WO2000031583A1 - Materiau optique non lineaire de second ordre et procede de fabrication d'un dispositif optique non lineaire de second ordre - Google Patents

Materiau optique non lineaire de second ordre et procede de fabrication d'un dispositif optique non lineaire de second ordre Download PDF

Info

Publication number
WO2000031583A1
WO2000031583A1 PCT/JP1999/006094 JP9906094W WO0031583A1 WO 2000031583 A1 WO2000031583 A1 WO 2000031583A1 JP 9906094 W JP9906094 W JP 9906094W WO 0031583 A1 WO0031583 A1 WO 0031583A1
Authority
WO
WIPO (PCT)
Prior art keywords
nonlinear optical
order nonlinear
thin film
optical
organic dye
Prior art date
Application number
PCT/JP1999/006094
Other languages
English (en)
Japanese (ja)
Inventor
Kenji Kitaoka
Jinhai Si
Kazuyuki Hirao
Original Assignee
Japan Science And Technology 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 Japan Science And Technology Corporation filed Critical Japan Science And Technology Corporation
Publication of WO2000031583A1 publication Critical patent/WO2000031583A1/fr

Links

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
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/361—Organic materials
    • G02F1/3615—Organic materials containing polymers
    • G02F1/3617—Organic materials containing polymers having the non-linear optical group in a side chain

Definitions

  • the present invention relates to an optical modulator widely used in the field of communication equipment.
  • a second-order nonlinear optical material containing an organic dye is given a second-order nonlinear optical characteristic by polarizing an organic dye inside the material by electric polling.
  • the temperature is set high for efficient polarization, and the polymerization reaction and densification are performed by the sol-gel method (K. Izawa et al., Jpn. J. Appl. Phys. Vol. 32 (1993) 807) -811)
  • the polarization treatment is performed while increasing the fluidity of the material (Japanese Patent Application Laid-Open No. 10-239720) or irradiating with ultraviolet rays.
  • the orientation direction of the organic dye is unidirectional. Therefore, the phase matching condition important as an optical element for transmitting the second harmonic in a waveguide structure such as an optical modulator or an optical switch is not satisfied due to the difference in chromatic dispersion of the material.
  • the significant attenuation of the second harmonic is due to the relaxation of the polarization structure. That is, a polymer material is generally a material that is liable to change easily due to poor stability against thermal effects of laser light and environmental temperature changes. A dye exhibiting a non-linear effect develops second-order nonlinear optical characteristics by orientation polarization by poling, but the second-order nonlinear optical characteristics deteriorate due to relaxation of the polarization structure. Disclosure of the invention
  • the present invention has been devised to solve such a problem.
  • an oxide formed by a sol-gel method as a matrix, the stability of the polarization structure is improved, It is an object of the present invention to provide an element that exhibits stable second-order nonlinear optical characteristics over a long period of time.
  • the present invention is to cast an organic dye having a second-order nonlinear optical effect or a sol-gel liquid in which a polymer precursor having an organic dye in a side chain and a metal oxide precursor are dispersed on a substrate. It is characterized in that the formed thin film is simultaneously irradiated with light beams of two wavelengths coaxially to perform light polling. Optical polling can be performed on either the heat-treated thin film or the heat-treated thin film.
  • the manufactured second-order nonlinear optical material or second-order nonlinear optical element is composed of an organometallic raw material to which at least one organic functional group that does not hydrolyze or an organometallic raw material to which at least one organic functional group that does not hydrolyze is added
  • Matrix materials have been synthesized using a mixture with an organic metal raw material to which only the organic functional group to be hydrolyzed is coordinated.
  • Figure 1 is a schematic diagram of the equipment used for optical polling.
  • FIG. 2 is a diagram illustrating a process of manufacturing the second harmonic element.
  • Organic dyes exhibiting a second-order nonlinear optical effect are not particularly limited in material, and include para-nitroaline, styryl-pyridin-ma-line, 414'tricyanovinyldimethylamino-diazostilbene, 3 Methyl 4-nitropyridine 1 oxide, 4—4 ′ dimethylaminocyanobiphenyl, dimethylaminophenyl urea, 4-amino 4 ′ nitrodiphenyl sulfide, 4-1 [diethyl (2H Deguchi quichetyl)] Amino 4'nitroazobenzene or the like is used.
  • the polymer precursor having an organic dye in the side chain is not particularly limited, either.
  • the organic dye or the polymer precursor having the organic dye in the side chain is mixed with a metal oxide raw material and a solvent constituting the matrix to prepare a uniform sol-gel solution.
  • the metal oxides used as the matrix are made of precursors such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxy titan, tetrabutoxy zirconium, tetrapropoxy zirconium, and trisecondary butoxy aluminum. Examples include silica, titania, zirconia, and alumina.
  • the sol-gel solution is not particularly limited as a raw material in which an organic functional group that does not cause hydrolysis is added to the side chain of the metal oxide precursor, but is not particularly limited. Methyltriethoxysilane, 3-methacryloxypropyl Trimethoxysilane, phenylethoxysilane, diphenyldimethoxysilane, etc. are added. You.
  • Raw materials such as organic dyes, polymer precursors having organic dyes in the side chain, and metal oxide precursors are dispersed in solvents such as lower alcohols such as ethanol, isopropanol, and 2-methoxyphenol, and acetic acid.
  • solvents such as lower alcohols such as ethanol, isopropanol, and 2-methoxyphenol, and acetic acid.
  • a stabilizer such as diethanolamine, monoethanolamine, dimethylformamide, etc. can be used in addition to the alcoholic solvent.
  • Stabilizers not only stabilize the metal oxide precursor against hydrolysis, but also coordinate with the organic precursor and the polymer precursor having an organic dye in the side chain to improve dispersibility.
  • the stabilizer is usually added in a proportion of 0.01 to 20 mol%, preferably 1 to 18 mol%.
  • the amount of water or acid to be introduced into the sol is appropriately adjusted depending on the type of the precursor so that the hydrolysis of the metal oxide precursor proceeds to some extent before the film formation.
  • precursors with a high rate of hydrolysis reaction do not require the introduction of water or acid, because they are hydrolyzed by atmospheric moisture even if they are left indoors after film formation.
  • hydrolysis is promoted by adding an appropriate amount of water or acid.
  • the sol-gel liquid containing various raw materials is cast into a thin film on a heat-resistant substrate and gelled.
  • the heat-resistant substrate include quartz glass. Glass substrates such as non-alkali glass, glass substrates coated with transparent electrodes such as ITO, and silicon substrates. Spin coating, immersion, spraying, etc. are used.
  • the sol-gel solution is cast by the method.
  • the coating thickness of the sol cast on the substrate is not particularly limited, but is generally adjusted to 100 to 100 nm, preferably to 100 to 500 nm. You.
  • a gel film is formed from the sol cast on the substrate, it is placed in an oven and heat-treated at 80 to 300 ° C, preferably 130 to 220 ° C.
  • 80 to 300 ° C preferably 130 to 220 ° C.
  • light poling is performed at the same time. You can also.
  • the thin film sample S is housed in an oven 1 that can transmit a laser beam and can control the temperature, and lenses 2 and 3 are placed before and after the oven 1.
  • the polling laser beam has a pulse width on the order of nanoseconds to femtoseconds, and is emitted from the laser oscillator 11.
  • the laser beam passes through the lens 12 and is split by the beam splitter 13.
  • the light transmitted through the shutter 14, the second-order nonlinear optical crystal 15, the fundamental wave power filter 16, the mirror 17, the polarization rotator 18, and the light simply reflected by the mirror 19 are Are combined by a dichroic mirror 20, then irradiate a thin film sample S in an oven 1, and enter a light intensity detector 23 via a fundamental wave power filter 21 and a shirt filter 22.
  • the angles and distances of the respective optical systems are adjusted so that the fundamental wave having the same polarization direction and its second harmonic are simultaneously and coaxially incident.
  • the laser beam may be incident on the thin film sample S in any thickness direction or in any direction that guides the light in the plane of the thin film sample S.
  • one of the simultaneously incident laser beams is twice as long as the other, interference results in a polarization structure that satisfies the phase matching condition in the thin film sample S due to the two beams. .
  • an SHG element that generates a second harmonic by making a long-wavelength laser beam incident is produced.
  • Matrix made from inorganic compounds is strong and can maintain the polarized structure for a long time.
  • the organic functional group remains in the matrix after hydrolysis and heat treatment.
  • the resulting matrix has a three-dimensional structure due to the organic functional group, which suppresses the generation of fine bubbles as compared to a matrix composed of only an inorganic material, and makes the film structure itself dense.
  • pulsed lasers are used for optical poling, but dye energy sublimation can be a problem depending on the energy of the pulsed laser. In such a case, The effective film structure effectively suppresses the sublimation of the dye.
  • Example 1 Although the dye is liable to change with time slightly as compared with a matrix containing only an inorganic compound, a large second-order nonlinear optical effect is obtained because the dye is easily polarized.
  • Example 1 the present invention will be described more specifically with reference to examples.
  • a sol-gel solution containing each component at a ratio of 05: 1. 18: 6 was prepared as follows. First, tetraethoxysilane and dimethylformamide are added to half the amount of ethanol, and the mixture is stirred. Further, 41- [N-ethyl N (2-hydroxyethyl)] amino 4'-nitroazobenzene is added, and the mixture is stirred. A solution was prepared. Separately from the solution, the remaining ethanolamine, hydrochloric acid and water were mixed to prepare a solution. The solution B was added dropwise to the solution to prepare a sol-gel solution.
  • the sol-gel solution was stirred for 1 hour, it was applied to a non-alkali glass substrate at 2,000 rpm by spin coating. Immediately after the application, it was placed in an oven and dried at 150 ° C for 5 minutes. Coating and drying were repeated twice, and finally a gel film was prepared by drying for 20 minutes.
  • the obtained gel film was subjected to optical poling during a heat treatment at 230 ° C. for 10 minutes using a polling apparatus shown in FIG.
  • a 50 mJ, 50 Hz Nd: YAG laser with a pulse time of 3 to 3.5 nanoseconds was used for optical polling.
  • the laser intensity was set to 0.23 W as the light intensity of the fundamental wave before focusing.
  • the thin film that had been optically poled at 230 ° C was cooled to room temperature and irradiated with 1064 nm light of the fundamental wave used for optical poling to evaluate the success or failure of optical polling.
  • the second harmonic of 532 ⁇ m was detected.
  • the intensity of the second harmonic is such that the second-order nonlinear optical constant Xeff for quartz is about 1.5, and the pulse of 1064 nm The signal intensity did not degrade even after irradiation with the laser for more than 30,000 shots.
  • a sol-gel solution containing each component at a ratio of 6 was prepared as follows. First, tetraethoxysilane and dimethylformamide are added to half the amount of ethanol, and the mixture is stirred. Further, 4- [Nethyl N (2hydroxyshethyl)] amino 4'nitroazobenzene is added, and the mixture is stirred. was prepared solution a 2 were uniformly dispersed. Apart from the solution A 2, it was prepared a solution B 2 were mixed remaining Etanoruami down and hydrochloric acid, water. The solution B 2 dropwise mixed Zoruge Le solution was prepared in solution A 2.
  • the sol-gel solution was stirred for 1 hour, the solution was applied to an alkali-free glass substrate at 2,000 rpm by spin coating. Immediately after the application, it was placed in an oven and heat-treated at 210 ° C for 20 minutes to produce a dye-dispersed phenyl group-silicone composite thin film.
  • the obtained thin film was subjected to optical polling using a laser beam of 1064 nm and 532 ⁇ m in the same manner as in Example 1.
  • the laser intensity was set to 0.22 W as the light intensity of the fundamental wave before focusing.
  • Optical polling was performed separately from the heat treatment.
  • Example 2 While heating the obtained thin film at 230 ° C. for 10 minutes, it was subjected to optical polling using laser beams of 1064 nm and 532 nm in the same manner as in Example 1.
  • the laser intensity was set to 0.22 W, which is the light intensity of the fundamental wave before focusing.
  • a sol-gel solution containing each component at a ratio of 6 was prepared as follows. First, ⁇ seton half volume by adding N [3 (Application Benefits triethoxysilyl) propyl] 2, 4 Gini Torofueniruami emissions and Te tiger silane stirred to prepare a solution A 4. Apart from the solution A 4, it was prepared a solution B 4 was mixed remaining acetone and hydrochloric acid, water. Solution B 4 was added dropwise to Solution A 4 to prepare a sol-gel solution.
  • the sol-gel solution was stirred for 10 minutes, the solution was applied to a glass substrate without spinning at 2000 rpm by spin coating. Immediately after the application, it was placed in an oven and dried at 130 ° C for 5 minutes to produce a gel film. While heating the obtained thin film at 230 ° C. for 10 minutes, it was subjected to optical polling using laser beams of 1064 nm and 532 nm in the same manner as in Example 1. The laser intensity was set to 0.22 W, which is the light intensity of the fundamental wave before focusing.
  • a second harmonic element was manufactured using the thin film provided on the substrate.
  • a gel film b provided on a glass substrate a without any force in Example 2 was used.
  • the polyimide film d is further spin-coated on the surface on which the waveguide has been formed, and is formed at 150 °.
  • C was thermally cured, and both end surfaces of the waveguide were polished.
  • Two luminous fluxes 6 of 800 nm and 400111 ⁇ were incident from the end face of the waveguide, and were subjected to optical poling to produce a second harmonic element ⁇ .
  • a sol-gel solution containing a non-linear optical organic dye is cast on a support such as a substrate to produce a gel film in which the non-linear optical organic dye is dispersed.
  • a second-order nonlinear optical material can be obtained.
  • the thin film formed by the sol-gel method is a second-order nonlinear optical material with stable performance because the polarization state of the organic dye is fixed stably over a long period of time.
  • a nonlinear optical element such as a second harmonic element is manufactured.

Landscapes

  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)

Abstract

L'invention concerne un colorant organique, présentant un effet optique non linéaire de second ordre ou un précurseur de polymère possédant une chaîne latérale de colorant organique, et un liquide sol-gel dans lequel est dispersé un précurseur d'oxyde métallique, coulés sur un substrat afin de former une couche mince. Cette couche mince est irradiée simultanément par des lumières coaxiales de différentes longueurs d'onde, afin de conduire une polarisation optique sur une couche mince dans ou après un traitement thermique. La polarisation du colorant optique est maintenue stable pendant un long moment, ce qui produit un dispositif optique linéaire de second ordre, préférable par exemple à un modulateur optique et à un commutateur optique.
PCT/JP1999/006094 1998-11-20 1999-11-02 Materiau optique non lineaire de second ordre et procede de fabrication d'un dispositif optique non lineaire de second ordre WO2000031583A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10331632A JP2000155346A (ja) 1998-11-20 1998-11-20 二次非線形光学材料及び二次非線形光学素子の製造方法
JP10/331632 1998-11-20

Publications (1)

Publication Number Publication Date
WO2000031583A1 true WO2000031583A1 (fr) 2000-06-02

Family

ID=18245837

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1999/006094 WO2000031583A1 (fr) 1998-11-20 1999-11-02 Materiau optique non lineaire de second ordre et procede de fabrication d'un dispositif optique non lineaire de second ordre

Country Status (2)

Country Link
JP (1) JP2000155346A (fr)
WO (1) WO2000031583A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6999639B2 (en) 2001-09-06 2006-02-14 Gilad Photonics Ltd. Tunable optical filters
CN109932827A (zh) * 2019-03-29 2019-06-25 惠州学院 基于协同利用偏振信息和强度信息的全光波导器件

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2005088409A1 (ja) * 2004-03-12 2008-01-31 独立行政法人科学技術振興機構 光導波路型ホログラフィックメモリ
CN106527013A (zh) * 2016-08-30 2017-03-22 惠州学院 一种高性能聚合物全光开关

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5656204A (en) * 1993-02-12 1997-08-12 Fuji Xerox Co., Ltd. Optical element and process for producing the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5656204A (en) * 1993-02-12 1997-08-12 Fuji Xerox Co., Ltd. Optical element and process for producing the same

Non-Patent Citations (13)

* Cited by examiner, † Cited by third party
Title
C. FIORINI ET AL., NONLINEAR OPTICS, vol. 9, no. 1-4, 1995, pages 339 - 347, XP002925229 *
C. FIORINI, F. CHARRA AND J.M. NUNZI, OPTICS LETTERS, vol. 20, no. 24, 1995, XP002925225 *
G. XU ET AL., APPLIED PHYSICS B, vol. 68, no. 4, June 1999 (1999-06-01), pages 693 - 696, XP002925235 *
G. XU ET AL., OPTICS COMMUNICATIONS, vol. 153, no. 1,2,3, 15 July 1998 (1998-07-15), pages 95 - 98, XP002925231 *
J. SI ET AL., OPTICS COMMUNICATIONS, vol. 142, no. 1,2,3, 1 October 1997 (1997-10-01), pages 71 - 74, XP002925230 *
J.A. GURNEY ET AL., PROCEEDINGS OF SPIE - THE INTERNATIONAL SOCIETY FOR OPTICAL ENGINEERING, vol. 3469, July 1998 (1998-07-01), pages 145 - 152, XP002925227 *
K. IZAWA ET AL., JAPANESE JOURNAL OF APPLIED PHYSICS, vol. 32, no. 2, February 1993 (1993-02-01), pages 807 - 811, SEE PART 1, XP002925228 *
K. KITAOKA ET AL., APPLIED PHYSICS LETTERS, vol. 75, no. 2, 12 July 1999 (1999-07-12), pages 157 - 159, XP002925234 *
K. KITAOKA ET AL., JAPANESE JOURNAL OF APPLIED PHYSICS, vol. 38, no. 9A/B, 15 September 1999 (1999-09-15), pages L1029 - L1031, SEE PART 2, XP002925232 *
K. KITAOKA ET AL., JOURNAL OF THE CERAMIC SOCIETY OF JAPAN, vol. 107, no. 6, 1 June 1999 (1999-06-01), pages 522 - 526, XP002925233 *
R.H. STOLEN AND H.W.K. TOM, OPTICS LETTERS, vol. 12, no. 8, August 1987 (1987-08-01), pages 585 - 587, XP002925236 *
S. BRASSELET AND J. ZYSS, PROCEEDINGS OF SPIE - THE INTERNATIONAL SOCIETY FOR OPTICAL ENGINEERING, vol. 3469, July 1998 (1998-07-01), pages 154 - 163, XP002925226 *
V. DOMINIC ET AL., OPTICS LETTERS, vol. 20, no. 5, 1 March 1995 (1995-03-01), pages 444 - 446, XP002925237 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6999639B2 (en) 2001-09-06 2006-02-14 Gilad Photonics Ltd. Tunable optical filters
CN109932827A (zh) * 2019-03-29 2019-06-25 惠州学院 基于协同利用偏振信息和强度信息的全光波导器件
CN109932827B (zh) * 2019-03-29 2021-12-31 惠州学院 基于协同利用偏振信息和强度信息的全光波导器件

Also Published As

Publication number Publication date
JP2000155346A (ja) 2000-06-06

Similar Documents

Publication Publication Date Title
JPH02199433A (ja) 周波数二倍化ポリマー導波装置
US5064265A (en) Optical parametric amplifier
US20100208757A1 (en) Method of ferroelectronic domain inversion and its applications
US5783319A (en) Waveguide tunable lasers and processes for the production thereof
Yamada et al. Processing and optical properties of patternable inorganic–organic hybrid films
US5247601A (en) Arrangement for producing large second-order optical nonlinearities in a waveguide structure including amorphous SiO2
US7085469B2 (en) Process for producing three-dimensional polyimide optical waveguide
JPH09304800A (ja) 光波長変換素子および分極反転の製造方法
WO2000031583A1 (fr) Materiau optique non lineaire de second ordre et procede de fabrication d'un dispositif optique non lineaire de second ordre
US6834151B1 (en) Optical waveguide and fabrication method
Kim et al. Photoassisted corona poled YLD-124/DR1-co-PMMA electrooptic device using photoisomerization
Floch et al. Optical thin films from the sol-gel process
Kitaoka et al. Optical poling of phenyl-silica hybrid thin films doped with azo-dye chromophore
JP3545270B2 (ja) 二次非線形光学材料の製造方法
KR102408995B1 (ko) 분산된 그래핀을 수용한 폴리머 도파로 및 이를 제조하는 방법, 그리고 이 폴리머 도파로 기반의 수동 모드 잠금 레이저
Burzynski et al. Photonics and nonlinear optics with sol-gel processed inorganic glass: organic polymer composites
Hayakawa et al. Newly designed organic/inorganic film for optical second-harmonic generation
KR0166907B1 (ko) 제 2 고조파 발생소자
JP3348297B2 (ja) 波長変換素子及び波長変換素子の製造方法
JPH0643511A (ja) 分極反転構造を有する光導波路及びその製造法並びに光導波路に分極反転構造を付与する装置
JPH0266524A (ja) 波長変換素子
Gang et al. Fabrication of polymeric optical waveguides by B-Staged Bisbenzocyclobutene (BCB)
JPH0757290A (ja) 光波長変換素子
WO1995015021A1 (fr) Lasers accordables, en guide d'onde et leurs procedes de production
Zeng et al. Laser direct writing of SiO2/TiO2 sol-gel films to fabricate stripe optical waveguides

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): DE FR GB

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
CFP Corrected version of a pamphlet front page

Free format text: REVISED ABSTRACT RECEIVED BY THE INTERNATIONAL BUREAU AFTER COMPLETION OF THE TECHNICAL PREPARATIONS FOR INTERNATIONAL PUBLICATION