si(100)-2× 1 Surface, J. Phys. Chem. B 105: 10340–10347
Maseras F, Morokuma K (1995) A New Ab Initio + Molecular Mechanics Geometry Optimization Scheme of Equilibrium Structures and Transition States, J. Comput. Chem. 16: 1170–1179
Kresse G, Furthmueller J (1996) Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set, Phys. Rev. B 54: 11169–11186
Perdew JP, Wang Y (1992) Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation, Phys. Rev. B 46: 6671–6687
Kresse G, Joubert J (1999) From ultrasoft pseudopotentials to the projector augmented-wave method, Phys. Rev. B 59: 1758
Blöchl PE (1994) Projector augmented-wave method, Phys. Rev. B 50: 17953–17979
Monkhorst HJ Pack JD (1976) Special points for Brillouin-zone integrations, Phys. Rev. B 13: 5188–5192
Ciani A, Sen P, Batra I (2004) Initial growth of Ba on Si(001), Phys. Rev. B 69: 245308–245319
Sen P, Ciraci S, Batra I, Grein C, Sivannthan S (2002) Finite temperature studies of Te adsorption on Si(001), Surf. Sci. 519: 79–89
Henkelman G, Uberuaga B, Jonsson H (2000) A climbing image nudged elastic band method for finding saddle points and minimum energy paths, J. Chem. Phys. 113: 9901–9904
Jonsson H, Mills G, Jacobsen KW Nudged Elastic Band Method for Finding Minimum Energy Paths of Transitions, in Classical and Quantum Dynamics in Condensed Phase Simulations, ed. Berne BJ, Ciccotti G and Coker DF, 385–405 (World Scientific, 1998)
Nosé S (1984) A unified formulation of the constant temperature molecular dynamics methods, J. Chem. Phys. 81: 511–519
Over H, Wasserfall J, Ranke W, Ambiatello C, Sawitzki R, Wolf D, Moritz W (1997) Surface atomic geometry of Si(001)-(2× 1): A low-energy electron-diffraction structure analysis Phys. Rev. B 55: 4731–4736
Ramstad A, Brocks G, Kelly P (1995) Theoretical study of the Si(100) surface reconstruction, Phys. Rev. B 51: 14504–14523
Miotto R, Oliveira M, Pinto M, de Leon-Perez F, Ferraz A (2004) Acetonitrile adsorption on Si(001), Phys. 31–2353 Rev. B 69: 235340
see12, p.18
Ogitsu T, Schwegler E, Gygi F, Galli G (2003) Melting of Lithium Hydride under Pressure, Phys. Rev. Lett. 91: 175502–175506
Lu Z, Wang C, Ho K-M (2000) Structures and dynamical properties of Cn, Sin, Gen, and Snn clusters with n up to 13, Phys. Rev. B 61: 2329–2334
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2007 Springer
About this chapter
Cite this chapter
Zhou, JG., Hagelberg, F. (2007). Electronic Properties and Fragmentation Dynamics of Organic Species Deposited on Silicon Surfaces. In: Sokalski, W.A. (eds) Molecular Materials with Specific Interactions – Modeling and Design. Challenges and Advances in Computational Chemistry and Physics, vol 4. Springer, Dordrecht. https://doi.org/10.1007/1-4020-5372-X_14
Download citation
DOI: https://doi.org/10.1007/1-4020-5372-X_14
Publisher Name: Springer, Dordrecht
Print ISBN: 978-1-4020-5371-9
Online ISBN: 978-1-4020-5372-6
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)