JP5923816B2 - High refractive index thermoplastic optical material and manufacturing method thereof - Google Patents
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- 239000000463 material Substances 0.000 title claims description 23
- 230000003287 optical effect Effects 0.000 title claims description 17
- 229920001169 thermoplastic Polymers 0.000 title claims description 8
- 239000004416 thermosoftening plastic Substances 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 239000013522 chelant Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 9
- 150000004703 alkoxides Chemical class 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 125000005594 diketone group Chemical group 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical class NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 150000003841 chloride salts Chemical class 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
この発明は、高屈折率熱可塑性光学材料とその製造方法に関する。この高屈折率熱可塑性光学材料は、発光デバイス、光学デバイス、電子デバイスなどの分野で好適に利用されうる。 The present invention relates to a high refractive index thermoplastic optical material and a method for producing the same. This high refractive index thermoplastic optical material can be suitably used in the fields of light emitting devices, optical devices, electronic devices and the like.
前記の各デバイス分野では光路を制御するために、高い屈折率と、キャスティング（鋳造）による成形を可能とする熱可塑性を兼ね備えた材料が望まれている。そのような材料の実現を目指して従来より、有機高分子をマトリックスあるいはバインダーとし、チタニアやジルコニアなどの高屈折率の金属酸化物の微粒子を分散させる（特許文献１）、有機高分子と、高屈折率のメタロキサンポリマーあるいは金属酸化物ナノ粒子を複合化させる（非特許文献１、２）などの技術が知られている。 In each of the above device fields, in order to control the optical path, a material having a high refractive index and thermoplasticity that enables molding by casting is desired. Aiming to realize such a material, conventionally, organic polymer is used as a matrix or binder, and fine particles of metal oxide having a high refractive index such as titania and zirconia are dispersed (Patent Document 1). Techniques are known in which a metalloxane polymer having a refractive index or metal oxide nanoparticles are combined (Non-Patent Documents 1 and 2).
しかし、従来の材料においては、有機高分子成分が熱可塑性を担い、金属酸化物あるいはメタロキサンポリマーが高屈折率を担っている。そのため、熱可塑性を高めるために有機高分子成分の含有比率を上げると高屈折率が実現できず、屈折率を高めるために金属酸化物あるいはメタロキサンポリマーの含有比率を上げると熱可塑性が実現できない。
それ故、この発明の課題は、高屈折率と熱可塑性を兼ね備えた有機・無機ハイブリッドの光学材料を提供することにある。
However, in conventional materials, the organic polymer component is responsible for thermoplasticity, and the metal oxide or metalloxane polymer is responsible for high refractive index. Therefore, if the content ratio of the organic polymer component is increased to increase the thermoplasticity, a high refractive index cannot be realized, and if the content ratio of the metal oxide or metalloxane polymer is increased to increase the refractive index, the thermoplasticity cannot be realized. .
Therefore, an object of the present invention is to provide an organic / inorganic hybrid optical material having both a high refractive index and thermoplasticity.
その課題を解決するために、この発明の有機・無機ハイブリッドの光学材料は、
メタロキサンポリマーと、このメタロキサンポリマー中の金属原子に対して配位可能なキレート化合物とを備え、メタロキサンポリマーの金属原子に前記キレート化合物が配位しており、配位前の前記キレート化合物が２５℃で固体であることを特徴とする。
In order to solve the problem, the organic / inorganic hybrid optical material of the present invention is
A metalloxane polymer and a chelate compound capable of coordinating with a metal atom in the metalloxane polymer, wherein the chelate compound is coordinated with the metal atom of the metalloxane polymer, and the chelate compound before coordination Is solid at 25 ° C.
メタロキサンポリマーは、繰り返し単位［金属原子−酸素原子］を骨格とする無機高分子である。このハイブリッド材料においてはメタロキサンポリマーの各金属原子にキレート化合物がほぼ均一に配位しており、メタロキサンポリマー中の金属−酸素結合部分が金属酸化物と同様に高屈折率を担う。一方、このハイブリッド材料の熱可塑性のメカニズムは、ハイブリッド材料中のキレート化合物同士のファンデアヴァールス結合に起因していると推定される。前記キレート化合物として２５℃で液体であるものを用いたハイブリッド材料は、熱可塑性を有しない。 The metalloxane polymer is an inorganic polymer having a repeating unit [metal atom-oxygen atom] as a skeleton. In this hybrid material, the chelate compound is almost uniformly coordinated to each metal atom of the metalloxane polymer, and the metal-oxygen bond portion in the metalloxane polymer bears a high refractive index as with the metal oxide. On the other hand, it is presumed that the thermoplastic mechanism of the hybrid material is caused by van der Waals bonds between chelate compounds in the hybrid material. A hybrid material using a chelate compound that is liquid at 25 ° C. does not have thermoplasticity.
前記金属原子は、好ましくはチタン、ジルコニウム及び亜鉛のうちから選ばれる一種以上である。これらの金属の酸化物は、高屈折率であることが知られているからである。前記キレート化合物は、好ましくはβジケトン、カルボン酸、またはエチレンジアミン誘導体である。これらの化合物は容易に入手可能だからである。 The metal atom is preferably one or more selected from titanium, zirconium and zinc. This is because these metal oxides are known to have a high refractive index. The chelate compound is preferably a β diketone, a carboxylic acid, or an ethylenediamine derivative. This is because these compounds are readily available.
この発明の有機・無機ハイブリッドの光学材料を製造する適切な方法は、
金属塩、有機溶剤、２５℃で固体であるキレート化合物及び水を含む有機・無機ハイブリッド材料前駆体溶液を準備し、この前駆体溶液を成形可能な程度に粘性が上がるまで濃縮し、前記キレート化合物の融点よりも高く沸点よりも低い温度で加熱することを特徴とする。そして、濃縮後、加熱前に所望の形状に成形する。この方法により、加熱時に溶液中の有機溶剤が蒸発するとともに、金属塩の重合と金属に対するキレート化とが進行し、熱可塑性材料が得られる。前記キレート化合物として２５℃で液体であるものを用いたハイブリッド材料が熱可塑性を有しないのは、加熱中にキレート化合物が蒸発してしまうからであると推定される。
A suitable method for producing the organic / inorganic hybrid optical material of this invention is:
An organic / inorganic hybrid material precursor solution containing a metal salt, an organic solvent, a chelate compound that is solid at 25 ° C., and water is prepared, and the precursor solution is concentrated until the viscosity is increased to a degree that can be molded. It is characterized by heating at a temperature higher than the melting point and lower than the boiling point. And it concentrates and shape | molds in a desired shape before a heating . By this method, the organic solvent in the solution evaporates at the time of heating, and polymerization of the metal salt and chelation with respect to the metal proceed to obtain a thermoplastic material. The reason why the hybrid material using the chelate compound that is liquid at 25 ° C. does not have thermoplasticity is presumably because the chelate compound evaporates during heating.
金属塩として、好ましい一つは金属アルコキシドであり、他の一つは金属硝酸塩、金属塩化物塩、金属酢酸塩等の金属カルボン酸塩又はそれらの組み合わせである。いずれも加水分解により容易に酸化物を生じうるからである。また、前記キレート化合物がβジケトンまたはエチレンジアミン誘導体であるときは、そのカルボニル基の炭素及びアミノ基の窒素が環状構造の構成要素ではないものが好ましい。官能基の原子が環状構造の構成要素であると、金属原子に配位することが極めて困難だからである。前記金属塩とキレート化合物の好ましいモル比は１：１．０〜２．５である。モル比がこの範囲にあるとき、キレート化合物が金属塩の周囲に過不足無くほぼ均等に配位すると想定できるからである。 As a metal salt, one preferred is a metal alkoxide, and the other is a metal carboxylate such as a metal nitrate, metal chloride, metal acetate, or a combination thereof. This is because any of them can easily generate an oxide by hydrolysis. Further, when the chelate compound is a β diketone or an ethylenediamine derivative, it is preferable that the carbon of the carbonyl group and the nitrogen of the amino group are not constituents of the cyclic structure. This is because it is extremely difficult to coordinate to a metal atom when the functional group atom is a component of a cyclic structure. A preferred molar ratio of the metal salt to the chelate compound is 1: 1.0 to 2.5. This is because when the molar ratio is within this range, it can be assumed that the chelate compound coordinates almost uniformly around the metal salt without excess or deficiency.
以上のように、この発明の有機・無機ハイブリッド材料は、高屈折率と熱可塑性を兼ね備えているので、これを所望の形状に成形することにより、様々な光路を実現することができる。 As described above, since the organic / inorganic hybrid material of the present invention has both a high refractive index and thermoplasticity, various optical paths can be realized by molding it into a desired shape.
―実施例１―
金属アルコキシドとしてチタンテトラノルマルブトキシドＴｉ（Ｏ−ｎＣ4Ｈ9）4及びジルコニウムテトラノルマルプロポキシドＺｒ（Ｏ−ｎＣ3Ｈ7）4を準備した。アセトン中に表１に記載のβジケトンのうち１種または２種、いずれかのアルコキシド及び脱イオン水を、モル比でアルコキシド：βジケトン：水：アセトンが１：２：１：２０となるように加えることにより、前駆体溶液を調製した。２種のβジケトンを加えるときはそれらが互いに等モルとなるように調製した。
—Example 1—
Titanium tetranormal butoxide Ti (O—nC 4 H 9 ) 4 and zirconium tetranormal propoxide Zr (O—nC 3 H 7 ) 4 were prepared as metal alkoxides. One or two of the β diketones listed in Table 1 in acetone and either alkoxide and deionized water are in a molar ratio of alkoxide: β diketone: water: acetone 1: 2: 1: 20. To prepare a precursor solution. When the two β diketones were added, they were prepared so that they were equimolar to each other.
溶液を室温で１時間撹拌した後、８０℃で表２に示す種々の時間濃縮したところ、粘りけのある樹脂状になった。この粘りけのある溶液をシリコン（１００）基板の上に滴下し、オーブンで１０分間表２に示す種々の温度で乾燥することにより、厚さ７００μｍの試料を製造した。室温まで放置した後、ピンセットで触れることにより、試料が硬いか軟らかいかを評価した。次に、同じ温度で再度３分間加熱して冷却前に硬さを評価した後、冷却して試料をポリエチレンの袋に１日間封入し、室温で再び硬さを評価した。 The solution was stirred at room temperature for 1 hour and then concentrated at 80 ° C. for various times as shown in Table 2 to obtain a sticky resin. This sticky solution was dropped on a silicon (100) substrate and dried in an oven at various temperatures shown in Table 2 for 10 minutes to produce 700 μm thick samples. After leaving to room temperature, it was evaluated whether the sample was hard or soft by touching with tweezers. Next, after heating again for 3 minutes at the same temperature and evaluating the hardness before cooling, the sample was cooled and sealed in a polyethylene bag for one day, and the hardness was evaluated again at room temperature.
また、各段階における試料の光学的透明度を評価するために、前記シリコン（１００）基板に代えて清浄なシリカガラス基板の上で試料を製造し、同じシリカガラス基板を対照とし、分光測光計（ジャスコ社製型式Ｖ−５７０）を用いて光吸収スペクトルを測定した。試料の厚さは、５μｍ及び２００μｍであった。評価結果を表２に併記する。一例として試料ｈのスペクトルを図１に示す。 In addition, in order to evaluate the optical transparency of the sample at each stage, a sample was produced on a clean silica glass substrate instead of the silicon (100) substrate, and the spectrophotometer ( The optical absorption spectrum was measured using a Jusco model V-570). Sample thicknesses were 5 μm and 200 μm. The evaluation results are also shown in Table 2. As an example, the spectrum of sample h is shown in FIG.
試料の屈折率を、屈折率１．９６４８のプリズムを備えるプリズムカップラー（メトリコン コーポレーション社製型式２０１０）を用いて測定した。測定結果を表３に示す。 The refractive index of the sample was measured using a prism coupler (Model 2010 manufactured by Metricon Corporation) having a prism with a refractive index of 1.9648. Table 3 shows the measurement results.
表２に示すように、常温で固体のβジケトンを少なくとも１種用いた試料ｄ、ｆ−ｏ、ｐ−ｒは、試料ｐを除く全てが熱可塑性を有し、クラックの無い、黄みがかった透明であった。いずれの試料もβジケトンの融点よりも高い温度で可塑性を示していること、及びβジケトンによるキレート環の存在を示す黄みがかっていることから、試料の熱可塑性はβジケトンの融点に起因するものではないと認められる。即ち、試料の熱可塑性は、試料中で金属に配位したキレート化合物同士のファンデアヴァールス結合に起因するものと推定される。 As shown in Table 2, samples d, fo, and pr using at least one kind of β-diketone that is solid at room temperature are all thermoplastic except sample p, have no cracks, and are yellowish. It was transparent. Both samples show plasticity at a temperature higher than the melting point of β-diketone and are yellowish indicating the presence of a chelate ring by β-diketone, so the thermoplasticity of the sample is due to the melting point of β-diketone It is recognized that it is not a thing. In other words, the thermoplasticity of the sample is presumed to be due to van der Waals bonds between chelate compounds coordinated to metals in the sample.
一方、常温で液体のβジケトンのみを用いた試料ａ−ｃ、ｅは、いずれも加熱時でさえ硬く、熱可塑性を有さず、しかも加熱時もしくは濃縮時の段階で不透明であった。これらの試料においては、βジケトンが濃縮時に蒸発してしまい、アルコキシドの重縮合反応が促進されたために、試料が硬化したものと推定される。尚、試料ｐは、βジケトンを用いているが、アルコキシドとβジケトンとのモル比が１：１であったので、加水分解と重縮合を抑制するのに十分にキレート化しなかったものと推定される。
表３に示すように、屈折率は１．６５〜１．７３の範囲であった。
On the other hand, the samples ac, e using only the β-diketone which is liquid at room temperature were both hard even when heated, had no thermoplasticity, and were opaque at the stage of heating or concentration. In these samples, it is presumed that the samples were cured because the β-diketone evaporated during concentration and the polycondensation reaction of the alkoxide was promoted. Sample p uses β-diketone, but since the molar ratio of alkoxide to β-diketone was 1: 1, it was estimated that it was not chelated sufficiently to suppress hydrolysis and polycondensation. Is done.
As shown in Table 3, the refractive index was in the range of 1.65 to 1.73.
―実施例２―
エタノールに酢酸亜鉛Ｚｎ（ＣＨ3ＣＯＯＨ）2・２Ｈ2Ｏ及び１−フェニルブタン−１，３−ジオンを、モル比で順に酢酸亜鉛：βジケトン：エタノール＝１：１：３０となるように加えることにより、白色沈殿を含む前駆体溶液を調製した。
—Example 2—
Zinc acetate Zn (CH 3 COOH) 2 .2H 2 O and 1-phenylbutane-1,3-dione are added to ethanol in this order in a molar ratio of zinc acetate: β-diketone: ethanol = 1: 1: 30. Thus, a precursor solution containing a white precipitate was prepared.
溶液を遠心分離し、上澄み液を８０℃で１時間濃縮したところ、粘りけのある樹脂状になった。再度遠心分離したところ、上澄み液の粘りけが増した。この粘りけのある溶液をシリコン（１００）基板の上に滴下し、オーブンで１０分間１２０℃で乾燥することにより、厚さ２７０μｍの試料を製造した。室温まで放置した後、ピンセットで触れたところ、試料は硬くなっていた。次に、同じ温度で再度３分間加熱して冷却前にピンセットで触れたところ、軟らかかった。 The solution was centrifuged, and the supernatant was concentrated at 80 ° C. for 1 hour. As a result, it became a sticky resin. When it was centrifuged again, the viscosity of the supernatant liquid increased. This sticky solution was dropped on a silicon (100) substrate and dried in an oven at 120 ° C. for 10 minutes to produce a sample having a thickness of 270 μm. After leaving to room temperature, when touched with tweezers, the sample was hard. Next, after heating again at the same temperature for 3 minutes and touching with tweezers before cooling, it was soft.
試料の屈折率は、１．６６であった。前記シリコン（１００）基板に代えて清浄なシリカガラス基板の上で試料を製造し、実施例１と同様に光吸収スペクトルを測定した。測定結果を図２に示す。
試料を熱分析したところ、温度が１０００℃に達しても重量が０にならなかった。従って、試料中に酸化亜鉛のメタロキサンポリマーが含まれていると認められた。
The refractive index of the sample was 1.66. A sample was produced on a clean silica glass substrate instead of the silicon (100) substrate, and the light absorption spectrum was measured in the same manner as in Example 1. The measurement results are shown in FIG.
As a result of thermal analysis of the sample, the weight did not become zero even when the temperature reached 1000 ° C. Therefore, it was confirmed that the metal oxide polymer of zinc oxide was contained in the sample.
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