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Low-temperature atmospheric pressure plasma conversion of polydimethylsiloxane and polysilazane precursor layers to oxide thin films

2023, Rudolph, Martin, Birtel, Peter, Arnold, Thomas, Prager, Andrea, Naumov, Sergej, Helmstedt, Ulrike, Anders, André, With, Patrick C.

We study the conversion of two polymeric silicon precursor compound layers (perhydropolysilazane and polydimethylsiloxane) on a silicon wafer and polyethylene terephthalate substrates to silicon oxide thin films using a pulsed atmospheric pressure plasma jet. Varying the scan velocity and the number of treatments results in various film compositions, as determined by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The mechanism suggested for the conversion process includes the decomposition of the precursor triggered by plasma-produced species, the oxidation of the surface, and finally, the diffusion of oxygen into the film, while gases produced during the precursor decomposition diffuse out of the film. The latter process is possibly facilitated by local plasma heating of the surface. The precursor conversion appears to depend sensitively on the balance between the different contributions to the conversion mechanism.

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Helium transmission rate as a rapid and reliable method for assessing the water vapour transmission rate of transparent PET-SiOx barrier foils

2021, Herbst, Florian, Großer, Stephan, With, Patrick C., Prager, Lutz, Pander, Matthias

A single quadrupole mass spectrometer coupled measuring setup was developed for the investigation of the helium transmission rate (HeTR) of SiOx-coated polyethylene terephthalate (PET) barrier films. The setup allows the pressure-less and time-resolved measurements of the helium permeation at transient and steady-state conditions. Whereas standard water vapour transmission rate (WVTR) experiments took extended test times (in the range of several days), HeTR measurements were finished after 1 h. For the material system investigated here, an excellent linear correlation of WVTR and HeTR was proven over two orders of magnitude (regarding WVTR). Experiments with application of different strain loads on the coated films revealed a significant increase of both, HeTR and WVTR. Scanning electron microscope (SEM) measurements evidenced multiple ruptures of the SiOx coating depending on the applied strain and initial thickness of the SiOx layer. Considering virgin barrier films and strain-ruptured barrier films, a good correlation of WVTR and HeTR was shown.

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Flexible Transparent Barrier Applications of Oxide Thin Films Prepared by Photochemical Conversion at Low Temperature and Ambient Pressure

2020, With, Patrick C., Helmstedt, Ulrike, Prager, Lutz

Photoconversion of metal-organic precursors to thin film metal oxides using ultraviolet (UV) radiation in oxidative atmosphere is an attractive technology because it can be applied at temperatures <80°C and at ambient pressure. Thus, it enables preparing this class of thin films in a cost-efficient manner on temperature sensitive substrates such as polymer films. In this article, various aspects of research and development in the field of photochemical thin-film fabrication, with particular focus to the application of the produced films as gas permeation barriers for the encapsulation of optoelectronic devices are reviewed. Thereby, it covers investigations on fundamental photochemically initiated reactions for precursor classes containing metal-oxygen and metal-nitrogen bonds, and emphazises the relevance of that understanding for applicative considerations like integration of the single-layer barrier films into relevant encapsulation films. Further perspectives are given concerning integration of additional functionalities like electrical conductivity to the flexible and transparent barrier films. © Copyright © 2020 With, Helmstedt and Prager.

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Reactive plasma cleaning and restoration of transition metal dichalcogenide monolayers

2021, Marinov, Daniil, de Marneffe, Jean-François, Smets, Quentin, Arutchelvan, Goutham, Bal, Kristof M., Voronina, Ekaterina, Rakhimova, Tatyana, Mankelevich, Yuri, El Kazzi, Salim, Nalin Mehta, Ankit, Wyndaele, Pieter-Jan, Heyne, Markus Hartmut, Zhang, Jianran, With, Patrick C., Banerjee, Sreetama, Neyts, Erik C., Asselberghs, Inge, Lin, Dennis, De Gendt, Stefan

The cleaning of two-dimensional (2D) materials is an essential step in the fabrication of future devices, leveraging their unique physical, optical, and chemical properties. Part of these emerging 2D materials are transition metal dichalcogenides (TMDs). So far there is limited understanding of the cleaning of “monolayer” TMD materials. In this study, we report on the use of downstream H2 plasma to clean the surface of monolayer WS2 grown by MOCVD. We demonstrate that high-temperature processing is essential, allowing to maximize the removal rate of polymers and to mitigate damage caused to the WS2 in the form of sulfur vacancies. We show that low temperature in situ carbonyl sulfide (OCS) soak is an efficient way to resulfurize the material, besides high-temperature H2S annealing. The cleaning processes and mechanisms elucidated in this work are tested on back-gated field-effect transistors, confirming that transport properties of WS2 devices can be maintained by the combination of H2 plasma cleaning and OCS restoration. The low-damage plasma cleaning based on H2 and OCS is very reproducible, fast (completed in a few minutes) and uses a 300 mm industrial plasma etch system qualified for standard semiconductor pilot production. This process is, therefore, expected to enable the industrial scale-up of 2D-based devices, co-integrated with silicon technology.