Group Contribution to Molar Refraction and Refractive Index of Conjugated Polymers.

Yang, Chen-Jen; Jenekhe, Samson A.

doi:10.21236/ada314812

Cited by 10 publications

(11 citation statements)

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“…[8][9][10]20 In this study, to achieve cross-linked thin films with high RI from sCVD, DVB was chosen as a comonomer because aromatic groups are characterized by high molar refractions and relatively compact molar volumes. 21 Furthermore, theoretical functionality (f) of DVB in the copolymerization with elemental sulfur is 6, because in addition to the two olefins, the benzylic radicals, formed from the abstraction of benzylic hydrogen atoms from DVB units by electrophilic sulfur radicals, can further react with sulfur to form C−S bonds. 22 Such a high accessible functionality value means that the DVB monomer can accommodate large amount of sulfur, which is desirable for SCPs with high sulfur content.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Transparent, Ultrahigh-Refractive Index Polymer Film (n ∼1.97) with Minimal Birefringence (Δn <0.0010)

Jang

Choi

et al. 2021

ACS Appl. Mater. Interfaces

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High refractive index (RI) thin films are of critical importance for advanced optical devices, and the high refractive index polymers (HRIPs) constitute an interesting class of materials for high RI thin films due to low cost, good processability, light weight, and high flexibility. However, HRIPs have yet to realize their full potential in high RI thin film applications due to their relatively low RI, strong absorption in the blue light region, and limited film formation methods such as rapid vitrification. Herein, we report a development of a new HRIP thin film generated through a one-step vapor-phase process, termed sulfur chemical vapor deposition (sCVD), using elemental sulfur and divinyl benzene. The developed poly(sulfur-co-divinyl benzene) (pSDVB-sCVD) film exhibited RI (measured at 632.8 nm) exceeding 1.97, one of the highest RIs among polymers without metallic elements reported to date. Because the sCVD utilized vaporized sulfur with a unique sulfur-cracking step, formation of long polysulfide chains was suppressed efficiently, while high sulfur content as high as 85 wt % could be achieved with no apparent phase separation. Unlike most of inorganic high RI materials, pSDVB-sCVD was highly transparent in the entire visible range and showed extremely low birefringence of 10 × 10–4. The HRIP thin film with unprecedentedly high RI, together with outstanding transparency and low birefringence, will serve as a key component in a wide range of high-end optical device applications.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Transparent, Ultrahigh-Refractive Index Polymer Film (n ∼1.97) with Minimal Birefringence (Δn <0.0010)

Jang

Choi

et al. 2021

ACS Appl. Mater. Interfaces

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“…For accurate predictions of the refractive index of hypothetical bulk polymers, calculations are typically made using the molar refractivity of specific functional groups (e.g., methylene, aromatic, and thioether), for which extensive tables exist. 24 The molar refractivity values of these functional groups are summed to generate the repeat unit of the polymer from which the refractive index of the bulk polymer can be estimated 24,26…”

Section: ■ Results and Discussionmentioning

confidence: 99%

High Refractive Index Polymers (n > 1.7), Based on Thiol–Ene Cross-Linking of Polarizable P═S and P═Se Organic/Inorganic Monomers

Filho

Peek

et al. 2019

Macromolecules

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A new class of high refractive index polymers was developed through the thiol−ene coupling reaction of trivinylphosphine chalcogenides, [(CH 2 CH−)3PX (X = S, Se)], with 1,2-ethane dithiol and 1,3-benzene dithiol. The polymers were obtained through a thermal initiation and polymerization process which yielded robust monolithic materials. The polymers have good transmission properties in the visible region of the spectrum with very high refractive indices ranging from 1.66 to 1.75, placing them in the top echelon of high refractive index polymers, with Abbe numbers between 22 and 31. The high refractive index is due, in large part, to the presence of the highly polarizable PS and PSe groups, which have molar refractivities of 13.84 and 17.33 mol/cm 3 , respectively. The polymers tend to have a high cross-link density that varies with the composition but results in rigid materials for most compositions. The glass-transition temperatures (T g ) for all but one composition were above 70 °C, and the storage moduli ranged from 1.5 to 3.8 GPa. The 1,2-ethane dithiol compositions had lower values of T g than the 1,3-benzene dithiol materials. This was attributed to a lower cross-link density in the 1,2-ethane dithiol polymers, as determined from the residual unreacted vinyl groups measured by Raman spectroscopy and 31 P solid-state nuclear magnetic resonance spectroscopy. The PSe polymers were slower to react and required higher temperatures; they also produced the hardest materials with the highest refractive indices.

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“…[38][39] The values of the refractive index n were found systematically lower for the developed thin films (n = 1.61 at 650 nm for instance) compared to those determined before development (n = 1.80 at 650 nm) (see ESI - Figure S5a). 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 15 the fact that photopolymerized layers loose compactness and gain free volume after development.…”

Section: Impact Of Photocrosslinking On the Density And Emission Propmentioning

confidence: 88%

All-Solution-Processed Organic Light-Emitting Diodes Based on Photostable Photo-cross-linkable Fluorescent Small Molecules

Derue

Olivier

Tondelier

et al. 2016

ACS Appl. Mater. Interfaces

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We demonstrate herein the fabrication of small molecule-based OLEDs where four organic layers from the hole- to the electron-transporting layers have successively been deposited by using an all-solution process. The key feature of the device relies on a novel photopolymerizable red-emitting material, made of small fluorophores substituted with two acrylate units, and displaying high-quality film-forming properties as well as high emission quantum yield as nondoped thin films. Insoluble emissive layers were obtained upon UV irradiation using low illumination doses, with no further need of postcuring. Very low photodegradation was noticed, giving rise to bright layers with a remarkable surface quality, characterized by a mean RMS roughness as low as 0.7 nm after development. Comparative experiments between solution-processed OLEDs and vacuum-processed OLEDs made of fluorophores with close architectures show external quantum efficiencies in the same range while displaying distinct behaviors in terms of current and power efficiencies. They validate the proof of concept of nondoped solution-processable emissive layers exclusively made of photopolymerized fluorophores, thereby reducing the amount of components and opening the way toward cost-effective fabrication of solution-processed OLED multilayer architectures.

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Group Contribution to Molar Refraction and Refractive Index of Conjugated Polymers.

Cited by 10 publications

References 0 publications

Transparent, Ultrahigh-Refractive Index Polymer Film (n ∼1.97) with Minimal Birefringence (Δn <0.0010)

Transparent, Ultrahigh-Refractive Index Polymer Film (n ∼1.97) with Minimal Birefringence (Δn <0.0010)

High Refractive Index Polymers (n > 1.7), Based on Thiol–Ene Cross-Linking of Polarizable P═S and P═Se Organic/Inorganic Monomers

All-Solution-Processed Organic Light-Emitting Diodes Based on Photostable Photo-cross-linkable Fluorescent Small Molecules

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