JPH0555201A - Insulating film, and the like for semiconductor and forming method thereof - Google Patents
Insulating film, and the like for semiconductor and forming method thereofInfo
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- JPH0555201A JPH0555201A JP23538891A JP23538891A JPH0555201A JP H0555201 A JPH0555201 A JP H0555201A JP 23538891 A JP23538891 A JP 23538891A JP 23538891 A JP23538891 A JP 23538891A JP H0555201 A JPH0555201 A JP H0555201A
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- insulating film
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は半導体における多層配線
化に必要とされる絶縁膜または平坦化膜膜としてポリオ
ルガノシルセスキオキサンを用いて製造された新規な半
導体用絶縁膜または平坦化膜及びそれらを形成する方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel semiconductor insulating film or flattening film produced by using polyorganosilsesquioxane as an insulating film or flattening film required for multilayer wiring in a semiconductor. And methods of forming them.
【０００２】[0002]
【従来の技術】ＬＳＩの高集積化とともに配線の多層化
が不可避となってきており、回路の信頼性を維持する上
で層間絶縁膜及び平坦化膜膜の重要性が増してきてい
る。2. Description of the Related Art With higher integration of LSIs, multi-layered wiring is inevitable, and the importance of an interlayer insulating film and a planarizing film is increasing in order to maintain circuit reliability.
【０００３】層間絶縁膜または平坦化膜（本発明におい
ては以下この両者を層間絶縁膜等という。）の形成方法
には一般に気相法（ＣＶＤ法）と塗布膜法（ＳＯＧ法）
とが従来知られている。すなわちこれらの層間絶縁膜等
は信頼性の高い気相法により緻密なＳｉＯ2 膜を堆積す
る方法、あるいはテトラヒドロキシシランに代表される
無機系のポリシロキサン被覆膜を塗布法で形成すると共
に、この被覆膜を上下面を気相法による緻密なＳｉＯ2
膜で包むサンドイッチする方法とが採用されてきた。Generally, vapor phase method (CVD method) and coating film method (SOG method) are used as a method for forming an interlayer insulating film or a planarizing film (in the present invention, both are referred to as an interlayer insulating film and the like hereinafter).
Is known in the past. That is, these interlayer insulating films and the like are formed by a method of depositing a dense SiO 2 film by a highly reliable vapor phase method, or by forming an inorganic polysiloxane coating film typified by tetrahydroxysilane by a coating method. The upper and lower surfaces of this coating film are made of dense SiO 2 by a vapor phase method.
Membrane-wrapped sandwich methods have been employed.
【０００４】しかし、半導体の高集積化が進むにつれ、
配線幅、パタン間の溝が狭くなり、従って素子表面の凹
凸は大きくなる方法にあり、従来の気相法のみではこの
凹凸によって上層の配線が断線等の欠陥を生ずる恐れが
出てきた。However, as semiconductors are highly integrated,
There is a method in which the wiring width and the groove between the patterns are narrowed, so that the unevenness on the surface of the element becomes large. With only the conventional vapor phase method, the unevenness may cause defects such as disconnection in the upper wiring.
【０００５】一方、塗布膜法においても、デバイス表面
の凹凸を埋めるには膜厚を従来より厚くしなければなら
ないわけであるが、無機ＳＯＧ膜であるテトラヒドロキ
シシラン硬化膜は膜厚０．２μｍ以上ではクラックを生
じやすい欠点があって、厚い配線の層間絶縁膜等に使用
するには問題があった。On the other hand, even in the coating film method, the film thickness must be made thicker than before in order to fill the irregularities on the device surface, but the tetrahydroxysilane cured film which is an inorganic SOG film has a film thickness of 0.2 μm. In the above case, there is a drawback that cracks are likely to occur, and there is a problem in using it for an interlayer insulating film of thick wiring.
【０００６】そこで近時塗布膜法に使用されるテトラヒ
ドロキシシラン系被膜の厚膜化、耐クラック性や平坦化
能力を改良したものとして、アルキルトリヒドロキシシ
ランなどのいわゆる有機ＳＯＧを層間絶縁膜等として使
用することが提案されている。この場合は溝部を除いて
硬化膜を除去するエッチバック法が併用されることが多
い。Therefore, as an improvement of the thickening, crack resistance and flattening ability of the tetrahydroxysilane coating used in the coating film method in recent years, so-called organic SOG such as alkyltrihydroxysilane is used as an interlayer insulating film or the like. Is proposed to be used as. In this case, an etch back method of removing the cured film except the groove is often used together.
【０００７】しかし、この有機ＳＯＧ硬化膜にもいくつ
かの問題点があることが指摘されている。その一つは高
温加熱時の収縮による応力が大きく、クラック発生の懸
念があることであり、また高温加熱時の脱ガスによる配
線の損傷も懸念される。更に有機ＳＯＧ膜は無機ＳＯＧ
膜と比較したときに吸湿性が高いことも配線の信頼性の
面で不安視されている。However, it has been pointed out that this organic SOG cured film has some problems. One of them is that the stress due to shrinkage during high temperature heating is large, and there is a concern that cracks may occur, and there is also concern about damage to the wiring due to degassing during high temperature heating. Furthermore, the organic SOG film is an inorganic SOG film.
Higher hygroscopicity compared to the film is also anxious about the reliability of the wiring.
【０００８】[0008]
【発明が解決しようとする課題】本発明は有機ＳＯＧに
おける上記の問題点を解決する目的でなされたものであ
り、絶縁性、平坦化性に優れると共に、前述の耐熱性、
耐湿性等について改善された半導体用絶縁膜、平坦化膜
及びそれらの形成方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made for the purpose of solving the above-mentioned problems in organic SOG, and is excellent in insulating property and flattening property as well as in the above heat resistance,
An object of the present invention is to provide an insulating film for a semiconductor, a planarizing film, and a method for forming them, which have improved moisture resistance and the like.
【０００９】[0009]
【課題を解決するための手段】本発明者らは上記目的を
達成するため鋭意検討を進めた結果、有機ＳＯＧにおけ
るアルキルトリヒドロキシシランに代えて特定の分子量
と末端基を有するポリオルガノシルセスキオキサンを用
いることにより、上記目的を達成する絶縁膜平坦化膜が
得られることを見いだし、本発明を完成するに至った。
即ち、本発明は一般式（Ｉ）でしめされる数平均分子量
が５００〜１０，０００であり、末端基として水酸基を
０．３〜６重量％、アルコキシ基を０．９〜１６重量
％、かつ両末端基のモル比は１：０．２〜２．０の範囲
に含有しているポリオルガノシルセスキオキサンを加熱
キュアしたことを特徴とする半導体用絶縁膜または平坦
化膜に関する。Means for Solving the Problems As a result of intensive investigations aimed at achieving the above object, the present inventors have found that polyorganosilsesquioxy having a specific molecular weight and a terminal group instead of alkyltrihydroxysilane in organic SOG. It was found that an insulating film flattening film that achieves the above object can be obtained by using sun, and the present invention has been completed.
That is, the present invention has a number average molecular weight represented by the general formula (I) of 500 to 10,000, a hydroxyl group as an end group of 0.3 to 6% by weight, an alkoxy group of 0.9 to 16% by weight, Further, the present invention relates to an insulating film for a semiconductor or a planarizing film, which is obtained by heat-curing polyorganosilsesquioxane containing both end groups in a molar ratio of 1: 0.2 to 2.0.
【００１０】[0010]
【化２】 （一般式（Ｉ）においてＲ1 はメチル基またはフェニル
基、Ｒ2 は炭素数１〜３のアルキル基または水素原子を
示し、ｎは分子量に対応する正の数であり、分散を伴う
集合体を示す。）[Chemical 2] (In the general formula (I), R 1 represents a methyl group or a phenyl group, R 2 represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, and n is a positive number corresponding to the molecular weight, and an aggregate accompanied by dispersion. Is shown.)
【００１１】また、上記半導体用層間絶縁膜等を形成す
るために、一般式（Ｉ）で示されるポリオルガノシロキ
サンを有機溶剤に溶解し、デバイス基板の配線上にコー
ティングし、加熱キュアする層間絶縁膜等を形成する方
法に関する。Further, in order to form the above-mentioned semiconductor interlayer insulating film, etc., the polyorganosiloxane represented by the general formula (I) is dissolved in an organic solvent, coated on the wiring of the device substrate and cured by heating. The present invention relates to a method for forming a film or the like.
【００１２】本発明において使用されるポリオルガノシ
ルセスキオキサンにおいて側鎖Ｒ1はメチル基またはフ
ェニル基であり、これ以外の置換基では耐熱性が不十分
となり不適当である。またメチル基は少なくとも８０モ
ル％以上含有することが耐熱性の面で好ましい。In the polyorganosilsesquioxane used in the present invention, the side chain R 1 is a methyl group or a phenyl group, and other substituents are not suitable because of insufficient heat resistance. Further, it is preferable that the methyl group is contained at least 80 mol% or more from the viewpoint of heat resistance.
【００１３】本発明に用いるポリオルガノシルセスキオ
キサンとしては、末端基は水酸基を０．３〜６重量％、
アルコキシ基を０．９〜１６重量％、かつ両末端基のモ
ル比は１：０．２〜２．０の範囲となるよう含有するも
のである。アルコキシ基としてはメトキシ、エトキシ、
ブトキシ基等が使用しうる。The polyorganosilsesquioxane used in the present invention has a terminal group of 0.3 to 6% by weight of a hydroxyl group,
The alkoxy group is contained in an amount of 0.9 to 16% by weight, and the molar ratio of both terminal groups is in the range of 1: 0.2 to 2.0. As the alkoxy group, methoxy, ethoxy,
Butoxy group and the like can be used.
【００１４】本発明のポリオルガノシルセスキオキサン
において末端基の水酸基が６重量％以上となるとキュア
後も未反応で残留する水酸基があり、これに起因して硬
化膜の吸湿性が高くなる欠点を生ずる。末端基のアルコ
キシ基が１６重量％以上では硬化膜の高温加熱時のガス
発生量が多くなる欠点を生ずる。また末端基の水酸基が
０．３重量％以下またはアルコキシ基が０．９重量％以
下の場合は基板との接着性や平坦化特性が不満足となる
ほかに、硬化膜の硬度なども目的に充分なレベルに達し
ない。また末端基の水酸基とアルコキシ基とのモル比は
１：０．２〜２．０、好ましくは１：０．５〜１．５で
あり、この範囲よりアルコキシ基が多くても少なくても
キュア時の性能発現はスムーズに進行しない。アルコキ
シ基が少ない場合は特に硬化膜の吸湿性が不満足とな
り、アルコキシ基が多い場合は高温加熱時のガス発生量
が問題となる。In the polyorganosilsesquioxane of the present invention, when the hydroxyl group of the terminal group is 6% by weight or more, there is a hydroxyl group which remains unreacted after curing, which results in high hygroscopicity of the cured film. Cause If the amount of the alkoxy group as the terminal group is 16% by weight or more, there arises a disadvantage that the amount of gas generated when the cured film is heated at high temperature increases. In addition, when the hydroxyl group of the terminal group is 0.3% by weight or less or the alkoxy group is 0.9% by weight or less, the adhesion to the substrate and the flattening property are unsatisfactory, and the hardness of the cured film is sufficient for the purpose. Not reach a certain level. Further, the molar ratio of the hydroxyl group of the terminal group to the alkoxy group is 1: 0.2 to 2.0, preferably 1: 0.5 to 1.5, and even if the alkoxy group is more or less than this range, it is cured. Time performance does not progress smoothly. When the amount of alkoxy groups is small, the hygroscopicity of the cured film becomes unsatisfactory, and when the amount of alkoxy groups is large, the amount of gas generated during high temperature heating becomes a problem.
【００１５】本発明におけるポリオルガノシルセスキオ
キサンの数平均分子量は５００〜１０，０００が好まし
く、数平均分子量が５００より小さいと本発明の目的の
一つである高温加熱時及び硬化時の収縮を抑制する点で
不十分となる。また数平均分子量が１０，０００より大
きいと有機溶剤に対する溶解性が不十分となるのみなら
ず、平坦化特性も不満足となる。The number average molecular weight of the polyorganosilsesquioxane in the present invention is preferably 500 to 10,000, and when the number average molecular weight is less than 500, shrinkage at the time of heating at high temperature and curing which is one of the objects of the present invention. Is insufficient in terms of suppressing If the number average molecular weight is more than 10,000, not only the solubility in an organic solvent will be insufficient, but also the flattening characteristics will be unsatisfactory.
【００１６】本発明のポリオルガノシルセスキオキサン
の基板配線上にコーティングするに当たっては有機溶剤
に溶解した液として用いる。本発明の分子量域のポリオ
ルガノシルセスキオキサンは多様な一般有機溶剤に可溶
であって、例えば次のような有機溶剤を用いることがで
きる。メチルアルコール、エチルアルコール、プロピル
アルコール、ブチルアルコールのようなアルコール類、
アセトン、メチルメチルケトン、メチルイソブチルケト
ンのようなケトン類、酢酸メチル、酢酸ブチルのような
エステル類、エチレングリコール、グリセリン、ジエチ
レングルコール、エチレングリコールモノメチルエーテ
ル、エチレングリコールエチルエーテル、エチレングリ
コールモノブチルエーテル、プロピレングリコールのよ
うな多価アルコールおよびそのエーテル類などを挙げる
ことができ、これらは単独で用いても２種以上混合して
用いてもよい。In coating the substrate wiring of the polyorganosilsesquioxane of the present invention, it is used as a solution dissolved in an organic solvent. The polyorganosilsesquioxane in the molecular weight range of the present invention is soluble in various general organic solvents, and for example, the following organic solvents can be used. Alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol,
Acetone, methyl methyl ketone, ketones such as methyl isobutyl ketone, methyl acetate, esters such as butyl acetate, ethylene glycol, glycerin, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, Examples thereof include polyhydric alcohols such as propylene glycol and ethers thereof, and these may be used alone or in combination of two or more kinds.
【００１７】有機溶液中のポリオルガノシルセスキオキ
サンの固形分濃度はコーティング方法にも依存するが、
通常は２〜３０重量％、好ましくは５〜２０重量％であ
る。また本発明のポリオルガノシルセスキオキサン溶液
には必要に応じてレベリング剤、カップリング剤、増粘
剤、充填剤、その他の添加剤を添加して用いてもよい。Although the solid content of polyorganosilsesquioxane in the organic solution depends on the coating method,
It is usually 2 to 30% by weight, preferably 5 to 20% by weight. Further, a leveling agent, a coupling agent, a thickener, a filler, and other additives may be added to the polyorganosilsesquioxane solution of the present invention, if necessary.
【００１８】本発明のポリオルガノシルセスキオキサン
溶液を基板配線上にコーティングするに際しては通常ス
ピンコーティングを行う。またこのとき配線上にあらか
じめ気相法によるＳｉＯ2 膜をつけておくのが一般的で
ある。When the polyorganosilsesquioxane solution of the present invention is coated on the substrate wiring, spin coating is usually performed. Further, at this time, it is general to preliminarily deposit a SiO 2 film on the wiring by a vapor phase method.
【００１９】本発明のポリオルガノシルセスキオキサン
の膜厚は０．０１〜５μｍ程度まで自由に選択すること
ができ、特に１μｍ以上の厚膜になってもクラックを生
じないことから配線幅の凹部を一度に埋め平坦化するこ
とが可能である。The film thickness of the polyorganosilsesquioxane of the present invention can be freely selected from about 0.01 to 5 μm. In particular, even if the film thickness is 1 μm or more, cracks do not occur, so that the wiring width can be reduced. It is possible to fill the recesses at once and planarize.
【００２０】加熱キュアとしてはポリオルガノシルセス
キオキサン溶液を基板にコーティングした後、１５０〜
５００℃において１０〜１２０分間加熱することによっ
て行う。このとき有機溶剤の種類によってはキュアに先
立ち１００〜３００℃、１〜１０分間の予備加熱を行
い、有機溶剤をあらかじめ除去してもよい。As the heating cure, after coating the substrate with a polyorganosilsesquioxane solution, 150-
It is carried out by heating at 500 ° C. for 10 to 120 minutes. At this time, depending on the kind of the organic solvent, the organic solvent may be removed in advance by performing preheating at 100 to 300 ° C. for 1 to 10 minutes before the curing.
【００２１】キュア温度は構成材料の耐熱性から許容さ
れる限り高温にすることが硬化後の膜の材質及び所要時
間の面から望ましいが、通常は３００〜４５０℃にする
ことが好ましい。It is desirable that the curing temperature is as high as the heat resistance of the constituent materials allows, from the viewpoint of the material of the film after curing and the required time, but it is usually preferably 300 to 450 ° C.
【００２２】本発明のポリオルガノシルセスキオキサン
は従来のアルキルトリヒドロキシシラン等の有機ＳＯＧ
よりは比較的低温でキュアすることができるばかりでな
く、このとき得られた硬化膜は比較的厚膜としてもクラ
ックは生じ難く、従来の有機ＳＯＧ膜に比して高温加熱
時にもガス発生量が少なく、また加熱に伴う収縮やクラ
ックも更に吸湿性、平坦化特性も良好な層間絶縁膜等が
得られる。The polyorganosilsesquioxane of the present invention is a conventional organic SOG such as alkyltrihydroxysilane.
Not only can it be cured at a relatively low temperature, but the cured film obtained at this time is less prone to cracking even if it is a relatively thick film. It is possible to obtain an interlayer insulating film or the like which has a small amount of heat, and has good hygroscopicity and shrinkage and cracks due to heating, and good flattening characteristics.
【００２３】[0023]
【作用】本発明のポリオルガノシロキサンは結果的には
テトラヒドロキシシランの問題点とアルキルトリヒドロ
キシシランの問題点を前記両者の長所を発揮できるよう
にポリオルガノシルセスキオキサンの分子量、置換基等
を適宜選択してこれを達成したものと考えることができ
る。The polyorganosiloxane of the present invention results in that the problems of tetrahydroxysilane and the problems of alkyltrihydroxysilane can be exhibited so that the molecular weight, substituents, etc. of polyorganosilsesquioxane can be exerted. Can be considered to have been achieved by appropriately selecting.
【００２４】特にラダータイプのオルガノシロキサンで
あるため熱安定性（加熱による収縮性の小さいこと）に
優れており、また末端基に一定範囲のアルキル基を含有
させることにより柔軟性（硬度）、接着性、平坦化特性
などをクラックや吸湿性によるトラブルがない適当な範
囲に納められるように分子設計された優れた層間絶縁膜
等を提供できた。In particular, since it is a ladder type organosiloxane, it is excellent in thermal stability (small in shrinkability by heating), and by containing an alkyl group in a certain range in the terminal group, flexibility (hardness) and adhesion can be obtained. It has been possible to provide an excellent interlayer insulating film or the like whose molecular design is designed so that the properties, flattening characteristics, etc. can be kept within an appropriate range without cracks or hygroscopicity.
【００２５】[0025]
【実施例】以下、実施例及び比較例を挙げて本発明を更
に詳細に説明する。但し、本発明はなんらこれらに限定
されるものではない。なお、実施例及び比較例中の各物
性値はベアシリコンウエハに塗布したものを下記の方法
に従って測定した。EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these. Each physical property value in Examples and Comparative Examples was measured by coating bare silicon wafers according to the following methods.
【００２６】（１）数平均分子量の測定 ＧＰＣ（ゲルバーミュレーションクロマトグラフィー）
法により測定したデータ（昭和電工（株）のＳｈｏｄｅ
ｘカラム使用）をポリスチレン標準試料の検量線に基づ
く換算値で表した。(1) Measurement of number average molecular weight GPC (gel permeation chromatography)
Data measured by the method (Showa Denko's Shode)
(using x column) is represented by a conversion value based on a calibration curve of a polystyrene standard sample.
【００２７】 （２）末端−ＯＨ、−ＯＣ2 Ｈ5 基量の測定 液中に酸を加えることにより−ＯＨ基はＨ2 Ｏ、−ＯＣ
2 Ｈ5 基はＣ2 Ｈ5 ＯＨとして適定法により末端−Ｏ
Ｈ、−ＯＣ2 Ｈ5 を定量した。(2) Measurement of the amount of terminal —OH and —OC 2 H 5 groups By adding an acid to the solution, —OH groups are converted into H 2 O and —OC.
The 2 H 5 group is C 2 H 5 OH and is converted to a terminal —O by a titration method.
H, was quantified -OC 2 H 5.
【００２８】（３）スピンコート法 スピナー１Ｈ３６０型（協栄セミコンダクター製）を使
用し、塗布膜を数ミリリットルシリコンウエハ基板上に
滴下し、１０００ｒｐｍ、５秒次いで４０００ｒｐｍ、
１５秒間回転し、塗布膜を形成した。(3) Spin coating method Using a spinner 1H360 type (manufactured by Kyoei Semiconductor), a coating film was dropped on a several milliliter silicon wafer substrate, and 1000 rpm, 5 seconds and then 4000 rpm,
It was rotated for 15 seconds to form a coating film.
【００２９】（４）膜厚の測定法 エリプソメーター（偏光解析装置）Ｌ−２Ｗ−１５Ｃ−
８３０（ガードナー社製）にてシリコン基板ウエハ上の
膜厚を測定した。(4) Method of measuring film thickness Ellipsometer (polarization analyzer) L-2W-15C-
830 (manufactured by Gardner) was used to measure the film thickness on the silicon substrate wafer.
【００３０】（５）塗膜物性の測定法 耐クラック性：６インチミラーウエハ上に膜厚１μ
ｍにて塗膜を形成し、５００℃、３０分熱処理したとき
のクラックの有無を見た。 脱ガス性：高真空中で５００℃まで加熱したときの
発生ガスの有無をマススペクトルメーターにより測定し
た。 収縮性：５００℃、３０分熱処理したときの膜厚変
化をエリプソメーターにより測定した。 吸湿性：塗膜を２８日間室温下に放置したときの吸
湿水分量をマススペクトル及びＴＧにより測定した。 平坦化特性：配線幅１．０以下〜数μｍ、配線間距
離１．０以下〜数μｍ、アスペクト比１．０以下〜数に
わたるさまざまなパターンを含むテストデバイスにコー
トしたときの断面走査電子顕微鏡により平坦化状態をみ
た（これのみテストデバイス使用）。(5) Method of measuring coating film physical properties Crack resistance: Film thickness of 1 μ on 6 inch mirror wafer
It was checked whether or not there was a crack when a coating film was formed at m and heat-treated at 500 ° C. for 30 minutes. Degassing property: The presence or absence of evolved gas when heated to 500 ° C. in a high vacuum was measured by a mass spectrometer. Shrinkability: The change in film thickness when heat-treated at 500 ° C. for 30 minutes was measured by an ellipsometer. Hygroscopicity: The amount of moisture absorbed when the coating film was left at room temperature for 28 days was measured by mass spectrum and TG. Planarization characteristics: Cross-sectional scanning electron microscope when a test device including various patterns with a wiring width of 1.0 or less to several μm, a distance between wirings of 1.0 to several μm, and an aspect ratio of 1.0 to several is coated. Showed the flattened state (using only the test device).
【００３１】（６）液安定性：塗布液を５℃冷蔵庫、お
よび２０℃下に保管し、粘度及びスピンコート時の塗布
膜厚変化の有無を見た。(6) Liquid stability: The coating liquid was stored in a refrigerator at 5 ° C. and at 20 ° C., and the viscosity and the presence or absence of change in the coating film thickness during spin coating were checked.
【００３２】（実施例１）前記一般式（Ｉ）においてＲ
1 がメチル基、Ｒ2 が水素とエチル基からなり、水酸基
含有量が１．４重量％、エトキシ基含有量が３．６重量
％、かつ両者のモル比が１：１で、数平均分子量ＭN が
２５００のラダー型シリコーンオリゴマー１３重量部を
エタノールとブタノールの混合溶剤（重量比１：１）８
７重量部に溶解して塗布液を得た。上記塗布液を６イン
チのベアシリコンウエハ上に膜厚４０００Åになるよう
にスピンコーティングし、１２０℃、１分、次いで、２
５０℃、２分のホットプレート処理を行った後、３５０
℃、３０分クリンオーブンにて加熱してキュアせしめ
た。キュア後、室温に冷却して諸物性を測定した。結果
を表１に示す。Example 1 In the above general formula (I), R
1 is a methyl group, R 2 is hydrogen and an ethyl group, the hydroxyl group content is 1.4% by weight, the ethoxy group content is 3.6% by weight, and the molar ratio of both is 1: 1 and the number average molecular weight is 1. 13 parts by weight of a ladder-type silicone oligomer having an M N of 2500 were mixed with a mixed solvent of ethanol and butanol (weight ratio 1: 1) 8
It was dissolved in 7 parts by weight to obtain a coating liquid. The above coating solution was spin-coated on a 6-inch bare silicon wafer to a film thickness of 4000 Å, 120 ° C. for 1 minute, and then 2
After hot plate treatment at 50 ° C for 2 minutes, 350
It was made to cure by heating in a clean oven at 30 ° C. for 30 minutes. After curing, it was cooled to room temperature and various physical properties were measured. The results are shown in Table 1.
【００３３】（実施例２）前記一般式（Ｉ）においてＲ
1 がメチル基９０モル％、フェニル基１０モル％からな
り、Ｒ2 が水素及びエチル基であり、水酸基含有量が
４．９重量％、エトキシ基含有量が６．６重量％、かつ
両者のモル比が１：０．５、数平均分子量がＭN が１３
００のラダー型シリコーンオリゴマー１５重量部をエチ
レングリコールモノエチルエーテル８５重量部に溶解し
て塗布液を得た。上記塗布液を実施例１と同様に６イン
チのベアシリコンウエハ上に膜厚４０００Åになるよう
コートし、キュア後諸物性を測定した。結果を表１に示
す。Example 2 In the above general formula (I), R
1 is composed of 90 mol% of methyl group and 10 mol% of phenyl group, R 2 is hydrogen and ethyl group, the content of hydroxyl group is 4.9% by weight, the content of ethoxy group is 6.6% by weight, and The molar ratio is 1: 0.5, the number average molecular weight is M N is 13
15 parts by weight of the ladder type silicone oligomer of No. 00 was dissolved in 85 parts by weight of ethylene glycol monoethyl ether to obtain a coating solution. The above coating solution was coated on a 6-inch bare silicon wafer in the same manner as in Example 1 to a film thickness of 4000 Å, and various physical properties were measured after curing. The results are shown in Table 1.
【００３４】（実施例３）前記一般式（Ｉ）においてＲ
1 がメチル基、Ｒ2 が水素とエチル基であり、水酸基含
有量が０．３重量％、エトキシ基含有量が１４．２重量
％、かつ両者のモル比が１：１．８、数平均分子量がＭ
N が７２００のラダー型シリコーンオリゴマー１３重量
部をエタノールとブタノールの混合溶剤（重量比１：
１）８７重量部に溶解して塗布液を得た。上記塗布液を
実施例１と同様にコートし、硬化後の諸物性を測定し
た。結果を表１に示す。(Example 3) R in the general formula (I)
1 is a methyl group, R 2 is hydrogen and an ethyl group, the hydroxyl group content is 0.3% by weight, the ethoxy group content is 14.2% by weight, and the molar ratio of both is 1: 1.8, the number average. Molecular weight is M
13 parts by weight of a ladder-type silicone oligomer having N of 7200 was mixed with a mixed solvent of ethanol and butanol (weight ratio 1:
1) It was dissolved in 87 parts by weight to obtain a coating liquid. The coating liquid was coated in the same manner as in Example 1 and the physical properties after curing were measured. The results are shown in Table 1.
【００３５】（比較例１）前記一般式（Ｉ）においてＲ
1 がメチル基、Ｒ2 が水素及びエチル基であり、水酸基
含有量が９．４重量％、エトキシ基含有量が２５重量
％、かつ両者のモル比が１：１で数平均分子量ＭN が４
００のラダー型シリコーンオリゴマー１３重量部をエタ
ノールとブタノールの混合溶剤（重量比１：１）８７重
量部に溶解して塗布液を得た。上記塗布液を実施例１と
同様にコートし、硬化後諸物性を測定した。結果を表１
に示す。Comparative Example 1 R in the general formula (I)
1 is a methyl group, R 2 is hydrogen and an ethyl group, the hydroxyl group content is 9.4% by weight, the ethoxy group content is 25% by weight, and the molar ratio of both is 1: 1 and the number average molecular weight M N is Four
13 parts by weight of the ladder type silicone oligomer of 00 was dissolved in 87 parts by weight of a mixed solvent of ethanol and butanol (weight ratio 1: 1) to obtain a coating solution. The above coating solution was coated in the same manner as in Example 1 and various physical properties were measured after curing. The results are shown in Table 1.
Shown in.
【００３６】（比較例２）前記一般式（Ｉ）においてＲ
1 がメチル基、Ｒ2 が水素及びエチル基であり、水酸基
含有量が０．２重量％、エトキシ基含有量が０．６重量
％、かつ両者のモル比が１：１で数平均分子量が１４０
００のラダー型シリコーンオリゴマー１３重量部をエタ
ノールとブタノールの混合溶剤（重量比１：１）８７重
量部に溶解して塗布液を得た。上記塗布液を実施例１と
同様にコートし、硬化後諸物性を測定した。結果を表１
に示す。Comparative Example 2 R in the general formula (I)
1 is a methyl group, R 2 is hydrogen and an ethyl group, the hydroxyl group content is 0.2% by weight, the ethoxy group content is 0.6% by weight, and the molar ratio of both is 1: 1 and the number average molecular weight is 140
13 parts by weight of the ladder type silicone oligomer of No. 00 was dissolved in 87 parts by weight of a mixed solvent of ethanol and butanol (weight ratio 1: 1) to obtain a coating solution. The above coating solution was coated in the same manner as in Example 1 and various physical properties were measured after curing. The results are shown in Table 1.
Shown in.
【００３７】（比較例３）前記一般式（Ｉ）においてＲ
1 がメチル基、Ｒ2 が水素及びエチル基であり、水酸基
含有量が３．９重量％、エトキシ基含有量が１．０重量
％、かつ両者のモル比が１：０．１で、数平均分子量が
２４００のラダー型シリコーンオリゴマー１３重量部を
エタノールとブタノールの混合溶剤（重量比１：１）８
７重量部に溶解して塗布液を得た。上記塗布液を実施例
１と同様にコートし、硬化後諸物性を測定した。結果を
表１に示す。(Comparative Example 3) In the general formula (I), R
1 is a methyl group, R 2 is hydrogen and an ethyl group, the hydroxyl group content is 3.9% by weight, the ethoxy group content is 1.0% by weight, and the molar ratio of the two is 1: 0.1. 13 parts by weight of a ladder type silicone oligomer having an average molecular weight of 2400 was mixed with a mixed solvent of ethanol and butanol (weight ratio 1: 1) 8
It was dissolved in 7 parts by weight to obtain a coating solution. The above coating solution was coated in the same manner as in Example 1 and various physical properties were measured after curing. The results are shown in Table 1.
【００３８】（比較例４）前記一般式（Ｉ）においてＲ
1 がメチル基、Ｒ2 が水素及びエチル基であり、水酸基
含有量が０．６重量％、エトキシ基含有量が４．３重量
％、かつ両者のモル比が１：２．５で、数平均分子量が
２８００のラダー型シリコーンオリゴマー１３重量部を
エタノールとブタノールの混合溶剤（重量比１：１）８
７重量部に溶解して塗布液を得た。上記塗布液を実施例
１と同様にコートし、硬化後諸物性を測定した。結果を
表１に示す。Comparative Example 4 R in the general formula (I)
1 is a methyl group, R 2 is hydrogen and an ethyl group, the hydroxyl group content is 0.6% by weight, the ethoxy group content is 4.3% by weight, and the molar ratio of the two is 1: 2.5. 13 parts by weight of a ladder-type silicone oligomer having an average molecular weight of 2800 was mixed with ethanol and butanol (weight ratio 1: 1) 8
It was dissolved in 7 parts by weight to obtain a coating liquid. The above coating solution was coated in the same manner as in Example 1 and various physical properties were measured after curing. The results are shown in Table 1.
【００３９】（比較例５）メチルトリヒドロキシシラン
１４重量部をメタノール８６重量部中に溶解した塗布液
を用いて実施例１と同様にコートし４００℃にて硬化後
諸物性を測定した。結果を表１に示す。Comparative Example 5 A coating solution prepared by dissolving 14 parts by weight of methyltrihydroxysilane in 86 parts by weight of methanol was coated in the same manner as in Example 1 and cured at 400 ° C., and various physical properties were measured. The results are shown in Table 1.
【００４０】（比較例６）テトラヒドロキシシラン６重
量部をエタノールと酢酸エチルの混合溶剤（重量比８：
２）９４重量部に溶解した塗布液を実施例１と同様に膜
厚２０００Åコートし、４００℃にて硬化後諸物性を測
定した。結果を表１に示す。(Comparative Example 6) 6 parts by weight of tetrahydroxysilane was mixed with a mixed solvent of ethanol and ethyl acetate (weight ratio: 8:
2) A coating solution dissolved in 94 parts by weight was coated in a film thickness of 2000Å in the same manner as in Example 1, and various physical properties were measured after curing at 400 ° C. The results are shown in Table 1.
【００４１】[0041]
【表１】 [Table 1]
【００４２】[0042]
【発明の効果】本発明の有機ＳＯＧにおいては、末端基
の縮合反応性が従来のものに比較して大幅に改良されて
おり、また分子量も従来に比較してオリゴマーからポリ
マー領域のものを採用している。INDUSTRIAL APPLICABILITY In the organic SOG of the present invention, the condensation reactivity of the terminal group is greatly improved as compared with the conventional one, and the molecular weight of the oligomer to polymer region is adopted as compared with the conventional one. is doing.
【００４３】このため液の保存安定性は良好である一
方、加熱硬化時の温度も比較的低い温度で行うことがで
き、またこのときの硬化収縮も従来知られている有機Ｓ
ＯＧよりずっと小さい。Therefore, while the storage stability of the liquid is good, the temperature at the time of heat curing can be performed at a relatively low temperature, and the curing shrinkage at this time is also known as organic S.
Much smaller than OG.
【００４４】また硬化反応の完結度も高く、高温加熱時
の収縮が小さく、発生ガスを少なくまた吸湿性も低い。Further, the degree of completion of the curing reaction is high, the shrinkage upon heating at high temperature is small, the generated gas is small, and the hygroscopicity is low.
【００４５】本発明の有機ＳＯＧは平坦化能力、絶縁性
にも優れており、上述の特性と合わせて半導体用絶縁
膜、平坦化膜として適している。The organic SOG of the present invention is excellent in flattening ability and insulating property, and is suitable as an insulating film for semiconductors and a flattening film in combination with the above characteristics.
【００４６】また本発明の有機ＳＯＧは金属、セラミッ
クス、プラスチックスなどの多様な基材表面にコーティ
ングし、特徴ある表面特性を付与するために用いること
もできる。The organic SOG of the present invention can also be used for coating various substrate surfaces such as metals, ceramics, and plastics to impart characteristic surface characteristics.
Claims (3)
５００〜１０，０００であり、末端基として水酸基を
０．３〜６重量％と、アルコキシ基を０．９〜１６重量
％、かつ両者のモル比が１：０．２〜２．０の範囲に含
有しているポリオルガノシルセスキオキサンを加熱キュ
アしたことを特徴とする半導体用絶縁膜または平坦化
膜。 【化１】 （一般式（Ｉ）においてＲ1 はメチル基またはフェニル
基、Ｒ2 は炭素数１〜３のアルキル基または水素原子を
示し、ｎは分子量に対応する正の数であり、分散を伴う
集合体を示す。）1. The number average molecular weight represented by the general formula (I) is 500 to 10,000, a hydroxyl group as an end group is 0.3 to 6% by weight, an alkoxy group is 0.9 to 16% by weight, An insulating film for a semiconductor or a flattening film, which is obtained by heat-curing polyorganosilsesquioxane containing both of them in a molar ratio of 1: 0.2 to 2.0. [Chemical 1] (In the general formula (I), R 1 represents a methyl group or a phenyl group, R 2 represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, and n is a positive number corresponding to the molecular weight, and an aggregate accompanied by dispersion. Indicates.)
またはフェニル基であり、全体としてのメチル基含有量
が８０モル％以上である請求項１記載の半導体用絶縁膜
または平坦化膜。2. The insulating film for a semiconductor or the planarization film according to claim 1, wherein in the general formula (I), R 1 is a methyl group or a phenyl group, and the total methyl group content is 80 mol% or more. ..
ロキサンを有機溶剤に溶解し、デバイス基板の配線上に
コーティングし、加熱キュアすることを特徴とする請求
項１記載の半導体絶縁膜または平坦化膜を形成する方
法。3. The semiconductor insulating film or flat surface according to claim 1, wherein the polyorganosiloxane represented by the general formula (I) is dissolved in an organic solvent, coated on the wiring of the device substrate, and cured by heating. Method for forming a chemical film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3235388A JP2997105B2 (en) | 1991-08-21 | 1991-08-21 | Insulating films for semiconductors and methods for forming them |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3235388A JP2997105B2 (en) | 1991-08-21 | 1991-08-21 | Insulating films for semiconductors and methods for forming them |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0555201A true JPH0555201A (en) | 1993-03-05 |
| JP2997105B2 JP2997105B2 (en) | 2000-01-11 |
Family
ID=16985346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3235388A Expired - Fee Related JP2997105B2 (en) | 1991-08-21 | 1991-08-21 | Insulating films for semiconductors and methods for forming them |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2997105B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001060880A3 (en) * | 2000-02-17 | 2001-12-27 | Lee Eung Chan | Polyorganosilsesquioxane and process for preparing the same |
| CN109111151A (en) * | 2018-09-12 | 2019-01-01 | 中国建材检验认证集团厦门宏业有限公司 | A kind of cement self-leveling agent and preparation method thereof |
-
1991
- 1991-08-21 JP JP3235388A patent/JP2997105B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001060880A3 (en) * | 2000-02-17 | 2001-12-27 | Lee Eung Chan | Polyorganosilsesquioxane and process for preparing the same |
| WO2001060881A3 (en) * | 2000-02-17 | 2002-01-17 | Lee Eung Chan | Polyorganosilsesquioxane and process for preparing the same |
| US6774202B2 (en) | 2000-02-17 | 2004-08-10 | Intersilicone, Ltd. | Polyorganosilsesquioxane and process for preparing the same |
| US6787625B2 (en) | 2000-02-17 | 2004-09-07 | Intersilicone Ltd. | Polyorganosilsesquioxane and process for preparing the same |
| CN109111151A (en) * | 2018-09-12 | 2019-01-01 | 中国建材检验认证集团厦门宏业有限公司 | A kind of cement self-leveling agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2997105B2 (en) | 2000-01-11 |
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