Metal−Organic Chemical Vapor Deposition of Palladium:  Spectroscopic Study of Cyclopentadienyl-allyl-palladium Deposition on a Palladium Substrate

Niklewski, Arno; Strunskus, Thomas; Witte, Gregor; Wöll, Christof

doi:10.1021/cm048798z

Cited by 15 publications

(10 citation statements)

References 19 publications

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“…In Figure 1d, two intense Pd emission lines are observed for the palladium precursor multilayer, assigned to Pd 2+ 3d 5/2 and Pd 2+ 3d 3/2 with binding energies at 337.6 eV and 342.9 eV, respectively. [18] After increasing the temperature to 225 K, the intensity of the Pd 2+ lines is found to be strongly reduced. At the same time two new emission lines appear at lower binding energies of 335.9 eV and 341.2 eV, respectively.…”

Section: As-received Si Surfacementioning

confidence: 95%

“…In an earlier study, [18] we investigated the decomposition of this Pd precursor on a Pd surface under UHV conditions and in the absence of a carrier gas. On the basis of results from XPS and near-edge X-ray absorption fine structure spectroscopy (NEXAFS), a detailed mechanism for the decomposition process on the palladium surface has been proposed.…”

Section: Introductionmentioning

confidence: 99%

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Deposition of Palladium from a Cylcopentadienyl‐allyl‐palladium Precursor on Si‐Based Substrates with Various Pretreatments: The Role of Surface Si–OH and Si‐H Species Studied by X‐Ray Photoelectron Spectroscopy

Wu¹,

Gunia²,

Strunskus³

et al. 2005

Chemical Vapor Deposition

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The decomposition reactions of a metal-organic precursor for the CVD of Pd, (Cp)Pd(allyl), on Si substrates with various terminated surfaces have been studied using X-ray photoelectron spectroscopy (XPS). The XPS data show that mixed hydrogen/ hydroxyl-terminated Si surfaces exhibit the highest activity ascribed to acidic Si-OH groups for precursor decomposition, followed by the as-received Si surface. Clean, well-defined SiO 2 surfaces prepared in ultrahigh vacuum (UHV) exhibit the lowest activity for the Pd precursor decomposition, whereas the hydrogen-terminated Si surface was rather active. Scanning electron microscopy (SEM) images show that Pd clusters were formed on the mixed hydrogen/hydroxyl-terminated Si surface with a coverage of about 10 %. The average size of the Pd clusters is about 30 nm. Based on the XPS experimental data, a hydrogenassisted decomposition mechanism of the Pd precursor is proposed.

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Section: As-received Si Surfacementioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Deposition of Palladium from a Cylcopentadienyl‐allyl‐palladium Precursor on Si‐Based Substrates with Various Pretreatments: The Role of Surface Si–OH and Si‐H Species Studied by X‐Ray Photoelectron Spectroscopy

Wu¹,

Gunia²,

Strunskus³

et al. 2005

Chemical Vapor Deposition

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“…Presently, the possibility of chemically binding other moieties to the organic surface exposed by the SAM is attracting an increasing amount of attention, for example, in connection with the coupling of biomolecules,2 in model studies regarding biomineralization3 and in anchoring zeolites4 or metal–organic frameworks 5. A special type of surface termination, SH groups, has recently attracted considerable attention with regard to metallization of SAMs 6…”

mentioning

confidence: 99%

Chemistry in Confined Geometries: Reactions at an Organic Surface

et al. 2007

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One of the most intriguing possibilities offered by organothiol (OT)-based self-assembled monolayers (SAMs) adsorbed on solid substrates is to create organic surfaces, the properties of which can be tailored by choosing organothiols with appropriate groups at the w-position.[1] The large variety of suitable functional groups allows for control of the physico-chemical properties of the surface. For example, the wettability can be varied smoothly between hydrophobic and hydrophilic. Presently, the possibility of chemically binding other moieties to the organic surface exposed by the SAM is attracting an increasing amount of attention, for example, in connection with the coupling of biomolecules, [2] in model studies regarding biomineralization [3] and in anchoring zeolites [4] or metal-organic frameworks.[5] A special type of surface termination, ÀSH groups, has recently attracted considerable attention with regard to metallization of SAMs. [6] In many cases the desired organic surface can be obtained by using an appropriately w-functionalized organothiol, but there are often complications resulting from undesired interactions either between the corresponding functional groups (as in the case of COOH···HOOC hydrogen bonding [7,8] or the functional group and the Au substrate [9,10] ). Recently, we have demonstrated that a protecting-group strategy can be used to avoid such problems by first fabricating a SAM from protected organothiols.[10] A subsequent deprotection carried out by immersing the SAM in a corresponding solution then yields an organic surface with the desired functionality.Herein, we demonstrate that the chemical reactions at the organic surface of the SAM proceed quite differently to the corresponding reactions in solution. Although these types of surface reactions have been studied earlier by several groups (see the papers by Sullivan and Huck [11] and Love et al. [12] for recent reviews of this field), still a careful and systematic understanding is lacking. A detailed analysis of our findings reveals that there are general phenomena resulting from confining the occurrence of a particular chemical reaction to two dimensions, which can affect reactions on highly ordered organic surfaces. We demonstrate the importance of this reduction in dimensionality for the chemical reactivity by investigating the case of removing an acetate group by a basic agent, shown schematically in Figure 1. This reaction, which is standard in solution chemistry, is found to be significantly hindered when confined to a two-dimensional system. Whereas the reaction in solution proceeds in minutes, the corresponding reaction at the organic surfaces requires, depending on the conditions, up to 84 hours. This is a surprising observation considering that the agent used for removing the protecting COCH 3 -group is a very small molecule, a hydroxide ion (OH À ). The reasons for this unexpected behavior are unraveled using IR spectroscopy, near edge X-ray absorption fine structure spectroscopy (NEXAFS) and scanning electron microscop...

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“…electrostatic adsorption 25 and grafting 26 ), vapour-or gas-phase deposition (i.e. chemical 27 and physical 28 ), electrochemistry 29 (i.e. electroless and electroplating 30 ), plasma or thermal spraying 31 have been previously reported.…”

Section: Introductionmentioning

confidence: 99%

Design and manufacture of functional catalyst-carrier structures for the bioorthogonal activation of anticancer agents

et al. 2019

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Metal−Organic Chemical Vapor Deposition of Palladium: Spectroscopic Study of Cyclopentadienyl-allyl-palladium Deposition on a Palladium Substrate

Cited by 15 publications

References 19 publications

Deposition of Palladium from a Cylcopentadienyl‐allyl‐palladium Precursor on Si‐Based Substrates with Various Pretreatments: The Role of Surface Si–OH and Si‐H Species Studied by X‐Ray Photoelectron Spectroscopy

Deposition of Palladium from a Cylcopentadienyl‐allyl‐palladium Precursor on Si‐Based Substrates with Various Pretreatments: The Role of Surface Si–OH and Si‐H Species Studied by X‐Ray Photoelectron Spectroscopy

Chemistry in Confined Geometries: Reactions at an Organic Surface

Design and manufacture of functional catalyst-carrier structures for the bioorthogonal activation of anticancer agents

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