Preparation of Polymer Thin Films by Physical Vapor Deposition

Usui, Hiroaki

doi:10.1002/9783527638482.ch9

Cited by 16 publications

(18 citation statements)

References 67 publications

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“…While there are many examples of reported ultrastable organic glasses made out from small molecules, the production of ultrastable polymers from the vapor is far more problematic. Because of the strong intermolecular forces between polymer chains, the polymer can thermally degrade rather than vaporize, manifested in some cases as a reduction of molecular weight or decomposition of some components [69]. Despite this difficulty, there are a few works reporting on the production of ultrastable polymer glasses from the vapor-phase, though most of them cannot be considered exactly equivalent to the physical vapor deposition, PVD, of molecular glasses.…”

Section: Polymer Glassesmentioning

confidence: 99%

Ultrastable glasses: new perspectives for an old problem

et al. 2022

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Ultrastable glasses (mostly prepared from the vapor phase under optimized deposition conditions) represent a unique class of materials with low enthalpies and high kinetic stabilities. These highly stable and dense glasses show unique physicochemical properties, such as high thermal stability, improved mechanical properties or anomalous transitions into the supercooled liquid, offering unprecedented opportunities to understand many aspects of the glassy state. Their improved properties with respect to liquid-cooled glasses also open new prospects to their use in applications where liquid-cooled glasses failed or where not considered as usable materials. In this review article we summarize the state of the art of vapor-deposited (and other) ultrastable glasses with a focus on the mechanism of equilibration, the transformation to the liquid state and the low temperature properties. The review contains information on organic, metallic, polymeric and chalcogenide glasses and an updated list with relevant properties of all materials known today to form a stable glass.

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Section: Polymer Glassesmentioning

confidence: 99%

Ultrastable glasses: new perspectives for an old problem

et al. 2022

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“…First, it is difficult to deposit blended films of polymers having different solubility characteristics, and second, the deposition of multilayer films with polymers having similar solubility characteristics is not possible without intermediate blocking layers. 7 One method to address such limitations is to deposit the polymer films using vacuum-based physical vapor deposition (PVD) techniques, 8,9 by which different polymers could be deposited onto substrates from separate sources and in a relatively dry state. In fact, thermal evaporation is a PVD technique that has shown great potential for organic material deposition and has been widely applied to deposit small organic molecules for organic light-emitting diodes (OLEDs).…”

Section: Introductionmentioning

confidence: 99%

Emulsion-Based RIR-MAPLE Deposition of Conjugated Polymers: Primary Solvent Effect and Its Implications on Organic Solar Cell Performance

McCormick

et al. 2016

ACS Appl. Mater. Interfaces

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Emulsion-based, resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) has been demonstrated as an alternative technique to deposit conjugated polymer films for photovoltaic applications; yet, a fundamental understanding of how the emulsion target characteristics translate into film properties and solar cell performance is unclear. Such understanding is crucial to enable the rational improvement of organic solar cell (OSC) efficiency and to realize the expected advantages of emulsionbased RIR-MAPLE for OSC fabrication. In this paper, the effect of the primary solvent used in the emulsion target is studied, both experimentally and theoretically, and it is found to determine the conjugated polymer cluster size in the emulsion as well as surface roughness and internal morphology of resulting polymer films. By using a primary solvent with low solubility-in-water and low vapor pressure, the surface roughness of deposited P3HT and PCPDTBT polymer films was reduced to 10 nm, and the efficiency of P3HT:PC 61 BM OSCs was increased to 3.2% (∼100 times higher compared to the first MAPLE OSC demonstration [Caricato, A. P.; et al. Appl. Phys. Lett. 2012, 100, 073306]). This work unveils the mechanism of polymer film formation using emulsion-based RIR-MAPLE and provides insight and direction to determine the best ways to take advantage of the emulsion target approach to control film properties for different applications.

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“…One of the challenging problems in producing polymeric films by VPD is the chain pyrolysis into shorter fragments. , Because of the strong intermolecular forces between polymer chains, the polymer chains can thermally degrade rather than vaporize. , Several studies ,, have reported that there is a molecular weight reduction of VPD polymer films caused by thermal degradation during the vapor deposition process. Although, amorphous Teflon is known to have weak molecular interactions and a low dielectric constant, ,, it is possible that the materials may degrade to some extent during the deposition process. To examine this possibility, we performed intrinsic viscosity measurements to estimate the molecular weight of our VPD Teflon by changing the value of [η] for the VPD and virgin materials.…”

Section: Results and Discussionmentioning

confidence: 99%

An Ultrastable Polymeric Glass: Amorphous Fluoropolymer with Extreme Fictive Temperature Reduction by Vacuum Pyrolysis

et al. 2017

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Vacuum pyrolysis deposition (VPD) has been used to create an ultrastable polymer glass having a fictive temperature T f of as much as 57 K below the nominal glass transition temperature of the thermally rejuvenated polymer. Amorphous fluoropolymer films 300 to 700 nm thick were created by VPD followed by characterization of the thermal response using rapid-scanning chip calorimetry. The deposition was performed for substrates held at temperatures from 30.0 °C (303.2 K) to 116.7 °C (389.9 K) corresponding to approximately 0.75 to 0.97 times the limiting fictive temperature T f ′ ≈ T g of the same material determined by cooling then heating at 600 K/s. Consistent with literature observations for small molecules that are vapor deposited in similar conditions relative to the material T g, large enthalpy overshoots are observed, typical of both highly aged and ultrastable glasses. The 57 K reduction in T f for the VPD polymers is greater than prior reports for physical vapor deposition of small molecules to form ultrastable glasses as well as greater than the T f reductions seen in ambers from 20 million to over 200 million years of age. The potential of using such materials to investigate systems extremely deep into the glassy condition is discussed.

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Preparation of Polymer Thin Films by Physical Vapor Deposition

Cited by 16 publications

References 67 publications

Ultrastable glasses: new perspectives for an old problem

Ultrastable glasses: new perspectives for an old problem

Emulsion-Based RIR-MAPLE Deposition of Conjugated Polymers: Primary Solvent Effect and Its Implications on Organic Solar Cell Performance

An Ultrastable Polymeric Glass: Amorphous Fluoropolymer with Extreme Fictive Temperature Reduction by Vacuum Pyrolysis

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