JPH1046108A - Silica-film-forming coating fluid and substrate coated with the film - Google Patents

Silica-film-forming coating fluid and substrate coated with the film

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Publication number
JPH1046108A
JPH1046108A JP20711896A JP20711896A JPH1046108A JP H1046108 A JPH1046108 A JP H1046108A JP 20711896 A JP20711896 A JP 20711896A JP 20711896 A JP20711896 A JP 20711896A JP H1046108 A JPH1046108 A JP H1046108A
Authority
JP
Japan
Prior art keywords
silica
coating
film
polysilazane
coating solution
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
Application number
JP20711896A
Other languages
Japanese (ja)
Other versions
JP3516815B2 (en
Inventor
Akira Nakajima
島 昭 中
Michio Komatsu
松 通 郎 小
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.)
JGC Catalysts and Chemicals Ltd
Original Assignee
Catalysts and Chemicals Industries Co Ltd
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Filing date
Publication date
Application filed by Catalysts and Chemicals Industries Co Ltd filed Critical Catalysts and Chemicals Industries Co Ltd
Priority to JP20711896A priority Critical patent/JP3516815B2/en
Publication of JPH1046108A publication Critical patent/JPH1046108A/en
Application granted granted Critical
Publication of JP3516815B2 publication Critical patent/JP3516815B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133345—Insulating layers

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  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a coating fluid which forms a dense silica-based coating film excellent in adhesion, mechanical strengths, chemical resistance, and cracking resistance by specifying the chlorine concentration of a coating fluid containing a specified polysilazane. SOLUTION: This coating fluid is prepared by dissolving 3-40wt.% (in terms of the solid concentration) at least one polysilazane essentially consisting of repeating units represented by the formula (wherein R1 , R2 and R3 are each H or a 1-8C alkyl) and having a number-average molecular weight of 500-10,000 in an organic solvent. The polysilazane is particularly desirably an inorganic polysilazane in which all of R1 , R2 and R3 are hydrogen atoms and which has a composition of 55-65wt.% silicon, 20-30wt.% nitrogen and 10-15wt.% hydrogen. This fluid is dechlorinated to a chlorine concentration of below 5ppm to obtain a coating fluid for forming a silica-based coating film.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の技術分野】本発明は、シリカ系被膜形成用塗布
液および被膜付基材に関し、さらに詳しくは、被塗布面
との密着性、機械的強度、耐アルカリ性などの耐薬品性
に優れ、同時に緻密で耐クラック性に優れ、しかも被塗
布面の凹凸を高度に平坦化することができるような被膜
形成用塗布液およびこのようなシリカ系被膜が形成され
た被膜付基材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating solution for forming a silica-based film and a substrate with a film, and more particularly to a coating solution having excellent adhesion to a surface to be coated, mechanical strength, and alkali resistance. At the same time, the present invention relates to a coating liquid for forming a coating, which is dense and excellent in crack resistance, and which can highly flatten the unevenness of a coated surface, and a coated substrate on which such a silica-based coating is formed.

【０００２】[0002]

【発明の技術的背景】従来より、シリカ系被膜は、下記
のような分野に用いられている。 １）半導体装置 半導体装置では、半導体基板とアルミニウム配線層など
の金属配線層との間、あるいは金属配線層間を絶縁する
ために、これらの間に絶縁膜が設けられている。さらに
半導体基板上に設けられているＰＮ接合半導体、および
コンデンサー素子、抵抗素子などの各種素子を保護する
ために、これらの素子が絶縁膜で被覆されている。BACKGROUND OF THE INVENTION Conventionally, silica-based coatings have been used in the following fields. 1) Semiconductor Device In a semiconductor device, an insulating film is provided between a semiconductor substrate and a metal wiring layer such as an aluminum wiring layer, or between metal wiring layers to insulate them. Further, in order to protect the PN junction semiconductor provided on the semiconductor substrate and various elements such as a capacitor element and a resistance element, these elements are covered with an insulating film.

【０００３】また、半導体基板上に金属配線層などを設
けると、金属配線層などによって半導体基板上に凹凸が
生じる。この凹凸面上にさらに金属配線層などを形成し
ようとしても、凹凸段差で断線が生じることがある。こ
のため、上記のような半導体基板と金属配線層との間、
金属配線層間に形成する絶縁膜、および各種素子を被覆
する絶縁膜には、上記のような金属配線層および各種素
子によって生じた凹凸面を高度に平坦化することが必要
である。このような半導体装置では、平坦化用絶縁膜と
してシリカ系被膜が用いられている。Further, when a metal wiring layer or the like is provided on a semiconductor substrate, unevenness occurs on the semiconductor substrate due to the metal wiring layer or the like. Even if an attempt is made to further form a metal wiring layer or the like on the uneven surface, disconnection may occur due to uneven steps. Therefore, between the semiconductor substrate and the metal wiring layer as described above,
It is necessary for an insulating film formed between metal wiring layers and an insulating film covering various elements to highly flatten the uneven surface generated by the metal wiring layer and various elements as described above. In such a semiconductor device, a silica-based coating is used as a planarizing insulating film.

【０００４】２）液晶表示装置 カラー液晶表示装置においては、ガラス基板上にＴＦＴ
（薄型トランジスタ）などで構成された画素電極を有す
る電極板と、ガラス基板上にカラーフィルターおよび透
明電極が順次形成されている対向電極板とを有し、電極
板と対向電極板との間に液晶層が充填されてなる液晶表
示セルが用いられているが、このような液晶表示セル
は、電極板から画素電極が突出し、対向電極板からカラ
ーフィルターが突出しており、それぞれの電極表面に段
差がある。このように電極表面に段差があると、セルギ
ャップが不均一になり、液晶表示セル内部に封入された
液晶材料の配向が乱れたり、表示画像に色むらなどの画
素むらが生じやすいといった傾向がある。2) Liquid crystal display device In a color liquid crystal display device, a TFT is provided on a glass substrate.
(A thin transistor) having an electrode plate having a pixel electrode, and a counter electrode plate on which a color filter and a transparent electrode are sequentially formed on a glass substrate, and between the electrode plate and the counter electrode plate. A liquid crystal display cell filled with a liquid crystal layer is used.In such a liquid crystal display cell, a pixel electrode protrudes from an electrode plate, and a color filter protrudes from a counter electrode plate. There is. If there is a step on the electrode surface, the cell gap becomes non-uniform, the orientation of the liquid crystal material sealed in the liquid crystal display cell is disturbed, and pixel unevenness such as color unevenness tends to occur in the displayed image. is there.

【０００５】このため、電極板の画素電極上および対向
電極板のカラーフィルター上に、シリカ系被膜を塗布法
で形成し、電極表面の段差を平坦化することが提案され
ている。For this reason, it has been proposed to form a silica-based coating on the pixel electrode of the electrode plate and the color filter of the counter electrode plate by a coating method to flatten the steps on the electrode surface.

【０００６】３）位相シフト付きフォトマスク リソグラフ法で高解像度の凹凸パターンを基板上に形成
するため、フォトマスク上に露光光の位相をずらす位相
シフタを付設し、これにより基板上に形成される凹凸パ
ターンの解像度を向上させる方法がある（日経マイクロ
デバイスＮｏ.７１、５２〜５８、(５)、１９９１）。
このような位相シフタとしては、一般にＣＶＤ法、スパ
ッタリング法などの気相成長法またはシリカ系被膜形成
用塗布液を用いてシリカ系被膜が基板上に形成されてい
る。3) Photomask with phase shift In order to form a high-resolution uneven pattern on the substrate by lithographic method, a phase shifter for shifting the phase of exposure light is provided on the photomask, thereby forming on the substrate. There is a method of improving the resolution of the uneven pattern (Nikkei Micro Devices No. 71, 52 to 58, (5), 1991).
As such a phase shifter, a silica-based film is generally formed on a substrate using a vapor-phase growth method such as a CVD method or a sputtering method or a coating solution for forming a silica-based film.

【０００７】しかしながら、気相成長法によってシリカ
系被膜を形成する方法は、手間がかかるとともに大きな
設備が必要であり、また凹凸面を平坦化することができ
ない。However, the method of forming a silica-based film by a vapor phase growth method is troublesome, requires large facilities, and cannot flatten an uneven surface.

【０００８】これに対し、塗布法によってシリカ系被膜
を形成すると上記のような問題点が解決できるため、近
年、塗布法によってシリカ系被膜を形成することが広く
行なわれている。On the other hand, since the above-mentioned problems can be solved by forming a silica-based coating by a coating method, formation of a silica-based coating by a coating method has been widely performed in recent years.

【０００９】従来、塗布法では、シリカ系被膜形成用塗
布液を用いてシリカ系被膜を形成する際に、被膜形成成
分としてアルコキシシラン部分加水分解物の縮重合物を
含むシリカ系被膜形成用塗布液が用いられてきた。Conventionally, in a coating method, when a silica-based coating is formed using a coating solution for forming a silica-based coating, a coating for forming a silica-based coating containing a condensation polymerization product of an alkoxysilane partial hydrolyzate as a coating forming component is used. Liquids have been used.

【００１０】しかしながら、被膜形成成分がアルコキシ
シラン部分加水分解物の縮重合物であるようなシリカ系
被膜形成用塗布液を基板上に塗布・乾燥させると、得ら
れた被膜中にはアルコキシシランが残存している。した
がって、この被膜を焼成すると、焼成時に被膜中で、ア
ルコキシシラン分子に含まれているアルキル基、アルコ
キシ基などのような有機基が分解し、この有機基の分解
によって被膜にピンホールやボイドが発生し、緻密なシ
リカ系被膜を得ることは難しい。さらにアルコキシシラ
ン部分加水分解物が縮合する過程で、縮合体の末端以外
でシラノール基同士が脱水反応を行って縮合体の架橋が
進行する。このためシリカ系被膜が形成される過程で、
縮合体の架橋度に応じて被膜の収縮ストレスが大きくな
って被膜にクラックが生じ、耐クラック性に優れたシリ
カ系被膜を得ることは難しい。However, when a coating solution for forming a silica-based film, in which the film-forming component is a condensation polymer of an alkoxysilane partial hydrolyzate, is applied and dried on the substrate, alkoxysilane is contained in the obtained film. It remains. Therefore, when this film is fired, organic groups such as alkyl groups and alkoxy groups contained in alkoxysilane molecules are decomposed in the film at the time of firing, and pinholes and voids are formed in the film due to the decomposition of the organic groups. It is difficult to obtain a dense and silica-based coating. Furthermore, during the process of condensation of the partial hydrolyzate of the alkoxysilane, silanol groups at other than the ends of the condensate undergo a dehydration reaction, and crosslinking of the condensate proceeds. Therefore, in the process of forming the silica-based coating,
The shrinkage stress of the coating increases in accordance with the degree of crosslinking of the condensate, causing cracks in the coating, making it difficult to obtain a silica coating excellent in crack resistance.

【００１１】これに対し、近年、シクロシラザン重合物
またはポリシラザンを含有してなるシリカ系被膜形成用
塗布液が提案され（特開昭６２−８８３２７号公報、特
開平１−２０３４７６号公報等参照）、これらの塗布液
を用いてシリカ系被膜を形成すると、シリカ系被膜の緻
密性および耐クラック性をある程度改良することができ
る。On the other hand, in recent years, a coating solution for forming a silica-based film containing a cyclosilazane polymer or polysilazane has been proposed (see JP-A-62-88327, JP-A-1-203476, etc.). When a silica-based coating is formed using these coating solutions, the denseness and crack resistance of the silica-based coating can be improved to some extent.

【００１２】本出願人も、ポリシラザン中の有機基が炭
素原子１〜８のアルキル基、または少なくともその一部
が水素原子であるような特定のポリシラザンを含むシリ
カ系被膜形成用塗布液を用いると、緻密性および耐クラ
ック性に優れ、かつ被膜形成時の膜収縮ストレスが小さ
い平坦化被膜が得られることを見出し、このようなシリ
カ系絶縁膜を有する半導体装置を提案している（国際公
開ＷＯ９３／０２４７２）。[0012] The present applicant also uses a coating solution for forming a silica-based film containing a specific polysilazane in which the organic group in the polysilazane is an alkyl group having 1 to 8 carbon atoms or at least a part of which is a hydrogen atom. It has been found that a flattened film having excellent denseness and crack resistance and small film shrinkage stress during film formation can be obtained, and a semiconductor device having such a silica-based insulating film has been proposed (International Publication WO93). / 02472).

【００１３】一方、このような従来用いられているポリ
シラザン類は、クロロシランのような塩素含有化合物を
原料としているため、得られるポリシラザンはその骨格
中に塩素が残存している。このような塩素が残存したポ
リシラザンを含む塗布液を用いて被膜を形成すると、こ
の残存塩素は被膜形成時にポリシラザン骨格から遊離す
るが、ポリシラザンが酸化されてシリカ系被膜に変化す
るときに発生するアンモニアとこの遊離塩素が反応し、
塩化アンモニウムの結晶粒が生成する。この結晶粒によ
り、得られる被膜は緻密性が低下するとともに平坦性も
悪くなることを本発明者らは見いだした。On the other hand, since such conventionally used polysilazanes use a chlorine-containing compound such as chlorosilane as a raw material, the resulting polysilazane has chlorine remaining in its skeleton. When a film is formed using a coating solution containing polysilazane in which such chlorine remains, the residual chlorine is released from the polysilazane skeleton at the time of film formation, but ammonia generated when the polysilazane is oxidized and changes to a silica-based film. And this free chlorine reacts,
Crystal grains of ammonium chloride are formed. The present inventors have found that, due to these crystal grains, the resulting coating film has reduced compactness and poor flatness.

【００１４】本発明者らは、さらに研究を重ねた結果、 a)ポリシラザン骨格中の残存塩素は、原料クロロシラン
の未反応塩素であること、 b)上記の残存塩素は、合成されたポリシラザンを、約１
５０℃以下の温度に保持しておくと、塩化アンモニウム
の結晶として析出し、ポリシラザン骨格中の塩素濃度が
減少すること、 c)この塩化アンモニウム結晶粒を除去し、残存塩素濃度
が減少したポリシラザンを含む塗布液を用いて被膜を形
成すると、残存塩素濃度が高い場合の被膜に比べて緻密
性、平坦性に優れた被膜が得られること、を見出し、本
発明を完成するに至った。The present inventors have further studied and found that a) the residual chlorine in the polysilazane skeleton is unreacted chlorine of the raw material chlorosilane, and b) the residual chlorine is About 1
If the temperature is kept at 50 ° C. or lower, it precipitates as ammonium chloride crystals, and the chlorine concentration in the polysilazane skeleton decreases.c) By removing the ammonium chloride crystal grains, the polysilazane having a reduced residual chlorine concentration is removed. It has been found that when a film is formed using a coating solution containing the same, a film excellent in denseness and flatness can be obtained as compared with a film having a high residual chlorine concentration, and the present invention has been completed.

【００１５】[0015]

【発明の目的】本発明は、上記のような従来技術の問題
点を解決し、被塗布面との密着性、機械的強度、耐アル
カリ性などの耐薬品性に優れるとともに、ボイド、ピン
ホールなどがほとんどなく、緻密で耐クラック性に優れ
た被膜を形成でき、しかも被塗布面の凹凸を高度に平坦
化することができるようなシリカ系被膜形成用塗布液、
および上記のような優れた性質を有する被膜が形成され
た基材を提供することを目的としている。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and is excellent in adhesiveness to a surface to be coated, mechanical strength, chemical resistance such as alkali resistance, and voids and pinholes. A coating solution for forming a silica-based coating, which can form a dense and excellent crack-resistant coating, and can highly flatten the unevenness of the coated surface,
It is another object of the present invention to provide a substrate on which a film having excellent properties as described above is formed.

【００１６】[0016]

【発明の概要】本発明に係るシリカ系被膜形成用塗布液
は、下記一般式［Ｉ］The coating solution for forming a silica-based film according to the present invention has the following general formula [I]:

【００１７】[0017]

【化２】 Embedded image

【００１８】（式中、Ｒ1、Ｒ2およびＲ3は、それぞれ
独立して水素原子および炭素数１〜８のアルキル基から
選ばれる基である。）で表わされる繰り返し単位を少な
くとも有する１種または２種以上のポリシラザンを含有
し、該塗布液中の塩素原子濃度が５ｐｐｍ未満であるこ
とを特徴としている。(Wherein R 1 , R 2 and R 3 are each independently a group selected from a hydrogen atom and an alkyl group having 1 to 8 carbon atoms). Alternatively, it is characterized by containing two or more kinds of polysilazanes and having a chlorine atom concentration of less than 5 ppm in the coating solution.

【００１９】また、本発明に係る被膜付基材は、上記塗
布液を用いて形成されたシリカ系被膜を有することを特
徴としている。Further, the coated substrate according to the present invention is characterized by having a silica-based coating formed using the above coating solution.

【００２０】[0020]

【発明の具体的説明】以下、本発明に係るシリカ系被膜
形成用塗布液について具体的に説明する。シリカ系被膜形成用塗布液 本発明に係るシリカ系被膜形成用塗布液は、下記一般式
［Ｉ］で表わされる繰り返し単位を少なくとも有するポ
リシラザンの１種または２種以上を含有するものであっ
て、該塗布液中の塩素原子濃度は５ｐｐｍ未満である。DETAILED DESCRIPTION OF THE INVENTION The coating liquid for forming a silica-based film according to the present invention will be specifically described below. The coating liquid for forming a silica-based coating The coating liquid for forming a silica-based coating according to the present invention contains one or more polysilazane having at least a repeating unit represented by the following general formula [I], The chlorine atom concentration in the coating solution is less than 5 ppm.

【００２１】[0021]

【化３】 Embedded image

【００２２】上記式［Ｉ］中のＲ1、Ｒ2およびＲ3は、
それぞれ水素原子、炭素原子数１〜８のアルキル基、炭
素原子数１〜８のアルコキシ基およびアリル基から選ば
れる基であり、炭素原子数１〜８のアルキル基、特にメ
チル基、エチル基またはプロピル基が好ましい。R 1 , R 2 and R 3 in the above formula [I] are
A hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms and an allyl group, each being an alkyl group having 1 to 8 carbon atoms, particularly a methyl group, an ethyl group or A propyl group is preferred.

【００２３】本発明で用いられるポリシラザンとして
は、上記式［Ｉ］でＲ1、Ｒ2およびＲ 3がすべて水素原
子であり、１分子中にケイ素原子が５５〜６５重量％、
窒素原子が２０〜３０重量％、水素原子が１０〜１５重
量％であるような量で存在している無機ポリシラザンが
特に好ましい。As the polysilazane used in the present invention,
Is represented by R in the above formula [I].1, RTwoAnd R ThreeAre all hydrogen sources
And 55 to 65% by weight of silicon atoms in one molecule;
20 to 30% by weight of nitrogen atoms, 10 to 15 times of hydrogen atoms
% Of inorganic polysilazane present in such an amount that
Particularly preferred.

【００２４】また、ポリシラザン中のＳｉ原子とＮ原子
との比（Ｓｉ／Ｎ比）は、１．０〜１．３であることが
好ましい。このような無機ポリシラザンは、たとえば、
ジハロシランと塩基とを反応させてジハロシランのアダ
クツを形成させたのち、アンモニアと反応させる方法
（特公昭６３−１６３２５号公報）、メチルフェニルジ
クロロシランやジメチルジクロロシランなどとアンモニ
アを反応させる方法（特開昭６２−８８３２７号公報）
などの公知の方法に従って製造することができる。The ratio of Si atoms to N atoms in the polysilazane (Si / N ratio) is preferably from 1.0 to 1.3. Such an inorganic polysilazane is, for example,
A method of reacting dihalosilane with a base to form an adduct of dihalosilane and then reacting with ammonia (Japanese Patent Publication No. 63-16325), and a method of reacting ammonia with methylphenyldichlorosilane, dimethyldichlorosilane, etc. JP-A-62-88327)
It can be manufactured according to a known method such as, for example.

【００２５】上記式［Ｉ］で表される繰り返し単位を有
するポリシラザンは、直鎖状であっても、環状であって
もよく、直鎖状のポリシラザンと環状のポリシラザンと
の混合物でもよい。The polysilazane having a repeating unit represented by the above formula [I] may be linear or cyclic, or may be a mixture of a linear polysilazane and a cyclic polysilazane.

【００２６】これらのポリシラザンの数平均分子量は、
５００〜１００００、好ましくは、１０００〜４０００
であることが望ましい。数平均分子量が５００未満の場
合は被膜を形成する場合の乾燥工程で低分子量の化合物
が揮発し、その後の焼成工程で被膜が大きく収縮する。
また、１００００を越える場合は塗布液の流動性が低下
する。したがって、いずれの場合でも凹凸面を被覆した
際に、充分に平坦化することは困難である。The number average molecular weight of these polysilazanes is
500 to 10000, preferably 1000 to 4000
It is desirable that When the number average molecular weight is less than 500, the low molecular weight compound is volatilized in a drying step for forming a film, and the film is greatly shrunk in a subsequent baking step.
On the other hand, when it exceeds 10,000, the fluidity of the coating solution is reduced. Therefore, in any case, when the uneven surface is covered, it is difficult to sufficiently planarize the surface.

【００２７】さらに、数平均分子量が１０００以下であ
る低分子量ポリシラザンは、ポリシラザン全体に対し、
１０〜４０重量％、好ましくは１５〜４０重量％である
ことが望ましい。低分子量ポリシラサンが、ポリシラザ
ン全体に対し、このような範囲にあれば、表面平滑性の
良い被膜を得ることができる。Further, the low molecular weight polysilazane having a number average molecular weight of 1,000 or less is more than polysilazane as a whole.
It is desirably 10 to 40% by weight, preferably 15 to 40% by weight. When the low molecular weight polysilazane is in such a range with respect to the entire polysilazane, a film having good surface smoothness can be obtained.

【００２８】本発明に係るシリカ系被膜形成用塗布液
は、上記ポリシラザンが、固形分濃度３〜４０重量％、
好ましくは５〜３０重量％で、有機溶媒に溶解してい
る。有機溶媒としては上記のポリシラザンを分散または
溶解し、塗布液に流動性を付与するものであれば特に制
限はないが、具体的には、シクロヘキサン、トルエン、
キシレン等の炭化水素類、エチルエーテル、エチルブチ
ルエーテル、ジブチルエーテル、ジオキサン、テトラヒ
ドロフラン等のエーテル類が挙げられる。これらの有機
溶媒は単独でもしくは２種以上を混合して用いられる。
この有機溶媒のうち、水の溶解度が０．５重量％以下で
あるような有機溶媒が好ましい。このような有機溶媒を
塗布液に用いると、塗布液の吸湿によるポリシラザンの
加水分解が防止され、ポットライフの長い塗布液を得る
ことができる。In the coating solution for forming a silica-based film according to the present invention, the polysilazane has a solid content of 3 to 40% by weight,
Preferably, it is 5 to 30% by weight and is dissolved in an organic solvent. The organic solvent is not particularly limited as long as it disperses or dissolves the above polysilazane and imparts fluidity to the coating solution.Specifically, cyclohexane, toluene,
Examples thereof include hydrocarbons such as xylene, and ethers such as ethyl ether, ethyl butyl ether, dibutyl ether, dioxane, and tetrahydrofuran. These organic solvents are used alone or in combination of two or more.
Among these organic solvents, those having a water solubility of 0.5% by weight or less are preferred. When such an organic solvent is used for the coating liquid, hydrolysis of polysilazane due to moisture absorption of the coating liquid is prevented, and a coating liquid having a long pot life can be obtained.

【００２９】シリカ系被膜形成用塗布液の調製方法 本発明に係るシリカ系被膜形成用塗布液は、上記のポリ
シラザンが溶解した有機溶液から、ポリシラザン中の塩
素を、塩化アンモニウムの結晶として析出させ、析出物
を濾別することにより、調製される。 Method for Preparing Coating Solution for Forming Silica-Based Film The coating solution for forming a silica-based film according to the present invention is obtained by precipitating chlorine in polysilazane as crystals of ammonium chloride from the organic solution in which polysilazane is dissolved. It is prepared by filtering off the precipitate.

【００３０】具体的には、以下のような方法で調製され
る。 上記のポリシラザンを固形分濃度が３〜４０重量％に
なるように有機溶媒に溶解する。Specifically, it is prepared by the following method. The above polysilazane is dissolved in an organic solvent so that the solid content concentration becomes 3 to 40% by weight.

【００３１】ポリシラザン溶液を、攪拌しながら、所
定温度で所定時間保持して、ポリシラザン骨格中に残存
する未反応のＳｉ−Ｃｌ基と、ポリシラザン中のＮＨ基
またはＮＨ2基とのアンモノリシス反応により塩化アン
モニウムとして析出させる。The polysilazane solution is kept at a predetermined temperature for a predetermined time while stirring, and the polysilazane solution is chlorided by an ammonolysis reaction between unreacted Si—Cl groups remaining in the polysilazane skeleton and NH groups or NH 2 groups in the polysilazane. Precipitates as ammonium.

【００３２】析出した塩化アンモニウムを濾過する。
有機溶媒としては、上記で例示した溶媒が使用される。
ポリシラザン溶液を保持する温度は、１５０℃以下、好
ましくは０〜８０℃、さらに好ましくは２０〜８０℃の
範囲であることが望ましい。このような温度範囲であれ
ば、短時間で残存塩素を５ｐｐｍ以下に下げることがで
き、ポリシラザンの架橋または重合が進むことがない。The precipitated ammonium chloride is filtered.
As the organic solvent, the solvents exemplified above are used.
The temperature at which the polysilazane solution is maintained is desirably 150 ° C. or lower, preferably 0 to 80 ° C., and more preferably 20 to 80 ° C. In such a temperature range, the residual chlorine can be reduced to 5 ppm or less in a short time, and the crosslinking or polymerization of polysilazane does not proceed.

【００３３】生成した塩化アンモニウムは、濾過するこ
とにより取り除かれる。濾材としては、濾紙、セラミッ
クフィルターなどが用いられ、特に、０.１〜１μ程度
の口径のメンブランフィルターが好ましい。The ammonium chloride formed is removed by filtration. The filter media, filter paper, and ceramic filters are used, in particular, 0. Membrane filter 1~1μ about caliber are preferred.

【００３４】上記のような本発明に係るシリカ系被膜形
成用塗布液を用いてシリカ系被膜を形成すると、被膜形
成成分として従来のポリシラザン系塗布液を用いてシリ
カ系被膜を形成した場合に比べて、低温で焼成しても緻
密性に優れ、かつ収縮ストレス、ボイド等の少ない平坦
性に優れた被膜が得られる。When a silica-based coating is formed using the coating solution for forming a silica-based coating according to the present invention as described above, compared with the case where a silica-based coating is formed using a conventional polysilazane-based coating solution as a coating forming component. As a result, a film excellent in denseness and excellent in flatness with few shrinkage stress and voids can be obtained even when fired at a low temperature.

【００３５】シリカ系被膜付基材 本発明に係る被膜付基材は、上記のような１種または２
種以上のポリシラザンを含有し、塗布液中の塩素原子濃
度が５ｐｐｍ未満であるような塗布液を用いて形成され
たシリカ系被膜を有している。このシリカ系被膜の膜厚
は、通常、０.０５〜２μｍ、好ましくは０.１〜１μｍ
程度である。 Substrate with Silica Coating The substrate with a coating according to the present invention may be one or two of
A silica-based coating formed using a coating solution containing at least one kind of polysilazane and having a chlorine atom concentration of less than 5 ppm in the coating solution. The thickness of the silica-based coating is usually 0.05 to 2 μm, preferably 0.1 to 1 μm.
It is about.

【００３６】このようなシリカ系被膜は、例えば上記の
ような本発明に係るシリカ系被膜形成用塗布液を、基材
の被塗布面にスプレー法、スピンコート法、ディッピン
グ法、ロールコート法、スクリーン印刷法、転写印刷法
などの各種方法で塗布し、次いで得られた塗膜を乾燥・
焼成することにより得ることができる。Such a silica-based coating can be prepared by, for example, applying the above-described coating liquid for forming a silica-based coating according to the present invention to a surface to be coated of a substrate by spraying, spin coating, dipping, roll coating, or the like. It is applied by various methods such as screen printing and transfer printing, and then the obtained coating film is dried and
It can be obtained by firing.

【００３７】なお、塗膜の加熱硬化処理に際して、加湿
雰囲気またはアンモニア雰囲気中での硬化処理、紫外線
照射または電子線照射による硬化処理を併用してもよ
い。本発明に係る被膜付基材としては、具体的には、前
記のような半導体装置、液晶表示装置、位相シフタ付フ
ォトマスク、さらには多層配線構造を有するＬＳＩ素子
およびプリント回路基板、ハイブリッドＩＣ、アルミナ
基板などの電子部品、三層レジストなどが挙げられる。In the heat curing treatment of the coating film, a curing treatment in a humidified atmosphere or an ammonia atmosphere, or a curing treatment by ultraviolet irradiation or electron beam irradiation may be used in combination. Specific examples of the substrate with a coating according to the present invention include the above-described semiconductor device, liquid crystal display device, photomask with phase shifter, LSI device and printed circuit board having a multilayer wiring structure, hybrid IC, Examples include electronic components such as an alumina substrate, and a three-layer resist.

【００３８】すなわち、半導体装置では、半導体基板と
金属配線層との間、金属配線層間にシリカ系絶縁膜が形
成され、半導体基板上に設けられたＰＮ接合半導体、お
よびコンデンサー素子、抵抗素子などの各種素子がシリ
カ系絶縁膜で被覆され、これらの素子によって形成され
た凹凸面が平坦化されている。That is, in a semiconductor device, a silica-based insulating film is formed between a semiconductor substrate and a metal wiring layer or between metal wiring layers, and a PN junction semiconductor provided on the semiconductor substrate, and a capacitor element, a resistance element, and the like. Various elements are covered with a silica-based insulating film, and the uneven surface formed by these elements is flattened.

【００３９】また、液晶表示装置における液晶表示セル
では、透明電極板の透明基板と透明電極との間に、さら
に透明電極上に配向膜を有する透明電極板の透明電極と
配向膜の間に、シリカ系被膜が形成され、カラー液晶表
示装置における液晶表示セルでは、電極板の画素電極上
および対向電極板のカラーフィルター上にシリカ系被膜
が形成され、画素電極およびカラーフィルターによって
形成された凹凸面が該シリカ系被膜によって平坦化され
ている。Further, in the liquid crystal display cell of the liquid crystal display device, the transparent electrode plate has an alignment film between the transparent substrate and the transparent electrode and the transparent electrode plate having an alignment film on the transparent electrode. In a liquid crystal display cell in a color liquid crystal display device, a silica-based coating is formed, and a silica-based coating is formed on a pixel electrode of an electrode plate and a color filter of a counter electrode plate, and the uneven surface formed by the pixel electrode and the color filter is formed. Are flattened by the silica-based coating.

【００４０】さらに位相シフタ付フォトマスクの位相シ
フタおよび三層レジストの中間層がシリカ系被膜で構成
され、上記電子部品においても半導体装置と同様にシリ
カ系被膜が設けられ、被塗布面が該シリカ系被膜によっ
て平坦化されている。Further, the phase shifter of the photomask with a phase shifter and the intermediate layer of the three-layer resist are composed of a silica-based coating, and the electronic component is also provided with a silica-based coating in the same manner as the semiconductor device. It is flattened by the system coating.

【００４１】[0041]

【発明の効果】本発明に係る被膜形成用塗布液によれ
ば、ボイド、ピンホールなどがほとんどなく、緻密であ
って、被塗布面との密着性、機械的強度、耐アルカリ性
などの耐薬品性、耐湿性、絶縁性などに優れたシリカ系
被膜を形成でき、しかも被塗布面の凹凸を高度に平坦化
することができる。According to the coating solution for forming a film according to the present invention, there are almost no voids, pinholes, etc., and it is dense and has chemical resistance such as adhesion to a surface to be coated, mechanical strength and alkali resistance. It is possible to form a silica-based film having excellent properties, moisture resistance, insulation properties, etc., and to highly flatten the unevenness of the surface to be coated.

【００４２】また、本発明に係る被膜形成用塗布液は、
塗布液中の塩素原子濃度が５ｐｐｍ未満であることか
ら、被膜形成の過程で塩化アンモニウムの結晶粒を生成
することがない。したがって、従来のポリシラザン系塗
布液から得られた被膜と比較して緻密性および平坦性に
優れた被膜を得ることができる。The coating solution for forming a film according to the present invention comprises:
Since the concentration of chlorine atoms in the coating solution is less than 5 ppm, crystal grains of ammonium chloride are not generated in the process of forming a film. Therefore, a film excellent in denseness and flatness can be obtained as compared with a film obtained from a conventional polysilazane-based coating solution.

【００４３】また、本発明によれば、半導体基板と金属
配線層との間、金属配線層間にシリカ系絶縁膜が形成さ
れ、半導体基板上に設けられたＰＮ接合半導体、および
コンデンサー素子、抵抗素子などの各種素子がシリカ系
絶縁膜で被覆され、これらの素子によって形成された凹
凸面が平坦化されている半導体装置、ガラス基板と透明
電極との間に、ガラス基板中に含まれているＮａなどの
アルカリ成分が透明電極中に移行したり、この透明電極
を通して透明電極間に封入された液晶中へ溶出したりす
ることが防止できるような、いわゆるアルカリパッシベ
ーション膜としてのシリカ系被膜が形成された液晶表示
装置、およびさらに透明電極上に配向膜を有する透明電
極板の透明電極と配向膜の間にシリカ系被膜が形成され
た透明電極板を有する液晶表示セルを備えた液晶表示装
置、画素電極上にシリカ系被膜が形成された電極板およ
びカラーフィルター上にシリカ系被膜が形成された対向
電極板を有し、画素電極およびカラーフィルターによっ
て形成された凹凸面が該シリカ系被膜によって平坦化さ
れている液晶表示セルを備えたカラー液晶表示装置、位
相シフタがシリカ系被膜であるような位相シフタ付フォ
トマスク、中間層がシリカ系被膜であるような三層レジ
スト、および半導体装置と同様にシリカ系被膜が設けら
れ、シリカ系被膜の被塗布面が該シリカ系被膜によって
平坦化されている電子部品、たとえば多層配線構造を有
するＬＳＩ素子およびプリント回路基板、ハイブリッド
ＩＣ、アルミナ基板などのような被膜付基材が提供でき
る。Further, according to the present invention, a PN junction semiconductor provided with a silica-based insulating film between a semiconductor substrate and a metal wiring layer and between metal wiring layers and provided on the semiconductor substrate, and a capacitor element and a resistance element Such as a semiconductor device in which various elements such as are covered with a silica-based insulating film, and the uneven surface formed by these elements is flattened, between a glass substrate and a transparent electrode, Na contained in the glass substrate. A silica-based coating as a so-called alkali passivation film is formed such that an alkali component such as can be prevented from migrating into the transparent electrode or eluting into the liquid crystal sealed between the transparent electrodes through the transparent electrode. And a transparent electrode plate having a silica-based coating between the transparent electrode and the alignment film. A liquid crystal display device having a liquid crystal display cell, an electrode plate having a silica-based coating formed on a pixel electrode, and a counter electrode plate having a silica-based coating formed on a color filter, formed by the pixel electrode and the color filter. A color liquid crystal display device having a liquid crystal display cell in which the roughened surface is flattened by the silica-based coating, a photomask with a phase shifter such that the phase shifter is a silica-based coating, and the intermediate layer is a silica-based coating. An electronic component, such as an LSI element having a multilayer wiring structure and a print, in which a silica-based coating is provided like the three-layer resist and the semiconductor device, and the coated surface of the silica-based coating is flattened by the silica-based coating. A coated substrate such as a circuit board, a hybrid IC, or an alumina substrate can be provided.

【００４４】[0044]

【実施例】以下、本発明を実施例により説明するが、本
発明はこれら実施例に限定されるものではない。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

【００４５】[0045]

【製造例】[Production example]

１）ポリシラザンＡの合成 特公昭６３−１６３２５号公報記載の製造法に準じて、
次のような製造法でポリシラザンＡを合成した。1) Synthesis of polysilazane A According to the production method described in JP-B-63-16325,
Polysilazane A was synthesized by the following production method.

【００４６】温度０℃の恒温槽内に設置された反応器内
にピリジン６００ミリリットルを入れ、攪拌しながらジ
クロロシラン２８．３ｇを加えて錯体（ピリジンアダク
ツ）を形成させた。次いでこのピリジンアダクツを含む
液中にアンモニアを２時間吹き込んで反応生成物と沈澱
物とを含む液を得た。この液中に含まれている沈澱物を
濾過して除去した後、濾液を８０℃で１０時間加熱し、
次いで減圧して濾液からピリジンを除去することによ
り、樹脂状のポリシラザンＡを得た。 ２）ポリシラザンＢの合成 塩化メチレン３００ミリリットルを入れた１リットルの
四つ口フラスコを−５℃に冷却した。次いでこのフラス
コ内にメチルジクロロシラン３４.２ｇを加え、攪拌し
ながらアンモニアを２時間吹き込んで反応生成物と沈澱
物を含む液を得た。この液中に含まれている沈澱物を濾
過して除去した後、濾液を減圧して濾液から塩化メチレ
ンを除去することにより、樹脂状のポリシラザンＢを得
た。600 ml of pyridine was placed in a reactor placed in a thermostat at a temperature of 0 ° C., and 28.3 g of dichlorosilane was added with stirring to form a complex (pyridine adduct). Then, ammonia was blown into the liquid containing the pyridine adduct for 2 hours to obtain a liquid containing a reaction product and a precipitate. After the precipitate contained in this solution was removed by filtration, the filtrate was heated at 80 ° C. for 10 hours,
Then, pyridine was removed from the filtrate under reduced pressure to obtain resinous polysilazane A. 2) Synthesis of polysilazane B A 1-liter four-necked flask containing 300 ml of methylene chloride was cooled to -5C. Then methyldichlorosilane 34. 2 g was added to the flask to obtain a stirred solution containing the precipitate and the reaction product is blown with ammonia for 2 hours while. After the precipitate contained in this solution was removed by filtration, the filtrate was depressurized to remove methylene chloride from the filtrate, thereby obtaining resinous polysilazane B.

【００４７】得られたポリシラザンＡ、Ｂの元素分析結
果、Ｓｉ／Ｎ比、数平均分子量および塩素濃度を表１に
示す。なお、上記数平均分子量は、ゲルクロマトグラフ
ィー法で測定した値のポリスチレン換算値である。ま
た、塩素濃度は下記に示す塗布液中の塩素濃度分析法に
準じて分析した。The results of elemental analysis, the Si / N ratio, the number average molecular weight and the chlorine concentration of the obtained polysilazanes A and B are shown in Table 1. In addition, the said number average molecular weight is a polystyrene conversion value of the value measured by the gel chromatography method. The chlorine concentration was analyzed according to the method for analyzing the chlorine concentration in a coating solution described below.

【００４８】[0048]

【表１】 [Table 1]

【００４９】[0049]

【実施例１】ポリシラザンＡをキシレンに溶解させて得
られた濃度２０重量％の溶液を、攪拌しながら、４０℃
で、２４０時間保持した。保持後、溶液中に白濁してい
る塩化アンモニウムの沈殿をメンブランフィルターで濾
過して除去し、シリカ系被膜形成用塗布液を調製した。
塗布液中の塩素濃度は１．５ｐｐｍであった。Example 1 A solution having a concentration of 20% by weight obtained by dissolving polysilazane A in xylene was stirred at 40 ° C.
For 240 hours. After the holding, the turbid precipitate of ammonium chloride in the solution was removed by filtration with a membrane filter to prepare a coating solution for forming a silica-based film.
The chlorine concentration in the coating solution was 1.5 ppm.

【００５０】この塗布液を半導体基板（４インチシリコ
ンウェハー）上にスピンコート法で塗布し、得られた塗
膜を２００℃で２分間加熱して乾燥させた後、水蒸気中
で４２０℃で１時間焼成して、厚さ２μｍのシリカ系被
膜を形成した。This coating solution was applied on a semiconductor substrate (4-inch silicon wafer) by spin coating, and the obtained coating film was dried by heating at 200 ° C. for 2 minutes, and then dried at 420 ° C. in water vapor. By firing for a time, a silica-based coating having a thickness of 2 μm was formed.

【００５１】このようにして形成されたシリカ系被膜の
耐クラック性、緻密性および耐アルカリ性を測定・評価
した。結果を表２に示す。The crack resistance, denseness, and alkali resistance of the silica-based coating thus formed were measured and evaluated. Table 2 shows the results.

【００５２】なお、塗布液中の塩素濃度の分析、被膜の
耐クラック性、緻密性および耐アルカリ性の測定は、以
下の方法で行った。 (a)塩素濃度 塗布液とエタノール／水（重量比：１／１）の混合液
を、塗布液／混合液＝９／１（重量比）の割合で混合し
て塗布液中のポリシラザンを加水分解し、生成した塩素
イオンをエタノール／水混合液相に抽出したのち、イオ
ンクロマトグラフ法で定量した。The analysis of the chlorine concentration in the coating solution and the measurement of the crack resistance, denseness and alkali resistance of the coating film were carried out by the following methods. (a) Chlorine concentration A mixture of a coating solution and ethanol / water (weight ratio: 1/1) was mixed at a ratio of coating solution / mixed solution = 9/1 (weight ratio) to hydrolyze polysilazane in the coating solution. After decomposing, the generated chlorine ions were extracted into a mixed liquid phase of ethanol / water, and then quantified by ion chromatography.

【００５３】(b)耐クラック性 上記で得られたシリカ系被膜のクラックの有無を顕微鏡
で観察した。 (c)緻密性 ＨＦとＨＮＯ3との混合溶液（ＨＦ／ＨＮＯ3＝１／１０
０重量比）からなるエッチング液に、上記のようにして
形成されたシリカ系被膜を２分間浸漬し、浸漬前後の時
間当たりの膜厚変化量から算出した。(B) Crack resistance The presence or absence of cracks in the silica-based coating obtained above was observed with a microscope. (c) Denseness A mixed solution of HF and HNO 3 (HF / HNO 3 = 1/10)
(0 weight ratio), the silica-based coating film formed as described above was immersed in the etching solution for 2 minutes, and calculated from the amount of change in film thickness per unit time before and after immersion.

【００５４】なお、単位時間当たり膜厚変化量が小さい
ほど、緻密性に優れていると評価される。 (d)耐アルカリ性 ５重量％ＮａＯＨ水溶液に上記のようにして形成された
シリカ系被膜を４０℃で、２０分間浸漬し、浸漬前後の
膜厚変化量から算出した。なお、この膜厚変化量が小さ
いほど、耐アルカリ性に優れていると評価される。The smaller the amount of change in film thickness per unit time, the better the fineness. (d) Alkali Resistance The silica-based coating formed as described above was immersed in a 5% by weight aqueous solution of NaOH at 40 ° C. for 20 minutes, and calculated from the change in film thickness before and after immersion. In addition, it is evaluated that the smaller the change in the film thickness is, the more excellent the alkali resistance is.

【００５５】[0055]

【実施例２】実施例１において、ポリシラザンＡの２０
重量％キシレン溶液を攪拌しながら３０℃の温度で５０
０時間保持する以外は、実施例１と同様にして、シリカ
系被膜形成用塗布液を調製した。塗布液中の塩素濃度は
１.０ｐｐｍであった。Example 2 In Example 1, 20 of polysilazane A was used.
The weight% xylene solution is stirred at a temperature of 30 ° C. for 50 minutes.
A coating solution for forming a silica-based film was prepared in the same manner as in Example 1 except that the coating solution was maintained for 0 hour. Chlorine concentration in the coating solution was 1. 0 ppm.

【００５６】このようにして得られた塗布液を用いて、
実施例１と同様に、シリカ系被膜を形成し、評価した。
結果を表２に示す。Using the thus obtained coating liquid,
A silica-based coating was formed and evaluated in the same manner as in Example 1.
Table 2 shows the results.

【００５７】[0057]

【実施例３】ポリシラザンＢをジブチチルエーテルに溶
解させて得られた濃度２５重量％の溶液を攪拌しなが
ら、１０℃で、２４００時間保持した。保持後、溶液中
に白濁している塩化アンモニウムの沈殿を、実施例１と
同様に濾過して除去し、シリカ系被膜形成用塗布液を調
製した。塗布液中の塩素濃度は２.４ｐｐｍであった。Example 3 A solution having a concentration of 25% by weight obtained by dissolving polysilazane B in dibutyltyl ether was kept at 10 ° C. for 2400 hours while stirring. After the holding, the precipitation of cloudy ammonium chloride in the solution was removed by filtration in the same manner as in Example 1 to prepare a coating solution for forming a silica-based film. Chlorine concentration in the coating solution was 2. 4 ppm.

【００５８】このようにして得られた塗布液を用いて、
実施例１と同様に、シリカ系被膜を形成し、評価した。
結果を表２に示す。Using the thus obtained coating solution,
A silica-based coating was formed and evaluated in the same manner as in Example 1.
Table 2 shows the results.

【００５９】[0059]

【比較例１】ポリシラザンＡの２０重量％キシレン溶液
を、塩素除去工程を経ずにそのままシリカ系被膜形成用
塗布液とした。塗布液中の塩素濃度は７.４ｐｐｍであ
った。Comparative Example 1 A 20% by weight xylene solution of polysilazane A was used as a coating solution for forming a silica-based film without going through a chlorine removing step. Chlorine concentration in the coating solution was 7. 4 ppm.

【００６０】このようにして得られた塗布液を用いて、
実施例１と同様に、シリカ系被膜を形成し、評価した。
結果を表２に示す。Using the thus obtained coating liquid,
A silica-based coating was formed and evaluated in the same manner as in Example 1.
Table 2 shows the results.

【００６１】[0061]

【比較例２】ポリシラザンＢの２５重量％ジブチチルエ
ーテル溶液を、塩素除去工程を経ずにそのままシリカ系
被膜形成用塗布液とした。塗布液中の塩素濃度は８.６
ｐｐｍであった。COMPARATIVE EXAMPLE 2 A 25% by weight solution of polysilazane B in dibutyl ether was directly used as a coating solution for forming a silica-based film without going through a chlorine removing step. Chlorine concentration in the coating solution is 8.6
ppm.

【００６２】このようにして得られた塗布液を用いて、
実施例１と同様に、シリカ系被膜を形成し、評価した。
結果を表２に示す。Using the thus obtained coating liquid,
A silica-based coating was formed and evaluated in the same manner as in Example 1.
Table 2 shows the results.

【００６３】[0063]

【表２】 [Table 2]

【００６４】[0064]

【実施例４】実施例１で得られたシリカ系被膜形成塗布
液を１μｍ段差の０.５μｍラインアンド スペースで
モデル的にアルミニウム配線を形成した４インチシリコ
ン半導体基板上にスピンコート法で塗布した。Example 4 The coating liquid for forming a silica-based film obtained in Example 1 was applied by a spin coating method to a 4-inch silicon semiconductor substrate on which aluminum wiring was modeled on a 0.5 μm line and space with a step of 1 μm. .

【００６５】得られた塗膜を２５０℃で３分間加熱して
乾燥させた後、水蒸気中で４００℃で３０分間焼成し
て、厚さ５０００Åのシリカ系絶縁膜を形成した。次い
で、コンタクトホールをリソグラフィー法およびエッチ
ング法で形成し、シリカ系絶縁膜上にスパッタリング法
で上層アルミニウム配線を形成して半導体装置を作成し
た。After the obtained coating film was dried by heating at 250 ° C. for 3 minutes, it was fired in steam at 400 ° C. for 30 minutes to form a 5000-mm-thick silica-based insulating film. Next, a contact hole was formed by lithography and etching, and an upper aluminum wiring was formed on the silica-based insulating film by sputtering to form a semiconductor device.

【００６６】このようにして作成された半導体装置の平
坦性、耐クラック性、エッチングレートおよび抵抗値の
変化を測定・評価した。結果を表３に示す。The flatness, crack resistance, etching rate, and change in resistance of the semiconductor device thus manufactured were measured and evaluated. Table 3 shows the results.

【００６７】なお、半導体装置の平坦性、クラックの有
無、エッチングレートおよび抵抗値の変化は、以下の方
法で評価した。 (e)平坦性、クラックの有無 半導体基板の表面および断面を電子顕微鏡で観察し、結
果から平坦性、クラックの有無を評価した。The flatness of the semiconductor device, the presence or absence of cracks, the change in the etching rate and the change in the resistance value were evaluated by the following methods. (e) Flatness, presence or absence of cracks The surface and cross section of the semiconductor substrate were observed with an electron microscope, and the flatness and presence or absence of cracks were evaluated from the results.

【００６８】(f)エッチングレート 四フッ化炭素と酸素との混合ガスによるドライエッチン
グで、エッチングレートを測定した。(F) Etching Rate The etching rate was measured by dry etching using a mixed gas of carbon tetrafluoride and oxygen.

【００６９】(g)抵抗値の変化 半導体装置を２５０℃で１０００時間加熱し、加熱前後
の上下アルミニウム配線間の抵抗値を下式により算出し
た。(G) Change in Resistance The semiconductor device was heated at 250 ° C. for 1000 hours, and the resistance between the upper and lower aluminum wires before and after heating was calculated by the following equation.

【００７０】[0070]

【数１】 (Equation 1)

【００７１】[0071]

【実施例５】実施例２で得られたシリカ系被膜形成塗布
液を用いる以外は、実施例４と同様にして、半導体装置
を作成し、評価した。Example 5 A semiconductor device was prepared and evaluated in the same manner as in Example 4, except that the coating solution for forming a silica-based film obtained in Example 2 was used.

【００７２】結果を表３に示す。Table 3 shows the results.

【００７３】[0073]

【実施例６】実施例３で得られたシリカ系被膜形成塗布
液を用いる以外は、実施例４と同様にして、半導体装置
を作成し、評価した。Example 6 A semiconductor device was prepared and evaluated in the same manner as in Example 4, except that the coating solution for forming a silica-based film obtained in Example 3 was used.

【００７４】結果を表３に示す。Table 3 shows the results.

【００７５】[0075]

【比較例３】比較例１で得られたシリカ系被膜形成塗布
液を用いる以外は、実施例４と同様にして、半導体装置
を作成し、評価した。Comparative Example 3 A semiconductor device was prepared and evaluated in the same manner as in Example 4 except that the coating solution for forming a silica-based film obtained in Comparative Example 1 was used.

【００７６】結果を表３に示す。Table 3 shows the results.

【００７７】[0077]

【表３】 [Table 3]

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】下記一般式［Ｉ］ 【化１】 （式中、Ｒ1 、Ｒ2 およびＲ3 は、それぞれ独立して水
素原子および炭素数１〜８のアルキル基から選ばれる基
である。）で表わされる繰り返し単位を少なくとも有す
る１種または２種以上のポリシラザンを含有する塗布液
であって、該塗布液中の塩素原子濃度が５ｐｐｍ未満で
あることを特徴とするシリカ系被膜形成用塗布液。1. A compound represented by the following general formula [I] (Wherein, R 1 , R 2 and R 3 are each independently a group selected from a hydrogen atom and an alkyl group having 1 to 8 carbon atoms). A coating solution containing a polysilazane as described above, wherein the chlorine atom concentration in the coating solution is less than 5 ppm. 【請求項２】請求項１に記載の塗布液を用いて形成され
たシリカ系被膜を有することを特徴とする被膜付基材。2. A coated substrate comprising a silica-based coating formed by using the coating solution according to claim 1.
JP20711896A 1996-08-06 1996-08-06 Coating solution for forming silica-based film and substrate with film Expired - Lifetime JP3516815B2 (en)

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