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WO1992002856A1 - Production de guides d'ondes optiques a base de polymeres - Google Patents

Production de guides d'ondes optiques a base de polymeres Download PDF

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Publication number
WO1992002856A1
WO1992002856A1 PCT/US1991/002016 US9102016W WO9202856A1 WO 1992002856 A1 WO1992002856 A1 WO 1992002856A1 US 9102016 W US9102016 W US 9102016W WO 9202856 A1 WO9202856 A1 WO 9202856A1
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WO
WIPO (PCT)
Prior art keywords
thin film
channel
polymer
medium
waveguide
Prior art date
Application number
PCT/US1991/002016
Other languages
English (en)
Inventor
David Haas
Chia-Chi Teng
Robert Norwood
Garo Khanarian
Original Assignee
Hoechst Celanese Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst Celanese Corporation filed Critical Hoechst Celanese Corporation
Publication of WO1992002856A1 publication Critical patent/WO1992002856A1/fr

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/37—Non-linear optics for second-harmonic generation
    • G02F1/377—Non-linear optics for second-harmonic generation in an optical waveguide structure
    • G02F1/3775—Non-linear optics for second-harmonic generation in an optical waveguide structure with a periodic structure, e.g. domain inversion, for quasi-phase-matching [QPM]
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/061—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on electro-optical organic material
    • G02F1/065—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on electro-optical organic material in an optical waveguide structure

Definitions

  • Optical waveguides consist of a transparent waveguiding core surrounded by
  • optical waveguides are formed by applying a dielectric material to a transparent substrate of lower refractive index.
  • thermoplastic polymer substrates are embossed with a metal die in a desired waveguide pattern, and subsequently filled or coated with a polymerizable higher index liquid monomer.
  • optical waveguides are formed by selectively altering the index of refraction of a bulk transparent material.
  • One technique involves ion bombardment in which selected regions of increased refractive index are provided by generating a molecular disorder pattern in a bulk matrix.
  • selected regions are either photo-induced in sensitized polymeric materials such as poly(methyl) methacrylate as described in Appl. Phys. Lett., 16, 486 (1970), or electrically induced by diffusing a higher index dopant into a transparent material.
  • polymeric optical waveguides which have a spatial periodic waveguiding channel structure.
  • One or more objects of the present invention are accomplished by the provision of a method for producing an optical waveguide with a two-dimensional channel structure for single mode wave transmission which comprises (1) forming a thin film optical matrix comprising an organic medium which exhibits nonlinear optical response and which has a ⁇ max absorption band in the range between about 250-600 nm; (2) masking an elongated channel section across the thin film matrix, and (3) applying radiation energy to the exposed thin film surface to modify the molecular configuration of the thin film organic medium and lower the refractive index of the organic medium.
  • quasi-phase matching of propagating wave energy comprising (1) forming a thin film optical matrix comprising an organic medium which exhibits nonlinear optical response and which as a ⁇ max absorption band in the range between about 250-600 nm; (2) masking a longitudinal channel section across the thin film matrix;
  • two-dimensional waveguiding channel for single mode wave transmission comprising a thin film channel of a side chain polymer medium which exhibits nonlinear optical response and has a ⁇ max absorption band in the range between about
  • a present invention process embodiment has utility for the fabrication of the optical waveguiding component of a frequency converting module adapted for the production of a short wavelength laser beam which comprises: a. a 600-1600 nm laser generating source, in coupled combination with
  • an optical waveguide comprising a substratesupported thin film of a polymeric medium which exhibits second order nonlinear optical response, and which has a spatial periodic structure for quasi-phase matching of
  • ⁇ is the propagation constant difference which is equal to ⁇ 0 (2 ⁇ 1 )-2 ⁇ 0 ( ⁇ 1 ), ⁇ 1 is the
  • ⁇ 0 and ⁇ 0 are the magnetic permeability and electric permittivity of free space
  • d eff is the effective nonlinear optical susceptibility of the waveguide medium
  • n( ⁇ ) and n(2 ⁇ ) are the linear refractive indices at
  • A is the area of the light beam
  • P( ⁇ ) is the light beam power
  • L is the length of the phase matching region of the waveguide medium
  • F is the overlap integral
  • ⁇ k is the phase mismatch between the fundamental and second harmonic light wave propagation
  • ⁇ k k(2 ⁇ )-k( ⁇ 1 )-k( ⁇ 2 )
  • k(2 ⁇ ) is the propagation constant for the generated second harmonic light beam
  • k( ⁇ 1 ) and k( ⁇ 2 ) are the propagation constants of the two fundamental field modes that generate the
  • the device has heat control means for temperature tuning of the waveguide medium to phase match the propagation constants of the fundamental and second harmonic light beams, so that ⁇ k in the above represented equations approaches zero.
  • a present invention process embodiment has further utility for the fabrication of the optical waveguiding component of an integrated optical parameter amplifier which comprises
  • a light signal source with a wavelength of about 0.5-4 ⁇ m
  • a laser beam source with a wavelength of about 0.6-1.3 ⁇ m and a power level of about 50-1000 mw
  • an optical waveguide comprising a twodimensional channel structure for single mode wave transmission, and the channel waveguiding matrix comprises a side chain polymer medium which has an external field-induced noncentrosymmetric
  • nonlinear optical coefficient d of at least about 10 pm/V, and which has a spatial periodic
  • the coherence lengthl c of the waveguide periodic polymer medium is in the range of about 10-100 ⁇ m, and is defined by the equation: where ⁇ is the propagation constant difference which is equal to ⁇ 0 ( ⁇ p )- ⁇ 0 ( ⁇ s )- ⁇ 0 ( ⁇ i ), ⁇ p is the pump frequency, ⁇ s is the signal frequency, ⁇ i is the idler frequency, and subscript zero denotes the zero-ordered mode in the waveguide medium; and wherein the output wave energy under operating conditions comprises the incident laser beam, a generated idler beam, and an amplified signal beam with a gain G of about 10-1000.
  • the radiation energy applied in the above described invention process embodiments is of sufficient intensity and duration to accomplish a molecular transformation in the exposed organic thin film regions, and a concomitant change in the refractive index and optical nonlinearity of the exposed medium.
  • a radiation energy density between about 700-1500 Joules is applied per square centimeter of exposed thin film
  • the radiation applied to the exposed thin film surface area normally will have a wavelength in the range of about 200-1300 nm.
  • the input of radiation energy preferably changes the refractive index of the modified organic by at least 0.005 up to about 0.2.
  • the radiation energy is applied with any conventional source of ultraviolet or visible light, such as a mercury arc lamp, argon ion laser, helium-cadmium ion laser, Nd:YAG laser, and the like.
  • the thin film organic medium having waveguiding properties can be in a laminated formation between two thin film electrodes.
  • the electrodes can function to provide an external field-induced noncentrosymmetric molecular
  • Poling of a thin film waveguide medium can be accomplished conveniently by heating the medium near or above its melting point or glass transition temperature, then applying a DC
  • An applied external field also is useful for tuning of quasi-phase matching conditions in a waveguiding medium. Additional fine tuning of phase matching of the preparation constants of light beams can be accomplished by the provision of heat control means.
  • the refractive indices of the polymeric waveguiding medium and/or cladding layers on a fabricated channel waveguide can be finely adjusted during light propagation
  • the organic thin film waveguiding medium of an invention optical device is transparent, either liquid crystalline or amorphous in physical properties, and exhibits nonlinear optical
  • the organic medium has a higher
  • refractive index e.g. 1.5
  • the supporting substrate or higher than the cladding layer
  • the transparent organic medium can be applied to the supporting substrate by
  • the organic thin film waveguiding medium can consist of a host polymer such as poly(methyl methacrylate), and a guest organic compound which exhibits nonlinear optical response, such as
  • a host polymer can be selected which also exhibits nonlinear optical response.
  • a present invention organic thin film waveguide medium preferably is a polymer having a comb structure of side chains which exhibit nonlinear optical response. This type of chemical structure is illustrated by thermoplastic polymers which are characterized by a recurring monomeric unit corresponding to the formula:
  • P' is a polymer main chain unit
  • S' is a flexible spacer group having a linear chain length of between about 2-20 atoms
  • M' is a pendant group which exhibits second order nonlinear optical susceptibility, and where the pendant groups comprise at least about 25 weight percent of the polymer, and the polymer has a glass transition temperature or softening point above about 40°C.
  • side chain polymers of interest are described in U.S. 4,694,066.
  • Illustrative of side chain polymer species are poly[6-(4-nitrobiphenyloxy)hexyl methacrylate], poly(L-N-p-nitrophenyl-2-piperidinemethyl acrylate), and stilbene-containing polymers such as those with a recurring 4-[N-(2-methacroyl-oxyethyl)-N-methylamine]-4'-nitrostilbene monomeric unit:
  • transparent refers to an organic thin film waveguide medium which is transparent or light transmitting with respect to incident fundamental and created light frequencies.
  • the organic thin film nonlinear optical medium is transparent to both the incident and exit light frequencies.
  • amorphous refers to a transparent polymeric optical medium which does not have a preferred short range molecular order that exhibits optical anisotropy.
  • external field refers to an electric, magnetic or mechanical stress field which is applied to a substrate of mobile polymer molecules, to induce dipolar alignment of the organic molecules parallel to the field.
  • parameter refers to interactions in wave energy states in an optical medium in which time variations in an input signal are translated into different time variations in an output signal as determined by a nonlinearity parameter.
  • optical waveguide components are presented as being typical, and various modifications in design and operation can be derived in view of the foregoing disclosure within the scope of the invention.
  • a nonlinear optically active organic layer of 2.0 ⁇ m thickness is spin-coated on a series of quartz plates at 3000 rpm.
  • spin-coating medium is a 20% solution of a
  • the organic thin film is dried in a vacuum oven at 160°C for one hour.
  • the thin film has a refractive index of 1.606.
  • An argon ion laser is used to apply one of three lines of radiation (457.8, 488 and
  • the sample thin film is tested for waveguiding of 1.3 ⁇ m light, and the refractive index of the thin film is measured.
  • FIG. 1 is a graphic representation of a comparison of the initial UV-VIS spectrum of a thin film with that of the thin film after
  • the average thin film sample exhibits an optical density decrease of about 50 percent in the 500-580 nm range.
  • FIG. 2 is a graphic representation in which the normalized integrated optical density for 514.5 nm light and a radiation input of
  • This Example illustrates the fabrication of a two-dimensional channel waveguide with a spatial periodic structure in accordance with the present invention, and operation of the waveguide as a light frequency doubling device.
  • a silicon dioxide-coated silicon wafer is placed in a Varian electron beam vacuum
  • the aluminum electrode surface is covered with a 2.0 micron cladding layer of polymethyl methacrylate by spin-coating a 20% cyclohexanone solution at 5000 rpm for 30 seconds, and the coated wafer is baked at 160°C for
  • a nonlinear optically active waveguiding layer of 1.3 micron thickness is spin-coated on the cladding layer at 7500 rpm.
  • the spin-coating medium is a 20% solution of a 50/50 copolymer of 4-[N-(6-methacroyloxyhexyl)-N-methylamino]-4'-nitrostilbene and methyl methacrylate in
  • the coated wafer is baked at 160°C in a vacuum oven as previously described.
  • An upper cladding layer of 2.0 micron thickness is applied by spin-coating a 20% PMMA solution in cyclohexanone at 5000 rpm for 30 seconds, and baking in the manner previously described.
  • a 1000 A electrode layer of gold is deposited on the upper cladding layer.
  • the refractive indices of the waveguiding thin films are measured at 1.34 micron and 0.67 micron, which correspond to the pump and second harmonic wavelengths under the light propagating conditions in the waveguide as
  • the waveguide thin film has refractive indices of 1.576 and 1.606, and the cladding layer has refractive indices of 1.485 and 1.490, respectively.
  • the waveguide structure is cleaved at opposite ends to provide two sharp faces to couple light in and out of the polymeric waveguiding medium. Wires are attached to the top and bottom electrodes.
  • the waveguide is poled by placing it in a Mettler hot stage. The waveguide is heated at 1°C/minute to 90°C (T g of copolymer), and a field of 70 V/ ⁇ m is applied for
  • the waveguide is cooled at
  • the top gold electrode is removed by a gold etch (Transene Corp.).
  • the waveguide is irradiated with the 488 nm line of an Argon laser (Spectra Physics) through a periodic mask
  • the periodic mask consists of lines and spaces 6 ⁇ m wide.
  • the mask is placed on the waveguide with a thin Kapton spacer.
  • the waveguide is photobleached for about 30 minutes with a radiation of 500 Joules per square
  • a one half wave plate is placed before the waveguide to make the input polarization in the waveguide TM.
  • the waveguide is placed on a hot stage with a 0.5°C temperature control.
  • the hot stage is mounted on a rotation stage, so that the effective periodicity of the grating can be changed. 1.34 ⁇ m light is coupled into the
  • phase matching occurs near the correct periodicity of 6.9 ⁇ m.
  • the polarization of the input and output signals is TM, indicating that the d 33 coefficient has been phase matched. Away from the phase matching periodicity, no second harmonic generation is observed.
  • a two-dimensional channel waveguiding structure is formed by the following procedure.
  • a light field mask containing a channel waveguide pattern is placed on the waveguide, with a Kapton filter spacer between the waveguide and the mask.
  • an index change of about 0.007 is effected by
  • the waveguide structure does not have sharply defined channel sidewalls.
  • Each channel sidewall is in the form of a refractive index gradient zone, which minimizes optical loss from light scattering under light propagating conditions.
  • the waveguide is placed in an optical test apparatus, and microscope objective lenses are utilized to couple light into the channel waveguiding medium. Since the angle of the channel waveguide is near its optimum position as previously determined, only minor wavelength tuning is required to provide phase matched frequency doubling.
  • This Example illustrates the fabrication of a two dimensional channel waveguide in
  • a silicon dioxide-coated silicon wafer is placed in a Varian electron beam vacuum
  • the aluminum electrode is coated with 2.5 ⁇ m of a UV curable epoxy resin (Norland 60).
  • Norland 60 a UV curable epoxy resin
  • the film is obtained by preparing a 20% solution of Norland 60 in trichloropropane, and spincoating the solution on the electrode at 8000 rpm for 30 seconds, and curing the formed film with a 300 W mercury lamp for 10 minutes.
  • a nonlinear optically active polymeric waveguide layer of 1.3 ⁇ m thickness is spin-coated on the cladding layer at 5000 rpm.
  • the spin coating solution is a 20% solution of a 50/50 copolymer of 4-[N-(2-methacroyloxyethyl)-N-methylamino]-4'-nitrostilbene/methylmethacrylate (weight average M.W. of about 30,000).
  • the polymeric thin film is dried in a vacuum oven at 160°C for 2 hours.
  • An upper cladding layer of polysiloxane is applied by spin coating a 35% solution in butanol at 8000 rpm for 30 seconds, and the 2 ⁇ m cladding layer is baked at 120°C for one hour.
  • a 1000 A electrode layer of gold is deposited on the upper cladding layer.
  • the resultant laminate structure is poled at 140°C at 100 V/ ⁇ m in a Mettler hot stage by raising the temperature to the T g of the polymeric waveguide layer, applying a DC voltage, and then cooling the structure slowly while maintaining the DC field.
  • the top gold electrode is removed with a gold etch (Transene Corp.). The remaining
  • the desired pattern for the channel waveguide is obtained by a dark field mask. (Photronics lab.)
  • a gold layer (1000 A) is deposited over the bleached area.
  • Photoresist (AZ-1518, Hoechst) is spin-coated at 3000 rpm to provide a 1.5 ⁇ m layer. The coating is baked at 100°C for
  • the photoresist layer is exposed in a Karl Suss model MJB3 mask aligner to give the desired electrode pattern.
  • the patterned photoresist is developed with AZ Developer in water, and washed with deionized water.
  • the gold is removed in all the exposed areas of the pattern, then the photoresist is removed to provide a thin film gold electrode over the channel waveguide.
  • the waveguide structure is cleaved at opposite ends to provide two sharp faces. Light is coupled into the channel waveguide with a microscope objective. When a voltage is applied across the electrodes, the intensity of an incident laser beam is modulated.

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Optical Integrated Circuits (AREA)

Abstract

Dans l'un de ses modes de réalisation, l'invention se rapporte à un procédé qui sert à produire, par photoblanchissage, un guide d'onde optique dont les canaux de guidage des ondes présentent une structure périodique dans l'espace et qui sert à modifier l'indice de réfraction et la non-linéarité optique dans les zones de surface exposées d'un mince film polymère qui absorbe l'énergie rayonnante. Un type préféré de polymère utilisé dans le support de guidage des ondes est constitué par un polymère à chaîne latérale se caractérisant par une structure du type 4-[(2-méthacroyloxyéthyl)-N-méthylamino]-4'-nitrostilbène récurrente, représentée par la formule (I).
PCT/US1991/002016 1990-08-03 1991-03-25 Production de guides d'ondes optiques a base de polymeres WO1992002856A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US562,519 1975-03-27
US56251990A 1990-08-03 1990-08-03

Publications (1)

Publication Number Publication Date
WO1992002856A1 true WO1992002856A1 (fr) 1992-02-20

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5219710A (en) * 1991-11-25 1993-06-15 Allied-Signal Inc. Polymeric nitrones having a styrene-derived backbone chain
US5470692A (en) * 1988-09-08 1995-11-28 Akzo Nobel N.V. Integrated optic components
WO1996042036A1 (fr) * 1995-06-12 1996-12-27 California Institute Of Technology Autopiegeage et autofocalisation de faisceaux optiques dans des photopolymeres
EP1147517B1 (fr) * 1999-01-21 2003-04-09 France Telecom Procede de photoinscription pour modifier l'orientation des molecules d'un materiau moleculaire photosensible

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4609252A (en) * 1979-04-02 1986-09-02 Hughes Aircraft Company Organic optical waveguide device and method of making
US4712854A (en) * 1983-07-11 1987-12-15 Omron Tateisi Electronics Co. Optical waveguide and method of making the same
US4767169A (en) * 1987-02-26 1988-08-30 Hoechst Celanese Corporation Thin film waveguide electrooptic modulator
US4983499A (en) * 1986-09-11 1991-01-08 Brother Kogyo Kabushiki Kaisha Method of forming waveguide lens having refractive index distribution
US4985178A (en) * 1988-11-22 1991-01-15 E. I. Du Pont De Nemours And Company Nonlinear optical device from 3-methyl-4-methoxy-4'-nitrostilbene
US5002361A (en) * 1986-10-03 1991-03-26 Hoechst Celanese Corp. Polymeric thin film waveguide media
US5006285A (en) * 1988-07-28 1991-04-09 Lockheed Missiles & Space Company, Inc. Electro-optic channel waveguide

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4609252A (en) * 1979-04-02 1986-09-02 Hughes Aircraft Company Organic optical waveguide device and method of making
US4712854A (en) * 1983-07-11 1987-12-15 Omron Tateisi Electronics Co. Optical waveguide and method of making the same
US4983499A (en) * 1986-09-11 1991-01-08 Brother Kogyo Kabushiki Kaisha Method of forming waveguide lens having refractive index distribution
US5002361A (en) * 1986-10-03 1991-03-26 Hoechst Celanese Corp. Polymeric thin film waveguide media
US4767169A (en) * 1987-02-26 1988-08-30 Hoechst Celanese Corporation Thin film waveguide electrooptic modulator
US5006285A (en) * 1988-07-28 1991-04-09 Lockheed Missiles & Space Company, Inc. Electro-optic channel waveguide
US4985178A (en) * 1988-11-22 1991-01-15 E. I. Du Pont De Nemours And Company Nonlinear optical device from 3-methyl-4-methoxy-4'-nitrostilbene

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5470692A (en) * 1988-09-08 1995-11-28 Akzo Nobel N.V. Integrated optic components
US5219710A (en) * 1991-11-25 1993-06-15 Allied-Signal Inc. Polymeric nitrones having a styrene-derived backbone chain
WO1996042036A1 (fr) * 1995-06-12 1996-12-27 California Institute Of Technology Autopiegeage et autofocalisation de faisceaux optiques dans des photopolymeres
EP1147517B1 (fr) * 1999-01-21 2003-04-09 France Telecom Procede de photoinscription pour modifier l'orientation des molecules d'un materiau moleculaire photosensible

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