Tuning the geometry of shape-restricted DNA molecules on the functionalized Si(111)

2010

Chem. Soc. Rev.

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As the cornerstone of multiple practical applications, silicon single crystal surfaces have attracted the interest of scientific and engineering communities for several decades. The most recent advances employ the surfaces precovered with a specific functionality to extend into the realm of organic and metal-organic films with well-defined interfaces, to protect the surfaces from oxidation and other contaminations, and to build the components of present and future molecular electronics and sensing devices. This critical review will focus on the reactivity of the selectively terminated Si(100) and Si(111) surfaces. The hydrogen and halogen-terminated surfaces are the most widely used and most heavily reviewed previously, thus only a brief summary will be given here with the emphasis of the most recent thermal approaches to functionalization of hydrogen-terminated silicon. The silicon surfaces precovered with NH(x) functionality are emerging as a very likely candidate both for the production of sharp interfaces and for coadsorption, co-assembly, and potential molecular templating of patterns on single crystalline surfaces. A brief overview of recent advances in achieving control over the hydroxyl-termination of silicon will be given. Some future directions for further development of chemistry, reactivity, and assembly on these surfaces, as well as potential applications, are highlighted in the last section (152 references).

Section: Ii2b Preparation Of Nhmentioning

confidence: 99%

Reactivity of selectively terminated single crystal silicon surfaces

Perrine

2010

Chem. Soc. Rev.

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“…By itself, surface functionalization is an important area in surface modification, which has been explored in great detail. A wide range of research is being performed on functionalizing silicon surface. − The corresponding modification techniques are of great general interest in microelectronics, biosensing, energy conversion, and catalysis. These processes can be performed with a variety of methods, from vacuum, such as chemical vapor deposition (CVD), physical vapor deposition (PVD), and magnetron sputtering to wet chemistry under ambient conditions.…”

Section: Introductionmentioning

confidence: 99%

Attachment Chemistry of PCBM to a Primary-Amine-Terminated Organic Monolayer on a Si(111) Surface

Miller

2014

Langmuir

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Interfacing multifunctional molecules with semiconductor surfaces has a variety of applications; however, it is important to understand the selectivity of target surface reactions to produce the surface with desired functionality. In this work, a silicon surface modified with 1-amino-10-undecene was reacted with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) in toluene. Two possible competing reactions for PCBM, via the ester group and by direct attachment to the C60 portion, are analyzed. X-ray photoelectron spectroscopy, atomic force microscopy, Fourier-transform infrared spectroscopy, and time-of-flight secondary ion mass spectroscopy, supplemented by density functional theory calculations, suggest that despite the similarity of the energetics for those two reaction pathways, predominant chemisorption occurs via the direct attachment of the C60 cage to the primary amino group of the functionalized silicon surface.

“…The analysis of the Si 2p spectra presented in Figure reveals that no silicon surface oxidation was observed during the experimental procedure for obtaining H-terminated and Cl-terminated Si(111) substrates, as shown in spectra (a) and (b). The dashed line in Figure indicates the expected position for the XPS feature corresponding to SiO x at approximately 103 eV. ,,,− A Si 2p spectrum obtained following phenylhydrazine treatment exhibits a very minor feature at 102.2 eV in addition to the typical signature of the clean silicon surface, and as reaction time increases from 1 h in Figure c to 3.5 h in Figure f, this minor feature increases in intensity and also shifts to the higher energy. Previous investigations of the feature observed at 102.2 eV suggest that it is most likely a signature of surface nitride ,, formed at the surface defect sites.…”

Section: Resultsmentioning

confidence: 91%

Dehydrohalogenation Condensation Reaction of Phenylhydrazine with Cl-Terminated Si(111) Surfaces

Gao

2016

J. Phys. Chem. C

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Formation of stable organic–inorganic contacts with silicon often requires oxygen- and carbon-free interfaces. Some of the general approaches to create such interfaces rely on the formation of a Si–N bond. A reaction of dehydrohalogenation condensation of Cl-terminated Si(111) surface with phenylhydrazine is investigated as a means to introduce a simple function to the surface using a –NH-NH2 moiety as opposed to previously investigated approaches. The use of substituted hydrazine allows for the formation of a stable structure that is less strained compared to the previously investigated primary amines and leads to minimal surface oxidation. The process is confirmed by a combination of infrared studies, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry investigations. Density functional theory is utilized to yield a plausible surface reaction mechanism and provide a set of experimental observables to compare with these data.