Chemical manipulation of multifunctional hydrocarbons on silicon surfaces

Leftwich, Timothy R.; Teplyakov, Andrew V.

doi:10.1016/j.surfrep.2007.08.001

Cited by 91 publications

(127 citation statements)

References 487 publications

(618 reference statements)

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“…The adsorption of organic molecules on silicon surfaces is of interest for the control of their preparation and processing for applications in device fabrication [1], but also interesting from a fundamental point of view, in terms of the interaction of the molecules with covalently bonded surface atom sites. The (7×7) reconstructed silicon (111) surface presents a rich array of such electronically inequivalent reaction sites, due to the unique electronic properties of reactive adatoms, rest atoms, and corner holes on the surface (see Fig.…”

Section: Introductionmentioning

confidence: 99%

Selective adsorption of coronene on Si(111)-(7×7)

2010

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The adsorption of coronene (C 24 H 12 ) on the Si(111)-(7×7) surface is studied using Scanning Tunneling Microscopy (STM). Upon room temperature submonolayer deposition, we find that the coronene molecules preferentially adsorb on the unfaulted half of the 7×7 unit cell. Molecules adsorbed on different sites can be induced to move to the preferential sites by the action of the tip in repeated image scans. Imaging of the molecules is strongly bias dependent, and also critically depends on the adsorption site. We analyze the results in terms of differential bonding strength for the different adsorption sites and we identify those substrate atoms which participate in the bonding with the molecule.

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Section: Introductionmentioning

confidence: 99%

Selective adsorption of coronene on Si(111)-(7×7)

2010

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“…Obviously that the adsorption of more complex (in regard geometry, the chemical structure -the presence of double/triple bonds or several functional groups) of molecules is even more nontrivial [14][15][16][17][18][19][20][21][22][23][24][25]. First of all this is manifested in that complex organic molecules (cyclic hydrocarbons, aromatic systems etc.)…”

Section: Introductionmentioning

confidence: 99%

“…Indeed, over the past ten years series of experimental works devoted to the study of organic selfassembled monolayers on metal surfaces has been published. The general conclusion of these studies is that the molecule orientation in the adlayer is a function of external parameters such as concentration, pressure, temperature, electrode potential and others [14][15][16][17][18][19][20][21][22][23][24][25]. Moreover, very interesting ordered structures have been experimentally found in some of similar systems.…”

Section: Introductionmentioning

confidence: 99%

Statistical Thermodynamics of Lattice Gas Models of Multisite Adsorption

Fefelov¹,

Горбунов²,

Myshlyavtsev³

et al. 2012

Thermodynamics - Fundamentals and Its Application in Science

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“…Surface chemistry may bring new states into the midgap region of the material as well as affect the positions of HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) (6), a degree of control that is especially important in surface functionalization of semiconductor nanostructures, where electronic properties can be affected tremendously by the functional group present on the surface (3). In other cases, modification of semiconductor surfaces is aimed at providing a chemical "hook" for further surface functionalization, without explicit regard to the electronic properties of the functional groups that are placed on the surface (7)(8)(9). Hence the functional groups, such as ─OH, ─COOH, and ─NH 2 , attached to the surface are normally thought of as a starting point for further processing rather than interesting entities whose electronic properties are affected by the surface being functionalized.…”

mentioning

confidence: 99%

“…The ability to add new functionalities to semiconductor surfaces builds upon two decades of research in which the concept of the surface as a chemical reagent in semiconductor surface chemistry has been shown to be a powerful construct (7)(8)(9)(10)(11)(12)(13)(14)(15). Specifically, surfaces of group IV elemental semiconductors are viewed as a collection of specific sites with different electrophilic or nucleophilic properties.…”

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confidence: 99%

Tuning the reactivity of semiconductor surfaces by functionalization with amines of different basicity

Bent

Kachian

Rodríguez‐Reyes

et al. 2010

Proc. Natl. Acad. Sci. U.S.A.

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Surface functionalization of semiconductors has been the backbone of the newest developments in microelectronics, energy conversion, sensing device design, and many other fields of science and technology. Over a decade ago, the notion of viewing the surface itself as a chemical reagent in surface reactions was introduced, and adding a variety of new functionalities to the semiconductor surface has become a target of research for many groups. The electronic effects on the substrate have been considered as an important consequence of chemical modification. In this work, we shift the focus to the electronic properties of the functional groups attached to the surface and their role on subsequent reactivity. We investigate surface functionalization of clean Sið100Þ-2 × 1 and Geð100Þ-2 × 1 surfaces with amines as a way to modify their reactivity and to fine tune this reactivity by considering the basicity of the attached functionality. The reactivity of silicon and germanium surfaces modified with ethylamine (CH 3 CH 2 NH 2 ) and aniline (C 6 H 5 NH 2 ) is predicted using density functional theory calculations of proton attachment to the nitrogen of the adsorbed amine to differ with respect to a nucleophilic attack of the surface species. These predictions are then tested using a model metalorganic reagent, tetrakis(dimethylamido)titanium (ððCH 3 Þ 2 NÞ 4 Ti, TDMAT), which undergoes a transamination reaction with sufficiently nucleophilic amines, and the reactivity tests confirm trends consistent with predicted basicities. The identity of the underlying semiconductor surface has a profound effect on the outcome of this reaction, and results comparing silicon and germanium are discussed.adsorption | organic | nucleophile | spectroscopy T he recent boom in the development of microelectronics, energy conversion, and sensing devices is tied very closely to our ability to selectively modify well-defined surfaces by chemical means. The opportunities offered by the passivation and functionalization of semiconductor surfaces have already led to the concepts of ultrathin films and molecular-size features in devices being used for practical applications (1). Further development of the field will require that our understanding of the chemical processes on semiconductor surfaces reach a truly molecular level. Surface functionalization can affect either the electronic properties or the chemical reactivity of the semiconductor (2-4). For example, similarly to high-spatial-resolution doping, functionalizing selected areas of a semiconductor surface with predesigned molecules affects the electronic state of the semiconductor (5). Surface chemistry may bring new states into the midgap region of the material as well as affect the positions of HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) (6), a degree of control that is especially important in surface functionalization of semiconductor nanostructures, where electronic properties can be affected tremendously by the functional group present on t...

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Chemical manipulation of multifunctional hydrocarbons on silicon surfaces

Cited by 91 publications

References 487 publications

Selective adsorption of coronene on Si(111)-(7×7)

Selective adsorption of coronene on Si(111)-(7×7)

Statistical Thermodynamics of Lattice Gas Models of Multisite Adsorption

Tuning the reactivity of semiconductor surfaces by functionalization with amines of different basicity

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