JPH11340219A - Silica film and method for forming the film - Google Patents
Silica film and method for forming the filmInfo
- Publication number
- JPH11340219A JPH11340219A JP14480798A JP14480798A JPH11340219A JP H11340219 A JPH11340219 A JP H11340219A JP 14480798 A JP14480798 A JP 14480798A JP 14480798 A JP14480798 A JP 14480798A JP H11340219 A JPH11340219 A JP H11340219A
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- JP
- Japan
- Prior art keywords
- silica
- film
- coating
- forming
- hydrolysis
- 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.)
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- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Formation Of Insulating Films (AREA)
- Organic Insulating Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、半導体素子の製造
において使用される平坦化膜や層間絶縁膜などとして有
用な誘電率の低いシリカ系被膜及びそれを塗布法により
効率よく形成させる方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silica-based film having a low dielectric constant useful as a flattening film or an interlayer insulating film used in the production of semiconductor devices, and a method for efficiently forming the same by a coating method. It is.
【０００２】[0002]
【従来の技術】従来、半導体素子の製造において使用さ
れる平坦化膜や層間絶縁膜には、通常シリカ系被膜が用
いられている。そして、このような用途に用いられるシ
リカ系被膜を形成させる方法としては、例えば化学的気
相成長法（ＣＶＤ法）や塗布法などが知られている。2. Description of the Related Art Conventionally, a silica-based coating is usually used for a flattening film and an interlayer insulating film used in manufacturing a semiconductor device. As a method for forming a silica-based film used for such a purpose, for example, a chemical vapor deposition method (CVD method), a coating method, and the like are known.
【０００３】ＣＶＤ法によるシリカ系被膜は、特殊な装
置を用いて、基板表面にシリカ又は必要に応じてリンや
ホウ素を含有させたシリカを蒸着、成長させることによ
り形成され、一方、塗布法によるシリカ系被膜は、一般
に、アルコキシシランの酸触媒による加水分解縮合生成
物を含有する有機溶剤溶液からなる塗布液を基板上に塗
布し、焼成することにより形成される。A silica-based film formed by a CVD method is formed by depositing and growing silica or silica containing phosphorus or boron as necessary on a substrate surface by using a special apparatus. The silica-based coating is generally formed by applying a coating solution composed of an organic solvent solution containing a hydrolysis-condensation product of an alkoxysilane with an acid catalyst onto a substrate and baking the coating solution.
【０００４】しかしながら、近年、半導体素子のますま
すの多層化、微細化に伴い、配線容量による信号伝達時
間が遅延し、超ＬＳＩの高速化が阻害されるという問題
が生じている。そこで、このような問題を解決するため
に、誘電率の低い材料を層間絶縁膜として用いること
が、最近多数提案されている。However, in recent years, with the increasing number of layers and miniaturization of semiconductor elements, there has been a problem that the signal transmission time due to the wiring capacitance is delayed and the speeding up of the VLSI is hindered. Therefore, in order to solve such a problem, many proposals have recently been made to use a material having a low dielectric constant as the interlayer insulating film.
【０００５】例えば、ＣＶＤ法により形成されたフッ素
原子を含むＳｉＯＦ膜が提案されている。しかしなが
ら、このＳｉＯＦ膜の形成には高価な装置を必要とし、
コストが高くつくのを免れない上、該ＳｉＯＦ膜は反応
性の高いＳｉ−Ｆ結合を含んでおり、これが水と反応し
てＳｉ−ＯＨが形成されるため、比誘電率は３．３程度
が限界であるといわれている。For example, a SiOF film containing a fluorine atom formed by a CVD method has been proposed. However, formation of this SiOF film requires expensive equipment,
In addition to the high cost, the SiOF film contains highly reactive Si-F bonds, which react with water to form Si-OH, so that the relative dielectric constant is about 3.3. Is said to be the limit.
【０００６】また、塗布法に用いられるＳＯＧ材料とし
て、比較的誘電率の低いジメチルアルコキシシランの加
水分解縮合物やメチルシルセスキオキサンのようなメチ
ルポリシロキサンや水素シルセスキオキサンが提案され
ているが、これらの比誘電率は、それぞれ約２．８及び
３．３が限界であり、それ以下にすることは困難であ
る。そして、ますます多層化、微細化が必要とされる半
導体素子においては、このような材料では、まだ誘電率
が高く、十分に満足しうるものとはいえない。As SOG materials used in the coating method, there have been proposed hydrolyzed condensates of dimethylalkoxysilane having relatively low dielectric constant, methylpolysiloxane such as methylsilsesquioxane, and hydrogen silsesquioxane. However, their relative dielectric constants are limited to about 2.8 and 3.3, respectively, and it is difficult to reduce them below that. And, in a semiconductor element which requires more and more layers and miniaturization, such a material still has a high dielectric constant and cannot be said to be sufficiently satisfactory.
【０００７】これまで、ポリアルコキシシラン化合物を
塩基性触媒により加水分解縮合して、合成樹脂ゴム用充
填剤として用いられるポリメチルシルセスキオキサン粉
末や（特開昭５４−７２３００号公報、特開平２−２０
９９２７号公報）、塗料組成物（特開平２−６７２号公
報）を製造することは知られているが、半導体素子用シ
リカ系被膜を得る方法は全く知られていない。Hitherto, a polyalkoxysilane compound has been hydrolyzed and condensed with a basic catalyst to obtain a polymethylsilsesquioxane powder used as a filler for synthetic resin rubber (see JP-A-54-72300, 2-20
No. 9927) and the production of a coating composition (Japanese Patent Application Laid-Open No. 2-672) is known, but there is no known method for obtaining a silica-based coating for a semiconductor device.
【０００８】また、トリアルコキシシランの初期加水分
解縮合物をアルカリ触媒でさらに縮合させる超高分子量
ポリオルガノシルセスキオキサンを製造する方法（特開
平５−１２５１８７号公報）や、アルコキシシランをア
ルカリ触媒の存在下で加水分解し、さらに該部分加水分
解液を酸触媒下で加水分解する二段階の加水分解を行う
ことにより、低誘電率の絶縁膜を製造する方法も提案さ
れているが、これらの方法では、安定したシリカ系被膜
は得られないし、また得られたとしても比誘電率はせい
ぜい３．８であり、比誘電率が２．５以下のシリカ系被
膜は得られない。Further, a method for producing an ultra-high-molecular-weight polyorganosilsesquioxane by further condensing an initial hydrolysis-condensation product of trialkoxysilane with an alkali catalyst (Japanese Patent Laid-Open No. 5-125187), and a method for preparing an alkoxysilane with an alkali catalyst Hydrolysis in the presence of, and further performing a two-stage hydrolysis of hydrolyzing the partially hydrolyzed solution under an acid catalyst, a method of producing an insulating film having a low dielectric constant has been proposed. According to the method (1), a stable silica-based coating cannot be obtained, and even if it is obtained, the relative dielectric constant is at most 3.8, and a silica-based coating having a relative dielectric constant of 2.5 or less cannot be obtained.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、半導体素子
の製造において使用される平坦化膜や層間絶縁膜などと
して有用な誘電率の低い、特に比誘電率が２．５以下程
度のシリカ系被膜及びそれを塗布法により効率よく形成
させる方法を提供することを目的としてなされたもので
ある。SUMMARY OF THE INVENTION The present invention relates to a silica-based material having a low dielectric constant, particularly a dielectric constant of about 2.5 or less, which is useful as a flattening film or interlayer insulating film used in the production of semiconductor devices. An object of the present invention is to provide a film and a method for efficiently forming the film by a coating method.
【００１０】[0010]
【課題を解決するための手段】本発明者らは、誘電率が
低く、半導体素子用として適したシリカ系被膜及びそれ
を得る方法について鋭意研究を重ねた結果、ポリアルコ
キシシラン化合物を有機溶媒中で塩基性触媒により加水
分解縮合して得られた反応生成物の溶液を基板上に塗布
し、加熱焼成することにより、前記目的を達成しうるこ
とを見出し、この知見に基づいて本発明を完成するに至
った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a silica-based coating having a low dielectric constant and suitable for a semiconductor device and a method for obtaining the same. By applying a solution of the reaction product obtained by hydrolysis and condensation with a basic catalyst onto a substrate and heating and calcining the solution, the inventors have found that the object can be achieved, and based on this finding, completed the present invention. I came to.
【００１１】すなわち、本発明は、ポリアルコキシシラ
ン化合物の塩基性加水分解縮合生成物焼成体からなる半
導体素子用シリカ系被膜を提供するものである。このシ
リカ系被膜は、ポリアルコキシシラン化合物を有機溶剤
中で塩基性触媒により加水分解縮合して得た塗布液を、
基板上に塗布し、乾燥したのち、３５０℃以上に加熱
し、焼成することによって形成することができる。That is, the present invention provides a silica-based coating for a semiconductor device, comprising a fired product of a basic hydrolysis-condensation product of a polyalkoxysilane compound. This silica-based coating is a coating solution obtained by hydrolyzing and condensing a polyalkoxysilane compound with a basic catalyst in an organic solvent,
It can be formed by coating on a substrate, drying, heating to 350 ° C. or more, and firing.
【００１２】[0012]
【発明の実施の形態】ここで、ポリアルコキシシラン化
合物とは、ケイ素原子に結合したアルコキシル基を少な
くとも２個有するシラン化合物のことである。このよう
なシラン化合物としては、例えばテトラメトキシシラ
ン、テトラエトキシシラン、テトラプロポキシシラン、
テトラブトキシシランなどのテトラ低級アルコキシシラ
ン類や、モノメチルトリメトキシシラン、モノメチルト
リエトキシシラン、モノエチルトリメトキシシラン、モ
ノエチルトリエトキシシラン、モノメチルジメトキシモ
ノエトキシシラン、モノエチルジメトキシモノエトキシ
シランなどのモノ低級アルキルトリ低級アルコキシシラ
ン類や、ジメチルジメトキシシラン、ジメチルジエトキ
シシラン、ジメチルジプロポキシシラン、ジエチルジメ
トキシシラン、ジエチルジエトキシシラン、ジエチルジ
プロポキシシラン、モノメチルモノエチルジメトキシシ
ラン、モノメチルモノエチルジエトキシシランなどのジ
低級アルキルジ低級アルコキシシラン類や、トリメトキ
シシラン、トリエトキシシラン、トリプロポキシシラ
ン、トリブトキシシランなどのトリ低級アルコキシシラ
ン類などが挙げられる。Here, the polyalkoxysilane compound is a silane compound having at least two alkoxyl groups bonded to silicon atoms. Such silane compounds include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane,
Tetra-lower alkoxysilanes such as tetrabutoxysilane and mono-lower such as monomethyltrimethoxysilane, monomethyltriethoxysilane, monoethyltrimethoxysilane, monoethyltriethoxysilane, monomethyldimethoxymonoethoxysilane, monoethyldimethoxymonoethoxysilane Alkyltri-lower alkoxysilanes, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, monomethylmonoethyldimethoxysilane, monomethylmonoethyldiethoxysilane, etc. Di-lower alkyldi-lower alkoxysilanes, trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxy Such as tri-lower alkoxysilanes such emissions and the like.
【００１３】これらの中で、テトラメトキシシラン、テ
トラエトキシシランなどのテトラ低級アルコキシシラン
類、トリメトキシシラン、トリエトキシシランなどのト
リ低級アルコキシシラン類及びモノメチルトリメトキシ
シラン、モノメチルトリエトキシシランなどのモノ低級
アルキルトリ低級アルコキシシラン類が好ましく、これ
らを用いることにより、より低誘電率のシリカ系被膜が
得られる。本発明においては、上記シラン化合物は単独
で用いてもよいし、２種以上を組み合わせて用いてもよ
い。Among these, tetra-lower alkoxysilanes such as tetramethoxysilane and tetraethoxysilane, tri-lower alkoxysilanes such as trimethoxysilane and triethoxysilane, and mono-lower alkoxysilanes such as monomethyltrimethoxysilane and monomethyltriethoxysilane Lower alkyltri-lower alkoxysilanes are preferred, and use of these can provide a silica-based coating having a lower dielectric constant. In the present invention, the above silane compounds may be used alone or in combination of two or more.
【００１４】本発明のシリカ系被膜を形成させるには、
まず、前記シラン化合物の塩基性加水分解縮合生成物を
含有するシリカ系被膜形成用塗布液を調製する。この際
用いられる塩基性触媒としては、形成されるシリカ被膜
が半導体素子の製造に使用されることから、ナトリウ
ム、カリウムなどの半導体素子に悪影響を及ぼす金属イ
オンを含まない塩基が用いられる。このような塩基とし
ては、アンモニア水及び有機アミンがあり、この有機ア
ミンとしては、アニリン、Ｎ‐メチルアニリンなどの芳
香族アミン、トリエチルアミン、トリプロピルアミン、
トリブチルアミン、トリエタノールアミン、トリプロパ
ノールアミンなどの脂肪族低級第三級アミンが好適であ
る。この塩基は、単独で用いてもよいし、２種以上を組
み合わせて用いてもよい。また、その使用量は、シラン
化合物１モルに対し、通常１０-1〜１０-5モル、好まし
くは１０-2〜１０-4モルの範囲で選ばれる。In order to form the silica-based coating of the present invention,
First, a coating solution for forming a silica-based film containing a basic hydrolysis-condensation product of the silane compound is prepared. As the basic catalyst used at this time, a base which does not contain metal ions such as sodium and potassium which adversely affect the semiconductor element is used because the silica coating to be formed is used for the production of the semiconductor element. Such bases include aqueous ammonia and organic amines, such as aniline, aromatic amines such as N-methylaniline, triethylamine, tripropylamine, and the like.
Aliphatic lower tertiary amines such as tributylamine, triethanolamine and tripropanolamine are preferred. These bases may be used alone or in combination of two or more. The amount of the silane compound to be used is generally selected within the range of 10 -1 to 10 -5 mol, preferably 10 -2 to 10 -4 mol, per 1 mol of the silane compound.
【００１５】加水分解縮合反応処理は、有機溶媒中にお
いて、前記シラン化合物を水及び上記塩基性触媒と接触
させることにより行われる。この際の水の量は、用いる
シラン化合物中のアルコキシル基の数に応じて変わる
が、通常シラン化合物１モルに対し、２．０〜２０モ
ル、好ましくは４．０〜１０モルの範囲で選ばれる。The hydrolytic condensation reaction is carried out by bringing the silane compound into contact with water and the above-mentioned basic catalyst in an organic solvent. The amount of water at this time varies depending on the number of alkoxyl groups in the silane compound to be used, but is usually selected in the range of 2.0 to 20 mol, preferably 4.0 to 10 mol, per 1 mol of the silane compound. It is.
【００１６】また、有機溶媒としては、シラン化合物、
水及び塩基性触媒を共に溶解することができ、しかも加
水分解反応及びそれに続く脱水縮合反応に支障のないも
のであればよく、特に制限はない。このようなものとし
ては、例えばメタノール、エタノール、プロパノールな
どの低級アルコール類や、アセトン、メチルエチルケト
ンなどのケトン類や、エチレングリコール、ジエチレン
グリコール、プロピレングリコール、ジプロピレングリ
コール又はそのモノメチルエーテル、モノエチルエーテ
ル、モノプロピルエーテル、モノブチルエーテル、ジメ
チルエーテル、ジエチルエーテル、ジプロピルエーテ
ル、ジブチルエーテル、モノメチルエーテルアセテー
ト、モノエチルエーテルアセテートなどの多価アルコー
ル類及びその誘導体などが挙げられる。これらは単独で
用いてもよいし、２種以上を混合して用いてもよい。As the organic solvent, a silane compound,
There is no particular limitation as long as it can dissolve both water and the basic catalyst and does not hinder the hydrolysis reaction and the subsequent dehydration condensation reaction. Such compounds include, for example, lower alcohols such as methanol, ethanol, and propanol; ketones such as acetone and methyl ethyl ketone; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol or its monomethyl ether, monoethyl ether, and monoethyl ether. Examples include polyhydric alcohols such as propyl ether, monobutyl ether, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, monomethyl ether acetate, monoethyl ether acetate, and derivatives thereof. These may be used alone or as a mixture of two or more.
【００１７】この加水分解縮合反応は、通常０〜７０
℃、好ましくは２０〜２５℃の範囲の温度において行わ
れる。また、反応時間は、加水分解縮合温度により左右
され一概に定めることができないが、加水分解反応に続
く脱水縮合反応を充分に進行させるために、通常１〜１
００時間、好ましくは５〜５０時間の範囲で選ばれる。This hydrolysis-condensation reaction is usually carried out at 0 to 70
C., preferably at a temperature in the range of 20-25C. The reaction time depends on the hydrolysis and condensation temperature and cannot be determined unconditionally. However, in order to allow the dehydration and condensation reaction following the hydrolysis reaction to proceed sufficiently, the reaction time is usually 1 to 1
00 hours, preferably 5 to 50 hours.
【００１８】塩基性触媒による加水分解反応は、酸触媒
による加水分解反応と異なり、複数の水酸基を有するシ
ラノールが生成しやすい。このものは脱水縮合反応を容
易に引き起こし、ゲル化しやすく、経時安定性に劣る傾
向があるので、まず、前述のように前記有機溶媒中で加
水分解反応及び脱水縮合反応させたのち、Ｎ‐メチルピ
ロリドン、ジメチルホルムアミド、ジメチルアセトアミ
ド及びこれらの混合物などの非プロトン性極性溶媒によ
り、溶剤置換してＳｉＯ2換算濃度の高いシリカ系被膜
形成用塗布液を調製するのが有利である。この塗布液の
ＳｉＯ2換算濃度としては、５〜２５重量％程度が好ま
しい。The hydrolysis reaction using a basic catalyst is different from the hydrolysis reaction using an acid catalyst in that a silanol having a plurality of hydroxyl groups is easily formed. Since this easily causes a dehydration-condensation reaction, easily gelates, and tends to be inferior in stability over time, first, as described above, a hydrolysis reaction and a dehydration-condensation reaction in the organic solvent are performed, and then N-methyl It is advantageous to prepare a coating solution for forming a silica-based film having a high concentration in terms of SiO 2 by replacing the solvent with an aprotic polar solvent such as pyrrolidone, dimethylformamide, dimethylacetamide and a mixture thereof. The concentration of this coating solution in terms of SiO 2 is preferably about 5 to 25% by weight.
【００１９】次に、このようにして調製したシリカ系被
膜形成用塗布液を基板上に塗布、乾燥して塗膜を形成す
る。この際用いる基板としては特に制限はなく、形成さ
れるシリカ系被膜の用途に応じて適宜選択される。例え
ば層間絶縁膜とする場合は、シリコンウエーハ上にアル
ミニウムなどの金属配線層を有するものを、中間膜の場
合は多層レジスト法における下層レジストを、平坦化膜
とする場合はシリコンウエーハ上に金属配線層とその上
にＣＶＤ法などによる層間絶縁膜を有するもの又はシリ
コンウエーハ上に多結晶シリコン層からなる配線層が設
けられたものをそれぞれ用いることができる。Next, the coating solution for forming a silica-based film thus prepared is applied to a substrate and dried to form a coating film. The substrate used at this time is not particularly limited, and is appropriately selected according to the use of the silica-based film to be formed. For example, when an interlayer insulating film is used, a metal wiring layer made of aluminum or the like is formed on a silicon wafer, when an intermediate film is used, a lower resist in a multilayer resist method is used, and when a flattening film is used, a metal wiring is formed on a silicon wafer. A layer having a layer and an interlayer insulating film formed thereon by a CVD method or the like or a layer provided with a wiring layer made of a polycrystalline silicon layer on a silicon wafer can be used.
【００２０】このような基板上に、該塗布液を塗布する
方法としては、例えばスプレー法、スピンコート法、デ
ィップコート法、ロールコート法など、任意の方法を用
いることができるが、半導体素子製造には、通常スピン
コート法が用いられる。As a method of applying the coating solution on such a substrate, any method such as a spray method, a spin coating method, a dip coating method, and a roll coating method can be used. For this, a spin coating method is usually used.
【００２１】また、乾燥処理は、塗布液中の溶媒が揮散
して塗膜が形成されればよく、その手段、温度、時間な
どについては特に制限はないが、一般的には、８０〜３
００℃程度のホットプレート上にて数分間程度加熱すれ
ばよい。好ましくは、数段階で、段階的に昇温するのが
有利である。具体的には、大気中又は窒素などの不活性
ガス雰囲気下、８０〜１００℃程度のホットプレート上
で３０秒〜２分間程度第１回目の乾燥処理を行ったの
ち、１２０〜１７０℃程度で３０秒〜２分間程度第２回
目の乾燥処理を行い、さらに１９０〜３００℃程度で３
０秒〜２分間程度第３回目の乾燥処理を行う。このよう
に、数段階の段階的な乾燥処理を行うことにより、形成
された塗膜の表面が均一なものとなる。The drying treatment may be carried out as long as the solvent in the coating solution is volatilized to form a coating film. The means, temperature, time and the like are not particularly limited.
What is necessary is just to heat on a hot plate of about 00 degreeC for about several minutes. Preferably, the temperature is increased stepwise in several steps. Specifically, after performing the first drying treatment for about 30 seconds to 2 minutes on a hot plate of about 80 to 100 ° C. in the air or in an atmosphere of an inert gas such as nitrogen, and then at about 120 to 170 ° C. The second drying treatment is performed for about 30 seconds to 2 minutes, and further performed at about 190 to 300 ° C. for 3 seconds.
The third drying process is performed for about 0 seconds to 2 minutes. As described above, by performing several stages of drying treatment, the surface of the formed coating film becomes uniform.
【００２２】次に、このようにして形成された乾燥塗膜
を、窒素などの不活性ガス雰囲気下又は大気中などの酸
素含有ガス雰囲気下で、３５０℃以上、好ましくは３５
０〜８００℃の範囲の温度において、焼成処理する。こ
の焼成処理温度が３５０℃未満では焼成が不十分でシリ
カ系被膜が得られない。また、焼成処理温度の上限は本
発明のシリカ系被膜を用いて最終的に製造される半導体
素子に依存する。例えばアルミニウムの配線層上の場合
は、５００℃を上限とするのが望ましい。Next, the dried coating film thus formed is heated at 350 ° C. or higher, preferably 35 ° C., in an atmosphere of an inert gas such as nitrogen or an atmosphere of an oxygen-containing gas such as air.
The firing treatment is performed at a temperature in the range of 0 to 800 ° C. If the firing temperature is lower than 350 ° C., the firing is insufficient and a silica-based coating cannot be obtained. The upper limit of the firing temperature depends on the semiconductor device finally manufactured using the silica-based coating of the present invention. For example, on an aluminum wiring layer, the upper limit is desirably 500 ° C.
【００２３】このようにして、比誘電率２．５以下程度
の誘電率の低いシリカ系被膜が形成される。この被膜の
厚さは、該シリカ系被膜の用途などに応じて適宜選択さ
れるが、一般的には０．２〜１．０μｍ程度である。Thus, a silica-based coating having a low dielectric constant of about 2.5 or less is formed. The thickness of this film is appropriately selected according to the use of the silica-based film and the like, but is generally about 0.2 to 1.0 μm.
【００２４】[0024]
【発明の効果】本発明方法によれば、半導体素子の製造
において使用される平坦化膜や層間絶縁膜などとして有
用な誘電率の低い、特に比誘電率２．５以下程度のシリ
カ系被膜を、塗布法により効率よく形成することができ
る。According to the method of the present invention, a silica-based film having a low dielectric constant, particularly about 2.5 or less, which is useful as a flattening film or an interlayer insulating film used in the manufacture of a semiconductor device, is provided. It can be formed efficiently by a coating method.
【００２５】[0025]
【実施例】次に、本発明を実施例により、さらに詳細に
説明するが、本発明は、これらの例によってなんら限定
されるものではない。Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００２６】参考例１ 純水３６．０ｇ（２．０モル）と２８重量％のアンモニ
ア水６９．４７μｇをメタノール８８７．９ｇに溶解
し、かきまぜ、均一な溶液とした。次いで、これにシラ
ン化合物として、ＳｉＯ2換算濃度が３重量％となるよ
うにテトラメトキシシラン７６．１０ｇ（０．５モル）
をゆっくりかきまぜながら滴下したのち、約５時間かき
まぜ、その後室温で２日間静置させた。次いで、Ｎ‐メ
チルピロリドンを加えてから、ロータリーエバポレータ
ーにてメタノールを蒸発させ、ＳｉＯ2換算濃度１０重
量％のシリカ系被膜形成用塗布液を調製した。REFERENCE EXAMPLE 1 36.0 g (2.0 mol) of pure water and 69.47 μg of 28% by weight aqueous ammonia were dissolved in 887.9 g of methanol, followed by stirring to obtain a uniform solution. Next, 76.10 g (0.5 mol) of tetramethoxysilane was added thereto as a silane compound so that the concentration in terms of SiO 2 became 3% by weight.
Was added dropwise with slow stirring, followed by stirring for about 5 hours, and then allowed to stand at room temperature for 2 days. Next, after adding N-methylpyrrolidone, methanol was evaporated using a rotary evaporator to prepare a coating solution for forming a silica-based film having a concentration of 10% by weight in terms of SiO 2 .
【００２７】参考例２ 参考例１において、純水の量を２７．０ｇに、メタノー
ルの量を９０５．９ｇに変え、かつシラン化合物として
モノメチルトリメトキシシラン６８．１０ｇを用いた以
外は、参考例１と同様にしてＳｉＯ2換算濃度１０重量
％のシリカ系被膜形成用塗布液を調製した。REFERENCE EXAMPLE 2 Reference Example 1 was repeated except that the amount of pure water was changed to 27.0 g, the amount of methanol was changed to 905.9 g, and 68.10 g of monomethyltrimethoxysilane was used as a silane compound. In the same manner as in Example 1, a coating solution for forming a silica-based film having a concentration of 10% by weight in terms of SiO 2 was prepared.
【００２８】参考例３ 参考例１において、純水の量を２７．０ｇに、メタノー
ルの量を８９０．９ｇに変え、かつシラン化合物として
トリエトキシシラン８２．１５ｇを用いた以外は、参考
例１と同様にしてＳｉＯ2換算濃度１０重量％のシリカ
系被膜形成用塗布液を調製した。Reference Example 3 Reference Example 1 was repeated except that the amount of pure water was changed to 27.0 g, the amount of methanol was changed to 890.9 g, and that 82.15 g of triethoxysilane was used as a silane compound. In the same manner as described above, a coating solution for forming a silica-based film having a concentration of 10% by weight in terms of SiO 2 was prepared.
【００２９】参考例４ モノメチルトリエトキシシランを酸触媒下、加水分解し
て得られたラダー型加水分解縮合生成物をエタノールに
溶解したＳｉＯ2換算濃度１０重量％のシリカ系被膜形
成用塗布液を調製した。Reference Example 4 A coating solution for forming a silica-based film having a concentration of 10% by weight in terms of SiO 2 was prepared by dissolving a ladder-type hydrolysis-condensation product obtained by hydrolyzing monomethyltriethoxysilane under an acid catalyst in ethanol. Prepared.
【００３０】実施例１ 参考例１で得られた塗布液を、シリコンウエーハ上にス
ピンナーにより塗布し、ホットプレートで８０℃、１５
０℃及び２００℃で順次それぞれ１分間乾燥させて塗膜
を得たのち、窒素雰囲気にて４００℃で３０分間焼成す
ることにより、厚さ０．４μｍのシリカ系被膜を形成さ
せた。このようにして形成されたシリカ系被膜の比誘電
率は２．２であった。Example 1 The coating solution obtained in Reference Example 1 was applied on a silicon wafer by a spinner, and was heated at 80 ° C. and 15 ° C. on a hot plate.
The coating was dried at 0 ° C. and 200 ° C. for 1 minute each to obtain a coating, and then baked at 400 ° C. for 30 minutes in a nitrogen atmosphere to form a silica-based coating having a thickness of 0.4 μm. The relative permittivity of the silica-based coating thus formed was 2.2.
【００３１】実施例２ 実施例１において、参考例１で得られた塗布液の代わり
に、参考例２で得られた塗布液を用いた以外は、実施例
１と同様にしてシリカ系被膜を形成させた。このように
して形成されたシリカ系被膜の比誘電率は２．３であっ
た。Example 2 A silica-based coating was prepared in the same manner as in Example 1 except that the coating liquid obtained in Reference Example 2 was used instead of the coating liquid obtained in Reference Example 1. Formed. The relative permittivity of the silica-based coating thus formed was 2.3.
【００３２】実施例３ 実施例１において、参考例１で得られた塗布液の代わり
に、参考例３で得られた塗布液を用いた以外は、実施例
１と同様にしてシリカ系被膜を形成させた。このように
して形成されたシリカ系被膜の比誘電率は２．２であっ
た。Example 3 A silica-based coating was prepared in the same manner as in Example 1 except that the coating liquid obtained in Reference Example 3 was used instead of the coating liquid obtained in Reference Example 1. Formed. The relative permittivity of the silica-based coating thus formed was 2.2.
【００３３】比較例 実施例１において、参考例１で得られた塗布液の代わり
に、参考例４で得られた塗布液を用いた以外は、実施例
１と同様にしてシリカ系被膜を形成させた。このように
して形成されたシリカ系被膜の比誘電率は２．８であっ
た。Comparative Example A silica-based coating was formed in the same manner as in Example 1 except that the coating liquid obtained in Reference Example 4 was used instead of the coating liquid obtained in Reference Example 1. I let it. The relative permittivity of the silica-based coating thus formed was 2.8.
Claims (6)
水分解縮合生成物焼成体からなる半導体素子用シリカ系
被膜。1. A silica-based coating for a semiconductor element comprising a fired product of a basic hydrolysis-condensation product of a polyalkoxysilane compound.
載の半導体素子用シリカ系被膜。2. The silica-based coating for a semiconductor device according to claim 1, which has a relative dielectric constant of 2.5 or less.
中で塩基性触媒により加水分解縮合して得た塗布液を、
基板上に塗布し、乾燥したのち、３５０℃以上に加熱
し、焼成することを特徴とする半導体素子用シリカ系被
膜の形成方法。3. A coating solution obtained by hydrolyzing and condensing a polyalkoxysilane compound in an organic solvent with a basic catalyst,
A method for forming a silica-based coating for a semiconductor element, comprising applying the composition to a substrate, drying the composition, heating the composition to 350 ° C. or higher, and calcining the composition.
トラアルコキシシラン類、低級トリアルコキシシラン類
及びモノアルキル低級トリアルコキシシラン類の中から
選ばれた少なくとも１種である請求項３記載の半導体素
子用シリカ系被膜の形成方法。4. The silica for a semiconductor element according to claim 3, wherein the polyalkoxysilane compound is at least one selected from lower tetraalkoxysilanes, lower trialkoxysilanes and monoalkyl lower trialkoxysilanes. Method for forming a system coating.
ンの中から選ばれた少なくとも１種である請求項３又は
４記載の半導体素子用シリカ系被膜の形成方法。5. The method for forming a silica-based film for a semiconductor device according to claim 3, wherein the basic catalyst is at least one selected from aqueous ammonia and an organic amine.
縮合生成物を含有する有機溶剤溶液が、低級アルコール
類、ケトン類、多価アルコール及びその誘導体の中から
選ばれた少なくとも１種の溶媒中において、ポリアルコ
キシシラン化合物を加水分解縮合させたのち、非プロト
ン性極性溶媒により溶剤置換したものである請求項３な
いし５のいずれかに記載の半導体素子用シリカ系被膜の
形成方法。6. An organic solvent solution containing a hydrolysis-condensation product of a polyalkoxysilane compound, wherein at least one solvent selected from lower alcohols, ketones, polyhydric alcohols and derivatives thereof, 6. The method for forming a silica-based film for a semiconductor device according to claim 3, wherein the polyalkoxysilane compound is subjected to hydrolysis and condensation and then solvent-replaced with an aprotic polar solvent.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14480798A JP4473352B2 (en) | 1998-05-26 | 1998-05-26 | Low dielectric constant silica-based coating, coating liquid for forming the same, and method for preparing the coating liquid |
| TW88106890A TWI234787B (en) | 1998-05-26 | 1999-04-28 | Silica-based coating film on substrate and coating solution therefor |
| US09/302,471 US6875262B1 (en) | 1998-05-26 | 1999-04-30 | Silica-based coating film on substrate and coating solution therefor |
| KR1019990018940A KR100334550B1 (en) | 1998-05-26 | 1999-05-25 | Silica-based coating film on substrate and coating solution therefor |
| US11/067,622 US7135064B2 (en) | 1998-05-26 | 2005-02-28 | Silica-based coating film on substrate and coating solution therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14480798A JP4473352B2 (en) | 1998-05-26 | 1998-05-26 | Low dielectric constant silica-based coating, coating liquid for forming the same, and method for preparing the coating liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11340219A true JPH11340219A (en) | 1999-12-10 |
| JP4473352B2 JP4473352B2 (en) | 2010-06-02 |
Family
ID=15370929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14480798A Expired - Fee Related JP4473352B2 (en) | 1998-05-26 | 1998-05-26 | Low dielectric constant silica-based coating, coating liquid for forming the same, and method for preparing the coating liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4473352B2 (en) |
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