• Bulletin of the Korean Chemical Society
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• 제19권11호
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• pp.1168-1171
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• 1998

Two kinds of second-order nonlinear optical copolymers were prepared by the copolymerization of the vinyl monomers containing NLO chromophore, methacrylic acid, and methyl methacrylate or butyl methacrylate. Glass transition temperatures (Tg of copolymers were around 130 ℃. The copolymers were soluble in common organic solvents such as tetrahydrofuran (THF), cyclohexanone, and N,N-dimethylformamide (DMF). The crosslinked copolymer was obtained by thermal treatment using pentaerythritol tetrakis(2-mercaptoacetate) as a crosslinker and became insoluble in tetrahydrofuran (THF) and N,N-dimethylformamide (DMF). Poling was carried out at 120 ℃ for 20 min and identified with UV-Vis spectroscopy. Electro-optic coefficient (r33) measurement showed a value of 35 pm/V for polymer 2 at 633 nm. Temporal stability of copolymers was improved owing to the crosslinked network, which was successfully obtained at 170 ℃ for 30 min after poling.

• Bulletin of the Korean Chemical Society
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• 제26권1호
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• pp.77-84
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• 2005

We prepared the new nonlinear optical chromophores that show fairly high microscopic nonlinearity through intramolecular charge transfer. Phenothiazine and carbazole units played an important role to contribute high electron donability and connect the resonance pathway via conjugative effect in the cyclized ring beside the aromatic ring. Theoretical calculation, electrochemical analysis, and absorption spectroscopic study gave us useful information about the energy states and microscopic nonlinearities of two serial chromophores. We compared the microscopic nonlinearities of four chromophores with the conjugation length and electron donability in the push-pull type NLO chromophores. The effect of gradient donability and lengthening the conjugation were investigated on the electronic state and microscopic nonlinearity.

• Journal of Photoscience
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• 제10권3호
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• pp.251-255
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• 2003

The composites fabricated by blending nonlinear optical (NLO) chromophore such as {4-[2-(4-nitrophenyl)-vinyl] phenyl}diphenylamine (NVPDA) with photoconducting crosslinkable matrix, bis-(4-ethynylphenyl)-(4-octyloxy-phenyl)amine (BEOPEA), showed photorefractive property. Many problems faced in typical organic photorefractive systems such as time-consuming chemical synthesis, difficulty in rational design, intrinsic instability and phase separation could be avoided by this fabrication method.

• 공업화학
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• 제9권5호
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• pp.704-709
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• 1998

${\alpha}$-Methyl styrene과 maleic anhydride를 공단량체로 사용하여 유리전이온도가 높고 내열성이 우수한 poly (${\alpha}$-methylstyrene-co-maleic anhydride) (MSMA) 기재 고분자 (substrate polymer)를 합성하고 여기에 니트로기를 가진 발색단을 고분자반응을 이용하여 도입하는 반응 및 생성된 비선형 광학 고분자의 전기 광학 특성에 대해 조사하였다. MSMA 기재 고분자에 hydroxyl기를 가지는 azo계 발색단 (chromophore) 2-[4-(4-nitrophenylazo)-N-ethylphenylamino]ethanol (DR1)을 고분자 반응 (polymer reaction)으로 maleic anhydride에 ester 결합으로 도입할 때 4-dimethylaminopyridine (DMAP) 촉매만을 쓴 것 (MSMA-D)보다 DMAP와 3-dicyclohexyl carbodiimid (DCC)를 동시에 사용한 경우 (MSMA-DC)가 DR1 발색단의 도입율이 높게 나타났다. 비선형 광학 고분자 (MSMA-DC)의 전기광학계수 ($r_{33}$)는 파장이 632.8 nm인 광원에서 18 pm/V의 값을 나타냈으며 열적 안정성도 유리전이 온도 ($T_g$)가 $175^{\circ}C$ 이상으로 우수하게 나타났다.

• 전기학회논문지P
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• 제51권3호
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• pp.142-148
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• 2002

Considerable progress has been made in organic photorefractive materials, since the first observation of photorefractive phenomena from organic materials. Within recent years, a large number of organic photorefractive materials, especially amorphous materials, have been developed based on polymeric composites, fully functional polymers and the multi-functional chromophore approach. Among these organic photorefractive materials, some of them containing carbazole components as a charge transporting function have been demonstrated to exhibit high performance photorefractive effects. The carbazole building blocks with charge transporting function or multifunctions play a very important role in photorefraction. In this paper, it confirmed that acceptor-substituted carbazoles show the multifunctionality both of photoconductivity and electro-optic(EO) activity and photorefractive materials newly can be developed with acceptor-substituted carbazoles.

• Bulletin of the Korean Chemical Society
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• 제23권4호
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• pp.571-574
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• 2002

The photorefractive polymeric composite with good performance was prepared. The carbazole-substituted polysiloxane sensitized by 2,4,7-trinitro-9-fluorenone was used as a photoconducting medium and 1-[4-(2-nitrovinyl)phenyl]piperidine was added as an optically nonlinear chromophore. The photorefractive property of polymer was determined by diffraction efficiency using a 100 ㎛-thick film. The maximum diffraction efficiency ( ηmax) of 71% was obtained at the electric field of 70 V/ ㎛. The potential of the current polymer material as a holographic recording medium was evaluated by the demonstration of holographic recording and subsequent reading of optical image.

• Bulletin of the Korean Chemical Society
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• 제20권5호
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• pp.567-572
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• 1999

5-Nitro-2-(2'-vinyloxyethoxy)benzylidenemalononitrile (2a), methyl 5-nitro-2-(2'-vinyloxyethoxy)benzylidenecyanoacetate (2b), 3-nitro-4-(2'-vinyloxyethoxy)benzylidenemalononitrile (4a), methyl 3-nitro-4-(2'-vinyloxyethoxy)benzylidenecyanoacetate (4b), 2-nitro-5-(2'-vinyloxyethoxy)benzylidenemalononitrile (6a), and methyl 2-nitro-5-(2'-vinyloxyetboxy)benzylidenecyanoacetate (6b) were prepared by the condensation of 5-nitro-2-(2'-vinyloxyethoxy)benzaldehyde (1), 3-nitro-4-(2'-vinyloxyethoxy)benzaldehyde (3), and 2-nitro-5-(2'-vinyloxyethoxy)benzaldehyde (5) with malononitrile or methyl cyanoacetate, respectively. Vinyl ether monomers 2a-b, 4a-b, and 6a-b were polymerized with boron trifluoride etherate as a cationic initiator to yield poly(vinyl ethers) 7-9 having oxynitrobenzylidenemalononitrile and oxynitrobenzylidenecyanoacetate, which is effective chromophore for second-order nonlinear optical applications. Polymers 7-9 were soluble in common organic solvents such as acetone and DMSO. Tg values of the resulting polymers were in the range of 67-83 ℃. Electrooptic coefficient (r33) of the poled polymer films were in the range of 15-27 pm/V at 633 nm. Polymers 7-9 showed a thermal stability up to 300 ℃ in TGA thermograms, which is acceptable for NLO device applications.

• Bulletin of the Korean Chemical Society
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• 제20권3호
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• pp.307-313
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• 1999

2,4-Di-(2'-vinyloxyethoxy)benzylidenemalononitrile (la), methyl 2,4-di-(2'-vinyloxyethoxy)benzylidenecyanoacetate (lb), 3,4-di-(2'-vinyloxyethoxy)benzylidene malononitrile (2a), methyl 3,4-di-(2'-vinyloxyethoxy)benzylidenecyanoacetate (2b), 2,5-di-(2'-vinyloxyethoxy)benzylidenemalononitrile (3a), methyl 2,5-di-(2'-vinyloxyethoxy)benzylidenecyanoacetate (3b), 2,3-di-(2'-vinyloxyethoxy)benzylidenemalononitrile (4a), and methyl 2,3-di-(2'-vinyloxyethoxy)benzylidenecyanoacetate (4b) were prepared by the condensation of 2,4-di-(2'-vinyloxyethoxy)benzaldehyde, 3,4-di-(2'-vinyloxyethoxy)benzaldehyde, 2,5-di-(2'-vinyloxyethoxy) benzaldehyde, and 2,3-di-(2'-vinyloxyethoxy)benzaldehyde with malononitrile or methyl cyanoacetate, respectively. Trifunctional divinyl ether monomers 1-4 were polymerized readily with boron trifluoride etherate as a cationic initiator to give optically transparent swelling poly(vinyl ethers) 5-8 havina oxybenzylidenemalononitrile and oxycyanocinnamate, which is presumably effective chromophore for second-order nonlinear optical applications. Polymers 5-8 were not soluble in common organic solvents such as acetone and DMSO due to crosslinking. Polymers 5-8 showed a thermal stability up to 300 ℃ in TGA thermograms, which is acceptable for electrooptic device applications.

• 한국광학회지
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• 제13권4호
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• pp.356-362
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• 2002

비선형광학(NLO) 곁가지형 고분자계 N-(4-nitrophenul)-(L)-prolinol-poly (p-phenylene terephthalates)로 제작된 박막의 분자 배향거동을 제2 고조파발생(SHG)의 비선형광응답을 사용하여 연구하였다. 새로운 펄스 corona 배향 방법으로 NLO 발색단과 고분자 줄기를 비중심대칭 구조로 배향시켜 SHG 신호를 발생시켰다. 유리전이온도 70$^{\circ}C$를 중심으로 25$^{\circ}C$에서 80$^{\circ}C$까지 온도영역에서 반복율을 0.5 ㎑에서 10 ㎑까지 변화시키면서 인가한 펄스 고압으로 corona 배향한 결과로 곁가지 발색단과 고분자 주사슬이 스스로 재 정렬하여 형성한 구역구조를 원자간력 현미경(AFM)으로 관측하였다. 펄스 corona 전압 인가로 NLO 발색단 배향도가 증가되고, 동시에 고분자박막의 가시적손상을 획기적으로 줄이면서 SHG 신호가 증대되었으며 배향 후 이완거동도 개선되었다. 이 새로운 펄스 corona 배향 실험으로 NLO 발색단 및 고분자 주사슬이 배향과정에서 비등방으로 재배열하는 현상을 in situ로 입증할 수 있었다.

• Macromolecular Research
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• 제11권4호
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• pp.250-255
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• 2003

We prepared the photorefractive sol-gel glass based on organic-inorganic hybrid materials containing a charge transporting molecule, second-order nonlinear optical (NLO) chromophore, photosensitizer, and plasticizer. Carbazole and 2-{ 4-[(2-hydroxy-ethyl)-methyl-amino]-benzylidene}-malononitrile were reacted with isocyanato-triethoxy silane and the functionalized silanes were employed to fabricate the efficient photorefractive media induding 2,4,7-trinitrot1uorenone (TNF) to form a charge transfer complex. The prepared sol-gel glass samples showed a large net gain coefficient and high diffraction efficiency at a certain composition. As the concentration of photosensitizer increased, the photorefractive properties were enhanced due to an increment of charge carrier density. Dynamic behavior of the diffraction efficiency was also investigated with the concentration of the photosensitizer.