JP2772411B2 - Nonlinear optical material and manufacturing method thereof - Google Patents
Nonlinear optical material and manufacturing method thereofInfo
- Publication number
- JP2772411B2 JP2772411B2 JP6067841A JP6784194A JP2772411B2 JP 2772411 B2 JP2772411 B2 JP 2772411B2 JP 6067841 A JP6067841 A JP 6067841A JP 6784194 A JP6784194 A JP 6784194A JP 2772411 B2 JP2772411 B2 JP 2772411B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- nonlinear optical
- metal oxide
- optical material
- order nonlinear
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
Links
- 230000003287 optical effect Effects 0.000 title claims description 72
- 239000000463 material Substances 0.000 title claims description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims description 81
- 150000004706 metal oxides Chemical class 0.000 claims description 81
- 229910052751 metal Inorganic materials 0.000 claims description 74
- 239000002184 metal Substances 0.000 claims description 74
- 239000010419 fine particle Substances 0.000 claims description 47
- 239000010409 thin film Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 43
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 21
- 229910052737 gold Inorganic materials 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 16
- 238000004544 sputter deposition Methods 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 13
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 150000004703 alkoxides Chemical class 0.000 claims description 5
- 239000012780 transparent material Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910005800 NiMnCo Inorganic materials 0.000 claims description 3
- -1 MnCo 2 O 4 Inorganic materials 0.000 claims description 2
- 229910003266 NiCo Inorganic materials 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 239000012266 salt solution Substances 0.000 claims 2
- 239000011521 glass Substances 0.000 description 28
- 239000010949 copper Substances 0.000 description 21
- 239000010931 gold Substances 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000011159 matrix material Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000005373 porous glass Substances 0.000 description 12
- 239000011651 chromium Substances 0.000 description 11
- 239000011572 manganese Substances 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000010944 silver (metal) Substances 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910001960 metal nitrate Inorganic materials 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 230000005476 size effect Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229940120693 copper naphthenate Drugs 0.000 description 2
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- AINHSHQYUIJWGW-UHFFFAOYSA-N ethanol;oxovanadium Chemical compound [V]=O.CCO.CCO AINHSHQYUIJWGW-UHFFFAOYSA-N 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は非線形光学効果を利用し
た光デバイスの基礎をなす非線形光学材料およびその製
造方法、さらに詳細には非線形光学効果の大きな金属酸
化物薄膜、金属微粒子を分散析出した金属酸化物薄膜、
および、金属酸化物および／または金属を微粒子化して
透明物質中に分散析出した物質およびそれらの製造方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-linear optical material and a method for producing the same, which form the basis of an optical device utilizing a non-linear optical effect. Metal oxide thin film,
In addition, the present invention relates to a substance in which a metal oxide and / or a metal is finely divided and dispersed and precipitated in a transparent substance, and a method for producing the same.
【０００２】[0002]
【従来の技術およびその問題点】従来見いだされてきた
比較的大きな非線形光学効果を有する物質として、CdS
等の半導体微粒子を分散析出したガラスやAu等の貴金属
微粒子を分散析出したガラス等が知られている。これら
の物質においては、半導体あるいは貴金属を微粒子化し
た場合においてのみ、大きな非線形光学効果が得られ、
微粒子化しない場合にはほとんど非線形光学効果を発現
しない。また、それらの材料においては、ガラスは微粒
子を分散するためのマトリックスとしての役割しかもた
ず、非線形光学効果の増大には寄与しないので、半導体
あるいは貴金属の微粒子をガラス中に多量に含有させる
程非線形光学効果は大きくなる。2. Description of the Related Art As a substance having a relatively large nonlinear optical effect which has been conventionally found, CdS
Glass and the like in which semiconductor fine particles such as Au are dispersed and deposited and noble metal fine particles such as Au and the like are dispersed and precipitated are known. In these substances, a large nonlinear optical effect can be obtained only when the semiconductor or noble metal is finely divided,
When the particles are not formed into a fine particle, the nonlinear optical effect is hardly exhibited. In these materials, the glass only serves as a matrix for dispersing the fine particles, and does not contribute to the increase in the nonlinear optical effect. The optical effect increases.
【０００３】しかしながら、このような半導体微粒子あ
るいは貴金属微粒子をガラス中に含有させ得る割合には
物質の性質および技術的制約による上限が存在する。金
微粒子を例にとると、現在最も多量にシリカガラス中に
分散析出させ得るイオン注入法を用いた技術によって
も、6.3原子％（40重量％）程度以上の割合で含有させ
ることは困難である。したがって、金微粒子に起因する
３次非線形光学効果も分散量に制限される。また、貴金
属微粒子分散ガラスは安定性は高いが、原料となる貴金
属が高価であるため、より安価な原料を用いた非線形光
学材料が要望されている。一方、CdS等の半導体微粒子
分散ガラスは光照射による非線形光学効果の低下や黒化
現象を起こし易く、また、多孔質ガラス中に分散析出し
たものでは長期間放置すると酸化分解が進んで硫黄を遊
離する等の経時変化を起こす場合があるので安定性に問
題があり、人体に有害なカドミウムを含むため安全面か
らも問題がある。さらに、半導体あるいは貴金属を微粒
子状にガラス中に分散析出させ、任意の形状のファイバ
ーや薄膜等に加工するには複雑な工程が必要であるた
め、生産性は高いとは言い難い。したがって、半導体微
粒子分散ガラスや貴金属微粒子分散ガラスは非線形光学
材料として難点がある。[0003] However, there is an upper limit due to the nature of the substance and technical restrictions on the proportion of such semiconductor fine particles or noble metal fine particles that can be contained in glass. In the case of gold particles as an example, it is difficult to contain gold particles at a ratio of about 6.3 atomic% (40% by weight) or more even by a technique using an ion implantation method capable of dispersing and precipitating a large amount in silica glass at present. . Therefore, the third-order nonlinear optical effect caused by the fine gold particles is also limited by the amount of dispersion. In addition, noble metal particle-dispersed glass has high stability, but the noble metal used as a raw material is expensive. Therefore, a nonlinear optical material using a less expensive raw material is demanded. On the other hand, semiconductor fine particle dispersed glass such as CdS is liable to decrease the non-linear optical effect and blackening phenomenon due to light irradiation. In some cases, there is a problem in stability because of aging such as cadmium, and there is also a problem in safety because it contains cadmium harmful to the human body. Further, since a semiconductor or a noble metal is dispersed and precipitated in the form of fine particles in glass and processed into a fiber, a thin film, or the like having an arbitrary shape, a complicated process is required, so that the productivity is hardly high. Therefore, the semiconductor fine particle dispersed glass and the noble metal fine particle dispersed glass have a problem as a nonlinear optical material.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、非線
形光学材料の現状に鑑み、高い非線形光学効果を安定に
発現し、かつ、安価で安全性にも優れた新たな非線形光
学材料及びその製造方法を提供することにある。SUMMARY OF THE INVENTION In view of the current situation of nonlinear optical materials, an object of the present invention is to provide a new nonlinear optical material which stably exhibits a high nonlinear optical effect, is inexpensive and has excellent safety, and a new nonlinear optical material. It is to provide a manufacturing method.
【０００５】[0005]
【課題を解決するための手段】本発明は、上記の目的を
達成するためになされたものであり、本発明の３次非線
形光学材料は、透明基板上に、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、
Ｃｏ、ＮｉおよびＣｕからなる群から選ばれた少なくと
も１種の金属の酸化物からなる薄膜を直接形成してなる
ものである（以下第１の発明という）。Means for Solving the Problems The present invention has been made to achieve the above object, and a tertiary nonlinear optical material of the present invention comprises V, Cr, Mn, Fe,
It is formed by directly forming a thin film made of an oxide of at least one metal selected from the group consisting of Co, Ni and Cu (hereinafter referred to as a first invention).
【０００６】本第１の発明において使用する「金属酸化
物」は、金属の酸化状態に関して特に限定はなく、例え
ばCr2O3, MnO2, Mn3O4, Fe2O3, Fe3O4, CoO, Co3O4, Cu
Oなどの種々の酸化状態のものがいずれも用いられ、特
に好ましい金属酸化物としては、Cr2O3, Mn3O4, Fe2O3,
Co3O4, CuOが挙げられる。なお、金属の酸化物には、
上記のような単一の金属の酸化物の他に、MnCo2O4, NiC
o2O4, NiMnCo4O8などの複合酸化物も含まれる。[0006] The "metal oxide" used in the first invention is not particularly limited with respect to the oxidation state of the metal. For example, Cr 2 O 3 , MnO 2 , Mn 3 O 4 , Fe 2 O 3 , Fe 3 O 4 , CoO, Co 3 O 4 , Cu
Any of various oxidation states such as O may be used, and particularly preferred metal oxides are Cr 2 O 3 , Mn 3 O 4 , Fe 2 O 3 ,
Co 3 O 4 and CuO are exemplified. In addition, metal oxides include
In addition to the single metal oxides described above, MnCo 2 O 4 , NiC
Composite oxides such as o 2 O 4 and NiMnCo 4 O 8 are also included.
【０００７】本第１発明の金属酸化物を含む物質の薄膜
には、それ自体は該金属酸化物の非線形光学効果に寄与
しないが、添加することによって該金属酸化物の薄膜製
造を容易にする働き、或いは薄膜の構造安定性や機械的
強度を向上させる働きを持ち、且つ光学的な透明性が高
い添加成分を加えてもよい。このような添加成分として
は、特に限定されないが、Al2O3, ZnO, ZrO2などが例示
される。金属酸化物中の金属原子数と、添加成分中の金
属原子数の比率は、通常（１：０．０１）〜（１：０．
１０）程度である。The thin film of the substance containing the metal oxide of the first invention does not itself contribute to the nonlinear optical effect of the metal oxide, but the addition thereof facilitates the production of the thin film of the metal oxide. An additive component having a function or a function of improving the structural stability or mechanical strength of the thin film and having high optical transparency may be added. Such additional components are not particularly limited, and examples thereof include Al 2 O 3 , ZnO, and ZrO 2 . The ratio of the number of metal atoms in the metal oxide to the number of metal atoms in the additive component is usually (1: 0.01) to (1: 0.
About 10).
【０００８】上記薄膜が適用される透明基板としては、
SiO2を主成分とするガラス、石英、Al2O3からなるサフ
ァイアなどが挙げられる。これらの材料は、平板状の形
状である。The transparent substrate to which the above thin film is applied includes:
Examples thereof include glass containing SiO 2 as a main component, quartz, and sapphire made of Al 2 O 3 . These materials have a flat plate shape.
【０００９】さらに、本発明の３次非線形光学材料は、
透明基板上に、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉおよ
びＣｕからなる群から選ばれた少なくとも１種の金属の
酸化物からなる薄膜の表面或いは内部にＡｕ、Ａｇおよ
びＣｕからなる群から選ばれた少なくとも１種の金属の
粒径５００ｎｍ以下の微粒子を分散析出させた複合体薄
膜（但し、金属酸化物がＣｕ２Ｏであり、金属がＣｕで
ある場合を除く）を形成してなるものである（以下第２
の発明という）。Furthermore, the third-order nonlinear optical material of the present invention is
On a transparent substrate, a thin film made of an oxide of at least one metal selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, and Cu is formed on the surface or inside of a thin film made of Au, Ag, and Cu. A composite thin film (excluding a case where the metal oxide is Cu 2 O and the metal is Cu) in which fine particles of at least one selected metal having a particle size of 500 nm or less are dispersed and deposited. (Hereinafter the second
Of the invention).
【００１０】本第２の発明において、金属の酸化物及び
透明基板は、上記第１の発明と同様である。In the second invention, the metal oxide and the transparent substrate are the same as in the first invention.
【００１１】本第２の発明で用いるAu, Ag, Cuは、通常
単体の金属として用いられる。Au, Ag, and Cu used in the second invention are usually used as a single metal.
【００１２】V, Cr, Mn, Fe, Co, Ni, Cuからなる群か
ら選ばれた少なくとも１種の金属の酸化物を含む物質中
の金属原子数と、Au, Ag, Cuからなる群から選ばれた少
なくとも１種の金属の原子数の配合比率は、特に限定さ
れないが、好ましくは（１：０．０５）〜（１：４）程
度、より好ましくは（１：０．２）〜（１：２）程度で
ある。上記の金属の酸化物とAu, Ag, Cuからなる群から
選ばれた少なくとも１種の金属が上記の範囲内のとき
は、レーザー光照射時の熱により金属微粒子同士が凝集
するなどの構造変化が起こり難く、また望まれる非線形
光学効果が得られるため好ましい。The number of metal atoms in a substance containing an oxide of at least one metal selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, and Cu, and the number of metal atoms in the group consisting of Au, Ag, and Cu The mixing ratio of the number of atoms of the selected at least one metal is not particularly limited, but is preferably about (1: 0.05) to (1: 4), and more preferably (1: 0.2) to ( 1: 2). When at least one metal selected from the group consisting of the above metal oxides and Au, Ag, Cu is within the above range, structural changes such as aggregation of metal fine particles due to heat during laser beam irradiation. Is less likely to occur and a desired nonlinear optical effect can be obtained.
【００１３】本第２の発明で用いられるAu, Ag, Cuから
なる群から選ばれた少なくとも１種の金属の微粒子の粒
径は、５００ｎｍ以下であるが、好ましくは５〜１００
ｎｍである。本第２発明において、V, Cr, Mn, Fe, Co,
Ni, Cuからなる群から選ばれた少なくとも１種の金属
の酸化物の粒径は、該酸化物を含む物質が薄膜である限
り任意であり、該薄膜が微粒子の集合体からなる場合で
も粒子径は任意である。The particle size of the fine particles of at least one metal selected from the group consisting of Au, Ag and Cu used in the second invention is not more than 500 nm, preferably 5 to 100 nm.
nm. In the second invention, V, Cr, Mn, Fe, Co,
The particle size of the oxide of at least one metal selected from the group consisting of Ni and Cu is arbitrary as long as the substance containing the oxide is a thin film. The diameter is arbitrary.
【００１４】さらに、本発明は、V, Cr, Mn, Fe, Co, N
i, Cuからなる群から選ばれた少なくとも１種の金属の
酸化物を含む物質を粒径500nm以下の微粒子として透明
物質中に分散析出させることを特徴とする３次非線形光
学材料の製造方法（以下第３の発明という）および第３
の発明の方法により製造される３次非線形光学材料でも
ある。Further, the present invention provides a method for producing V, Cr, Mn, Fe, Co, N
A method for producing a tertiary nonlinear optical material, comprising: dispersing and depositing a substance containing an oxide of at least one metal selected from the group consisting of i and Cu as fine particles having a particle diameter of 500 nm or less in a transparent substance ( Hereinafter referred to as the third invention) and the third invention
It is also a third-order nonlinear optical material manufactured by the method of the present invention.
【００１５】金属の酸化物としては、上記第１及び第２
発明と同様のものが用いられる。As the metal oxide, the first and second metal oxides
The same thing as the invention is used.
【００１６】本第３の発明で使用する透明物質として
は、第１の発明で使用する透明基板で使用されるものが
すべて使用できる。但し、その形状は限定されない。As the transparent substance used in the third invention, all the substances used for the transparent substrate used in the first invention can be used. However, the shape is not limited.
【００１７】本第３発明で使用される金属の酸化物は、
第１及び第２の発明と同様なものが用いられるが、その
粒子径としては５００ｎｍ以下、好ましくは５〜１００
ｎｍである。The metal oxide used in the third invention is:
The same ones as those of the first and second inventions are used, and the particle diameter is 500 nm or less, preferably 5 to 100 nm.
nm.
【００１８】さらに、本発明は、V, Cr, Mn, Fe, Co, N
i, Cuからなる群から選ばれた少なくとも１種の金属の
酸化物を含む物質、並びに、Au, Ag, Cuからなる群から
選ばれた少なくとも１種の金属を、粒径500nm以下の微
粒子として透明物質中に分散析出することを特徴とする
３次非線形光学材料の製造方法（以下、第４の発明とい
う）および第４の発明の方法により製造される３次非線
形光学材料でもある。Further, the present invention provides a method for producing V, Cr, Mn, Fe, Co, N
i, a substance containing an oxide of at least one metal selected from the group consisting of Cu, and at least one metal selected from the group consisting of Au, Ag, Cu as fine particles having a particle size of 500 nm or less. The present invention is also a method for producing a third-order nonlinear optical material characterized by being dispersed and precipitated in a transparent substance (hereinafter, referred to as a fourth invention) and a third-order nonlinear optical material produced by the method of the fourth invention.
【００１９】以下、本第１から第４の発明を詳細に説明
する。Hereinafter, the first to fourth inventions will be described in detail.
【００２０】本第１の発明では、非線形光学材料の主成
分としては、V, Cr, Mn, Fe, Co, Ni, Cuから選ばれた
少なくとも１種の金属の酸化物を用いる。これらの酸化
物は、レーザー光のような強い光の照射下において高い
３次非線形光学効果を発現する性質を有するものであ
る。このような現象の生じる理由は明確ではないが、以
下のような原理によるものであると推測される。即ち、
これらの金属酸化物は、紫外・可視・近赤外におよぶ広
い波長範囲に連続的な吸収帯をもち、半導体的な性質を
もつ。したがって、バンドギャップ近傍の周波数のレー
ザー光を金属酸化物に照射したとき、励起状態のキャリ
ア密度が顕著に増大し、飽和吸収を起こして屈折率が変
化する、いわゆるバンドフィリング効果によって高い３
次非線形光学効果が発現すると推測される。また、レー
ザー光の照射に伴う温度上昇による屈折率の変化も３次
非線形光学効果の発現に寄与していると考えられる。In the first invention, an oxide of at least one metal selected from V, Cr, Mn, Fe, Co, Ni and Cu is used as a main component of the nonlinear optical material. These oxides have a property of exhibiting a high third-order nonlinear optical effect under irradiation of strong light such as laser light. The reason why such a phenomenon occurs is not clear, but is presumed to be due to the following principle. That is,
These metal oxides have a continuous absorption band in a wide wavelength range from ultraviolet to visible to near infrared, and have semiconductor properties. Therefore, when a metal oxide is irradiated with a laser beam having a frequency in the vicinity of the band gap, the carrier density in the excited state is remarkably increased, causing saturation absorption to change the refractive index.
It is assumed that the next nonlinear optical effect appears. Further, it is considered that the change in the refractive index due to the temperature rise accompanying the irradiation of the laser beam also contributes to the expression of the third-order nonlinear optical effect.
【００２１】このような現象は全ての金属酸化物で現れ
るのではなく、（イ）照射レーザー光の波長に吸収帯を
もつこと、（ロ）半導体的性質をもつこと、の２条件を
満足する金属酸化物でのみ達成されるものと考えられ
る。上記したV, Cr, Mn, Fe, Co, Ni, Cuから選ばれた
少なくとも１種の金属の酸化物の薄膜は、いずれも高い
３次非線形光学効果を示すものである。Such a phenomenon does not appear in all metal oxides but satisfies the two conditions of (a) having an absorption band at the wavelength of the irradiated laser beam and (b) having semiconductor properties. It is believed that this is achieved only with metal oxides. The above-mentioned thin films of oxides of at least one metal selected from V, Cr, Mn, Fe, Co, Ni, and Cu all exhibit high third-order nonlinear optical effects.
【００２２】薄膜は、通常ガラス、石英、サファイア等
の透明基板上に形成する。薄膜の形成方法は特に限定は
なく、スパッタ堆積法、真空蒸着法、ＣＶＤ法等のいわ
ゆる気相法や、金属アルコキシド、金属硝酸塩、有機酸
金属塩等の溶液を基板上に塗布し、熱分解する方法等、
各種の公知法が適用できる。薄膜の厚さは特に限定され
ないが、薄膜にレーザー光を透過して非線形光学材料と
して使用する場合には、薄膜が厚くなりすぎると、光の
透過割合が少なくなり、出力光が薄膜に再吸収されて弱
まるので非線形光学材料としての有用性が低下する。通
常、スパッタ堆積法で形成される薄膜のように緻密な薄
膜の場合には、通常2〜50nm程度、好ましくは5〜20nmが
適当であり、溶液を塗布し、熱分解する方法では、形成
される薄膜が比較的緻密でないので、より厚い膜厚でも
非線形光学材料として用いることができる。一方、光導
波路表面に非線形光学材料の薄膜を形成し、光導波路か
らしみ出すエバネッセント波を用いる場合には、薄膜が
厚過ぎても使用上問題はないが、薄膜が薄過ぎると非線
形光学効果に優れた材料とならないため、薄膜の厚さは
2nm以上であることが好ましく、より好ましくは2〜100n
m、さらに好ましくは5〜50nm程度である。The thin film is usually formed on a transparent substrate such as glass, quartz, sapphire and the like. The method for forming the thin film is not particularly limited. A so-called gas phase method such as a sputter deposition method, a vacuum evaporation method, or a CVD method, or a solution of a metal alkoxide, a metal nitrate, an organic acid metal salt, or the like is applied on a substrate and thermally decomposed. How to do
Various known methods can be applied. Although the thickness of the thin film is not particularly limited, when the thin film is used as a nonlinear optical material by transmitting a laser beam, if the thin film is too thick, the light transmission ratio decreases, and the output light is re-absorbed by the thin film. As a result, the usefulness as a nonlinear optical material is reduced. Usually, in the case of a dense thin film such as a thin film formed by a sputter deposition method, the thickness is usually about 2 to 50 nm, preferably 5 to 20 nm. Since the thin film is relatively dense, a thicker film can be used as a nonlinear optical material. On the other hand, when a thin film of a nonlinear optical material is formed on the surface of an optical waveguide and an evanescent wave oozing out of the optical waveguide is used, there is no problem in using the film even if the film is too thick. Because it is not a good material, the thickness of the thin film is
It is preferably at least 2 nm, more preferably 2 to 100 n
m, more preferably about 5 to 50 nm.
【００２３】本第２の発明では、上記の金属酸化物から
なる薄膜中或いは薄膜表面にＡｕ、ＡｇおよびＣｕから
なる群から選ばれた少なくとも１種の金属の微粒子を分
散析出させている（但し、金属酸化物がＣｕ２Ｏであ
り、金属がＣｕである場合を除く）。本発明の複合材料
における金属微粒子の混入の目的は、金属酸化物薄膜の
非線形光学効果を増強するためである。上記の金属酸化
物薄膜と金属微粒子とはいずれも高い非線形光学効果を
示すので、本発明による複合体薄膜においては、いずれ
か単独成分のみを含む薄膜と比較して、非線形光学効果
により一層改善される。In the second aspect of the present invention, fine particles of at least one metal selected from the group consisting of Au, Ag and Cu are dispersed and deposited in or on the thin film made of the above-mentioned metal oxide (provided that the thin film is made of Au, Ag and Cu). , The metal oxide is Cu 2 O and the metal is Cu). The purpose of mixing the metal fine particles in the composite material of the present invention is to enhance the nonlinear optical effect of the metal oxide thin film. Since both the metal oxide thin film and the metal fine particles show a high nonlinear optical effect, the composite thin film according to the present invention is further improved by the nonlinear optical effect, as compared with a thin film containing only one component alone. You.
【００２４】この様な第２の発明による金属微粒子分散
金属複合膜の形成方法は、特に限定なく、金属酸化物タ
ーゲットと金属ターゲットとを用いて基板上に同時スパ
ッタ法或いは交互スパッタ法により堆積させる方法、金
属酸化物の前駆体となる金属アルコキシド、金属硝酸
塩、有機酸金属塩などの溶液と金属微粒子の前駆体とな
る塩化金酸などの物質の溶液とを混合し、スピンコート
法などにより基板上に成膜した後、空気などの酸素含有
雰囲気下で焼成する方法、多孔質或いは平滑な金属酸化
物薄膜上にスパッタ法により堆積させる方法、金属微粒
子分散液を塗布した後、熱分解させる方法などにより、
金属微粒子を固定化する方法などが挙げられる。The method for forming the metal fine particle-dispersed metal composite film according to the second aspect of the present invention is not particularly limited, and the metal oxide target and the metal target are deposited on a substrate by simultaneous sputtering or alternate sputtering. Method: A solution of a metal alkoxide, a metal nitrate, a metal salt of an organic acid, etc., which is a precursor of a metal oxide, and a solution of a substance, such as chloroauric acid, which is a precursor of metal fine particles, are mixed, and the substrate is spin-coated or the like. A method of baking in an oxygen-containing atmosphere such as air after film formation, a method of depositing on a porous or smooth metal oxide thin film by a sputtering method, and a method of applying a metal fine particle dispersion and then thermally decomposing it. For example,
A method of immobilizing metal fine particles is exemplified.
【００２５】本第３の発明では、透明物質としては、Si
O2を含むガラスマトリックス、Al2O3, ZrO2などが挙げ
られ、上記の金属酸化物の微粒子が透明物質中に0.1重
量％以上、好ましくは２〜８０重量％、より好ましくは
１０〜５０重量％の割合で分散析出している。第１の発
明における金属酸化物は、微粒子化することにより、Cd
S等の半導体と同様に、量子サイズ効果によって、単位
原子数当たりで比較すると、微粒子化しない薄膜状の金
属酸化物よりも大きな非線形光学効果を示す。したがっ
て、ガラス等の透明なマトリックス中にある一定量以上
の金属酸化物微粒子を分散させた材料は、微粒子化しな
い連続的な金属酸化物薄膜よりも大きな非線形光学効果
を示す。ガラスマトリックス中に析出させる金属酸化物
の粒径は、量子サイズ効果により非線形光学効果を増大
させるため、500nm以下であることが必要であり、好ま
しくは5〜100nm、より好ましくは5〜50nmである。In the third invention, the transparent substance is Si
O 2 -containing glass matrix, Al 2 O 3 , ZrO 2, etc., and the above-mentioned metal oxide fine particles are 0.1% by weight or more, preferably 2 to 80% by weight, more preferably 10 to 50% by weight in the transparent substance. It is dispersed and precipitated at a ratio of weight%. The metal oxide in the first invention is Cd
Similar to semiconductors such as S, when compared per unit number of atoms due to the quantum size effect, they exhibit a larger nonlinear optical effect than metal oxides in the form of thin films that are not finely divided. Therefore, a material in which a certain amount or more of metal oxide fine particles are dispersed in a transparent matrix such as glass exhibits a larger nonlinear optical effect than a continuous metal oxide thin film that is not finely divided. The particle diameter of the metal oxide deposited in the glass matrix is required to be 500 nm or less, preferably 5 to 100 nm, more preferably 5 to 50 nm, in order to increase the nonlinear optical effect due to the quantum size effect. .
【００２６】このような第３の発明により製造される金
属酸化物含有ガラスは、金属酸化物微粒子の含有濃度を
高くすることが容易である点、金属酸化物微粒子の大き
さの制御が可能である点、分散析出させ得る金属酸化物
の種類が豊富である点等から、多孔質ガラスマトリック
スを利用して製造、あるいはスパッタ堆積法により製造
する。The metal oxide-containing glass produced according to the third aspect of the present invention can easily increase the concentration of the metal oxide fine particles, and can control the size of the metal oxide fine particles. In view of the fact that there are abundant types of metal oxides that can be dispersed and deposited, they are manufactured using a porous glass matrix or manufactured by a sputter deposition method.
【００２７】従来、多孔質ガラスマトリックスに金属酸
化物微粒子分散液を浸透させ、乾燥後、酸素を含む雰囲
気中で1500℃まで加熱して非線形光学材料を作製する方
法が開示されている（特開平2-44031）。しかし、この
方法では金属酸化物微粒子の直径よりも大きな細孔径を
もつ多孔質ガラスマトリックスしか用いることができ
ず、また、金属酸化物微粒子分散液が得られる金属酸化
物の種類および金属酸化物微粒子の寸法も限られている
欠点がある。従って、目的に応じた高い自由度で金属酸
化物微粒子の種類および寸法を選択して多孔質ガラスマ
トリックス中に分散析出できる方法が要望されている。Conventionally, a method has been disclosed in which a dispersion of metal oxide fine particles is permeated into a porous glass matrix, dried, and then heated to 1500 ° C. in an atmosphere containing oxygen to produce a nonlinear optical material (Japanese Patent Laid-Open Publication No. Hei 9 (1994)). 2-44031). However, in this method, only a porous glass matrix having a pore diameter larger than the diameter of the metal oxide fine particles can be used, and the type of the metal oxide from which the metal oxide fine particle dispersion is obtained and the metal oxide fine particles Has the disadvantage that its dimensions are also limited. Therefore, there is a demand for a method capable of selecting the type and size of the metal oxide fine particles with a high degree of freedom according to the purpose and dispersing and depositing them in a porous glass matrix.
【００２８】このような問題点を解決するため、多孔質
ガラスマトリックスを用いて第３の発明の金属酸化物含
有ガラスを製造するにあたっては、例えば多孔質ガラス
マトリックスにバナジルイソプロポキシド、バナジルエ
トキシドなどの金属アルコキシド、硝酸マンガン、硝酸
コバルト、硝酸第１鉄、硝酸銅などの金属硝酸塩、オク
チル酸バナジウム、オクチル酸ニッケル、ナフテン酸ク
ロム、ナフテン酸銅などの有機酸金属塩等の溶液を含浸
させ、乾燥後、熱分解する方法等を用いる。In order to solve such a problem, when producing the metal oxide-containing glass of the third invention using a porous glass matrix, for example, vanadyl isopropoxide, vanadyl ethoxide, Impregnated with a solution such as metal alkoxides, metal nitrates such as manganese nitrate, cobalt nitrate, ferrous nitrate, and copper nitrate; and organic acid metal salts such as vanadium octylate, nickel octylate, chromium naphthenate, and copper naphthenate. After drying, a method of thermal decomposition is used.
【００２９】スパッタ堆積法を用いて第３の発明の金属
酸化物含有ガラスの製造法を行うにあたっては、例えば
シリカガラスターゲットと金属酸化物ターゲットを用い
て、同時スパッタあるいは交互スパッタ法で基板上、あ
るいは、光導波路を構成する屈折率の異なるガラス上に
堆積させる方法等をとることができる。In carrying out the method for producing the metal oxide-containing glass of the third invention by using the sputter deposition method, for example, using a silica glass target and a metal oxide target, simultaneous sputtering or alternate sputtering is performed on a substrate. Alternatively, it is possible to adopt a method of depositing on glass having a different refractive index constituting the optical waveguide.
【００３０】本第４の発明では、上記の金属酸化物の微
粒子と共に金属の微粒子がそれぞれ０．１重量％以上好
ましくは２〜８０重量％、より好ましくは１０〜５０重
量％の割合でガラスマトリックスなどの透明物質中に分
散析出している。本発明の複合材料における金属微粒子
の混入の目的は、金属酸化物微粒子の非線形光学効果を
増強するためである。上記の金属酸化物微粒子と金属微
粒子はいずれも高い非線形光学効果を示すので、いずれ
か単独成分のみが透明物質中に分散析出されている材料
と比較して非線形光学効果が増強される。透明物質中に
析出させる金属酸化物の粒径および金属の粒径は、量子
サイズ効果により非線形光学効果を増大させるため、50
0nm以下であることが必要である。透明物質中に析出さ
せる金属酸化物および金属の割合は特に限定的ではない
が、金属酸化物および金属の透明物質に対する割合が0.
1重量％未満では、非線形光学効果に優れた金属酸化物
・金属含有ガラスとならないため、金属酸化物および金
属の割合は0.1重量％以上とすることが好ましい。In the fourth aspect of the present invention, the fine particles of the metal together with the fine particles of the metal oxide are contained in a glass matrix in an amount of 0.1% by weight or more, preferably 2 to 80% by weight, more preferably 10 to 50% by weight. And dispersed in a transparent substance such as The purpose of mixing the metal fine particles in the composite material of the present invention is to enhance the nonlinear optical effect of the metal oxide fine particles. Since both the metal oxide fine particles and the metal fine particles show a high nonlinear optical effect, the nonlinear optical effect is enhanced as compared with a material in which only one of the components is dispersed and precipitated in a transparent substance. The particle size of the metal oxide and the particle size of the metal deposited in the transparent material are 50% because the nonlinear optical effect is increased by the quantum size effect.
It must be less than 0 nm. The ratio of the metal oxide and the metal deposited in the transparent material is not particularly limited, but the ratio of the metal oxide and the metal to the transparent material is 0.
If the content is less than 1% by weight, a metal oxide / metal-containing glass having an excellent nonlinear optical effect is not obtained, so that the ratio of the metal oxide and the metal is preferably 0.1% by weight or more.
【００３１】このような第４の発明により製造される金
属酸化物・金属含有ガラスは、金属酸化物・金属微粒子
の含有濃度を高くすることが容易である点、金属酸化物
・金属微粒子の大きさの制御が可能である点、分散析出
させ得る金属酸化物・金属の種類が豊富である点等か
ら、多孔質ガラスマトリックスを利用して製造、あるい
はスパッタ堆積法により製造する。The glass containing metal oxide and metal produced according to the fourth aspect of the invention is easy to increase the concentration of metal oxide and metal fine particles, and the size of the metal oxide and metal fine particles is large. The production is performed by using a porous glass matrix or by a sputter deposition method in view of controllability of the surface and abundant types of metal oxides and metals that can be dispersed and deposited.
【００３２】多孔質ガラスマトリックスを用いて第４の
発明の方法に従い金属酸化物・金属含有ガラスを製造す
るにあたっては、例えば多孔質ガラスマトリックスに金
属酸化物の前駆体となる金属アルコキシド、金属硝酸
塩、有機酸金属塩等の溶液および金属の前駆体となる塩
化金酸のような物質の溶液を含浸させ、乾燥後、熱分解
する方法等をとることができる。In producing a metal oxide / metal-containing glass according to the method of the fourth invention using a porous glass matrix, for example, a metal alkoxide, a metal nitrate, which is a precursor of a metal oxide, A method of impregnating with a solution of a metal salt of an organic acid or the like and a solution of a substance such as chloroauric acid which is a precursor of a metal, followed by drying and thermal decomposition can be employed.
【００３３】スパッタ堆積法を用いて第４の発明の方法
に従い金属酸化物・金属含有ガラスを製造するにあたっ
ては、例えばシリカガラスターゲット、金属酸化物ター
ゲット、ならびに金属ターゲットを用いて、同時スパッ
タ法あるいは交互スパッタ法で基板上、あるいは光導波
路を構成する屈折率の異なるガラス上に堆積させる方法
等をとることができる。In producing a metal oxide / metal-containing glass according to the method of the fourth invention using a sputter deposition method, for example, a simultaneous sputtering method or a metal oxide target using a metal oxide target and a metal target is used. For example, a method of depositing on a substrate or glass having a different refractive index constituting an optical waveguide by an alternate sputtering method can be employed.
【００３４】本第１〜第４の発明では、これらの金属酸
化物を単独または混合して用いることができる。また、
単成分の金属元素の酸化物として用いるだけでなく、複
合酸化物として用いてもよい。In the first to fourth inventions, these metal oxides can be used alone or as a mixture. Also,
It may be used not only as a single component metal element oxide but also as a composite oxide.
【００３５】本第３および第４の発明では、多孔質ガラ
ス中に残存する空隙に起因する光の散乱を減少させ、非
線形光学効果を向上させるために、製造した材料を600
℃以上の高温で熱処理する等の後処理を行ってもよい。According to the third and fourth aspects of the present invention, in order to reduce the scattering of light due to the voids remaining in the porous glass and to improve the nonlinear optical effect, the manufactured material is treated with 600
Post-treatment such as heat treatment at a high temperature of not less than ° C. may be performed.
【００３６】[0036]
【発明の効果】本発明によれば、高い非線形光学効果を
安定に発現し、かつ、安価で安全性にも優れた新たな非
線形光学材料およびその製造方法を提供できる。According to the present invention, it is possible to provide a new non-linear optical material which stably exhibits a high non-linear optical effect, is inexpensive and has excellent safety, and a method of manufacturing the same.
【００３７】[0037]
【実施例】以下、本発明の実施例を実施例を用いてより
詳細に説明するが、本発明はこれら実施例に限定される
ものではない。EXAMPLES Examples of the present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.
【００３８】実施例１ ガラス基板上（片面）にナフテン酸銅膜をスピンコート
法で形成し、380℃で２時間焼成し、厚み約35nmの淡褐
色透明を呈する酸化銅(CuO)薄膜を調製した。この酸化
銅薄膜の３次非線形感受率（χ(3)）は波長532nmで縮退
４光波混合法(DFWM)によって測定した結果5x10-8esuで
あり非線形光学材料として使用できる高い性能をもつこ
とがわかった。Example 1 A copper naphthenate film was formed on a glass substrate (one side) by spin coating and baked at 380 ° C. for 2 hours to prepare a light brown transparent copper oxide (CuO) thin film having a thickness of about 35 nm. did. The third-order nonlinear susceptibility (χ (3) ) of this copper oxide thin film was 5 × 10 -8 esu measured at 532 nm by the degenerate four-wave mixing method (DFWM), indicating that it has high performance that can be used as a nonlinear optical material. all right.
【００３９】実施例２ ガラス基板上（片面）にスパッタ法で厚み約60nmの淡褐
色透明を呈する酸化コバルト(Co3O4)薄膜を調製した。
この酸化コバルト薄膜の３次非線形感受率（χ(3)）は
波長532nmで縮退４光波混合法(DFWM)によって測定した
結果4x10-8esuであった。Example 2 A light brown transparent cobalt oxide (Co 3 O 4 ) thin film having a thickness of about 60 nm was prepared on a glass substrate (one side) by a sputtering method.
The third-order nonlinear susceptibility (χ (3) ) of this cobalt oxide thin film was 4 × 10 −8 esu as measured by a degenerate four-wave mixing method (DFWM) at a wavelength of 532 nm.
【００４０】実施例３ ナフテン酸鉄のトルエン溶液と、平均粒径10nmの金微粒
子のトルエン分散液を混合し、この溶液をガラス基板上
（片面）にスピンコートしてナフテン酸鉄と金微粒子の
混合膜を形成した。この混合膜を380℃で２時間焼成
し、厚み約30nmの赤紫色を帯びた淡褐色透明を呈する酸
化鉄(Fe2O3)・金微粒子複合薄膜を調製した。この複合
薄膜の３次非線形感受率（χ(3)）は波長532nmで縮退４
光波混合法(DFWM)によって測定した結果1x10-7esuであ
り複合化によって非線形光学材料としての性能が向上し
た。Example 3 A toluene solution of iron naphthenate and a toluene dispersion of gold fine particles having an average particle diameter of 10 nm were mixed, and this solution was spin-coated on a glass substrate (one side) to form a mixture of iron naphthenate and gold fine particles. A mixed film was formed. The mixed film was fired at 380 ° C. for 2 hours to prepare a red-purple, light brown, transparent iron oxide (Fe 2 O 3 ) / gold fine particle composite thin film having a thickness of about 30 nm. The third-order nonlinear susceptibility (χ (3) ) of this composite thin film is degenerate at 532 nm.
The result was 1x10 -7 esu measured by the light wave mixing method (DFWM), and the performance as a nonlinear optical material was improved by compounding.
【００４１】実施例４ 硝酸マンガンと硝酸コバルトの混合トルエン溶液を、平
均細孔径4nm、気孔率28%、比表面積200m2/gの多孔質ガ
ラスマトリックスに含浸させ、乾燥後、380℃で２時間
焼成し、マンガン・コバルト複合酸化物を多孔質ガラス
の細孔内に固定化した褐色の材料を調製した。このマン
ガン・コバルト複合酸化物微粒子分散ガラスの３次非線
形感受率（χ(3)）は波長532nmで縮退４光波混合法(DFW
M)によって測定した結果10-10esuであった。Example 4 A mixed toluene solution of manganese nitrate and cobalt nitrate was impregnated into a porous glass matrix having an average pore diameter of 4 nm, a porosity of 28%, and a specific surface area of 200 m 2 / g, and dried at 380 ° C. for 2 hours. It was calcined to prepare a brown material in which the manganese-cobalt composite oxide was fixed in the pores of the porous glass. The third-order nonlinear susceptibility (χ (3) ) of the manganese-cobalt composite oxide fine particle-dispersed glass is 532 nm at a degenerate four-wave mixing method (DFW).
M) was 10 -10 esu.
【００４２】実施例５ オクチル酸コバルトのトルエン・ブタノール混合溶液に
塩化金酸を加えて溶解し、得られた混合溶液を、平均細
孔径4nm、気孔率28%、比表面積200m2/gの多孔質ガラス
マトリックスに含浸させ、乾燥後、380℃で２時間焼成
し、酸化コバルトと金を多孔質ガラスの細孔内に固定化
した紫褐色の材料を調製した。この酸化コバルト微粒子
・金微粒子分散ガラスの３次非線形感受率（χ(3)）は
波長532nmで縮退４光波混合法(DFWM)によって測定した
結果10-9esuであった。Example 5 Chloroauric acid was added to and dissolved in a mixed solution of cobalt octylate in toluene and butanol, and the obtained mixed solution was subjected to porosity having an average pore diameter of 4 nm, a porosity of 28%, and a specific surface area of 200 m 2 / g. Impregnated in a porous glass matrix, dried, and calcined at 380 ° C. for 2 hours to prepare a purple-brown material in which cobalt oxide and gold were immobilized in the pores of the porous glass. The third-order nonlinear susceptibility (χ (3) ) of the cobalt oxide fine particle / gold fine particle dispersed glass was 10 -9 esu as measured by a degenerate four-wave mixing method (DFWM) at a wavelength of 532 nm.
【図１】本発明の第１の実施例で作製した薄膜の光吸収
特性を表す図である。FIG. 1 is a diagram showing light absorption characteristics of a thin film manufactured in a first embodiment of the present invention.
【図２】本発明の第３の実施例で作製した薄膜の光吸収
特性を表す図である。FIG. 2 is a diagram illustrating light absorption characteristics of a thin film manufactured in a third embodiment of the present invention.
【図３】本発明の第５の実施例のプロセスを表す図であ
る。FIG. 3 is a diagram showing a process of a fifth embodiment of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 阪口 享 大阪府池田市緑丘１丁目８番31号 工業 技術院大阪工業技術研究所内 (72)発明者 見矢 勝 大阪府池田市緑丘１丁目８番31号 工業 技術院大阪工業技術研究所内 (56)参考文献 特開 平５−224262（ＪＰ，Ａ) 特開 平６−167728（ＪＰ，Ａ) Ｊｏｕｒｎａｌ ｏｆ ｔｈｅ Ｃｅ ｒａｍｉｃ Ｓｏｃｉｅｔｙ ｏｆ Ｊ ａｐａｎ 101（１） Ｐ．64−68 （1993) (58)調査した分野(Int.Cl.6，ＤＢ名) G02F 1/35 ＪＩＣＳＴ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Sakaguchi 1-8-31 Midorigaoka, Ikeda-shi, Osaka Pref. Osaka Institute of Industrial Technology (72) Inventor Masaru Miya 1-8-1, Midorigaoka, Ikeda-shi, Osaka No. 31 Osaka Institute of Industrial Technology (56) References JP-A-5-224262 (JP, A) JP-A-6-167728 (JP, A) Journal of the Ceramic Society of Japan 101 (1) P. 64-68 (1993) (58) Field surveyed (Int. Cl. 6 , DB name) G02F 1/35 JICST
Claims (16)
からなる群から選ばれた少なくとも１種の金属の酸化物
（ただし、ＶＯ２を除く。Ｃｏの酸化物は、ＣｏＯ及び
Ｃｏ２Ｏ３を除く。）、または、ＮｉＣｏ２Ｏ４、Ｎｉ
ＭｎＣｏ４Ｏ８からなる薄膜を形成してなる３次非線形
光学材料。1. V, Cr, Mn, Co, Cu on a transparent substrate
At least one metal oxide selected from the group consisting of (where oxides of .Co except VO 2 except the CoO and Co 2 O 3.), Or, NiCo2O 4, Ni
A third-order nonlinear optical material formed by forming a thin film made of MnCo 4 O 8 .
３Ｏ４，ＣｕＯ、Ｃｏ３Ｏ４，ＭｎＣｏ２Ｏ４，ＮｉＣ
ｏ２Ｏ４及びＮｉＭｎＣｏ４Ｏ８からなる群から選ばれ
る請求項１記載の３次非線形光学材料。2. The method according to claim 1, wherein the metal oxide is Cr 2 O 3 , MnO 2 , Mn.
3 O 4 , CuO, Co 3 O 4 , MnCo 2 O 4 , NiC
o 2 O 4 and third-order nonlinear optical material according to claim 1 wherein is selected from the group consisting of NiMnCo 4 O 8.
ｕＯからなる群から選ばれる請求項２記載の３次非線形
光学材料。3. The method according to claim 1, wherein the metal oxide is Cr 2 O 3 , Mn 3 O 4 , C
3. The third-order nonlinear optical material according to claim 2, which is selected from the group consisting of uO.
ｎＯ及びＺｒＯ２からなる群から選ばれる添加成分を含
有しており、金属酸化物中の金属原子数と、添加成分中
の金属原子数との比が、１：０．０１〜０．１０の範囲
にある請求項１記載の３次非線形光学材料。4. A thin film made of a metal oxide is made of Al 2 O 3 , Z
An additive component selected from the group consisting of nO and ZrO 2 is contained, and the ratio of the number of metal atoms in the metal oxide to the number of metal atoms in the additive component is 1: 0.01 to 0.10. The third-order nonlinear optical material according to claim 1, which is in a range.
ｏ，Ｎｉ，Ｃｕからなる群から選ばれた少なくとも１種
の金属の酸化物からなる薄膜の表面あるいは内部にＡ
ｕ，Ａｇ，Ｃｕからなる群から選ばれた少なくとも１種
の金属の粒径５００ｎｍ以下の微粒子を分散析出させた
複合体薄膜（但し、金属酸化物がＣｕ２Ｏであり、金属
がＣｕである複合体薄膜を除く）を形成してなる３次非
線形光学材料。5. V, Cr, Mn, Fe, C on a transparent substrate.
A on the surface or inside of a thin film made of an oxide of at least one metal selected from the group consisting of o, Ni, and Cu.
a composite thin film in which fine particles of at least one metal selected from the group consisting of u, Ag, and Cu having a particle diameter of 500 nm or less are dispersed and deposited (provided that the metal oxide is Cu 2 O and the metal is Cu Third-order nonlinear optical material formed by excluding a composite thin film).
３Ｏ４，Ｆｅ２Ｏ３，Ｆｅ３Ｏ４，ＣｏＯ，Ｃｏ
３Ｏ４，ＣｕＯ、ＭｎＣｏ２Ｏ４，ＮｉＣｏ２Ｏ４及び
ＮｉＭｎＣｏ４Ｏ８からなる群から選ばれる請求項５記
載の３次非線形光学材料。6. The method according to claim 1, wherein the metal oxide is Cr 2 O 3 , MnO 2 , Mn.
3 O 4 , Fe 2 O 3 , Fe 3 O 4 , CoO, Co
3 O 4, CuO, MnCo 2 O 4, NiCo 2 O 4 and third-order nonlinear optical material according to claim 5, wherein is selected from the group consisting of NiMnCo 4 O 8.
ｅ２Ｏ３，Ｃｏ３Ｏ４，ＣｕＯからなる群から選ばれる
請求項６記載の３次非線形光学材料。7. The method according to claim 1, wherein the metal oxide is Cr 2 O 3 , Mn 3 O 4 , F
e 2 O 3, Co 3 O 4, 3 -order nonlinear optical material according to claim 6, wherein is selected from the group consisting of CuO.
びＣｕからなる群から選ばれた少なくとも１種の金属の
金属原子数との比が、１：０．０５〜４の範囲にある請
求項５記載の３次非線形光学材料。8. The ratio of the number of metal atoms in the metal oxide to the number of metal atoms of at least one metal selected from the group consisting of Au, Ag and Cu is in the range of 1: 0.05 to 4. The third-order nonlinear optical material according to claim 5.
びＣｕからなる群から選ばれた少なくとも１種の金属の
金属原子数との比が、１：０．２〜２の範囲にある請求
項８記載の３次非線形光学材料。9. The ratio of the number of metal atoms in the metal oxide to the number of metal atoms of at least one metal selected from the group consisting of Au, Ag and Cu is in the range of 1: 0.2 to 2: 2. 9. The third-order nonlinear optical material according to claim 8.
内部にＡｕ微粒子を分散析出させた複合体薄膜を形成し
てなる請求項５記載の３次非線形光学材料。10. The third-order nonlinear optical material according to claim 5, wherein a composite thin film is formed by dispersing and depositing Au fine particles on the surface or inside of a thin film made of a metal oxide.
ｕからなる群から選ばれた少なくとも１種の金属の酸化
物の粒径５００ｎｍ以下の微粒子とＡｕ、Ａｇ及びＣｕ
からなる群から選ばれた少なくとも１種の金属の粒径５
００ｎｍ以下の微粒子とを透明物質中に分散析出させる
ことを特徴とする３次非線形光学材料の製造方法。11. V, Cr, Mn, Fe, Co, Ni, C
and fine particles of at least one metal oxide selected from the group consisting of
Particle size of at least one metal selected from the group consisting of
A method for producing a third-order nonlinear optical material, wherein fine particles having a size of 00 nm or less are dispersed and precipitated in a transparent substance.
たは金属アルコキシド溶液と金属の前駆体である金属塩
溶液とを透明多孔質物質中に含浸させ、乾燥した後、熱
分解させる請求項１１記載の３次非線形光学材料の製造
方法。12. A transparent porous material is impregnated with a metal salt solution or a metal alkoxide solution as a precursor of a metal oxide and a metal salt solution as a precursor of a metal, dried, and then thermally decomposed. 12. The method for producing a third-order nonlinear optical material according to item 11.
ット及び金属ターゲットを使用する同時スパッタ法また
は交互スパッタ法により、基板上に透明物質と金属酸化
物及び金属を堆積させる請求項１１記載の３次非線形光
学材料の製造方法。13. The third-order nonlinear material according to claim 11, wherein a transparent material, a metal oxide and a metal are deposited on the substrate by a simultaneous sputtering method or an alternate sputtering method using a transparent material target, a metal oxide target and a metal target. Manufacturing method of optical material.
ｎ３Ｏ４，Ｆｅ２Ｏ３，Ｆｅ３Ｏ４，ＣｏＯ，Ｃｏ３Ｏ
４，ＣｕＯ、ＭｎＣｏ２Ｏ４，ＮｉＣｏ２Ｏ４及びＮｉ
ＭｎＣｏ４Ｏ８からなる群から選ばれる請求項１１記載
の３次非線形光学材料の製造方法。14. The method according to claim 14, wherein the metal oxide is Cr 2 O 3 , MnO 2 , M
n 3 O 4 , Fe 2 O 3 , Fe 3 O 4 , CoO, Co 3 O
4 , CuO, MnCo 2 O 4 , NiCo 2 O 4 and Ni
The method for producing a third-order nonlinear optical material according to claim 11, wherein the method is selected from the group consisting of MnCo 4 O 8 .
Ｆｅ２Ｏ３，Ｃｏ３Ｏ４，ＣｕＯからなる群から選ばれ
る請求項１４記載の３次非線形光学材料の製造方法。15. The method according to claim 15, wherein the metal oxide is Cr 2 O 3 , Mn 3 O 4 ,
Fe 2 O 3, Co 3 O 4, the manufacturing method of the third-order nonlinear optical material according to claim 14, wherein is selected from the group consisting of CuO.
方法により製造できる３次非線形光学材料。16. A third-order nonlinear optical material which can be manufactured by the method according to claim 11. Description:
Priority Applications (2)
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| US08/640,714 US5688442A (en) | 1994-03-11 | 1996-05-01 | Nonlinear optical materials and process for producing the same |
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|---|---|---|---|
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| Publication Number | Publication Date |
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| US6790502B1 (en) | 1999-10-15 | 2004-09-14 | Hitachi, Ltd. | Optically functional element and production method and application therefor |
| US6844092B2 (en) | 2002-08-22 | 2005-01-18 | Hitachi, Ltd. | Optically functional element and production method and application therefor |
| JP4512746B2 (en) * | 2005-01-21 | 2010-07-28 | 独立行政法人産業技術総合研究所 | Metal fine particle dispersed composite and method for producing the same |
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| JPH05127206A (en) * | 1991-11-05 | 1993-05-25 | Matsushita Electric Ind Co Ltd | Nonlinear optical material and production thereof |
| JPH05224262A (en) * | 1992-02-17 | 1993-09-03 | Ricoh Co Ltd | Nonlinear optical material |
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Non-Patent Citations (1)
| Title |
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| Ｊｏｕｒｎａｌ ｏｆ ｔｈｅ Ｃｅｒａｍｉｃ Ｓｏｃｉｅｔｙ ｏｆ Ｊａｐａｎ １０１（１） Ｐ．６４−６８ （１９９３） |
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