Large Photoinduced Refractive Index Change of Polymer Films Containing and Bearing Norbornadiene Groups and Its Application to Submicron-Scale Refractive-Index Patterning

Kato, Yuichi; Muta, Hirokazu; Takahashi, Satoshi; Horie, Kazuyuki; Nagai, Takabumi

doi:10.1295/polymj.33.868

Cited by 28 publications

(21 citation statements)

References 27 publications

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“…Horie and Nishikubo 18 experimentally confirmed a marked refractive-index change upon photo-irradiation of poly(methyl methacrylate) containing 2-phenyl-2,5-norbornadiene moieties; the value of the refractive index change (Án D ) was about 0.01. Furthermore, Horie et al 19 reported large Án D 's (0.05-0.06) of films of poly(methyl methacrylate) doped with NBD derivatives and poly(vinyl ether)s bearing NBD moieties. They also found that poly(vinyl cinnamate) showed a large Án D (0.037) upon photodimerization.…”

Section: Calixarene Derivatives As Refractive-index-changing Materialsmentioning

confidence: 99%

Development of Novel Photo-Functional Materials Based on Cyclic Oligomers

Kudo

Nishikubo

2009

Polym. J.

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Novel photo-functional materials, such as refractive-index-changing materials, argon fluoride (ArF) resist materials, and electron beam (EB) resist materials, were designed based on the structures of calixarenes, cyclodextrin, and noria. The synthesis and refractive-index properties of calixarene derivatives containing photo-reactive groups, including azobenzene, norbornadiene, anthracene, cinnamate, and chalcone, were examined, and refractive-index changes (Án D 's) of between 0.007 and 0.061 were observed. The synthesis and patterning properties of a single-layer ArF photoresist system of -CD derivative containing t-butyl ester and fluorine were examined, and a well-resolved 100 nm line and space pattern was obtained on a silicon wafer. A new ladder-like macrocycle, noria (water wheel in Latin), was also synthesized and its application as an EB resist material was examined. The noria derivatives noria-COO t Bu containing t-butyl ester groups, noria-BOC containing t-butyloxycarbonyl group, and noria-acetal containing acetal groups had good physical properties and photo-reactivity. EBresist based on noria-COO t Bu and noria-BOC provided clear line and space patterns at a resolution of 70 and 50 nm, respectively.The development of novel photo-functional materials has contributed substantially to progress in the electronic and optoelectronic industries. Photo-reactive groups, such as radical-or cation-polymerizable groups, photo-isomerizable groups, and photo-removable groups, are useful for obtaining ultraviolet (UV)-cured resins, refractive-index-changing materials, and photo-resist materials, respectively. The physical properties of photo-functional materials, such as film-forming characteristics, thermal stability, mechanical properties, and photo-reactivity, depend primarily on the polymer or oligomer structure. Generally, the photochemical reactivity increases with decreasing glass transition temperature (T g ), due to increase of the molecular motion of polymer chains and functional groups.The photo-chemical reactivity of oligomers is usually greater than that of polymers, due to the lower T g of oligomers compared with polymers. However, the mechanical properties, thermal stability and film-forming properties of oligomer derivatives are inferior to those of polymer derivatives. However, if a linear oligomer is changed to a cyclic oligomer by coupling reaction of the two ends, the physical properties of the resulting cyclic oligomer are expected to be superior to those of the linear oligomer. Therefore, we considered that photofunctional cyclic oligomers might combine the advantages of photo-functional polymers and photo-functional oligomers. That is, photo-functional cyclic oligomers might have both high photo-chemical reactivity and good physical properties.Calixarenes are typical cyclic oligomers containing many hydroxyl groups, and are prepared easily by the reaction of phenols with aldehydes (Scheme 1). 1Although it is well known that calixarenes are attractive materials for use as host molecules in th...

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Section: Calixarene Derivatives As Refractive-index-changing Materialsmentioning

confidence: 99%

Development of Novel Photo-Functional Materials Based on Cyclic Oligomers

Kudo

Nishikubo

2009

Polym. J.

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“…Since nonctivated alkynes are poor dienophiles in DielsAlder cycloadditions, [10] the variety of 2,3-disubstituted norbornadienes which could be synthesized using the Diels-Alder method is rather limited (they usually contain at least one electronic withdrawing group such as an ester, an amide or a cyano group etc). We have recently reported the synthesis of a variety of 2,3-disubstituted norbornadienes by a double lithium-halide exchange of 2,3-dibromonorbor-In our case, we found that among various phosphane ligands tested, only tBu 3 P provided good yields in the coupling reactions between 2,3-dibromonorbornadiene 2 and 4-ethylphenylboronic acid 8b (entries [1][2][3][4][5][6][7][8]. In the presence of [Pd 2 (dba) 3 ] (0.5 mol%), a monodentate phosphane (1.4 mol%; Ph 3 P, Cy 3 P, nBu 3 P, (2-furyl) 3 P or TTMPP, entries 1-4, 6) or phosphite (1.4 mol%, entry 5) or a bidentate phosphane (entry 7) and CsF (6.6 equiv.)…”

Section: Introductionmentioning

confidence: 99%

“…[4,5] Extensive investigations of 2,3-disubstituted norbornadienes/quadricyclanes for solar energy storage have demonstrated the efficiency and switching potential of these reversible systems. [6] This photochemical isomerization reaction has recently been investigated as an optical waveguide utilising photoinduced refractive index changes, [7] as a photochromic system potentially applicable to data storage [8] or as light-driven, carrier-mediated, active transport across a membrane against a concentration gradient. [9] Syntheses of the 2,3-disubstituted norbornadienes used in the above studies rely mainly on the Diels-Alder reaction between cyclopentadiene and the corresponding alkyne.…”

Section: Introductionmentioning

confidence: 99%

Palladium‐Catalyzed Suzuki Couplings of 2,3‐Dibromonorbornadiene: Synthesis of Symmetrical and Unsymmetrical Aryl‐Substituted Norbornadienes

2005

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Palladium-catalyzed Suzuki coupling reactions between 2,3-dibromonorbornadiene and arylboronic acids were investigated. These reactions provide an efficient method for the synthesis of symmetrical 2,3-diarylnorbornadienes which are not accessible using the traditional Diels-Alder cycloaddition reactions. The optimized reaction conditions of the Suzuki coupling reactions were found using [Pd 2 (dba) 3 ] (0.5 mol%), tBu 3 P (1.4 mol%) and CsF in THF. High yields of the Suzuki coupling products were obtained when electron-rich aryl-

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“…[1][2][3] Recently, much attention has been devoted to the photochemical control of refractive indices for polymer films, owing to their potential in optical network technology. 3 Although there are extensive studies directed toward a photoinduced decrease in refractive indices for polymer films, [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] only a few attempts have been made to enhance the refractive index through photochemical transformations. 12,[20][21][22][23][24][25] For example, Langer et al 21 reported that irradiation of a polymerbearing thiocyanate pendants enhanced the refractive index (n) of the polymer by 0.031.…”

Section: Introductionmentioning

confidence: 99%

Effects of aryl substituents in N-acetyl-α-dehydroarylalanine naphthyl ester additive on the photoinduced refractive index change of poly(methyl methacrylate) film

Nakajima

Komatsu

Iikura

et al. 2010

Polym J

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Aryl substituent effects on photoinduced refractive index changes were investigated with the use of poly(methyl methacrylate) (PMMA) films doped with (Z)-N-acetyl-a-dehydroarylalanine naphthyl esters ((Z)-1). Upon irradiation with Pyrex-filtered or unfiltered light from a high-pressure mercury lamp, (Z)-1 underwent heterolytic cleavage of the ester C(¼O)-O bond preferentially in both solution and PMMA film to afford arylmethylene-substituted (Z) oxazolone and naphthol derivatives as major products, irrespective of the aryl substituents introduced. Irradiation of (Z)-1 in the film with the unfiltered light enabled much more rapid photochemical transformation into the oxazolones and the intense ultraviolet absorption shifted to longer wavelength relative to that of the starting naphthyl esters. Analysis of the aryl substituent effects confirmed that the PMMA/(Z)-1 system, in which 1-naphthylmethylene-substituted oxazolone was formed along with 1-naphthol, enhanced the refractive index of this polymer film by as much as 0.020.

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Large Photoinduced Refractive Index Change of Polymer Films Containing and Bearing Norbornadiene Groups and Its Application to Submicron-Scale Refractive-Index Patterning

Cited by 28 publications

References 27 publications

Development of Novel Photo-Functional Materials Based on Cyclic Oligomers

Development of Novel Photo-Functional Materials Based on Cyclic Oligomers

Palladium‐Catalyzed Suzuki Couplings of 2,3‐Dibromonorbornadiene: Synthesis of Symmetrical and Unsymmetrical Aryl‐Substituted Norbornadienes

Effects of aryl substituents in N-acetyl-α-dehydroarylalanine naphthyl ester additive on the photoinduced refractive index change of poly(methyl methacrylate) film

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