JPH0869024A - Nonlinear optical material and optical circuit device and optical circuit board using the material - Google Patents

Abstract

PURPOSE: To obtain such a nonlinear optical material that is stable and suitable for low power driving or fast driving and is easily made into a multilayered structure, into a large size or into a composite structure with other elements and that has low dielectric const. and large degree of freedom to constitute a circuit board, and to obtain an optical circuit device and an optical circuit board using this material. CONSTITUTION: In a multilayered film containing amorphous or polycrystalline inorg. materialsw or org. crystal materials, amorphous materials, polycrystalline materials or single crystal materials, nonlinear optical material in which the central symmetry of the material is eliminated by laminating different materials into layers, changing compsns. of materials, changing kinds of dopants or amts. of dopants, thickness of layers or amts. of dopants and combining two or more methods of these, is used, or nonlinear optical material prepared by incorporating rare earth ions or molecules containing rare earth ions into a nonlinear optical polymer is used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nonlinear optical material and an optical circuit device and an optical circuit board using the same.

[0002]

2. Description of the Related Art Optical circuits are expected to become important in various optical systems such as optical interconnections of parallel computers and optical switches in the future. Non-linear optical devices, especially electro-optical (EO) devices, optical waveguide amplifiers, and optical waveguide lasers are essential elemental technologies for functionalizing such optical circuits.

Conventionally, there are LN single crystals and compound semiconductor superlattices as EO materials. However, in these materials, the degree of freedom of the substrate structure is small, a large amount of labor is required for multilayering, and the dielectric constant is high. There are problems such as difficulty in low-power driving and high-speed driving, difficulty in increasing the area, and difficulty in combining with other elements. On the other hand, the organic polymer material has a large degree of freedom in the structure of the substrate, is easy to be multilayered, has a low dielectric constant, is suitable for low power driving and high speed driving, and is easy to have a large area. It is suitable for high functionality and high integration of optical circuits because it has the characteristics that it can be easily combined with the above elements. But now,
I am worried about the reliability in terms of relaxation deterioration.

In addition, as a useful optical wiring method, we have
A method using an optical power source has been proposed (Japanese Patent Application No. 6-50092).
31). This is to pump light into a waveguide optical amplifier or a waveguide laser, form an optical power source, pick up the light with an EO switch, and send an optical signal. In this case, since the optical power source itself does not have a remarkable EO effect,
It was necessary to stack or insert O layers.

[0005]

The object of the present invention is to further improve the above-mentioned proposed technology, to provide a high degree of freedom in the structure of the substrate, easy multi-layering, low dielectric constant, low power driving and high speed driving. Suitable for, easy to increase in area, easy to combine with other elements, and stable, non-linear optical material, optical power source having EO effect, optical waveguide laser, optical waveguide amplifier, and Non-linear optical device used,
A non-linear optical amplifier, an optical waveguide laser, and an optical circuit board are provided.

[0006]

In order to solve the above-mentioned problems, according to the present invention, in a multilayer film containing an amorphous or polycrystalline inorganic substance, different substances are laminated to eliminate the central symmetry in the film thickness direction. Or changing the composition of materials of the same family, changing the type and / or the amount of doping material, or changing the layer thickness and / or
Further, there is provided a nonlinear optical material characterized in that the central symmetry is eliminated by changing the doping amount, or the central symmetry is eliminated by combining any two or more of the above methods.

According to the present invention, in a multilayer film containing an organic crystal material, an amorphous material, a polycrystalline material or a single crystal material, different substances are laminated to eliminate the central symmetry in the film thickness direction, or the same. Changing the composition of the material of the system, changing the type and / or the doping amount of the doping material, or changing the layer thickness and / or the doping amount to eliminate the central symmetry, or Provided is a non-linear optical material characterized by eliminating central symmetry by combining any two or more of the methods.

The present invention also provides a non-linear optical material characterized by containing a rare earth ion or a molecule containing a rare earth ion in a non-linear optical polymer. The present invention
Furthermore, a nonlinear optical device, a nonlinear optical optical amplifier, an optical waveguide laser, and an optical circuit board are provided by using the above materials. In the first nonlinear optical material according to the present invention, the multilayer film is a-Si: H, a-SiN _y , a-S.
A material selected from the group consisting of iO _x , a-SiC _z and a-Ge: H or a mixed crystal of two or more kinds of the above materials is preferable as a main component. Alternatively, the multilayer film may contain a transition metal compound as a main component or may contain a glass material as a main component, and these materials may contain a rare earth ion if desired. Good.

In the second nonlinear optical material according to the present invention, the multilayer film preferably contains an organic polymer as a main component, and optionally contains a rare earth ion and / or a molecule containing a rare earth ion. May be. Hereinafter, preferred embodiments of the present invention will be further described with reference to the drawings.

1 to 4 are conceptual views of the nonlinear optical material of the present invention. FIG. 1 shows an example of material modulation. In this example, the materials of the layers are different in the multilayer structure, and the inversion symmetry in the film thickness direction is eliminated by controlling the stacking order. In this example, when the electric field is applied in the film thickness direction and the polarization of light is in the film thickness direction, the maximum Pockels effect is obtained.

FIG. 2 shows an example of composition modulation. In this example,
In the multilayer structure, the composition of each layer is different, and the inversion symmetry in the film thickness direction is eliminated by controlling the stacking order. Also in this example, when the electric field is applied in the film thickness direction and the polarization of light is in the film thickness direction, the maximum Pockels effect is obtained. FIG. 3 shows an example of doping modulation. In this example, in the multilayer structure, the doping material and the doping concentration of each layer are different, and the inversion symmetry in the film thickness direction is eliminated by controlling the stacking order. Also in this example, when the electric field is applied in the film thickness direction and the polarization of light is in the film thickness direction, the maximum Pockels effect is obtained.

FIG. 4 shows an example of film thickness modulation. In this example,
In the multilayer structure, the film thickness of each layer is different, and the inversion symmetry in the film thickness direction is eliminated by controlling the stacking order. Also in this example, when the electric field is applied in the film thickness direction and the polarization of light is in the film thickness direction, the maximum Pockels effect is obtained. In any of the above examples, by making the modulation periodic, the effect from each repeating unit becomes uniform, and a great effect is obtained.

5 to 17 show examples of the nonlinear optical material of the present invention. 5 to 8 are examples of substance modulation. In the example shown in FIG. 5 in which a-SiO _x , a-SiN _y, and a-Si: H are sequentially laminated on a substrate, a film is formed on a Si wafer by ordinary plasma CVD. a-S
i: H is hydrogen diluted to 20 at a substrate temperature of 230 ° C.
% Silane at 50 sccm and 0.2 torr for 15W
Was applied to form a film. A-SiN _y was formed into a film by adding 50 sccm of ammonia to the above conditions. a
For —SiO _x , an oxidation reactive gas (N ₂ O or the like) is added. A multilayer structure can be obtained by sequentially repeating film formation. The thickness of each layer can be controlled by the film formation time. Since the film forming speed is 30Å / min, the film thickness is 3Å in 6 seconds, 5Å in 10 seconds, and 10 in 20 seconds.
Å, 30 Å in 60 seconds. However, the film forming conditions are not limited to the above, and faster film forming is possible. Since this structure does not have inversion symmetry in the film thickness direction, when a voltage is applied, the refractive index changes due to the EO effect. In particular, the thus-fabricated multi-layer structure has a property that electrons move from the nitride film side to the silicon side (Philosophical Magazine B, 1987 Vol.55, 409-41).
6.). Therefore, a large polarization can be achieved, which is effective in increasing the nonlinear optical characteristics.

A glass material or a transition metal oxide can be formed into a film by, for example, multi-target co-sputtering. In addition, various film forming methods such as EB vapor deposition and CVD utilizing the reaction of transition metal chloride and water vapor can be used. As shown in FIG. 6, when W, Ir, and Ta are used as the transition metals, IrO _x has an electron-accepting property, WO _y has an electron-donating property, and TaO _Z has a carrier-blocking property. Occurs, and a large non-linear optical characteristic appears.

Further, as shown in FIG. 7, a rare earth ion-doped material is obtained by forming a part of the layer, for example, LHG-5: Nd glass made of Hoya glass. As a result,
A material having an EO effect and serving as an optical power source, a waveguide laser, or an amplifier can be realized. When this material is made into a waveguide and pump light of 800 nm is introduced, light of 1052 nm is oscillated. Further, it becomes possible to amplify the light of 1052 nm.

Further, as shown in FIG. 8, by laminating a rare earth ion-doped glass layer and various glass layers, E
It is possible to realize a material having an O effect and serving as an optical power source, a waveguide laser, or an amplifier. As the film forming method, in addition to the above-described sputtering, CVD, plasma CVD, EB vapor deposition, various methods such as photo CVD, sol-gel method and flame deposition method can be used.

9 to 11 are examples of composition modulation. For example, as shown in FIG. 9, the composition of a-SiN is a-SiN.
_A structure having no inversion symmetry in the film thickness direction can be realized by changing _x , a-SiN _y and a-SiN _z . Therefore, when a voltage is applied, the refractive index changes due to the EO effect. The band gap and electron donating property of the nitride film change depending on its composition (Phil
osophical Magazine B, 1987 Vol.55, 409-416.). Therefore, a large polarization can be formed, which is effective in increasing the nonlinear optical characteristics. The composition of a-SiN can be changed, for example, by changing the ammonia flow rate to 25, 50 and 100 sccm. The thickness of each layer is
As in the case of the substance modulation, it can be controlled by the film formation time.

With glass materials and transition metal oxides, for example, as shown in FIGS. 10 and 11, a nonlinear optical material can be formed by changing the composition ratio of transition metals. When multi-target co-sputtering is used, the power supplied to the target may be changed. Other, E
It is also possible to use various film forming methods such as B vapor deposition and CVD utilizing the reaction of transition metal chloride and water vapor. When W, Ir, and Ta are used as the transition metals, IrO _x
Has an electron-accepting property, WO _y has an electron-donating property, and TaO _Z has a carrier-blocking property, so that the properties change depending on the composition ratio of these and nonlinear optical characteristics appear.

Also, a part of the layer may be made of, for example, squirrel glass L.
A rare earth ion-doped material is obtained by using HG5: Nd glass as a component. As a result, a material having an EO effect and serving as an optical power source, a waveguide laser, or an amplifier can be realized. When this material is made into a waveguide and pump light of 800 nm is introduced, light of 1052 nm is oscillated. Also, 10
It is also possible to amplify the light of 52 nm.

Further, by doping rare earth ions, a material having an EO effect and serving as an optical power source, a waveguide laser or an amplifier can be realized, and a switch function of an optical pickup or the like can be imparted thereby. , Variable wavelength light source, tunable optical switch, etc. can be realized. As the film forming method, in addition to the above-described sputtering, CVD, plasma CVD, EB vapor deposition, various methods such as photo CVD, sol-gel method and flame deposition method can be used.

12-14 are examples of doped modulation.
For example, as shown in FIG. 12, a non-doped a-
Si: H, B-doped a-Si: H and P-doped a-S
By sequentially laminating i: H, a structure having no inversion symmetry in the film thickness direction can be realized. For this reason,
When a voltage is applied, the refractive index changes due to the EO effect. Since a pn junction is formed in the film, a large polarization can be formed, which is effective in increasing the nonlinear optical characteristics. B-doping can be performed by flowing diborane, and P-doping can be performed by flowing phosphine into the a-Si: H film. The thickness of each layer can be controlled by the film formation time, as in the case of the substance modulation.

Another example is a glass material. For example,
As shown in FIG. 13, the dopant is modulated in SiO _x . In this case, various film forming methods such as plasma CVD, multi-target simultaneous sputtering, EB vapor deposition, and CVD can be used. For example, when W, Ir, and Ta are used as the dopant transition metal, IrO _x has an electron-accepting property, WO _y has an electron-donating property, and TaO _Z has a carrier-blocking property. It changes and a nonlinear optical characteristic appears.

Further, a part of the layer is made of, for example, frosted glass L
By using HG5: Nd glass as a component, a rare earth ion-doped material as shown in FIG. 14 is obtained. As a result,
A material having an EO effect and serving as an optical power source, a waveguide laser, or an amplifier can be realized. When this material is made into a waveguide and pump light of 800 nm is introduced, light of 1052 nm is oscillated. Further, it becomes possible to amplify the light of 1052 nm.

By doping rare earth ions, a material having an EO effect and serving as an optical power source, a waveguide laser or an amplifier can be realized. As a result, a switch function such as an optical pickup can be added, so that a wavelength tunable light source, a tunable optical switch, etc. can be realized. Further, for example, laser glass such as LHG5 may be modulation-doped with rare earth ions such as Nd ions.

As the film forming method, in addition to the above-mentioned sputtering, CVD, plasma CVD, EB vapor deposition, etc.,
Various methods such as photo CVD, sol-gel method, and flame deposition method can be used. 15 to 17 are examples of film thickness modulation. With these, a structure having no inversion symmetry in the film thickness direction can be realized. Therefore, when voltage is applied, EO
A change in the refractive index occurs due to the effect. As the material, for example, the materials described for the substance modulation, composition modulation, and doping modulation can be used. Also, as the film forming method, various methods such as plasma CVD, multi-target simultaneous sputtering, EB vapor deposition, and CVD can be used.

The substance modulation, composition modulation, dope modulation and film thickness modulation as described with reference to FIGS. 5 to 17 can be realized not only by using an inorganic material but also by using an organic material. For organic crystalline, polycrystalline or amorphous materials, for example:

[0027]

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[0028]

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[0029]

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[0030]

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[0032]

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[0033]

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[0034]

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[0038]

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[0039]

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[0040]

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[0041]

[Chemical 15]

A substance can be modulated by laminating several kinds of porphyrins having a structure as shown in. Since polarization occurs between the layers and there is no inversion symmetry in the film thickness direction, a second-order nonlinear optical effect occurs. These materials are
Basically, it is polycrystalline. It is also possible to make a single crystal by epitaxially growing it on the substrate.
Other materials include cyclic molecules such as phthalocyanine and naphthalocyanine, and MNBA-based materials (Fukuda and Goto: Materials of the 6th Nonlinear Optical Effect Device Technology Research Group Open Research Group, Laser Society), PTCDA (perylenenetr).
acarboxy lianhydride),
NTCDA (naphthalenetratracar)
There are various materials such as boxy dic hydride. Each layer has a mixed composition of multiple types of molecules,
The composition can be modulated by changing the mixing ratio, the doping can be controlled by controlling the addition of impurity molecules, and the film thickness can be controlled by controlling the film thickness. As the film forming method, for example,
Organic MBE, organic MBD, vapor deposition, LB method, spin coating method and the like can be used.

In the organic polymer material, substance modulation is possible by laminating a plurality of types of polymer layers. For example, in a film in which polyimide, polyazomethine, polyphenylene vinylene, polyimide, polyazomethine, polyphenylene vinylene ...
Since polarization occurs between the layers and there is no inversion symmetry in the film thickness direction, a second-order nonlinear optical effect as well as a third-order nonlinear optical effect occurs. Further, for example, a polyimide, a polyimide to which a donor group (for example, a methoxy group) is sequentially added, a polyimide to which an acceptor group (for example, a nitro group) is added, a polyimide, a polyimide to which a donor group is added, a polyimide to which an acceptor group is added ... Such as laminated film, azomethine, azomethine with a donor group, azomethine with an acceptor group, azomethine, azomethine with a donor group, azomethine with an acceptor group.
.. Various films such as laminated films such as can be used. Each layer is a mixture or copolymer of a plurality of types of polymer molecules, compositional change can be performed by changing the composition ratio, dope modulation can be performed by controlling addition of impurities, and film thickness modulation can be performed by controlling film thickness. As a film forming method, for example, it is desirable to use a vapor phase film forming method represented by CVD, MLD, vapor deposition polymerization or MBD as shown in JP-A-5-80370 and 4-296729. Further, various film forming methods such as ordinary organic MBE, organic MBD, vapor deposition, LB method and spin coating method can also be used.

In such a film, polymer chains may be connected between layers. Moreover, a rare earth ion-doped material can be obtained by using a part of the layer, for example, LHG5: Nd glass made of ascidian glass as a component. As a result, E
It is possible to realize a material having the O effect and serving as an optical power source, a waveguide laser, or an amplifier. This material is made into a waveguide,
When pumping 800 nm of pump light, it emits 1052 nm of light. Further, it becomes possible to amplify the light of 1052 nm.

In addition, rare earth ions and / or FIG.
A molecule containing a rare earth ion (M ³⁺ ) as schematically shown in FIG.
20A to 20F, a material having an EO effect and serving as an optical power source, a waveguide laser, or an amplifier can be realized by including it in the O molecule). Then, since a switch function such as an optical pickup can be added, a wavelength tunable light source, a tunable optical switch, etc. can be realized.

In addition, in inorganic or organic materials, FIG.
As shown in 1 to 23, by changing the layer on the scale of 1 atom or 1 molecule and including the 1 atom layer or 1 molecule layer in the multilayer film, it becomes possible to control the wave function at the micro level, and the large nonlinear An optical effect can be generated. Also, almost the same is possible when the film is thin, preferably including 10 Å or less layers.

24A to 24F schematically show the film formation process controlled at the atomic level. As such a film forming method, for example, Ta, Ir and W are alternately supplied to the substrate by a sputtering method in an oxygen atmosphere,
Alternatively, based on silane gas, by the CVD method,
There are various methods such as switching and introducing ammonia, N ₂ O and methane. Alternatively, as shown in FIGS. 25A to 25F, there is also a method of utilizing a chemical reaction between reactive gases. For example, by introducing tantalum chloride, iridium chloride and tungsten fluoride gas by CVD in an atmosphere such as H ₂ O, a layered structure can be formed. That is, tantalum chloride, H ₂ O,
Iridium chloride, H ₂ O, tungsten fluoride, H
₂ O, tantalum chloride, H ₂ O, iridium chloride, H
Atomic Layer Deposition (ALD) becomes possible by switching to ₂ O, tungsten fluoride, etc. 26A to 26D are examples in which a compound such as an oxide is skipped by vapor deposition or CVD to form a layer structure.

The above-mentioned films are used for various nonlinear optical devices including electro-optical devices such as optical modulators, optical switches, tunable filters, optical amplifiers and optical waveguide lasers having a nonlinear optical effect, and further, For example, it can be applied to an optical circuit board as shown in FIGS. 27A is a side view and FIG. 27B is a plan view.
FIG. 27C is an enlarged view of the switch unit of FIG. 27A. Further, the film of the present invention is used for optical wiring and switches for parallel processors, various optical modules for information processing and communication, and E
It can be widely applied to / O circuit boards and the like.

[0049]

According to the present invention, the degree of freedom of the substrate structure is large, the number of layers can be increased easily, the dielectric constant is low, the low power driving and the high speed driving are suitable, and the large area can be easily obtained. A nonlinear optical material that is easy to combine with a device and is stable, an optical power source having an EO effect, an optical waveguide laser, an optical waveguide amplifier, and a nonlinear optical device using the same, a nonlinear optical amplifier, an optical waveguide A laser and optical circuit board can be provided.

[Brief description of drawings]

FIG. 1 is a conceptual diagram of a material-modulated nonlinear optical material.

FIG. 2 is a conceptual diagram of a composition-modulated nonlinear optical material.

FIG. 3 is a conceptual diagram of a non-linear optical material of doped modulation.

FIG. 4 is a conceptual diagram of a film thickness modulation nonlinear optical material.

FIG. 5 is a schematic diagram showing an example of a non-linear optical material for material modulation.

FIG. 6 is a schematic diagram showing another example of a non-linear optical material for material modulation.

FIG. 7 is a schematic diagram showing another example of a nonlinear optical material for material modulation.

FIG. 8 is a schematic diagram showing another example of a nonlinear optical material for material modulation.

FIG. 9 is a schematic view showing an example of a composition-modulated nonlinear optical material.

FIG. 10 is a schematic diagram showing another example of a composition-modulated nonlinear optical material.

FIG. 11 is a schematic diagram showing another example of a composition-modulated nonlinear optical material.

FIG. 12 is a schematic diagram showing an example of a non-linear optical material of doped modulation.

FIG. 13 is a schematic view showing another example of a non-linear optical material of doped modulation.

FIG. 14 is a schematic diagram showing another example of a non-linear optical material of doped modulation.

FIG. 15 is a schematic view showing an example of a nonlinear optical material of film thickness modulation.

FIG. 16 is a schematic diagram showing another example of a nonlinear optical material of film thickness modulation.

FIG. 17 is a schematic diagram showing another example of a nonlinear optical material of film thickness modulation.

FIG. 18 is a schematic diagram of a molecule containing a rare earth ion.

FIG. 19 is a schematic diagram of a nonlinear optical material molecule.

FIG. 20 is a schematic diagram of a nonlinear optical material containing a molecule containing a rare earth ion.

FIG. 21 is a schematic diagram showing an example of a nonlinear optical material containing one atomic layer or one molecular layer.

FIG. 22 is a schematic view showing another example of the nonlinear optical material containing one atomic layer or one molecular layer.

FIG. 23 is a schematic diagram showing another example of a nonlinear optical material containing one atomic layer or one molecular layer.

FIG. 24 is a schematic diagram showing a film formation process controlled at the atomic level.

FIG. 25 is a schematic diagram showing a film forming process utilizing a chemical reaction between reactive gases.

FIG. 26 is a schematic diagram showing a film forming process by vapor deposition or CVD of a compound.

FIG. 27 is a schematic view showing an example of an optical circuit board using the nonlinear optical material of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Go Ishizuka 1015 Kamiodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture, Fujitsu Limited (72) Inventor, Koji Tsukamoto 1015, Kamedotachu, Nakahara-ku, Kawasaki, Kanagawa Prefecture, Fujitsu Limited ( 72) Inventor Katsada Motoyoshi 1015 Kamiodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture, Fujitsu Limited

Claims (18)

[Claims] 1. In a multilayer film containing an amorphous or polycrystalline inorganic substance, different substances are laminated to eliminate centrosymmetry in the film thickness direction, or the composition of the substance of the same system is changed, or doped. Change the type of material and / or the amount of doping or change the layer thickness and / or
Alternatively, the non-linear optical material is characterized in that the central symmetry is eliminated by changing the doping amount, or the central symmetry is eliminated by combining any two or more of the above methods. 2. The multilayer film is a-Si: H, a-Si.
_{N y, a-SiO x,} a-SiC z and a-Ge: H
The nonlinear optical material according to claim 1, which comprises a material selected from the group consisting of or a mixed crystal of two or more kinds of the materials as a main component. 3. The nonlinear optical material according to claim 1, wherein the multilayer film contains a transition metal compound as a main component. 4. The nonlinear optical material according to claim 1, wherein the multilayer film contains a glass material as a main component. 5. The nonlinear optical material according to claim 1, wherein the multilayer film contains rare earth ions. 6. In a multilayer film containing an organic crystalline material, an amorphous material, a polycrystalline material or a single crystalline material, different substances are laminated to eliminate the central symmetry in the film thickness direction, or Whether the composition is changed, the type and / or the amount of the doping material is changed,
Alternatively, the central symmetry is eliminated by changing the layer thickness and / or the doping amount to eliminate the central symmetry, or by combining any two or more of the above methods to eliminate the central symmetry. material. 7. The nonlinear optical material according to claim 6, wherein the multilayer film contains an organic polymer as a main component. 8. The nonlinear optical material according to claim 6, wherein the multilayer film contains a rare earth ion and / or a molecule containing a rare earth ion. 9. The nonlinear optical material according to claim 1, wherein the multilayer film contains one atomic layer or one molecular layer. 10. The nonlinear optical material according to claim 1, wherein the multilayer film includes a layer having a thickness of 10 Å or less. 11. The laminated structure is periodical.
The nonlinear optical material according to any one of 0. 12. A non-linear optical material comprising a non-linear optical polymer containing a rare earth ion or a molecule containing a rare earth ion. 13. The nonlinear optical material according to claim 1, wherein the film is formed by vapor phase film formation. 14. The nonlinear optical material according to claim 6, wherein the film is formed by a method selected from the group consisting of vapor deposition polymerization, CVD, MLD and MBD. 15. A non-linear optical device made of the material according to claim 1. 16. A nonlinear optical amplifier using the material according to any one of claims 1 to 14. 17. A nonlinear optical waveguide laser made of the material according to claim 1. 18. An optical circuit board made of the material according to claim 1.