JPH02289414A - Production of silicon dioxide film - Google Patents
Production of silicon dioxide filmInfo
- Publication number
- JPH02289414A JPH02289414A JP10813189A JP10813189A JPH02289414A JP H02289414 A JPH02289414 A JP H02289414A JP 10813189 A JP10813189 A JP 10813189A JP 10813189 A JP10813189 A JP 10813189A JP H02289414 A JPH02289414 A JP H02289414A
- Authority
- JP
- Japan
- Prior art keywords
- silicon dioxide
- liquid
- substrate
- treatment
- processing liquid
- 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.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 55
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000007788 liquid Substances 0.000 claims abstract description 52
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 230000005484 gravity Effects 0.000 claims description 5
- 230000009257 reactivity Effects 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- 239000002245 particle Substances 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 239000005361 soda-lime glass Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910003638 H2SiF6 Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910004014 SiF4 Inorganic materials 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野〕
本発明は二酸化珪素被膜の製造方法に関し、特に珪弗化
水素酸の二酸化珪素過飽和溶液を含む処理液と基材とを
接触させて、基材表面に二酸化珪素被膜を製造する方法
の改良法に関する。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a method for producing a silicon dioxide coating, and in particular, the present invention relates to a method for producing a silicon dioxide film, and in particular, a method for producing a silicon dioxide film by contacting a substrate with a treatment solution containing a supersaturated solution of silicon dioxide of hydrosilicofluoric acid to form a silicon dioxide film. This invention relates to an improved method for producing a silicon dioxide film on the surface of a material.
［従来の技術］
従来、二酸化珪素被膜形成法として、珪弗化水素酸の二
酸化珪素過飽和水溶液に基材を浸せきして基材表面に二
酸化珪素被膜を形成する方法（以後析出法と呼ぶ）が知
られている。（例えば、特開昭５７−１９６７４４、特
開昭６１−２８１０４７、特開昭６２−２０８７６＞上
記析出法で成膜速度を増加させるためには、処理液であ
る珪弗化水素酸の分解を促進させるような物質または熱
エネルギーの供給速度を増加させることが有効であるが
、供給速度が速すぎると処理液中で二酸化珪素粒子が発
生し、成膜速度が逆に減少することが知られている。こ
れは、 （二酸化珪素被膜成膜量）／（珪弗化水素酸の
分解を促進させるような物質または熱エネルギーの供給
量）の比で表わされる成膜効率（以後、成膜効率と略す
）が低下する事を意味する。上記二酸化珪素粒子の発生
・成長を抑制し、かつ成膜速度を増加させる（つまり、
成膜効率を増加させる）ためには、珪弗化水素酸の分解
を促進させるような物質または熱エネルギーを連続的に
供給し、処理液の一部を循環させ処理液中に発生する二
酸化珪素粒子を濾過するという方法（以後改良法１と呼
ぶ）が知られている。[Prior Art] Conventionally, as a method for forming a silicon dioxide film, there has been a method (hereinafter referred to as a precipitation method) in which a base material is immersed in a silicon dioxide supersaturated aqueous solution of hydrosilicofluoric acid to form a silicon dioxide film on the surface of the base material. Are known. (For example, JP-A-57-196744, JP-A-61-281047, JP-A-62-20876) In order to increase the film formation rate with the above precipitation method, it is necessary to decompose the hydrosilicic acid, which is the processing liquid. Although it is effective to increase the supply rate of accelerating substances or thermal energy, it is known that if the supply rate is too fast, silicon dioxide particles will be generated in the processing solution and the film formation rate will decrease. This is the film-forming efficiency (hereinafter referred to as film-forming efficiency), which is expressed as the ratio of (amount of silicon dioxide film formed)/(amount of material or thermal energy supplied that promotes the decomposition of hydrosilicofluoric acid). This means that the generation and growth of the silicon dioxide particles mentioned above is suppressed and the film formation rate is increased (that is,
In order to increase the film formation efficiency, a substance or heat energy that accelerates the decomposition of hydrosilicofluoric acid is continuously supplied, and a part of the processing solution is circulated to reduce the silicon dioxide generated in the processing solution. A method of filtering particles (hereinafter referred to as improved method 1) is known.
（例えば、特開昭６０−３３２３３、特開昭６３また、
上記析出法で緻密な二酸化珪素被膜を形成する方法とし
ては、高い処理液温度で二酸化珪素被膜を形成する方法
（例えば、特願昭６２−１８４５６９ 以後改良法２
と呼ぶ）や、処理液として高濃度の珪弗化水素酸水溶液
を用いる方法（例えば、特願昭６２−１７４５６１
以後改良法３と呼ぶ）が知られている。(For example, JP-A-60-33233, JP-A-63,
As a method for forming a dense silicon dioxide film using the above precipitation method, a method of forming a silicon dioxide film at a high processing solution temperature (for example, Japanese Patent Application No. 184569/1989, improved method 2)
) or a method using a highly concentrated aqueous solution of hydrosilicofluoric acid as a treatment liquid (for example, Japanese Patent Application No. 174561/1983).
(hereinafter referred to as improved method 3) is known.
［発明が解決しようとする問題点］
しかし上記改良法ｌで得られる成膜速度は、処理条件に
より多少異なるが約３３０−１Ｏ０ｎ／ｈであり、工業
的に十分とはいえない。更に上記改良法１の場合に於い
ても、二酸化珪素粒子の発生はおこっており、成膜効率
は必ずしも十分ではない。[Problems to be Solved by the Invention] However, the film formation rate obtained by the above-mentioned improved method 1 is about 330-1 O0 n/h, although it varies somewhat depending on the processing conditions, which is not industrially sufficient. Furthermore, even in the case of the improved method 1, silicon dioxide particles are generated, and the film formation efficiency is not necessarily sufficient.
また、上記改良法２や上記改良法３では、処理液からの
３１成分（Ｈ２ＳｉＦ６またはＳｉＦ４と推定される）
の蒸発が激しく、処理液と大気との界面や処理液液面上
の容器壁に二酸化珪素粒子が生成してしまう。これらの
二酸化珪素粒子は、本来処理液中で二酸化珪素被膜とな
り得ると推定され、大気中に飛散してしまう結果、成膜
効率が低下してしまうという問題があった。In addition, in the above improved method 2 and the above improved method 3, 31 components (estimated to be H2SiF6 or SiF4) from the treatment liquid
evaporation is intense, and silicon dioxide particles are generated at the interface between the processing liquid and the atmosphere and on the container wall above the surface of the processing liquid. It is estimated that these silicon dioxide particles can originally form a silicon dioxide film in the processing solution, and as a result, they are scattered into the atmosphere, resulting in a reduction in film formation efficiency.
［問題点を解決するための手段］
本発明は前記問題点を解決するためになされたものであ
って、二酸化珪素が過飽和状態となった珪弗化水素酸溶
液を含む処理液と基材とを接触させて基材表面に二酸化
珪素被膜を析出させる二酸化珪素被膜の製造方法におい
て、該処理液からのｓｉ酸成分蒸発を防ぐため、該珪弗
化水素酸溶液を含む処理液と気体との界面をなくすと言
う方法を用いている。[Means for Solving the Problems] The present invention has been made to solve the above problems, and includes a treatment liquid containing a hydrosilicofluoric acid solution in which silicon dioxide is supersaturated, and a base material. In the method for producing a silicon dioxide film in which a silicon dioxide film is deposited on the surface of a substrate by contacting the solution, in order to prevent evaporation of the siic acid component from the processing solution, the processing solution containing the hydrosilicofluoric acid solution and gas are mixed. A method called eliminating interfaces is used.
該処理液と気体の界面をなくす方法としては、密閉容器
中に該処理液を満たす、該処理液上に固体を浮かべる等
の方法でも良いが、該処理液との反応性が低く、かつ該
処理液より比重の軽い液状物質を浮遊させると言う方法
が、簡便で、かつ該処理液と気体との界面をくまな（な
くすことが出来るため望ましい。As a method of eliminating the interface between the processing liquid and gas, methods such as filling the processing liquid in a closed container or floating a solid on the processing liquid may be used. A method of suspending a liquid substance having a specific gravity lower than that of the processing liquid is desirable because it is simple and can eliminate the interface between the processing liquid and gas.
該液状物質としては、該処理液との反応性が低く、かつ
該処理液より比重の軽い物質であれば特に限定されない
。例えば一般弐Ｃ１Ｈ２ｎ＊２で表される脂肪族炭化水
素ではｎ＝４〜３１のものが使用できるが本発明を実施
するときの処理液温度及び該液状物質の融点、沸点、該
処理液温度での蒸気圧等を考慮′して選択したほうがよ
い。The liquid substance is not particularly limited as long as it has low reactivity with the processing liquid and has a specific gravity lighter than that of the processing liquid. For example, among the aliphatic hydrocarbons generally represented by 2C1H2n*2, those with n=4 to 31 can be used, but depending on the processing liquid temperature, the melting point, boiling point of the liquid substance, and the processing liquid temperature when carrying out the present invention, It is better to make a selection taking into account the vapor pressure, etc.
上記二酸化珪素の過飽和状態となった珪弗化水素酸溶液
を含む処理液の調整方法は特に限定されず、例えば二酸
化珪素の略飽和状態となった珪弗化水素酸溶液に、Ｈ３
ＢＯ３，ＡＩ等の珪弗化水素酸の分解を促進させる物質
を添加する方法、及び二酸化珪素の略飽和状態となった
珪弗化水素酸溶液の温度を上昇させる方法等が利用でき
る。The method for preparing the treatment liquid containing the hydrosilicofluoric acid solution that has become supersaturated with silicon dioxide is not particularly limited. For example, H3
A method of adding a substance that accelerates the decomposition of hydrosilicofluoric acid, such as BO3 or AI, and a method of increasing the temperature of a hydrosilicic acid solution that has reached a substantially saturated state of silicon dioxide, etc., can be used.
本発明に適用される基材は、特に限定されず、アルカリ
金属含有ガラス、シリカガラス、無アルカリガラス等の
各種ガラスや、各種セラミックス、シリコンやガリウム
砒素等の各種半導体等、該処理液と不都合な反応を生じ
にくいあらゆる基材に適用できる。The base materials applied to the present invention are not particularly limited, and include various glasses such as alkali metal-containing glass, silica glass, and alkali-free glass, various ceramics, and various semiconductors such as silicon and gallium arsenide, which are inconvenient with the processing liquid. It can be applied to any base material that is unlikely to cause a reaction.
［作用］
本発明によれば、二酸化珪素の過飽和状態となった珪弗
化水素酸を含む処理液と気体の界面をな（しているため
、該処理液からのＳｉ成分（Ｈ２ＳｉＦ６または５ＩＦ
４と推定される）の蒸発を防ぐことが出来る。その結果
、成膜効率が大幅に増加し、成膜速度も増加する。特に
、処理液中の珪弗化水素酸溶液の濃度が高い場合や、処
理液温度が高い場合、高成膜速度を得る場合等の、処理
液からのＳｉ成分の蒸発が激しい場合に有効である。[Function] According to the present invention, since silicon dioxide forms an interface between the processing liquid containing hydrosilicofluoric acid in a supersaturated state and the gas, the Si component (H2SiF6 or 5IF) from the processing liquid
4) can be prevented from evaporating. As a result, the deposition efficiency is significantly increased and the deposition rate is also increased. This is particularly effective when the Si component from the processing solution evaporates rapidly, such as when the concentration of the hydrosilicofluoric acid solution in the processing solution is high, when the processing solution temperature is high, or when obtaining a high film formation rate. be.
以下処理液より比重の軽い物質としてＣ７Ｈ＋ｓ（ヘプ
タン）を使用した場合の実施例について述べる。An example will be described below in which C7H+s (heptane) is used as a substance with a lighter specific gravity than the treatment liquid.
［実施例］
実施例１
第１図に示す二酸化珪素被膜製造装置を用いて、縦１０
０ｍｍ、横１００ｍｍ、厚さ１．１ｍｍのソーダライム
ガラス上に、二酸化珪素被膜を以下の手順で作成した。[Example] Example 1 Using the silicon dioxide coating manufacturing apparatus shown in FIG.
A silicon dioxide film was created on soda lime glass with a size of 0 mm, a width of 100 mm, and a thickness of 1.1 mm using the following procedure.
二酸化珪素被膜製造装置は、外槽（１）と内槽（２）か
らなり、内槽と外槽の間には水（３）が満たしである。The silicon dioxide coating manufacturing apparatus consists of an outer tank (1) and an inner tank (2), and the space between the inner tank and the outer tank is filled with water (3).
本実施例ではこの水の温度が３５℃となるよう、温度調
節器（４）で調節した。In this example, the temperature of this water was adjusted to 35° C. using a temperature controller (4).
また、水（３）は温度均一化のため、攪拌機（５）によ
り攪拌されている。内槽は前部（６）、中部（７）、後
部（８）からなり、各部にはシリカゲル粉末を溶解飽和
した２、５モル、ＱＺの濃度の珪弗化水素酸水溶液６７
χが処理液として満たしである。Further, the water (3) is stirred by a stirrer (5) in order to equalize the temperature. The inner tank consists of a front part (6), a middle part (7), and a rear part (8), and each part contains a saturated aqueous solution of hydrosilicic fluoride acid with a concentration of 2.5 mol, QZ, containing silica gel powder (67).
χ is filled as a processing liquid.
ここでまず循環ポンプ（１０）を始動させ、内槽後部（
８）の処理液を一定量ずつ（み出してフィルター（１１
）で濾過し、内槽前部（６）へ戻す処理液循環を開始し
た。その後、内槽後部（８）に縦５（１ｍｍ、横５０ｍ
ｍ、厚さ３ｍｍの金属ＡＩ板を３枚浸漬し、１０時間保
持した。この状態で処理液は適度な二酸化珪素過飽和度
を有する処理液となった。First, start the circulation pump (10), and then start the rear part of the inner tank (
Squeeze out a certain amount of the processing solution from step 8) and pass it through the filter (11).
) and started circulating the treatment liquid, which was then returned to the front part of the inner tank (6). After that, the rear part of the inner tank (8) was
Three metal AI plates with a thickness of 3 mm and a thickness of 3 mm were immersed and held for 10 hours. In this state, the treatment liquid had an appropriate degree of silicon dioxide supersaturation.
ここで、フィルター（ｌ ｌ）の絶対除去率を１．５６
ｍ（１，５ｐｍ以上のものは１００％通さない）および
、処理液循環流量を５００ｍ１／ｍ１ｎ（処理液全量が
６″１２であるので、循環流量は約８％／ ｍ １ ｎ
である）とし、処理液と気体の界面をなくす目的で処理
液上にヘプタン（１４）を浮遊させた。Here, the absolute removal rate of filter (l l) is 1.56
m (100% does not pass anything over 1.5 pm) and the processing liquid circulation flow rate is 500 m1/m1n (since the total amount of processing liquid is 6"12, the circulation flow rate is about 8%/m1n
), and heptane (14) was suspended on the processing liquid in order to eliminate the interface between the processing liquid and gas.
その後、上記ソーダライムガラス基板（９）を内槽中部
（７）に垂直に浸漬した。そして、前記条件（内槽後部
（８）に縦５０ｍｍ、 横５０ｍｍ、厚さ３ｍｍの金
属ＡＩ板を３枚浸漬し、８％／ｍ１ｎの循環をし、絶対
除去率１．５μｍフィルターで濾過する。）を継続して
８時間保持した。Thereafter, the soda lime glass substrate (9) was vertically immersed in the middle part (7) of the inner tank. Then, under the above conditions (3 metal AI plates with a length of 50 mm, a width of 50 mm, and a thickness of 3 mm are immersed in the rear part of the inner tank (8), circulated at a rate of 8%/m1n, and filtered with an absolute removal rate of 1.5 μm filter. ) was continuously held for 8 hours.
処理終了後、処理液とへブタンとの界面や、ヘプタンと
大気との界面、処理液液面上の容器壁には二酸化珪素粒
子はみられなかった。After the treatment was completed, no silicon dioxide particles were observed at the interface between the treatment solution and hebutane, at the interface between heptane and the atmosphere, or on the container wall above the surface of the treatment solution.
８時間の間に溶解したＡＩの量は３．１８ｇであり、上
記処理で得られた二酸化珪素被膜の膜厚は、約６７８
ｎｍであった。したがって、平均の成膜速度は約８５ｎ
ｍ／時間、（二酸化珪素被膜成膜量）／（珪弗化水素酸
の分解を促進させるような物質または熱エネルギーの供
給量（本実施例の場合はＡＩ溶解量））の比で表わされ
る成膜効率は０． Ｑ ２１３ ｎ ｍ／ ｍ ｍ２
・ｇと計算できる。The amount of AI dissolved during 8 hours was 3.18 g, and the thickness of the silicon dioxide film obtained by the above treatment was approximately 678 g.
It was nm. Therefore, the average deposition rate is approximately 85n
m/hour, expressed as the ratio of (amount of silicon dioxide film formed)/(amount of substance or thermal energy supplied that promotes the decomposition of hydrosilicofluoric acid (in the case of this example, the amount of AI dissolved)) Film-forming efficiency is 0. Q 213 nm/m m2
・Can be calculated as g.
比較例１
実施例１と同様の装置を用いて、適度な二酸化珪素過飽
和度を有する処理液を得た。Comparative Example 1 Using the same apparatus as in Example 1, a treatment liquid having an appropriate degree of silicon dioxide supersaturation was obtained.
ここで、フィルター（１１）の絶対除去率ヲ１、 ５μ
ｍおよび、処理液循環流量を５００ｍ１／ ｍ ｉ ｎ
（処理液全量が６１Ｘであるので、循環流量は約８％
／ ｍ ｉ ｎである）としたが、処理液上には何も浮
遊させず、大気と直接接するようにした。Here, the absolute removal rate of filter (11) is 1.5μ
m and the processing liquid circulation flow rate to 500 m1/min
(Since the total amount of processing liquid is 61X, the circulation flow rate is approximately 8%.
/min), but nothing was suspended on the processing solution, and it was placed in direct contact with the atmosphere.
その後、上記ソーダライムガラス基板（９）を内槽中部
（７）に垂直に浸漬し、前記条件（内槽後部（８）に縦
５０ｍｍ５ 横５０ｍｍ、厚さ３ｍｍの金属ＡＩ板を３
枚浸漬し、８％／ ｍ ｉ ｎの循環をし、絶対除去率
１． ５μｍフィルターで濾過する。）で８時間保持し
た。Thereafter, the above-mentioned soda lime glass substrate (9) is vertically immersed in the middle part of the inner tank (7), and under the above conditions (3 metal AI plates of 50 mm long x 50 mm wide and 3 mm thick are placed at the rear part of the inner tank (8)).
The absolute removal rate was 1. Filter through a 5 μm filter. ) for 8 hours.
処理終了後、処理液と大気との界面や処理液液面上の容
器壁には微量の二酸化珪素粒子が見られた。After the treatment was completed, trace amounts of silicon dioxide particles were observed at the interface between the treatment solution and the atmosphere and on the container wall above the surface of the treatment solution.
８時間の間に溶解したＡ１の鳳は１．９８ｇであり、上
記処理で得られた二酸化珪素被膜の膜厚は、約４０５ｎ
ｍであった。したがって、平均の成膜速度は約５１ｎｍ
／時間、（二酸化珪素被膜成膜量）／（珪弗化水素酸の
分解を促進させるような物質または熱エネルギーの供給
量（本実施例の場合はＡ１溶解量））の比で表わされる
成膜効率は、０． ０２０５ ｎｍ／ｍｍ２・ｇと計算
できる。The amount of A1 dissolved during 8 hours was 1.98 g, and the thickness of the silicon dioxide film obtained by the above treatment was approximately 405 nm.
It was m. Therefore, the average deposition rate is approximately 51 nm.
/time, (amount of silicon dioxide film formed)/(amount of material or thermal energy supplied that promotes the decomposition of hydrosilicofluoric acid (in the case of this example, the amount of A1 dissolved)). The membrane efficiency is 0. It can be calculated as 0205 nm/mm2·g.
実施例２
３．８モル／１χの濃度の珪弗化水素酸水溶液を一３℃
に冷却し、二酸化珪素〈工業用シリカゲル〉を溶解飽和
して処理液とした。Example 2 Aqueous solution of hydrosilicic acid with a concentration of 3.8 mol/1χ was heated to -3°C.
Then, silicon dioxide (industrial silica gel) was dissolved and saturated to obtain a treatment liquid.
この処理液を１００ｍ１ずつ４ケの容器にいれ、それぞ
れに縦５０ｍｍ、横２５ｍｍ、 厚さ１．１ｍｍのソー
ダライムガラスを浸漬した。次いで、各容器の処理液上
にヘプタンを浮遊させ、直ちに容器を３５°Ｃに加熱し
、それぞれ、３時間、６時間、１６時間、２４時間保持
した。その後、ガラス表面に積層された二酸化珪素被膜
の膜厚を測定した。100 ml of this treatment solution was poured into four containers, and soda lime glass measuring 50 mm long, 25 mm wide, and 1.1 mm thick was immersed in each container. Next, heptane was suspended on the treatment liquid in each container, and the containers were immediately heated to 35° C. and maintained for 3 hours, 6 hours, 16 hours, and 24 hours, respectively. Thereafter, the thickness of the silicon dioxide film laminated on the glass surface was measured.
結果を第１表に示す。二酸化珪素被膜の膜厚は、ソーダ
ライムガラスを処理液中に保持した時間にほぼ比例して
増加していることがわかる。The results are shown in Table 1. It can be seen that the thickness of the silicon dioxide film increases approximately in proportion to the time that the soda lime glass was held in the treatment solution.
第１表
また、処理終了後の処理液とへブタンとの界面及びヘプ
タンと大気との界面、処理液液面上の容器壁には、二酸
化珪素粒子はみられなかった。Table 1 also shows that no silicon dioxide particles were found at the interface between the processing solution and hebutane, at the interface between heptane and the atmosphere, and on the container wall above the surface of the processing solution after the completion of the treatment.
比較例２
実施例２と同様にソーダライムガラス上に二酸化珪素被
膜を作成した。ただし、処理液上にはへブタンを浮遊さ
せず、処理液と大気が直接接触した状態で行なった。Comparative Example 2 A silicon dioxide film was formed on soda lime glass in the same manner as in Example 2. However, hebutane was not suspended on the processing solution, and the processing was carried out in a state where the processing solution was in direct contact with the atmosphere.
結果を第２表に示す。二酸化珪素被膜の膜厚は、６時間
以下の処理では実施例２とあまり差が無いが、１６時間
以上の処理ではあまり増加せず１６時間処理では約４０
％、２４時間処理では約３５％の膜厚の二酸化珪素被膜
しか得られなかった。The results are shown in Table 2. The film thickness of the silicon dioxide film is not much different from Example 2 when the treatment time is 6 hours or less, but it does not increase much when the treatment time is 16 hours or more, and the thickness of the silicon dioxide film is about 40.
%, and a 24-hour treatment resulted in a silicon dioxide film with a thickness of only about 35%.
また、処理終了後、処理液と大気との界面や処理液液面
上の容器壁には二酸化珪素粒子が見られ、特に１６時間
処理と２４時間処理の場合は、多量の二酸化珪素粒子が
生成していた。In addition, after the treatment, silicon dioxide particles can be seen at the interface between the treatment liquid and the atmosphere and on the container wall above the treatment liquid surface, and especially in the case of 16-hour treatment and 24-hour treatment, a large amount of silicon dioxide particles are generated. Was.
第２表
［発明の効果］
本発明によれば、成膜効率を大幅に増加させ、成膜速度
も増加させることができる。そのため、珪弗化水素酸の
分解を促進させるような物質または熱エネルギーの供給
量を減少させることが出来るため、製造コストが低くな
るという利点がある。Table 2 [Effects of the Invention] According to the present invention, the film formation efficiency can be significantly increased and the film formation rate can also be increased. Therefore, it is possible to reduce the supply amount of a substance or thermal energy that promotes the decomposition of hydrosilicofluoric acid, which has the advantage of lowering manufacturing costs.
さらに、処理液からのＳｉ成分（Ｈ２Ｓ ｉ Ｆｓまた
は５ｉＦｎと推定される）の蒸発を抑制し、その結果、
処理液中以外での二酸化珪素粒子の発生を防止できるた
め、蒸発したＳｉ成分による作業環境の悪化や、二酸化
珪素被膜による製品歩留まりの低下を防ぐことができる
という効果がある。Furthermore, the evaporation of the Si component (estimated to be H2S i Fs or 5iFn) from the treatment liquid is suppressed, and as a result,
Since the generation of silicon dioxide particles outside of the processing liquid can be prevented, it is possible to prevent deterioration of the working environment due to evaporated Si components and a decrease in product yield due to the silicon dioxide coating.
第１図は、本発明の実施例に使用した二酸化珪素被膜製
造装置の系統説明図である。
（１）外槽 （２）内槽
（３）水 （４）温度調節器（５）攪拌器
（６）内槽前部
（７）内槽中部 （８）内槽後部
（９）ソーダライムガラス
（１０）循環ポンプ （１１）フィルター（１２）金属
ＡＩ板 （１３）攪拌器
（１４）比重の軽い物質FIG. 1 is an explanatory diagram of a system for manufacturing a silicon dioxide film used in an example of the present invention. (1) Outer tank (2) Inner tank (3) Water (4) Temperature controller (5) Stirrer
(6) Front part of the inner tank (7) Middle part of the inner tank (8) Rear part of the inner tank (9) Soda lime glass (10) Circulation pump (11) Filter (12) Metal AI plate (13) Stirrer (14) Specific gravity light substance
Claims (2)
含む処理液と基材とを接触させて基材表面に二酸化珪素
被膜を析出させる二酸化珪素被膜の製造方法において、
該処理液と気体との界面をなくすことを特徴とする二酸
化珪素被膜の製造方法。(1) In a method for producing a silicon dioxide coating, the method includes depositing a silicon dioxide coating on the surface of the substrate by bringing the substrate into contact with a treatment solution containing hydrosilicofluoric acid in which silicon dioxide is supersaturated,
A method for producing a silicon dioxide film, characterized by eliminating an interface between the treatment liquid and gas.
液上に該処理液との反応性の低い、かつ該処理液より比
重の軽い液状物質を浮遊させる方法である特許請求の範
囲第１項記載の二酸化珪素被膜の製造方法。(2) The method of eliminating the interface between the processing liquid and gas is a method of suspending a liquid substance having low reactivity with the processing liquid and having a specific gravity lower than that of the processing liquid on the processing liquid. A method for producing a silicon dioxide film according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10813189A JPH0694368B2 (en) | 1989-04-27 | 1989-04-27 | Method for producing silicon dioxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10813189A JPH0694368B2 (en) | 1989-04-27 | 1989-04-27 | Method for producing silicon dioxide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02289414A true JPH02289414A (en) | 1990-11-29 |
| JPH0694368B2 JPH0694368B2 (en) | 1994-11-24 |
Family
ID=14476721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10813189A Expired - Lifetime JPH0694368B2 (en) | 1989-04-27 | 1989-04-27 | Method for producing silicon dioxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0694368B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5153035A (en) * | 1990-09-29 | 1992-10-06 | Nippon Sheet Glass Co., Ltd. | Process for forming silica films |
| US5326720A (en) * | 1990-10-25 | 1994-07-05 | Nippon Sheet Glass Co., Ltd. | Method for producing silicon dioxide film which prevents escape of Si component to the environment |
-
1989
- 1989-04-27 JP JP10813189A patent/JPH0694368B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5153035A (en) * | 1990-09-29 | 1992-10-06 | Nippon Sheet Glass Co., Ltd. | Process for forming silica films |
| US5326720A (en) * | 1990-10-25 | 1994-07-05 | Nippon Sheet Glass Co., Ltd. | Method for producing silicon dioxide film which prevents escape of Si component to the environment |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0694368B2 (en) | 1994-11-24 |
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