Plasmons as the primary mechanism of ion-induced modifications in polymers

Moliton, Jean-Pierre; Jussiaux–Devilder, C.; Trigaud, Thierry; Lazzaroni, Roberto; Brédas, Jean‐Luc; Galaup, S.; Kihn, Y.; Sévely, J.

doi:10.1080/13642819908205750

Cited by 12 publications

(13 citation statements)

References 37 publications

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“…Their existence in PMMA has also been demonstrated 20 although while it is clear that plasmons participate in the delocalization of energy away from the primary path of the charged particle, their role in breaking the polymeric bonds of PMMA for lithographic purposes is still disputed. [21][22][23] DEEP incorporates the contributions from plasmons and the plasmon generation mean-free path used 18 is…”

Section: A Electronsmentioning

confidence: 99%

Stochastic spatial energy deposition profiles for MeV protons and keV electrons

2009

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With the rapid advances being made in novel high-energy ion-beam techniques such as proton beam writing, single-ion-event effects, ion-beam-radiation therapy, ion-induced fluorescence imaging, proton/ion microscopy, and ion-induced electron imaging, it is becoming increasingly important to understand the spatial energydeposition profiles of energetic ions as they penetrate matter. In this work we present the results of comprehensive yet straightforward event-by-event Monte Carlo calculations that simulate ion/electron propagation and secondary electron ͑␦ ray͒ generation to yield spatial energy-deposition data. These calculations combine SRIM/TRIM features, EEDL97 data and volume-plasmon-localization models with a modified version of one of the newer ␦ ray generation models, namely, the Hansen-Kocbach-Stolterfoht. The development of the computer code DEEP ͑deposition of energy due to electrons and protons͒ offers a unique means of studying the energy-deposition/redistribution problem while still retaining the important stochastic nature inherent in these processes which cannot be achieved with analytical modeling. As an example of an application of DEEP we present results that compare the energy-deposition profiles of primary MeV protons and primary keV electrons in polymethymethacrylate. Such data are important when comparing proximity effects in the direct write lithography processes of proton-beam writing and electron-beam writing. Our calculations demonstrate that protons are able to maintain highly compact spatial energy-deposition profiles compared with electrons.

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Section: A Electronsmentioning

confidence: 99%

Stochastic spatial energy deposition profiles for MeV protons and keV electrons

2009

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“…Considering quantum-chemical calculations concerning the electronic band structure of PC by Moliton et al, we attribute the origin of this peak to CO and a mixture of O 2p and C 2p orbitals with emphasis on the O 2p emission. 10 Further deposition of PC is accompanied by a small shift of this peak of 0.2 eV toward lower binding energy. In addition, a second feature arises at about 3.9 eV (A), superimposing the emission of the Au 5d band (III), which is derived most probably from the C 2p band and the π-orbitals of the phenyl rings, respectively.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Monolayer Deposition of Bisphenol A Polycarbonate Oligomers on Au(111)

et al. 2014

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The deposition behavior of bisphenol A polycarbonate (BPA-PC) on a Au(111) single crystal has been studied. Thin films of PC were prepared by in situ evaporation of PC pellets under UHV conditions. The resulting PC/Au(111) interfaces were characterized by means of Ultraviolet Photoelectron Spectroscopy (UPS), X-ray Photoelectron Spectroscopy (XPS) and Scanning Tunneling Microscopy (STM). XPS and UPS revealed that no decomposition of the polymer takes place during evaporation. The C 1s and O 1s XPS core level analysis as well as the UPS spectra show distinct features which can be attributed to chemical bonding states of the PC molecule. Therefore, we conclude that the molecular structure within the monomeric unit remains intact after evaporation. Furthermore, STM measurements in the submonolayer regime revealed a selfassembly of small polymer chains of 2−4 monomeric units on the Au(111) surface.

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“…Secondary Ion Mass Spectrometry (SIMS) studies revealed that hydrogen is expelled in large quantity and is the first molecular fragment driven out from the sample surface. [2] According to the literature, [10] the C-C bonds in the backbone as well as the C-C and the C-O bonds in the methacrylate side group are susceptible to cleavage by ions. Bond cleavage in the side groups produces small mobile fragments while broken bonds in the backbone chain will result in large immobile sections of the macromolecule with some trend to recombination of the radical states, at least at low Ga + ion currents.…”

Section: Resultsmentioning

confidence: 99%

Focused ion beam irradiation—morphological and chemical evolution in PMMA

Kochumalayil

Meiser

Soldera

et al. 2009

Surface & Interface Analysis

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For poly(methyl methacrylate) (PMMA) as a representative of amorphous thermoplastic polymers, the milling effects, and the chemical changes due to ion bombardment with a focused ion beam (FIB) at normal incidence are studied with scanning force microscopy (SFM), scanning electron microscopy (SEM)/energy dispersive X-ray (EDX), and infrared (IR) spectroscopy for varying conditions of Ga + treatment, including the effect of partial water pressure. Stopping and Range of Ions in Matter (SRIM) simulation results for 30 keV Ga + at normal incidence show that the zone of primary ion-polymer interaction extends ca 100 nm into the PMMA. Accordingly, this interaction region is much wider than the original beam diameter. The width of the region where the recoiled ions interact strongly with the polymer chains is larger. Secondary processes, such as fragment diffusion and phonon transport, are expected to extend even farther into the polymer. SEM and SFM reveal distinct topologies of areas milled without or in presence of water vapour. Water vapour-assisted FIB milling produces more roughness and defects. The infrared attenuated total reflection spectroscopy (IR-ATR) spectra indicate that ion milling in PMMA damages methacrylate side groups in particular. In contrary to metals, an increase in the degree of milling is found when the beam spot overlap parameter increases.

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Plasmons as the primary mechanism of ion-induced modifications in polymers

Cited by 12 publications

References 37 publications

Stochastic spatial energy deposition profiles for MeV protons and keV electrons

Stochastic spatial energy deposition profiles for MeV protons and keV electrons

Monolayer Deposition of Bisphenol A Polycarbonate Oligomers on Au(111)

Focused ion beam irradiation—morphological and chemical evolution in PMMA

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