Determination of the Glass Transition Temperature of Freestanding and Supported Azo-Polymer Thin Films by Thermal Assisted Atomic Force Microscopy

Chernykh, E. A.; Kharintsev, S. S.; Фишман, А. И.; Алексеев, А. В.; Салахов, М. Х.

doi:10.1051/epjconf/201713900007

Cited by 5 publications

(3 citation statements)

References 19 publications

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“…Polymer thin films of different thickness were produced by spin coating 1 μL of PMMA solution onto a refractory metasurface at 3000 rpm for 2 min. To eliminate solvent remains the thin film was annealed at a temperature exceeding the T g by 10 °C and pressure of 10 mbar for 2 h. The thickness of the PMMA film was determined by starching its surface with a c -AFM cantilever, as highlighted in ref . The depth of lithographically fabricated grooves was controlled by the set point driven applied force of the c -AFM cantilever.…”

Section: Methodsmentioning

confidence: 99%

Nanoscale Sensing Vitrification of 3D Confined Glassy Polymers Through Refractory Thermoplasmonics

et al. 2021

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Advances in plasmonics have been fundamentally rooted in minimizing ohmic losses in metallic nanostructures. However, the losses at resonance can play a positive role; for instance, in optical heating, there are two sides to every story. Under laser illumination, plasmonic nanostructures serve not only as near-field enhancers but heat generators. The emerging field of thermoplasmonics opens up unprecedented possibilities to probe temperature-dependent phase transitions locally. In this paper, we develop a new approach behind plasmon-assisted optical heating for spectroscopically recognizing the glass transition temperature (T g) of spatially confined poly(methyl methacrylate) (PMMA) polymers deposited on a square-shaped titanium nitride (TiN) pad. A local photoheating is controlled through Raman thermometry of a c-Si (100) substrate that functions as a temperature-sensing Raman reporter. The reliability of temperature measurements is corroborated by using both the anti-Stokes/Stokes ratio and the Raman peak shift. We show that optical heating can be adjusted by extruding a c-Si substrate, for example, the temperature increase is achieved by making c-Si pillars beneath the TiN pads longer. This peculiarity gives the possibility to probe the T g in a broad temperature range for the diversity of glassy polymers. We believe that the developed method will pave the way for 2D mapping structural glass transitions of heterogeneous glassy polymers, polymeric blends, and eventually, 3D confined polymers.

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Section: Methodsmentioning

confidence: 99%

Nanoscale Sensing Vitrification of 3D Confined Glassy Polymers Through Refractory Thermoplasmonics

et al. 2021

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“…Thin polymer films were created by centrifugation by applying 0.2 μl of the polymer on the thermoplasmonic metasurface. The film thickness was determined using a multi-mode scanning probe microscope (NT-MDT) PRIMA in the lithography mode [12].…”

Section: Methodsmentioning

confidence: 99%

Nanoscale Sensing Glass Transition of Nanoconfined Polymers Through Thermoplasmonic

Chernykh

Kharintsev

2023

J. Phys.: Conf. Ser.

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It is known that downsizing of polymers at the nanoscale causes their physical properties, such as glass formation temperature, to deviate from the corresponding bulk properties. This fact requires the control of such parameters, since today nanoscale polymers are part of the architecture of many devices and are becoming increasingly important in modern technologies. To register temperature parameters in nanosized materials, localized heat sources are required. These can be metal nanostructures that generate heat on a nanoscale under the action of light. Enhanced absorption under conditions of plasmon resonance makes it possible to induce heat at the nanoscale and, therefore, as a result, plasmonic nanostructures can act as nano-heaters. We propose an approach to create enhanced heating of plasmonic nanostructures by nanostructuring the substrate surface (thermostat), which is demonstrated on titanium/silicon nitride (TiN:Si) hybrid structures using Raman thermometry. Using this approach, we detect the local glass transition temperature in nanosized polymers (PMMA and PMMA-DR1) by heating it with a thermoplasmonic metasurface using Raman spectroscopy.

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“…The thickness of the DR1-PMMA film was determined by starching its surface with a multimode scanning probe microscope Prima (NT-MDT), as reported in ref ( 35 ). The depth of lithographically fabricated grooves on the DR1:PMMA film was controlled by the set point driven applied force of the c-AFM cantilever.…”

Section: Methodsmentioning

confidence: 99%

Nanoscale Melting of 3D Confined Azopolymers through Tunable Thermoplasmonics

Kharintsev

Kazarian

2022

J. Phys. Chem. Lett.

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Phase transitions that are thermally induced by using light at the nanoscale play a vital role in material science. Enhanced optical heating sustained by resonant nanostructures can turn out to be insignificant when a higher thermal conductivity of a heatsink, regardless of the pumping intensity. In this Letter, we demonstrate an approach to control an operating temperature range due to excess heating of a structured heatsink. A design rationale has been performed by using a 2D array of TiN:Si voxels, consisting of stacked TiN and Si pillars. All the TiN nanoheaters responsible for enhanced light absorption at plasmon resonance are of equal size, and the height of the Si pillars varies to control heat localization. A height-dependent temperature rise of the Si pillars is found from Raman thermometry. Herein, for the first time, we have determined the melting temperature of azobenzene-functionalized polymers at the nanoscale using the tunable plasmonic metasurface.

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Determination of the Glass Transition Temperature of Freestanding and Supported Azo-Polymer Thin Films by Thermal Assisted Atomic Force Microscopy

Cited by 5 publications

References 19 publications

Nanoscale Sensing Vitrification of 3D Confined Glassy Polymers Through Refractory Thermoplasmonics

Nanoscale Sensing Vitrification of 3D Confined Glassy Polymers Through Refractory Thermoplasmonics

Nanoscale Sensing Glass Transition of Nanoconfined Polymers Through Thermoplasmonic

Nanoscale Melting of 3D Confined Azopolymers through Tunable Thermoplasmonics

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