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Process for mass producing uniform multi-layer non-linear optical polymer thin polar films

a technology of nonlinear optical polymer and thin polar film, which is applied in the field of multi-layer nonlinear optical polymer (nlop) film formation, can solve the problems of field poling, less well ordered chromophores, and high temperature of utilized hea

Inactive Publication Date: 2002-09-03
THE UNITED STATES OF AMERICA AS REPRESENTED BY THE SECRETARY OF THE NAVY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

Additionally, it is an object of the present invention to provide a process for producing NLOP film using a solution deposition scheme which results in an electro-optic (EO) film which is not required to undergo electric-field poling.

Problems solved by technology

There are several problems associated with electric-field poling.
First, the polymer utilized must be heated to high temperatures.
At these high temperatures thermal disordering of the chromophores works against the torque of the electric field resulting in the chromophores being less well ordered.
In addition, polymers containing formal mobile charges are very difficult to pole with an electric field because the charges tend to migrate through the polymer causing dielectric breakdown (i.e. shorting out the electrode).
Previous materials utilizing the LB methodology for the fabrication of waveguides (U.S. Pat. No. 5,162,453 issued Nov. 10, 1992 to Hall et al., U.S. Pat. No. 5,225,285 issued Jul. 6, 1993 to Hall et al., U.S. Pat. No. 4,830,952 issued May 16, 1989 to Penner et al, and U.S. Pat. No. 4,792,208 issued Dec. 20, 1988 to Ulman et al.) have suffered from thermal instability due to the presence of low melting alkyl and fluoroalkyl hydrophobic chains.
However, attaching sidechain chromophores to polyimides failed to provide stable multilayer NLOP films.
A limitation of LB technology is the amount of time required to build up films of sufficient thickness (>0.5 micrometers) for waveguiding.

Method used

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  • Process for mass producing uniform multi-layer non-linear optical polymer thin polar films
  • Process for mass producing uniform multi-layer non-linear optical polymer thin polar films
  • Process for mass producing uniform multi-layer non-linear optical polymer thin polar films

Examples

Experimental program
Comparison scheme
Effect test

example 1

APD of stilbazolium-substituted polyepichlorohydrin and polystyrenesulfonate bi-layers:

A process for depositing films was developed having alternating layers of the NLO-active polycation, stilbazolium-substituted polyepichlorohydrin, and the NLO-active polyanion, poly(sodium 4-styrenesulfonate). These layers were alternately deposited from aqueous solution to make thin polar films.

A. Preparation of stilbazolium-substituted polymer: Poly(epichlorohydrin) having 0.05 moles of chloromethyl groups and a molecular weight between 500 and 4000 g / mol, was dissolved in 0.15 to 0.50 moles of freshly distilled 4-picoline. The solution was degassed by stirring under reduced pressure, purged with nitrogen gas and heated in reflux in a nitrogen gas atmosphere. A reflux condition was maintained for 24 hours during which time poly(picolinium epichlorohydrin) precipitated from solution. The product was stripped of excess picoline under reduced pressure and dissolved in 100 ml of methanol. The methan...

example 2

APD of stilbazolium-substituted polyepichlorohydrin and the sodium salt of poly(2-((4-(2-(N-(2-hydroxyethyl)carbamoyl)-2-cyanovinyl)phenyl) (2-((4-(2-(N-methylcarbamoyl)-2-cyanovinyl)phenyl) (carboxymethyl)amino)ethyl)amino)acetic acid) bi-layers:

A process for depositing layers was developed having alternating layers of the polycation, stilbazolium-substituted polyepichlorohydrin and the polyanion, sodium salt of poly (2-((4-(2- (N-(2-hydroxyethyl)carbamoyl)-2-cyanovinyl)phenyl) (2-((4-(2-(N-methylcarbamoyl)-2-cyanovinyl)phenyl)(carboxymethyl) amino)ethyl)amino)acetic acid). The latter is a NLO-active polymer with chromophore configured in the mainchain syndioregically with two carboxylate anions per repeat unit. The NLO-active polycation and NLO-active polyanion were alternately deposited from aqueous solution to make thin polar films.

A. Preparation of stilbazolium-substituted polymer: The polycation was prepared in the same manner as described in Ex. 1.

B. Preparation of sodium sal...

example 3

APD of stilbazolium-substituted polyepichlorohydrin and polystyrenesulfonate bi-layers:

A process for depositing films was developed having alternating layers of the polycation, stilbazolium-substituted polyepichlorohydrin, and the polyanion, poly(sodium 4-styrenesulfonate). NLO-active polycation and inactive polyanion were alternately deposited from aqueous solution to make thin polar films.

A. Preparation of 4-(N-diethyl)aminostilbazolium-substituted polyepichlorohydrin: Poly(epichlorohydrin) having 0.05 moles of chloromethyl groups and a molecular weight between 500 and 4000 g / mol, was dissolved in 0.15 to 0.50 moles of freshly distilled 4-picoline. The solution was degassed by stirring under reduced pressure, purged with nitrogen gas and heated in reflux in a nitrogen gas atmosphere. A reflux condition was maintained for 24 hours during which time poly(picolinium epichlorohydrin) precipitated from solution. The product was stripped of excess picoline under reduced pressure and dis...

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Abstract

A process that lends itself to automation for producing multi-layer second-order nonlinear optical polymer (NLOP) thin films by the forming of a polycation layer containing an NLO-active cationic polymer, having non-centrosymmetric chromophores, on a substrate followed by the forming of a polyanion layer, also having non-centrosymmetric chromophores, on the polycation layer. A predetermind number of the polycation and the polyanion layers may be alternated upon the surface as well as one or more buffer layers. An added benefit is the formation of an ultra-smooth surface of the same order of roughness as the substrate upon which the layers are formed.

Description

MICROFICHE APPENDIXNot Applicable.BACKGROUND OF THE INVENTION1. Field of the InventionThe present invention relates to the formation of stable multi-layer nonlinear optical polymer (NLOP) films. More particularly, the invention relates to a process of second-order nonlinear optical polymer films which are formed by a solution deposition scheme which results in an electro-optic (EO) film. Still more particularly, the electro-optic films do not require electric-field poling nor undergo high temperature processing treatment.2. Description of the Related ArtThe art of organic polymeric thin films for photonic applications has been a rapidly evolving area of research. One class of materials within this field, NLOP films, has potential for breakthroughs in low cost integrated devices for the telecommunication and data-communication industries. NLOP films are desired in the fabrication of electro-optic (EO) waveguides. This application of the nonlinear optical (NLO) films permits optical s...

Claims

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Application Information

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Patent Type & Authority Patents(United States)
IPC IPC(8): G02B27/00
CPCG02B1/10B05D5/06G02B27/0006G02F1/3615
Inventor ROBERTS, M. JOELINDSAY, GEOFF A.WYNNE, KENNETH J.CHAFIN, ANDREW P.STENGER-SMITH, JOHN D.ZARRAS, PETERYEE, RENA Y.HOLLOINS, RICHARD A.
Owner THE UNITED STATES OF AMERICA AS REPRESENTED BY THE SECRETARY OF THE NAVY
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