JP2726732B2 - Method for producing organic substance-containing silicon dioxide thin film - Google Patents

Method for producing organic substance-containing silicon dioxide thin film

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Publication number
JP2726732B2
JP2726732B2 JP2074623A JP7462390A JP2726732B2 JP 2726732 B2 JP2726732 B2 JP 2726732B2 JP 2074623 A JP2074623 A JP 2074623A JP 7462390 A JP7462390 A JP 7462390A JP 2726732 B2 JP2726732 B2 JP 2726732B2
Authority
JP
Japan
Prior art keywords
silicon dioxide
solution
film
substrate
thin film
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 - Fee Related
Application number
JP2074623A
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Japanese (ja)
Other versions
JPH0350111A (en
Inventor
和夫 竹村
壽一 猪野
秀夫 河原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Sheet Glass Co Ltd
Original Assignee
Nippon Sheet Glass Co Ltd
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Priority to JP2074623A priority Critical patent/JP2726732B2/en
Publication of JPH0350111A publication Critical patent/JPH0350111A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
    • C03C2217/45—Inorganic continuous phases
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
    • C03C2217/485—Pigments

Description

【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、有機物を含んだ二酸化珪素薄膜の製造方法
に関する。Description: TECHNICAL FIELD The present invention relates to a method for producing a silicon dioxide thin film containing an organic substance.

［従来の技術］ 有機物を二酸化珪素膜中に導入することは、新しい機
能性材料を得る手段として既に試みられている。しかし
ながら、有機物は高い温度にさらされると分解するた
め、ゾル−ゲル法でしか製造されていない。この製造方
法に関する文献としては「J.Non−Cryst.Solids,74（19
85）395」があり、二酸化珪素薄膜中に有機蛍光色素を
導入しているが、得られる有機物含有薄膜は多孔質であ
った。また、「セラミックス、21,No.2（1986）111」で
は、ゾル−ゲル法によって有機分子を非晶質石英にドー
プしているが、得られたガラス構造には残留不純物やひ
ずみ、欠陥等が含まれていることが報告されている。[Prior Art] Introduction of an organic substance into a silicon dioxide film has already been attempted as a means for obtaining a new functional material. However, organic substances decompose when exposed to high temperatures, and are therefore produced only by the sol-gel method. References relating to this production method include “J. Non-Cryst. Solids, 74 (19)
85) 395 ", and an organic fluorescent dye was introduced into the silicon dioxide thin film, but the resulting organic-containing thin film was porous. In “Ceramics, 21, No. 2 (1986) 111,” organic molecules are doped into amorphous quartz by the sol-gel method, but the resulting glass structure has residual impurities, strain, defects, etc. Is reported to be included.

［発明が解決しようとする課題］ 上記の従来技術ではゾル−ゲル法を用いており、膜を
基材に固着させるためには最終工程で加熱する必要があ
る。しかしながら、有機物が分解するような高い温度で
加熱処理することはできないので、生成した膜はどうし
ても多孔質となる問題があった。また、低い温度での加
熱によっても分解してしまうような有機物は、膜中に導
入することができなかった。さらに、低い温度でしか加
熱できないことは、ゾル−ゲル法固有の問題をいっそう
大きなものにし、膜中には未分解の原料や溶媒等の不純
物が残存していた。その他の問題としては、出発原料と
して高価な金属アルコキシドを用いるため、膜の製造コ
ストが高くなることである。[Problems to be Solved by the Invention] In the above-mentioned conventional technology, a sol-gel method is used, and it is necessary to heat in a final step in order to fix a film to a substrate. However, since heat treatment cannot be performed at such a high temperature that organic substances are decomposed, there is a problem that the formed film is necessarily porous. Further, an organic substance which is decomposed even by heating at a low temperature could not be introduced into the film. Further, the fact that heating can be performed only at a low temperature further exacerbates the problem inherent in the sol-gel method, and undecomposed raw materials and impurities such as solvents remain in the film. Another problem is that the use of expensive metal alkoxide as a starting material increases the production cost of the membrane.

また、コーティング方法としてはディップコート等を
用いているが、この方法では複雑な形状を持った基材に
は適用できなかった。In addition, dip coating or the like is used as a coating method, but this method cannot be applied to a substrate having a complicated shape.

本発明は、従来の有機物含有二酸化珪素膜の製造方法
が持つ、上記の欠点を取り除いた製造方法を提供するこ
とを目的としている。An object of the present invention is to provide a manufacturing method which eliminates the above-mentioned disadvantages of the conventional method for manufacturing an organic-containing silicon dioxide film.

［課題を解決するための手段］ 発明者らは、有機物を二酸化珪素薄膜中に導入する研
究を長年に渡り続けてきた。その結果、二酸化珪素の過
飽和状態となった珪弗化水素酸水溶液を含む処理液と基
材とを室温付近で接触させて、その基材表面に緻密な二
酸化珪素薄膜を製造する方法（特開昭57−196744号）に
おいて、この処理液に有機物を添加することによって、
有機物を含んだ二酸化珪素薄膜が生成することを見いだ
し、本発明を完成させることができた。[Means for Solving the Problems] The inventors have continued research for introducing an organic substance into a silicon dioxide thin film for many years. As a result, a treatment solution containing an aqueous solution of hydrosilicofluoric acid in which silicon dioxide is supersaturated is brought into contact with a substrate at around room temperature to produce a dense silicon dioxide thin film on the surface of the substrate (Japanese Patent Application Laid-Open No. 57-196744), by adding an organic substance to this treatment liquid,
The inventors have found that a silicon dioxide thin film containing an organic substance is generated, and the present invention has been completed.

本発明は、珪弗化水素酸水溶液を二酸化珪素で過飽和
状態にする工程（第１段階）、有機物の添加（第２段
階）、有機物含有二酸化珪素薄膜の形成（第３段階）の
３つの工程からなっている。The present invention comprises three steps of a step of supersaturating an aqueous solution of hydrosilicofluoric acid with silicon dioxide (first step), addition of an organic substance (second step), and formation of an organic substance-containing silicon dioxide thin film (third step). Consists of

第１段階では、二酸化珪素を含んだ珪弗化水素酸水溶
液を過飽和状態にして処理液を調整する。この方法は特
に限定されたものではなく、上記の溶液にH3BO3、Al、A
l（OH）３等を添加したり、上記の溶液を加温する方法
など従来知られた種々の方法が使用できる。In the first stage, a treatment liquid is prepared by supersaturating an aqueous hydrosilicofluoric acid solution containing silicon dioxide. This method is not particularly limited, and H 3 BO 3 , Al, A
Various conventionally known methods such as adding l (OH) 3 or the like or heating the above solution can be used.

第２段階では、上記の処理液に有機物が添加される。
有機物は、通常は水またはメタノール、エタノール等の
水溶性溶剤に溶かしたり、分散させてから添加するが、
直接に添加することもできる。本発明で二酸化珪素薄膜
に導入することのできる有機物の具体例は第１表に示さ
れるものである。In the second stage, an organic substance is added to the above processing liquid.
Organic substances are usually dissolved in water or a water-soluble solvent such as methanol or ethanol, or added after being dispersed.
It can also be added directly. Specific examples of organic substances that can be introduced into the silicon dioxide thin film in the present invention are shown in Table 1.

なお、この第２段階の工程は第１段階で行うことも可
能である。 Note that the process of the second stage can be performed in the first stage.

第３段階では、処理液と基材とを接触させる。この方
法としては、基材表面に処理液を流下させる等の接触方
法も可能であるが、処理液を満たした浸漬槽にこの基材
を浸漬する方法が簡単で好ましい。それは、この方法に
よれば、複雑な形状を持つ基材上でも均一な有機物含有
二酸化珪素膜が得られるからである。In the third stage, the treatment liquid is brought into contact with the substrate. As this method, a contact method such as flowing down the treatment liquid onto the surface of the substrate is also possible, but a method of immersing the substrate in an immersion tank filled with the treatment liquid is simple and preferable. This is because according to this method, a uniform organic substance-containing silicon dioxide film can be obtained even on a substrate having a complicated shape.

また、処理液と基材とを接触させる際の処理液の温度
は、室温付近で充分であり、その上限は特に限定されな
いが、35℃程度が好ましい。いたずらに処理液の温度を
高めることは、添加した有機物の分解を招く可能性があ
るからである。In addition, the temperature of the treatment liquid when bringing the treatment liquid into contact with the substrate is sufficient at around room temperature, and the upper limit thereof is not particularly limited, but is preferably about 35 ° C. This is because raising the temperature of the processing liquid unnecessarily may cause decomposition of the added organic substance.

以上の一連の工程によって作製された有機物含有二酸
化珪素膜は、ゾル−ゲル法で得られた従来の膜とは異な
って非常に緻密であり、気泡等の膜欠陥が混入していな
い。The organic substance-containing silicon dioxide film formed by the above series of steps is very dense unlike a conventional film obtained by a sol-gel method, and does not contain film defects such as bubbles.

［作 用］ 本発明では、均一な溶液内で有機物を含む二酸化珪素
薄膜を形成している。この成膜反応は室温付近で進むた
め、溶液中の有機物は分解することなく均一に膜中に取
り込まれる。[Operation] In the present invention, a silicon dioxide thin film containing an organic substance is formed in a uniform solution. Since this film formation reaction proceeds at around room temperature, organic substances in the solution are uniformly taken into the film without decomposition.

また、この膜質は緻密であり、基材と固着しているた
め、加熱処理する必要がない。薄膜形成が過飽和溶液か
らの析出によって行われるため、本発明で得られる有機
物含有二酸化珪素膜中には、未分解原料や溶媒等の不純
物がほとんど混入しない。本発明の出発原料は非常に安
価であり、高温での加熱処理工程もないことから、膜の
製造コストを低く押えることができる。さらに、均一な
溶液内で反応させているため、複雑な形状を持った基材
上にも均一な有機物含有二酸化珪素薄膜を形成させるこ
とができる。Further, since the film quality is dense and fixed to the substrate, it is not necessary to perform a heat treatment. Since the thin film is formed by deposition from a supersaturated solution, impurities such as undecomposed raw materials and solvents hardly enter the organic matter-containing silicon dioxide film obtained in the present invention. Since the starting material of the present invention is very inexpensive and has no heat treatment step at a high temperature, the production cost of the film can be kept low. Furthermore, since the reaction is performed in a uniform solution, a uniform organic substance-containing silicon dioxide thin film can be formed even on a substrate having a complicated shape.

［実施例］ 次に実施例を挙げて、本発明をより具体的に説明する
が、本発明はその要旨を越えない限り以下の実施例に限
定されるものではない。[Examples] Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples as long as the gist is not exceeded.

実施例１ 縦75mm、横25mm、厚さ1mmのスライドガラスを充分に
洗浄、乾燥し、試料基材とした。Example 1 A slide glass having a length of 75 mm, a width of 25 mm and a thickness of 1 mm was sufficiently washed and dried to obtain a sample substrate.

次に、種々の染料を蒸留水に室温にて混合または、溶
解させ、５重量％または飽和の添加溶液とした。Next, various dyes were mixed or dissolved in distilled water at room temperature to obtain a 5% by weight or saturated additive solution.

また、シリカゲルを飽和させた珪弗化水素酸水溶液10
0ccに、0.5mol/Lのほう酸水溶液を8cc加えたもの、ある
いは上記珪弗化水素酸水溶液100ccに、金属アルミニウ
ム0.4g溶解させたものを処理液とした。この処理液100c
cをビーカーに取り、各々の染料液1ccずつを添加攪拌
し、35℃の水浴上にセット、加温した。この溶液中に、
上記試料基材をそれぞれ１枚ずつ浸漬し、16時間保持し
た後、取り出して洗浄乾燥した。In addition, an aqueous solution of hydrosilicofluoric acid saturated with silica gel 10
A treatment solution was prepared by adding 8 cc of a 0.5 mol / L boric acid aqueous solution to 0 cc, or dissolving 0.4 g of metal aluminum in 100 cc of the above hydrosilicofluoric acid aqueous solution. This treatment liquid 100c
c was placed in a beaker, 1 cc of each dye solution was added and stirred, set on a 35 ° C. water bath, and heated. In this solution,
Each of the sample substrates was immersed one by one, held for 16 hours, taken out and washed and dried.

添加染料の種類及び実験結果を第２表に示す。二酸化
珪素膜の膜厚は接触針式膜厚測定機にて測定した。Table 2 shows the types of the added dyes and the experimental results. The thickness of the silicon dioxide film was measured by a contact needle type film thickness measuring device.

これらの有機染料は、ESCA（Ｘ線光電子分光法）、SI
MS（二次イオン質量分析法）、IR（赤外線分光法）など
により分析した結果、膜中に均一に取り込まれているこ
とが確認された。These organic dyes are available from ESCA (X-ray photoelectron spectroscopy), SI
Analysis by MS (Secondary Ion Mass Spectrometry), IR (Infrared Spectroscopy), and the like confirmed that it was uniformly incorporated into the film.

さらに、二酸化珪素成膜後の基板を99.5％エタノール
溶液の中に24時間浸漬したが、有機染料の溶出はみられ
なかった。また、テープテスト、スポンジ払拭テストに
よる二酸化珪素膜の剥離も見られなかった。Further, the substrate after the formation of the silicon dioxide was immersed in a 99.5% ethanol solution for 24 hours, but no elution of the organic dye was observed. Further, no peeling of the silicon dioxide film was observed in the tape test and the sponge wiping test.

実施例２ 縦75mm、横25mm、厚さ1mmのスライドガラスを充分に
洗浄、乾燥し、試料基材とした。 Example 2 A slide glass having a length of 75 mm, a width of 25 mm and a thickness of 1 mm was sufficiently washed and dried to obtain a sample substrate.

次に種々のレーザー用色素をエタノールに室温にて混
合または溶解させ、５重量％または飽和の添加溶液とし
た。また、シリカゲルを飽和させた珪弗化水素酸水溶液
100ccに、0.5mol/Lのほう酸水溶液を8cc加えたもの、あ
るいは上記珪弗化水素酸水溶液100ccに、金属アルミニ
ウム0.4g溶解させたものを処理液とした。この処理液10
0ccをビーカーに取り、各々のレーザー用色素液1ccずつ
を添加攪拌し、35℃の水浴上にセット、加温した。この
溶液中に、上記試料基材をそれぞれ１枚ずつ浸漬し、16
時間保持した後、取り出して洗浄乾燥した。Next, various laser dyes were mixed or dissolved in ethanol at room temperature to obtain a 5% by weight or saturated additive solution. Also, an aqueous solution of hydrofluoric acid saturated with silica gel
A treatment solution was prepared by adding 8 cc of a 0.5 mol / L boric acid aqueous solution to 100 cc, or dissolving 0.4 g of metallic aluminum in 100 cc of the above hydrosilicofluoric acid aqueous solution. This treatment liquid 10
0 cc was taken in a beaker, and 1 cc of each laser dye solution was added and stirred, set on a 35 ° C. water bath, and heated. Each of the sample substrates was immersed in this solution one by one,
After holding for a period of time, it was taken out and washed and dried.

添加レーザー用色素の種類及び実験結果を第３表に示
す。二酸化珪素膜の膜厚は接触針式膜厚測定機にて測定
した。Table 3 shows the types of laser dyes added and the experimental results. The thickness of the silicon dioxide film was measured by a contact needle type film thickness measuring device.

これらのレーザー用色素は、ESCA、SIMS、IRなどによ
り分析した結果、膜中に均一に取り込まれていることが
確認された。また、これらの色素含有膜にそれぞれの励
起光を照射したところ蛍光が観測され、レーザー色素と
しての機能も保持されていることが確認された。As a result of analyzing these laser dyes by ESCA, SIMS, IR and the like, it was confirmed that they were uniformly incorporated into the film. Further, when these dye-containing films were irradiated with respective excitation lights, fluorescence was observed, and it was confirmed that the function as a laser dye was maintained.

さらに、二酸化珪素成膜後の基板を99.5％エタノール
溶液の中に24時間浸漬したが、有機染料の溶出はみられ
なかった。また、テープテスト、スポンジ払拭テストに
よる二酸化珪素膜の剥離も見られなかった。Further, the substrate after the formation of the silicon dioxide was immersed in a 99.5% ethanol solution for 24 hours, but no elution of the organic dye was observed. Further, no peeling of the silicon dioxide film was observed in the tape test and the sponge wiping test.

実施例３ 縦75mm、横25mm、厚さ1mmのスライドガラスを充分に
洗浄、乾燥し、試料基材とした。 Example 3 A slide glass having a length of 75 mm, a width of 25 mm and a thickness of 1 mm was sufficiently washed and dried to obtain a sample substrate.

次に種々のレーザー用色素を蒸留水に室温にて混合ま
たは溶解させ、５重量％または飽和の添加溶液とした。Next, various laser dyes were mixed or dissolved in distilled water at room temperature to obtain a 5% by weight or saturated additive solution.

また、シリカゲルを飽和させた珪弗化水素酸水溶液10
0ccに、0.5mol/Lのほう酸水溶液を8cc加えたもの、ある
いは上記珪弗化水素酸水溶液100ccに、金属アルミニウ
ム0.4g溶解させたものを処理液とした。この処理液100c
cをビーカーに取り、各々のレーザー用色素液1ccずつを
添加攪拌し、35℃の水浴上にセット、加温した。この溶
液中に、上記試料基材をそれぞれ１枚ずつ浸漬し、16時
間保持した後、取り出して洗浄乾燥した。In addition, an aqueous solution of hydrosilicofluoric acid saturated with silica gel 10
A treatment solution was prepared by adding 8 cc of a 0.5 mol / L boric acid aqueous solution to 0 cc, or dissolving 0.4 g of metal aluminum in 100 cc of the above hydrosilicofluoric acid aqueous solution. This treatment liquid 100c
c was placed in a beaker, and 1 cc of each dye solution for laser was added and stirred, set on a 35 ° C. water bath, and heated. Each of the sample substrates was immersed in this solution one by one, held for 16 hours, taken out and washed and dried.

添加レーザー用色素の種類及び実験結果を第４表に示
す。二酸化珪素膜の膜厚は接触針式膜厚測定機にて測定
した。Table 4 shows the types of laser dyes added and the experimental results. The thickness of the silicon dioxide film was measured by a contact needle type film thickness measuring device.

これらのレーザー用色素は、ESCA、SIMS、IRなどによ
り分析した結果、膜中に均一に取り込まれていることが
確認された。また、これらの色素含有膜にそれぞれの励
起光を照射したところ蛍光が観測され、レーザー色素と
しての機能も保持されていることが確認された。さら
に、二酸化珪素成膜後の基板を99.5％エタノール溶液の
中に24時間浸漬したが、有機染料の溶出はみられなかっ
た。As a result of analyzing these laser dyes by ESCA, SIMS, IR and the like, it was confirmed that they were uniformly incorporated into the film. Further, when these dye-containing films were irradiated with respective excitation lights, fluorescence was observed, and it was confirmed that the function as a laser dye was maintained. Further, the substrate after the formation of the silicon dioxide was immersed in a 99.5% ethanol solution for 24 hours, but no elution of the organic dye was observed.

また、テープテスト、スポンジ払拭テストによる二酸
化珪素膜の剥離も見られなかった。Further, no peeling of the silicon dioxide film was observed in the tape test and the sponge wiping test.

実施例４ 縦75mm、横25mm、厚さ1mmのスライドガラスを充分に
洗浄、乾燥し、試料基材とした。 Example 4 A slide glass having a length of 75 mm, a width of 25 mm and a thickness of 1 mm was sufficiently washed and dried to obtain a sample substrate.

次に分散染料ダイヤセリトン ファスト レッド（三
菱化成）を蒸留水に室温にて分散させ、５重量％の添加
液とした。Next, the disperse dye DiaSeriton Fast Red (Mitsubishi Kasei) was dispersed in distilled water at room temperature to obtain a 5% by weight additive solution.

また、シリカゲルを飽和させた珪弗化水素酸水溶液10
0ccに、金属アルミニウム0.4g溶解させたものを処理液
とした。この処理液をビーカーに取り、上記分散染料液
1ccを添加攪拌し、35℃の水浴上にセット、加温した。
この溶液中に、上記試料基材を１枚浸漬し、16時間保持
した後、取り出して洗浄乾燥した。In addition, an aqueous solution of hydrosilicofluoric acid saturated with silica gel 10
A solution in which 0.4 g of metallic aluminum was dissolved in 0 cc was used as a treatment liquid. Take this treatment liquid into a beaker,
1 cc was added and stirred, set on a 35 ° C. water bath, and heated.
One of the sample substrates was immersed in this solution, held for 16 hours, taken out and washed and dried.

作製された二酸化珪素膜は赤色を示し、接触針式膜厚
測定機にて測定した膜厚は7605Åであった。The produced silicon dioxide film showed a red color, and the film thickness measured by a contact needle film thickness measuring device was 7605 °.

この分散染料は、ESCA、SIMS、IRなどにより分析した
結果、膜中に均一に取り込まれていることが確認され
た。さらに、二酸化珪素成膜後の基板を99.5％エタノー
ル溶液の中に24時間浸漬したが、分散染料の溶出はみら
れなかった。The disperse dye was analyzed by ESCA, SIMS, IR and the like, and as a result, it was confirmed that the disperse dye was uniformly incorporated in the film. Further, the substrate after forming the silicon dioxide film was immersed in a 99.5% ethanol solution for 24 hours, but no dissolution of the disperse dye was observed.

また、テープテスト、スポンジ払拭テストによる二酸
化珪素膜の剥離も見られなかった。Further, no peeling of the silicon dioxide film was observed in the tape test and the sponge wiping test.

実施例５ 縦75mm、横25mm、厚さ1mmのスライドガラスを充分に
洗浄、乾燥し、試料基材とした。Example 5 A slide glass having a length of 75 mm, a width of 25 mm and a thickness of 1 mm was sufficiently washed and dried to obtain a sample substrate.

次にローダミン 6G（レーザー色素）を蒸留水に室温
にて混合または溶解させ、５重量％または飽和の添加液
とした。Next, Rhodamine 6G (laser dye) was mixed or dissolved in distilled water at room temperature to obtain a 5% by weight or saturated additive solution.

また、シリカゲルを飽和させた珪弗化水素酸水溶液10
0ccに、金属アルミニウム0.4g溶解させたものを処理液
とした。この処理液100ccをビーカーに取り、上記添加
溶液1ccを添加攪拌し、35℃のの水浴上にセット、加温
した。この溶液中に、上記試料基材を１枚浸漬し、16時
間保持した後、取り出して洗浄乾燥、試料Ａとした。In addition, an aqueous solution of hydrosilicofluoric acid saturated with silica gel 10
A solution in which 0.4 g of metallic aluminum was dissolved in 0 cc was used as a treatment liquid. 100 cc of the treatment liquid was placed in a beaker, 1 cc of the above-mentioned additional solution was added, stirred, set on a 35 ° C. water bath, and heated. One piece of the sample substrate was immersed in this solution, held for 16 hours, taken out, washed and dried, and used as sample A.

また、比較例としてゾル−ゲル法による有機物含有二
酸化珪素膜を作製した。原料としてエチルシリケイト
［Si（OC2H5）４］50g、エタノール［C2H5OH］75.2g、3
5％塩酸0.6g、水47g、ローダミン 6G0.1gを用い、各々
を１時間攪拌混合した。この溶液をさらに１時間放置
し、浸漬法にて上記試料基材に塗布した。塗布時の引き
上げ速度は1.5mm/Sとした。塗布した試料は室温の大気
中で約16時間乾燥した後、110℃、７時間電気炉にて加
熱、試料Ｂとした。Further, as a comparative example, an organic-containing silicon dioxide film was produced by a sol-gel method. Ethyl silicate [Si (OC 2 H 5 ) 4 ] 50 g, ethanol [C 2 H 5 OH] 75.2 g, 3
Using 0.6 g of 5% hydrochloric acid, 47 g of water and 0.1 g of rhodamine 6G, each was stirred and mixed for 1 hour. This solution was allowed to stand for another hour, and was applied to the sample substrate by a dipping method. The lifting speed during coating was 1.5 mm / S. The coated sample was dried in the air at room temperature for about 16 hours, and then heated in an electric furnace at 110 ° C. for 7 hours to obtain Sample B.

これらの試料について、Ｐ−ETCH液（48％HF:70％HNO
3:H2O＝3:2:60）を10倍希釈した溶液を用い、22℃で二
酸化珪素膜のエッチングレートを測定した。For these samples, a P-ETCH solution (48% HF: 70% HNO
(3 : H 2 O = 3: 2: 60) was diluted 10 times, and the etching rate of the silicon dioxide film was measured at 22 ° C.

測定結果を第１図に示す。試料Ｂに比べ試料Ａのエッ
チングレートは小さく、試料Ａの方が緻密な膜であるこ
とが判る。FIG. 1 shows the measurement results. The etching rate of sample A is smaller than that of sample B, and it can be seen that sample A is a denser film.

実施例６ 縦75mm、横25mm、厚さ1mmのスライドガラスを充分に
洗浄、乾燥し、試料基材とした。Example 6 A slide glass having a length of 75 mm, a width of 25 mm and a thickness of 1 mm was sufficiently washed and dried to obtain a sample substrate.

次に、種々の染料を蒸留水に室温にて混合または溶解
させ、５重量％または飽和の添加溶液とした。また、シ
リカゲルを飽和させた珪弗化水素酸水溶液100ccに、0.5
mol/Lのほう酸水溶液を8cc加えたもの、あるいは上記珪
弗化水素酸水溶液100ccに、金属アルミニウム0.4g溶解
させたものを処理液とした。この処理液100ccをビーカ
ーに取り、各々の染料液1ccずつを添加攪拌し、35℃の
水浴上にセット、加温した。この溶液中に、上記試料基
材をそれぞれ１枚ずつ浸漬し、16時間保持した後、取り
出して洗浄乾燥した。Next, various dyes were mixed or dissolved in distilled water at room temperature to obtain a 5% by weight or saturated additive solution. Also, 0.5 cc to 100 cc of hydrosilicofluoric acid aqueous solution saturated with silica gel
A treatment liquid was prepared by adding 8 cc of a mol / L boric acid aqueous solution or dissolving 0.4 g of metallic aluminum in 100 cc of the above hydrosilicofluoric acid aqueous solution. 100 cc of the treatment solution was placed in a beaker, 1 cc of each dye solution was added, stirred, set on a 35 ° C. water bath, and heated. Each of the sample substrates was immersed in this solution one by one, held for 16 hours, taken out and washed and dried.

添加染料の種類及び実験結果を第５表に示す。二酸化
珪素膜の膜厚は、接触針式膜厚測定機にて測定した。Table 5 shows the types of the added dyes and the experimental results. The thickness of the silicon dioxide film was measured by a contact needle type film thickness measuring device.

これらの有機染料は、ESCA、SIMS、IRなどにより分析
した結果、膜中に均一に取り込まれていることが確認さ
れた。さらに、二酸化珪素成膜後の基板を99.5％エタノ
ール溶液の中に24時間浸漬したが、分散染料の溶出はみ
られなかった。また、テープテスト、スポンジ払拭テス
トによる二酸化珪素膜の剥離も見られなかった。These organic dyes were analyzed by ESCA, SIMS, IR and the like, and as a result, it was confirmed that they were uniformly incorporated into the film. Further, the substrate after forming the silicon dioxide film was immersed in a 99.5% ethanol solution for 24 hours, but no dissolution of the disperse dye was observed. Further, no peeling of the silicon dioxide film was observed in the tape test and the sponge wiping test.

実施例７ 縦75mm、横25mm、厚さ1mmのスライドガラスを充分に
洗浄、乾燥し、試料基材とした。 Example 7 A slide glass having a length of 75 mm, a width of 25 mm and a thickness of 1 mm was sufficiently washed and dried to obtain a sample substrate.

次に、種々の染料を蒸留水に室温にて混合または溶解
させ、５重量％または飽和の添加溶液とした。Next, various dyes were mixed or dissolved in distilled water at room temperature to obtain a 5% by weight or saturated additive solution.

また、シリカゲルを飽和させた珪弗化水素酸水溶液10
0ccに、0.5mol/Lのほう酸水溶液を8cc加えたもの、ある
いは上記珪弗化水素酸水溶液100ccに、金属アルミニウ
ム0.4g溶解させたものを処理液とした。この処理液100c
cをビーカーに取り、各々の染料液1ccずつを添加攪拌
し、35℃の水浴上にセット、加温した。この溶液中に上
記試料基材をそれぞれ１枚ずつ浸漬し、16時間保持した
後、取り出して洗浄乾燥した。In addition, an aqueous solution of hydrosilicofluoric acid saturated with silica gel 10
A treatment solution was prepared by adding 8 cc of a 0.5 mol / L boric acid aqueous solution to 0 cc, or dissolving 0.4 g of metal aluminum in 100 cc of the above hydrosilicofluoric acid aqueous solution. This treatment liquid 100c
c was placed in a beaker, 1 cc of each dye solution was added and stirred, set on a 35 ° C. water bath, and heated. Each of the sample substrates was immersed in this solution one by one, held for 16 hours, taken out and washed and dried.

添加染料の種類及び実験結果を第６表に示す。二酸化
珪素膜の膜厚は、接触針式膜厚測定機にて測定した。Table 6 shows the types of the added dyes and the experimental results. The thickness of the silicon dioxide film was measured by a contact needle type film thickness measuring device.

これらの有機染料は、ESCA、SIMS、IRなどにより分析
した結果、膜中に均一に取り込まれていることが確認さ
れた。さらに、二酸化珪素成膜後の基板を99.5％エタノ
ール溶液の中に24時間浸漬したが、分散染料の溶出はみ
られなかった。また、テープテスト、スポンジ払拭テス
トによる二酸化珪素膜の剥離も見られなかった。These organic dyes were analyzed by ESCA, SIMS, IR and the like, and as a result, it was confirmed that they were uniformly incorporated into the film. Further, the substrate after forming the silicon dioxide film was immersed in a 99.5% ethanol solution for 24 hours, but no dissolution of the disperse dye was observed. Further, no peeling of the silicon dioxide film was observed in the tape test and the sponge wiping test.

実施例８ 縦75mm、横25mm、厚さ1mmのスライドガラスを充分に
洗浄、乾燥し、試料基材とした。 Example 8 A slide glass having a length of 75 mm, a width of 25 mm and a thickness of 1 mm was sufficiently washed and dried to obtain a sample substrate.

次に、種々のレーザー用色素を蒸留水に室温にて混合
または溶解させ、５重量％または飽和の添加溶液とし
た。また、シリカゲルを飽和させた珪弗化水素酸水溶液
100ccに、0.5mol/Lのほう酸水溶液を8cc加えたもの、あ
るいは上記珪弗化水素酸水溶液100ccに、金属アルミニ
ウム0.4g溶解させたものを処理液とした。この処理液10
0ccをビーカーに取り、各々のレーザー用色素液1ccずつ
を添加攪拌し、35℃の水浴上にセット、加温した。この
溶液中に、上記試料基材をそれぞれ１枚ずつ浸漬し、16
時間保持した後、取り出して洗浄乾燥した。Next, various laser dyes were mixed or dissolved in distilled water at room temperature to obtain a 5% by weight or saturated additive solution. Also, an aqueous solution of hydrofluoric acid saturated with silica gel
A treatment solution was prepared by adding 8 cc of a 0.5 mol / L boric acid aqueous solution to 100 cc, or dissolving 0.4 g of metallic aluminum in 100 cc of the above hydrosilicofluoric acid aqueous solution. This treatment liquid 10
0 cc was taken in a beaker, and 1 cc of each laser dye solution was added and stirred, set on a 35 ° C. water bath, and heated. Each of the sample substrates was immersed in this solution one by one,
After holding for a period of time, it was taken out and washed and dried.

添加レーザー用色素の種類及び実験結果を第７表に示
す。二酸化珪素膜の膜厚は接触針式膜厚測定機にて測定
した。Table 7 shows the types of laser dyes added and the experimental results. The thickness of the silicon dioxide film was measured by a contact needle type film thickness measuring device.

これらのレーザー用色素は、ESCA、SIMS、IRなどによ
り分析した結果、膜中に均一に取り込まれていることが
確認された。また、これらの色素含有膜にそれぞれの励
起光を照射したところ蛍光が観測され、レーザー色素と
しての機能も保持されていることが確認された。さら
に、二酸化珪素成膜後の基板を99.5％エタノール溶液の
中に24時間浸漬したが、レーザー用色素の溶出はみられ
なかった。また、テープテスト、スポンジ払拭テストに
よる二酸化珪素膜の剥離も見られなかった。As a result of analyzing these laser dyes by ESCA, SIMS, IR and the like, it was confirmed that they were uniformly incorporated into the film. Further, when these dye-containing films were irradiated with respective excitation lights, fluorescence was observed, and it was confirmed that the function as a laser dye was maintained. Further, the substrate after the formation of the silicon dioxide was immersed in a 99.5% ethanol solution for 24 hours, but no elution of the laser dye was observed. Further, no peeling of the silicon dioxide film was observed in the tape test and the sponge wiping test.

実施例９ 縦75mm、横25mm、厚さ1mmのスライドガラスを充分に
洗浄、乾燥し、試料基材とした。 Example 9 A slide glass having a length of 75 mm, a width of 25 mm and a thickness of 1 mm was sufficiently washed and dried to obtain a sample substrate.

次にシリカゲルを飽和させた珪弗化水素酸水溶液100c
cに、金属アルミニウム0.4gを溶解させて処理液とし
た。この処理液100ccをビーカーに取り、各々の色素0.0
1gずつを添加した後充分に攪拌してから35℃の水浴上で
加温した。なお、TG−21については、いったん濃酢酸溶
液としてから処理液に添加した。この溶液中に、上記試
料基材をそれぞれ１枚ずつ浸漬し、16時間経過した後、
取り出して洗浄乾燥した。Next, an aqueous solution of hydrofluoric acid saturated with silica gel 100c
0.4 g of metallic aluminum was dissolved in c to obtain a treatment liquid. Take 100 cc of this treatment solution into a beaker, and add 0.0
After adding 1 g each, the mixture was sufficiently stirred and heated on a 35 ° C. water bath. TG-21 was once added as a concentrated acetic acid solution to the treatment solution. In this solution, each of the sample substrates was immersed one by one, and after 16 hours,
It was taken out, washed and dried.

添加色素の種類および実験結果を第８表に示す。二酸
化珪素膜の膜厚は接触針式膜厚測定機にて測定した。Table 8 shows the types of the added dyes and the experimental results. The thickness of the silicon dioxide film was measured by a contact needle type film thickness measuring device.

これらの色素は、ESCA、SIMS、IRなどにより分析した
結果、膜中に均一に取り込まれていることが確認され
た。さらに、二酸化珪素成膜後の基板を99.5％エタノー
ル溶液の中に24時間浸漬したが、色素の溶出はみられな
かった。またテープテスト、スポンジ払拭テストによる
二酸化珪素膜の剥離も見られなかった。These dyes were analyzed by ESCA, SIMS, IR and the like, and as a result, it was confirmed that they were uniformly incorporated in the film. Further, the substrate after the formation of the silicon dioxide was immersed in a 99.5% ethanol solution for 24 hours, but no elution of the dye was observed. Also, no peeling of the silicon dioxide film was observed in the tape test and the sponge wiping test.

実施例10 縦75mm、横25mm、厚さ1mmのスライドガラスを充分に
洗浄、乾燥し、試料基材とした。 Example 10 A slide glass having a length of 75 mm, a width of 25 mm and a thickness of 1 mm was sufficiently washed and dried to obtain a sample substrate.

次にシリカゲルを飽和させた珪弗化水素酸水溶液100c
cに、金属アルミニウム0.4gを溶解させて処理液とし
た。この処理液100ccをビーカーに取り、各々の色素0.0
5gずつを添加した後、充分に攪拌してから35℃の水浴上
で加温した。この溶液中に、上記試料基材をそれぞれ１
枚ずつ浸漬し、16時間経過した後、取り出して洗浄乾燥
した。Next, an aqueous solution of hydrofluoric acid saturated with silica gel 100c
0.4 g of metallic aluminum was dissolved in c to obtain a treatment liquid. Take 100 cc of this treatment solution into a beaker, and add 0.0
After adding 5 g each, the mixture was sufficiently stirred and then heated on a 35 ° C. water bath. In this solution, each of the sample substrates was
The sheets were immersed one by one, and after 16 hours, they were taken out, washed and dried.

添加色素の種類及び実験結果を第９表に示す。二酸化
珪素膜の膜厚は接触針式膜厚測定機にて測定した。Table 9 shows the types of the added dyes and the experimental results. The thickness of the silicon dioxide film was measured by a contact needle type film thickness measuring device.

これらの色素は、ESCA、SIMS、IRなどにより分析した
結果、膜中に均一に取り込まれていることが確認され
た。さらに、二酸化珪素成膜後の基板を99.5％エタノー
ル溶液の中に24時間浸漬したが、色素の溶出はみられな
かった。また、テープテスト、スポンジ払拭テストによ
る二酸化珪素膜の剥離も見られなかった。These dyes were analyzed by ESCA, SIMS, IR and the like, and as a result, it was confirmed that they were uniformly incorporated in the film. Further, the substrate after the formation of the silicon dioxide was immersed in a 99.5% ethanol solution for 24 hours, but no elution of the dye was observed. Further, no peeling of the silicon dioxide film was observed in the tape test and the sponge wiping test.

実施例11 縦75mm、横25mm、厚さ1mmのスライドガラスを充分に
洗浄、乾燥し、試料基材とした。 Example 11 A slide glass having a length of 75 mm, a width of 25 mm and a thickness of 1 mm was sufficiently washed and dried to obtain a sample substrate.

次に種々の染料を蒸留水に室温にて混合または溶解さ
せ、５重量％または飽和の添加液とした。また、シリカ
ゲルを飽和させた珪弗化水素酸水溶液100ccに、金属ア
ルミニウム0.4g溶解させたものを処理液とした。この処
理液100ccをビーカーに取り、各々の染料液1ccずつを添
加攪拌し、35℃の水浴上にセット、加温した。この溶液
中に、上記試料基材をそれぞれ１枚ずつ浸漬し、16時間
保持した後、取り出して洗浄乾燥した。Next, various dyes were mixed or dissolved in distilled water at room temperature to obtain a 5% by weight or saturated additive solution. Also, a solution prepared by dissolving 0.4 g of metallic aluminum in 100 cc of a hydrosilicofluoric acid aqueous solution saturated with silica gel was used. 100 cc of the treatment solution was placed in a beaker, 1 cc of each dye solution was added, stirred, set on a 35 ° C. water bath, and heated. Each of the sample substrates was immersed in this solution one by one, held for 16 hours, taken out and washed and dried.

添加染料の種類及び実験結果を第10表に示す。二酸化
珪素膜の膜厚は、接触針式膜厚測定機にて測定した。Table 10 shows the types of added dyes and the experimental results. The thickness of the silicon dioxide film was measured by a contact needle type film thickness measuring device.

これらの染料は、ESCA、SIMS、IRなどにより分析した
結果、膜中に均一に取り込まれていることが確認され
た。さらに、二酸化珪素成膜後の基板を99.5％エタノー
ル溶液の中に24時間浸漬したが、染料の溶出はみられな
かった。また、テープテスト、スポンジ払拭テストによ
る二酸化珪素膜の剥離も見られなかった。These dyes were analyzed by ESCA, SIMS, IR and the like, and as a result, it was confirmed that the dyes were uniformly incorporated into the film. Further, the substrate after the formation of silicon dioxide was immersed in a 99.5% ethanol solution for 24 hours, but no dye was eluted. Further, no peeling of the silicon dioxide film was observed in the tape test and the sponge wiping test.

実施例12 縦75mm、横25mm、厚さ1mmのスライドガラスを充分に
洗浄、乾燥し、試料基材とした。 Example 12 A slide glass having a length of 75 mm, a width of 25 mm and a thickness of 1 mm was sufficiently washed and dried to obtain a sample substrate.

次に種々のレーザー用色素をエタノールに室温にて溶
解させ、0.01mol/Lまたは飽和の添加溶液とした。また
シリカゲルを飽和させた珪弗化水素酸水溶液100ccに、
金属アルミニウム0.4g溶解させたものを処理液とした。
この処理液100ccをビーカーに取り、各々の色素溶液1cc
ずつを添加攪拌し、35℃の水浴上にセットし、加温し
た。この溶液中に、上記試料基材をそれぞれ１枚ずつ浸
漬し、16時間保持した後、取り出して洗浄乾燥した。Next, various laser dyes were dissolved in ethanol at room temperature to obtain a 0.01 mol / L or saturated additive solution. In addition, to 100 cc of hydrosilicofluoric acid aqueous solution saturated with silica gel,
A solution in which 0.4 g of metallic aluminum was dissolved was used as a treatment liquid.
Take 100 cc of this treatment solution into a beaker and add 1 cc of each dye solution.
Each was added and stirred, set on a water bath at 35 ° C., and heated. Each of the sample substrates was immersed in this solution one by one, held for 16 hours, taken out and washed and dried.

添加レーザー用色素の種類及び実験結果を第11表に示
す。二酸化珪素膜の膜厚は接触針式膜厚測定機にて測定
した。Table 11 shows the types of laser dyes added and the experimental results. The thickness of the silicon dioxide film was measured by a contact needle type film thickness measuring device.

これらのレーザー用色素は、ESCA、SIMS、IRなどによ
り分析した結果、膜中に均一に取り込まれていることが
確認された。また、これらの色素含有膜にそれぞれの励
起光を照射したところ蛍光が観測され、レーザー色素と
しての機能も保持されていることが確認された。さら
に、二酸化珪素成膜後の基板を99.5％エタノール溶液の
中に24時間浸漬したが、レーザー用色素の溶出はみられ
なかった。また、テープテスト、スポンジ払拭テストに
よる二酸化珪素膜の剥離も見られなかった。As a result of analyzing these laser dyes by ESCA, SIMS, IR and the like, it was confirmed that they were uniformly incorporated into the film. Further, when these dye-containing films were irradiated with respective excitation lights, fluorescence was observed, and it was confirmed that the function as a laser dye was maintained. Further, the substrate after the formation of the silicon dioxide was immersed in a 99.5% ethanol solution for 24 hours, but no elution of the laser dye was observed. Further, no peeling of the silicon dioxide film was observed in the tape test and the sponge wiping test.

［発明の効果］ 以上説明したごとく本発明は、以下のような優れた効
果を有している。 [Effects of the Invention] As described above, the present invention has the following excellent effects.

得られる有機物含有二酸化珪素薄膜は緻密であり、
気泡等の膜欠陥の混入がない。The resulting organic-containing silicon dioxide thin film is dense,
No film defects such as bubbles are mixed.

高い高温で加熱することなく、室温付近で有機物含
有二酸化珪素膜を製造することができる。このため、熱
分解し易い有機物にも適用することができる。An organic-containing silicon dioxide film can be manufactured at around room temperature without heating at a high temperature. Therefore, the present invention can be applied to organic substances which are easily thermally decomposed.

不純物濃度の極めて少ない有機物含有二酸化珪素薄
膜が得られる。An organic-containing silicon dioxide thin film having an extremely low impurity concentration can be obtained.

原料が安価であり、膜の製造コストを低くすること
ができる。Raw materials are inexpensive, and the production cost of the film can be reduced.

複雑な形状の基材上にでも、有機物含有二酸化珪素
薄膜を形成することができる。An organic-containing silicon dioxide thin film can be formed even on a substrate having a complicated shape.

【図面の簡単な説明】[Brief description of the drawings]

第１図は本発明の有機物含有二酸化珪素膜Ａと比較膜Ｂ
とのエッチング結果を示すものである。FIG. 1 shows an organic-containing silicon dioxide film A of the present invention and a comparative film B.
3 shows the etching result.

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】二酸化珪素の過飽和状態となった珪弗化水
素酸水溶液を含む処理液と基材とを接触させて、その基
材表面に二酸化珪素薄膜を形成せしめる方法において、
該処理液に有機物を添加して二酸化珪素薄膜中に有機物
を含有せしめることを特徴とする有機物含有二酸化珪素
薄膜の製造方法。1. A method of contacting a substrate with a processing solution containing an aqueous solution of hydrosilicofluoric acid in which silicon dioxide is supersaturated to form a silicon dioxide thin film on the surface of the substrate.
A method for producing an organic-containing silicon dioxide thin film, comprising adding an organic substance to the treatment liquid to cause the organic substance to be contained in the silicon dioxide thin film.
JP2074623A 1989-04-01 1990-03-24 Method for producing organic substance-containing silicon dioxide thin film Expired - Fee Related JP2726732B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2074623A JP2726732B2 (en) 1989-04-01 1990-03-24 Method for producing organic substance-containing silicon dioxide thin film

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP8381689 1989-04-01
JP1-83816 1989-04-01
JP2074623A JP2726732B2 (en) 1989-04-01 1990-03-24 Method for producing organic substance-containing silicon dioxide thin film

Publications (2)

Publication Number Publication Date
JPH0350111A JPH0350111A (en) 1991-03-04
JP2726732B2 true JP2726732B2 (en) 1998-03-11

Family

ID=26415790

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2074623A Expired - Fee Related JP2726732B2 (en) 1989-04-01 1990-03-24 Method for producing organic substance-containing silicon dioxide thin film

Country Status (1)

Country Link
JP (1) JP2726732B2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4310415B2 (en) * 2003-04-28 2009-08-12 財団法人新産業創造研究機構 Micro patterning method by liquid phase deposition

Also Published As

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JPH0350111A (en) 1991-03-04

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