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

Rodríguez‐Reyes, Juan Carlos F.; Teplyakov, Andrew V.

doi:10.1021/jp067929b

Cited by 47 publications

(71 citation statements)

References 69 publications

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“…The comparison of Ti-N and N-C dissociation pathways is shown in Fig. 3.44 and compared with amines in Table 3.2 [367]. Parallels with the amine chemistry illustrated in the previous example can be quite relevant in designing depositions schemes involving alkylaminometallic compounds.…”

Section: Effect Of Metal Atoms On the Pathways Of Chemical Reactions mentioning

confidence: 86%

“…Adsorption models considered for (hfac)Cu(VTMS) adsorption on Si(100)-2×1 followed by VTMS desorption [356]. The recent studies of Rodriguez-Reyes and Teplyakov addressed the need to understand the chemical bonding of complex organometallic precursors of this type with Si(100)-2×1 [367][368][369]. Despite apparent complexity, the initial step in the interaction of TDMAT with the Si(100)-2×1 surface is quite similar to the reactions of amines.…”

Section: Effect Of Metal Atoms On the Pathways Of Chemical Reactions mentioning

confidence: 99%

“…The lone pair or nitrogen atom on one of the dimethylamino groups forms a dative bond with silicon surface atom as shown in structure A1 in Fig. 3.43 [367]. Interestingly, even though the size of a TDMAT molecule could easily allow for binding of several nitrogen atoms to several surface reactive sites, only a single structure A1 was produced in computational studies [367].…”

Section: Effect Of Metal Atoms On the Pathways Of Chemical Reactions mentioning

confidence: 99%

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2007

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Section: Effect Of Metal Atoms On the Pathways Of Chemical Reactions mentioning

confidence: 86%

Section: Effect Of Metal Atoms On the Pathways Of Chemical Reactions mentioning

confidence: 99%

Section: Effect Of Metal Atoms On the Pathways Of Chemical Reactions mentioning

confidence: 99%

See 1 more Smart Citation

Chemical manipulation of multifunctional hydrocarbons on silicon surfaces

Leftwich

Teplyakov

2007

Surface Science Reports

123

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“…TDMAT is known to undergo a transamination reaction with the amine-terminated surface (35) produced by adsorption of ammonia on Sið100Þ-2 × 1 (36), as illustrated in Scheme 2. This process has been well studied because the transamination reaction can be used as an initial step in thin film growth targeting diffusion barrier films such as TiCN (35,(37)(38)(39). The transamination reaction is known to follow the nucleophilic attack of the lone electron pair of a nitrogen atom of the surface functionality onto a metal center of the metal-organic precursor.…”

Section: Resultsmentioning

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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“…The use of TDMAT as a precursor for TiO 2 ALD has been reported in the literature before [3,[37][38][39][40]. Maeng and Kim reported an ALD window in the range between 150°C and 250°C [3].…”

Section: Introductionmentioning

confidence: 99%