When chemistry of the substrate drastically controls morphogenesis of plasma polymer thin films

Le, Nghia Huu; Bonne, Magali; Airoudj, Aissam; Fioux, Philippe; Boubon, Rémi; Rébiscoul, Diane; Gall, Florence Bally‐Le; Lebeau, Bénédicte; Roucoules, Vincent

doi:10.1002/ppap.202000183

Cited by 4 publications

(3 citation statements)

References 45 publications

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“…Furthermore, that interface/interphase might be also pertinent for a prospective mechanical analysis of ultrathin plasma films. The influence of the substrate on the rate of deposition and chemistry of ultrathin films is known for some time [56] and a recent publication reports how the chemistry of the substrate creates different morphologies of plasma thin films during early stages of growth [57]. Those latter results open up for questions on the possibility to measure localized mechanical properties within plasma polymerized thin films.…”

Section: Nature Of Substratementioning

confidence: 99%

Mechanical properties of plasma polymer films: a review

et al. 2021

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Plasma polymers are micro-, or more commonly, nano-sized coatings that can be deposited on a variety of substrates through different approaches. The versatility of these polymers is incremented by the possibility to use other precursors than conventional polymerization reactions and by potential changes in the polymerization mechanisms according to the intrinsic physical and chemical properties of the plasma. That flexibility offers a fruitful ground to a great range of scientific and engineering fields, but it also brings many challenges for universalization of empirical observations. In this review, the use of different precursors, substrates and changes in plasma external parameters were evaluated as common, but not necessarily ideal nor exhaustive, variables for the analysis of mechanical properties of plasma polymer films. The commonly reported trends are complemented with the exceptions, and a variety of hypothesis drawn by the empirical observations are shown. The techniques and methods used for determining the mechanical properties of plasma polymers, the effect of post-treatments on them and some applications are evaluated. Finally, a general conclusion highlighting the challenges of the field is provided. Article highlights The mechanical properties of plasma polymers are evaluated as a function of selected parameters. The techniques of characterization of mechanical properties of plasma polymers are summarized. A discussion of future and current demands for the analysis of mechanical properties of plasma polymers is done.

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Section: Nature Of Substratementioning

confidence: 99%

Mechanical properties of plasma polymer films: a review

et al. 2021

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“…[5] Meanwhile, this approach was demonstrated to be applicable for many different monomers, that is, polymerizable molecules, yielding plasma polymerization. [6][7][8][9][10][11] Moreover, the concept also comprises the use of power modulation by applying on/ off pulses to reduce the average power input in the plasma aiming to enhance the structural retention of monomers. [12,13] Likewise, replacing temperature by SEI following an Arrhenius-like form might be useful for plasma conversion, plasma catalysis, and plasma jet sintering [14][15][16] -though this is still a debated subject.…”

Section: Introductionmentioning

confidence: 99%

Plasma activation mechanisms governed by specific energy input: Potential and perspectives

Hegemann

2023

Plasma Processes & Polymers

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In a low‐temperature plasma, the electrons pick up energy from the electric field in collisions with atoms and molecules, gaining high kinetic energy that must be sufficient for ionizing reactions to sustain the plasma. For molecular gases, an average energy per heavy gas particle is thus available in the plasma, the specific energy input, yielding plasma activation by inelastic collisions. Following a distribution law, the probability for the activation mechanism can be described by an Arrhenius‐like equation. The potential of this approach is demonstrated on the basis of plasma polymerization and plasma CO2 conversion. For perspective, energy efficiencies are discussed as a function of conversion indicating the optimum that can be achieved by electron impact activation compared with additional ways of energy transfer, probably depending on certain constraints.

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“…Furthermore, recent studies challenge the typically held belief that plasma polymerisation is a surfaceindependent process. The properties in the early stages of plasma polymerisation differ from thicker films in terms of chemistry [28][29][30][31][32] , morphology 28,[31][32][33] , growth rate 28 , and adhesion 31,34 because the monomers land on the pristine substrate rather than an already coated polymeric layer.…”

Section: Introductionmentioning

confidence: 99%

Surface Directed Growth of a Stable Free Radical Polymer Layer

Quadrelli,

Robson,

Bashayr

et al. 2023

Preprint

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Molecular radicals such as nitric oxide (NO) play a role in numerous important biological processes. NO, however, is inherently unstable, and there is considerable interest in stable radicals with analogous behaviour, such as (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), and their potential as biologically active surface coatings. Here we show that it is possible to grow stable TEMPO monolayers with an ordered arrangement and specific orientation of the nitroxide group. A combination of high-resolution atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations reveal that strong dipole-dipole interactions between neighbouring TEMPO molecules determine their orientation, resulting in an anti-parallel arrangement with upwards and downwards facing nitroxide groups. Surface coating is made possible using plasma polymerisation, a surface molecular engineering technique suitable for growing functional coatings of highly stable organic molecules. Typically, plasma polymerisation is considered a surface-independent process, with the plasma power and pressure dominating the deposited film's properties. We therefore test this assumption and its impact on TEMPO layers by studying initial stage growth on multiple material surfaces. We show that whilst plasma polymer growth creates ordered layers on gold and graphite surfaces, there is substantial substrate-dependence with less ordered growth on other materials up to a film thickness of 30 nm, suggesting variation in molecular packing and retention. Beyond that thickness, films convergence to a flat, uniform, surface-agnostic structure. These findings establish the utility of plasma polymerisation as a method for ordered growth and demonstrate the ability to direct the orientation of TEMPO molecules and NO free radicals within a thin film.

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When chemistry of the substrate drastically controls morphogenesis of plasma polymer thin films

Cited by 4 publications

References 45 publications

Mechanical properties of plasma polymer films: a review

Mechanical properties of plasma polymer films: a review

Plasma activation mechanisms governed by specific energy input: Potential and perspectives

Surface Directed Growth of a Stable Free Radical Polymer Layer

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