Disperse Red-labeled poly(methyl methacrylate) monolayer at interfaces studied by second-harmonic generation and surface potential

Kajikawa, Kotaro; Yamaguchi, Takashi; Anzai, Takeshi; Takezoe, Hideo; Fukuda, Atsuo; Okada, Shuji; Matsuda, Hiro; Nakanishi, Hachiro; Abe, Takashi; Itô, Hiroshi

doi:10.1021/la00047a030

Cited by 13 publications

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“…[48][49][50] When LB films are fabricated in the vertical dipping method, the resultant LB films have two consecutive layers with either head-to-head or tail-to-tail type structures, thereby creating a centrosymmetric structure. The formation of that structure can be avoided by alternate deposition 51 of the NLO active molecular layer with a passive spacer molecular layer.…”

Section: Second Harmonic Generation From Hybrid Polymer Nanoassembliesmentioning

confidence: 99%

Hybrid Polymer Nanoassemblies: Polymer Nanosheets Organized with Metal Nanoparticle Arrays for Surface Plasmon Photonics

Mitsuishi

Ishifuji

Endô

et al. 2007

Polym J

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ABSTRACT:The paper describes fabrication of hybrid polymer nanoassemblies possessing polymer nanosheets and metal nanoparticle arrays. Based on a bottom-up approach with ultrathin polymer Langmuir-Blodgett films (polymer nanosheets) and metal nanoparticles, we constructed hybrid nanoassemblies for opto/electric nanodevice applications: nanoscale positioning of metal nanoparticles, free-standing hybrid polymer nanosheets, hybrid polymer nanoassemblies for luminescence sensor application, and enhancement of nonlinear optical (NLO) efficiency via surface plasmon coupling. Assembling nanomaterials such as nanoparticles and organic functional molecules through a bottom-up approach makes it possible to strengthen free-standing nanofilm stability, enhance luminescence of luminescent molecules, and enhance second harmonic light from NLO molecules under the influence of localized surface plasmons. The high potential of hybrid polymer nanoassemblies for precise nanoscale design is also demonstrated.[doi:10.1295/polymj.PJ2006235] KEY WORDS Polymer / LB Film / Metal Nanoparticle / Surface Plasmon / Hybrid / Design of nanostructures using polymer materials has been widely explored and has now become prevalent. Bottom-up approaches such as layer-by-layer (LbL) adsorption, 1 surface-initiated polymerization exemplified by atom transfer radical polymerization (ATRP), 2 and Langmuir-Blodgett (LB) technique [3][4][5][6][7] make it possible to develop myriad nanoarchitectures on solid substrates. These approaches and their combinations offer a promising route to polymer nanoarchitectures for a wide variety of functional materials and surfaces. Using these nanostructures, for instance, the surface properties can be controlled uniformly, even on a nanoscale. These compelling qualities of ultrathin polymer films have been expanded to broad scientific fields. It is important to intensify the interdisciplinary interactions, for example, between polymer materials and inorganic nanoparticles in basic and application-oriented work.We have investigated functionalization of polymer LB films consisting of poly(alkylacrylamide)s. Poly-(N-dodecylacrylamide) (pDDA) proved to be excellent for LB assembly; the material provides a highly oriented and densely packed monolayer at the airwater interface. 8,9 Varying the side chain length, the film thickness is tuned at a nanometer scale (1-2 nm in length). Widely various functional molecules were incorporated and distributed uniformly in a two-dimensional (2D) field. The key factor is the existence of a 2D hydrogen-bonding network between polymer backbones, which enhances the monolayer stability at the air-water interface, leading to quantitative deposition onto solid substrates via vertical dipping. We recently designated polymer LB films consisting of alkyl acrylamide polymer as polymer nanosheets. Using these advantages, directional (vectorial) electron transfer between several redox components was achieved in multilayered polymer nanosheets, 10,11 extending to logic gate operations.12, 13 We have...

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Section: Second Harmonic Generation From Hybrid Polymer Nanoassembliesmentioning

confidence: 99%

Hybrid Polymer Nanoassemblies: Polymer Nanosheets Organized with Metal Nanoparticle Arrays for Surface Plasmon Photonics

Mitsuishi

Ishifuji

Endô

et al. 2007

Polym J

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“…The average orientation is usually determined by assuming a very sharp ͑␦-functional͒ distribution. 4,[15][16][17][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38] In this article, we propose a novel method to unambiguously determine the orientational distribution function ͑ODF͒ of molecules at interfaces with C ϱv symmetry. In order to apply this method to films with a finite thickness, we consider the system as five layers, i.e., air, an SHG-active layer at a polymer-air interface, a bulk SHG-inactive layer, an SHG-active layer at a polymer-substrate interface and a substrate.…”

Section: Determination Of Molecular Orientational Distribution Using mentioning

confidence: 99%

Determination of molecular orientational distribution using surface second-harmonic generation analyzed by five-layer model and maximum-entropy method

Yoo

Hoshi

Sakai

et al. 1998

Journal of Applied Physics

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Articles you may be interested inQuantitative analysis of orientational order in the molecular monolayer by surface second harmonic generation Liquid-crystal alignment on polytetrafluoroethylene and high-density polyethylene thin films studied by optical second-harmonic generation Mapping of the lateral polar orientational distribution in second-order nonlinear thin films by scanning secondharmonic microscopy Appl. Phys. Lett. 72, 275 (1998); 10.1063/1.120711Surface second-harmonic generation from two interfaces of polyimide film coated on a substrate A novel analytical method to determine molecular orientational distribution functions ͑ODFs͒ at interfaces has been developed to apply to polymer film possessing second-harmonic generation ͑SHG͒ active side chains with C ϱv symmetry. This method treats SHG in five layers, i.e., air, an upper SHG-active layer, an SHG-inactive polymer bulk, a lower SHG-active layer and a substrate ͑five-layer model͒. We first obtain tentative ODFs of the side chains at two SHG-active layers by the assumption of two undetermined multipliers in the maximum-entropy method. These ODFs give the order parameters of the side chains and in turn the dielectric constants of the SHG-active layers. Achieving the best fit of the theoretical SHG intensity to the experimental results obtained in four different geometries, we succeeded in obtaining unbiased ODFs together with the dielectric constants of the SHG-active layers.

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“…Generally, structure of monomeric LB film does not exhibit higher mechanical and thermal stabilities, thereby degrading NLO properties. Meanwhile, this defect is expected to be improved if the noncentrosymmetric film is prepared by using an amphiphilic NLO polymer functionalized with azo-dye chromophores [4][5][6][7].…”

Section: Introductionmentioning

confidence: 99%

“…Here, I3xxx can be used that of DR-1 azo-dye (1.2 x 10'28esu [6]). N is 2.95 x 10"20mol By using eq.…”

Section: Introductionmentioning

confidence: 99%

Preparation of Langmuir-Blodgett Films of Methacrylate Copolymer Bearing Azo-dye Chromophores and Their Nonlinear Optical Properties.

Kato

Ohono

Ishii

et al. 1996

J. Photopol. Sci. Technol.

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A methacrylate copolymer, poly(MO), was prepared from radical copolymerization of octadecyl methacrylate and methacrylamide bearing DR-1 type azo-dye chromophore as NLO active group, which was synthesized through 7 reaction steps. Poly(MO) gave LB film on quartz substrate by the vertical dipping method. Transfer of the monolayer at the water-air interface was easier in upstroke than in down stroke. By SHG measurement for the multilayers it was found that only in the first monolayer exists an effective noncentrosymmetric structure of NLO chromophores, showing SHG. Unexpectedly, when a heat treatment was performed SH intensity of the monolayer decreased, whereas that of the multilayers increased significantly. More detailed investigations about this heat response behavior were carried out.

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Disperse Red-labeled poly(methyl methacrylate) monolayer at interfaces studied by second-harmonic generation and surface potential

Cited by 13 publications

References 0 publications

Hybrid Polymer Nanoassemblies: Polymer Nanosheets Organized with Metal Nanoparticle Arrays for Surface Plasmon Photonics

Hybrid Polymer Nanoassemblies: Polymer Nanosheets Organized with Metal Nanoparticle Arrays for Surface Plasmon Photonics

Determination of molecular orientational distribution using surface second-harmonic generation analyzed by five-layer model and maximum-entropy method

Preparation of Langmuir-Blodgett Films of Methacrylate Copolymer Bearing Azo-dye Chromophores and Their Nonlinear Optical Properties.

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