JPH09289205A - Org. insulation film material and forming method thereof - Google Patents
Org. insulation film material and forming method thereofInfo
- Publication number
- JPH09289205A JPH09289205A JP10103196A JP10103196A JPH09289205A JP H09289205 A JPH09289205 A JP H09289205A JP 10103196 A JP10103196 A JP 10103196A JP 10103196 A JP10103196 A JP 10103196A JP H09289205 A JPH09289205 A JP H09289205A
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- Prior art keywords
- insulating film
- org
- organic insulating
- film material
- insulation film
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- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、半導体装置などの
製造プロセスに用いられる有機絶縁膜材料及びその形成
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 an organic insulating film material used in a manufacturing process of semiconductor devices and the like and a method for forming the same.
【０００２】[0002]
【従来の技術】従来、このような分野の技術としては、
例えば、文献名：ＤＵＭＩＣ Ｃｏｎｆｅｒｅｎｃｅ，
Ｆｅｂｒｕａｒｙ ２１−２２，１９９５，ｐ．２８３
に開示されるものがあった。半導体装置の製造におい
て、絶縁膜としてシリコン酸化膜が用いられている。一
般的にシリコン酸化膜はＣＶＤ法で形成される。2. Description of the Related Art Conventionally, techniques in such a field include:
For example, literature name: DUMIC Conference,
February 21-22, 1995, p. 283
Was disclosed. In manufacturing a semiconductor device, a silicon oxide film is used as an insulating film. Generally, the silicon oxide film is formed by the CVD method.
【０００３】一方、今後、パターンサイズの微細化に伴
い、配線による信号遅延と電力消費が顕著となることが
予想される。信号遅延は通常ＲＣ（Ｒ；配線抵抗、Ｃ；
配線間容量）で表わされ、特に、サブクォーターミクロ
ン級では配線間容量が大きくなるため、信号遅延に多大
な影響を及ぼす。この配線間容量は絶縁膜の比誘電率に
より決定されるため、比誘電率の低下は信号遅延の防止
に効果的である。On the other hand, it is expected that signal delay due to wiring and power consumption will become remarkable as the pattern size becomes finer in the future. Signal delay is usually RC (R; wiring resistance, C;
The capacitance between wirings is large, and particularly in the sub-quarter micron class, the capacitance between wirings is large, which has a great influence on the signal delay. Since the inter-wiring capacitance is determined by the relative permittivity of the insulating film, the reduction of the relative permittivity is effective in preventing signal delay.
【０００４】また、電力消費も配線間容量で規定される
ため、同様に低減できる。そのため、絶縁膜の低誘電率
化が必要となる。誘電率の低減のためには、有機膜の利
用が有効である。また、その利用には新規なプロセスが
必要である。例えば、上記文献（ＤＵＭＩＣ Ｃｏｎｆ
ｅｒｅｎｃｅ，Ｆｅｂｒｕａｒｙ２１−２２，１９９
５，ｐ．２８３）においては、フロロ化ポリ（アリール
エーテル）を用いて、比誘電率２．６の有機絶縁膜を得
ている。Further, since the power consumption is regulated by the capacitance between wirings, it can be reduced similarly. Therefore, it is necessary to reduce the dielectric constant of the insulating film. The use of an organic film is effective for reducing the dielectric constant. Moreover, a new process is required for its use. For example, the above-mentioned document (DUMIC Conf
erence, February 21-22, 199
5, p. 283), an organic insulating film having a relative dielectric constant of 2.6 is obtained by using fluoropoly (aryl ether).
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記文
献の有機絶縁膜の比誘電率は未だ高く、さらに比誘電率
を低減する必要がある。一般的には比誘電率を下げるた
めにはフッ素の導入が有効である。また、比誘電率を上
げる要因としては共有結合が上げられる。ただし、ポリ
マーに耐熱性を付与するためには共有結合を有する芳香
環は必須である。これらのことより、共有結合の小さ
い、かつフッ素の置換されたポリマー〔−（Ｓｉ（ＣＦ
3 ）2 −Ｐｈ）ｎ−〕を設計し、合成、評価を行った。However, the relative dielectric constant of the organic insulating film of the above document is still high, and it is necessary to further reduce the relative dielectric constant. Generally, the introduction of fluorine is effective for lowering the relative dielectric constant. Further, covalent bond is raised as a factor for increasing the relative dielectric constant. However, an aromatic ring having a covalent bond is essential to impart heat resistance to the polymer. From these facts, a polymer having a small covalent bond and substituted with fluorine [-(Si (CF
3 ) 2- Ph) n-] was designed, synthesized, and evaluated.
【０００６】本発明は、上記状況に鑑みて、比誘電率を
低減可能な有機絶縁膜材料及びその形成方法を提供する
ことを目的とする。In view of the above situation, it is an object of the present invention to provide an organic insulating film material capable of reducing the relative dielectric constant and a method for forming the same.
【０００７】[0007]
【課題を解決するための手段】本発明は上記目的を達成
するために、 〔１〕有機絶縁膜材料において、主鎖中にケイ素−芳香
環結合を有し、ポリマー中にフッ素を含むことを特徴と
する。 〔２〕下記に示される構造を有することを特徴とする有
機絶縁膜材料。In order to achieve the above object, the present invention relates to [1] an organic insulating film material, which has a silicon-aromatic ring bond in the main chain and contains fluorine in the polymer. Characterize. [2] An organic insulating film material having the structure shown below.
【０００８】−ＳｉＲ1 Ｒ2 Ａｒ− ただし、式中Ｒ1 、Ｒ2 はフッ素、アルキル基、フロロ
アルキル基を表し、同一でも異なっていてもよい。Ａｒ
は置換、無置換の芳香環誘導基を表わす。 〔３〕上記〔１〕又は〔２〕記載の有機絶縁膜材料を用
い、塗布、加熱により有機絶縁膜を形成することを特徴
とする。-SiR 1 R 2 Ar-However, in the formula, R 1 and R 2 represent fluorine, an alkyl group or a fluoroalkyl group, and may be the same or different. Ar
Represents a substituted or unsubstituted aromatic ring derivative group. [3] The organic insulating film material according to the above [1] or [2] is used to form an organic insulating film by coating and heating.
【０００９】上記した有機絶縁膜材料によれば、従来の
有機絶縁膜材料に比して、誘電率の低減を図ることがで
きる。また、簡単な工程により、有機絶縁膜を形成する
ことができる。According to the above-mentioned organic insulating film material, the dielectric constant can be reduced as compared with the conventional organic insulating film material. Further, the organic insulating film can be formed by a simple process.
【００１０】[0010]
【発明の実施の形態】以下、本発明の実施の形態につい
て説明する。なお、以下の説明に述べる使用材料、およ
びその量、プロセス条件（処理時間、温度、その他）に
ついては一例を示したものに過ぎない。従って、以下の
発明がこれらの条件にのみ限定されるものではない。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. The materials used, their amounts, and process conditions (processing time, temperature, etc.) described below are merely examples. Therefore, the following invention is not limited only to these conditions.
【００１１】〔樹脂の合成〕以下、樹脂の合成について
説明する。まず、ジカルボキシジクロロシラン３７８ｇ
（２ｍｏｌ）〔化学式（１）〕とＭｏＦ6 ５１６ｇ
（３．０ｍｏｌ）を、１０００ｍｌのトルエン溶液中に
攪拌した。[Synthesis of Resin] The synthesis of resin will be described below. First, dicarboxydichlorosilane 378g
(2 mol) [chemical formula (1)] and MoF 6 516 g
(3.0 mol) was stirred in 1000 ml of toluene solution.
【００１２】[0012]
【化１】 Embedded image
【００１３】その後、還流温度まで加熱し、２０時間反
応させた。その後、溶液を濾過し、溶媒を留去し、３４
０ｇ（収率７２％）のビストリフロロメチルジクロロシ
ラン〔化学式（２）〕を得た。Then, the mixture was heated to the reflux temperature and reacted for 20 hours. Then the solution is filtered and the solvent is distilled off,
0 g (yield 72%) of bistrifluoromethyldichlorosilane [chemical formula (2)] was obtained.
【００１４】[0014]
【化２】 Embedded image
【００１５】次いで、ｐ−ジクロロベンゼン１４７ｇ
（１ｍｏｌ）〔化学式（３）〕とマグネシウム２７ｇ
（０．５ｍｏｌ）を３００ｍｌのＴＨＦ溶液に溶解さ
せ、攪拌した。Then, 147 g of p-dichlorobenzene
(1 mol) [chemical formula (3)] and magnesium 27 g
(0.5 mol) was dissolved in 300 ml of THF solution and stirred.
【００１６】[0016]
【化３】 Embedded image
【００１７】この溶液にビストリフロロメチルジクロロ
シラン２６１ｇ（１．１ｍｏｌ）のＴＨＦ溶液（２００
ｍｌ）を加えた。反応液を５０℃に熱し、５時間重合さ
せた。その後、溶媒を留去し、トルエンを加えた。溶液
を濾過し、溶媒を留去し、クロロ−ｐ−クロロフェニル
−ビストリフロロメチルシラン７８ｇ（収率２５％）
〔化学式（４）〕を得た。To this solution, a solution of 261 g (1.1 mol) of bistrifluoromethyldichlorosilane in THF (200
ml) was added. The reaction solution was heated to 50 ° C. and polymerized for 5 hours. Then, the solvent was distilled off and toluene was added. The solution was filtered, the solvent was distilled off, and 78 g of chloro-p-chlorophenyl-bistrifluoromethylsilane (yield 25%)
[Chemical formula (4)] was obtained.
【００１８】[0018]
【化４】 Embedded image
【００１９】次いで、クロロ−ｐ−クロロフェニル−ビ
ストリフロロメチルシラン７８ｇ（０．２５ｍｏｌ）を
５００ｍｌのトルエン中で攪拌し、１１．５ｇ（０．５
ｍｏｌ）のナトリウムを加え、１℃／ｍｉｎで徐々に加
熱し、トルエンの還流温度まで上げた。そして、トルエ
ンを還流させながら、９６時間重合させた。反応液を濾
過し、溶液をメタノールに加え、ポリマーを沈澱させ
た。ポリマーをメチルイソブチルケトンに溶解させ、水
で洗浄した。溶媒を留去し、ポリマー〔−（Ｓｉ（ＣＦ
3 ）2 −Ｐｈ）ｎ−〕２８ｇ（収率４６％）〔化学式
（５）〕を得た。Then, 78 g (0.25 mol) of chloro-p-chlorophenyl-bistrifluoromethylsilane was stirred in 500 ml of toluene, and 11.5 g (0.5
mol) of sodium was added, and the mixture was gradually heated at 1 ° C./min to raise the reflux temperature of toluene. Then, polymerization was carried out for 96 hours while refluxing toluene. The reaction solution was filtered, and the solution was added to methanol to precipitate the polymer. The polymer was dissolved in methyl isobutyl ketone and washed with water. The solvent was distilled off, and the polymer [-(Si (CF
3 ) 2- Ph) n-] 28 g (yield 46%) [chemical formula (5)] was obtained.
【００２０】[0020]
【化５】 Embedded image
【００２１】ＧＰＣ（ポリスチレン換算）により平均分
子量を測定したところ、Ｍｗ３２０００、Ｍｗ／Ｍｎ＝
３．７であった。ＩＲスペクトル分析を行ったところ、
７２０ｃｍ-1にＳｉ−Ｐｈ、８５０ｃｍ-1にベンゼン
環、１２５０ｃｍ-1のＣＦ3 、１３００ｃｍ-1のＳｉ−
Ｃのピークにより、所望のポリマーであることを確認し
た。When the average molecular weight was measured by GPC (polystyrene conversion), Mw32000, Mw / Mn =
3.7. When IR spectrum analysis was performed,
Si-Ph in 720 cm -1, the benzene ring to 850 cm -1, CF 3 of 1250 cm -1, 1300 cm -1 of Si-
The peak of C was confirmed to be the desired polymer.
【００２２】このポリマーはトリフロロメチル基（ＣＦ
3 ）を有するために、誘電率を低くすることができ、か
つ耐熱性を付与するための共有結合を芳香環の最小単位
であるフェニル基（Ｐｈ）とすることで誘電率が高くな
ることを防いでいる。 〔膜の形成〕以下、有機絶縁膜の形成方法について説明
する。This polymer has a trifluoromethyl group (CF
3 ), the dielectric constant can be lowered, and the dielectric constant can be increased by using a phenyl group (Ph) which is the minimum unit of the aromatic ring as a covalent bond for imparting heat resistance. It is preventing. [Formation of Film] The method of forming the organic insulating film will be described below.
【００２３】まず、ポリマー１２ｇ（０．０５ｍｏｌ）
を溶剤であるトルエン６８ｇに溶解し、０．２μｍ孔メ
ンブレンフィルターで濾過し、塗布液を調製した。この
溶液をシリコン基板上に膜厚１．０μｍにて回転塗布
し、ホットプレート上で１００℃、２分間のプリベーク
を行った。その後、３００℃で１時間、Ｎ2 中でベーク
を行い、有機絶縁膜を得た。First, 12 g of polymer (0.05 mol)
Was dissolved in 68 g of toluene as a solvent and filtered through a 0.2 μm pore membrane filter to prepare a coating solution. This solution was spin-coated on a silicon substrate to a film thickness of 1.0 μm, and prebaked at 100 ° C. for 2 minutes on a hot plate. After that, baking was performed in N 2 at 300 ° C. for 1 hour to obtain an organic insulating film.
【００２４】この基板にアルミニウム電極をスパッタ法
により形成し、Ｃ−Ｖ曲線を測定した。この有機絶縁膜
の比誘電率は２．４であった。以上のように、上記した
実施例によれば、例えば、従来のフロロ化ポリ（アリー
ルエーテル）を用いた有機絶縁膜（比誘電率２．６）に
比べて、比誘電率の低減が可能となった。An aluminum electrode was formed on this substrate by a sputtering method, and a CV curve was measured. The relative dielectric constant of this organic insulating film was 2.4. As described above, according to the above-described embodiment, it is possible to reduce the relative permittivity as compared with, for example, the conventional organic insulating film (relative permittivity of 2.6) using fluoropoly (aryl ether). became.
【００２５】更に、本発明は以下の利用形態を有する。 （１）すべての実施例における基板としては、配線金
属、例えば、Ｃｕ、Ａｌ、Ｗや酸化膜などを有するもの
の使用が可能である。 （２）すべての実施例における樹脂としては、主鎖中の
フェニル基には置換、無置換の芳香環誘導基の適用が可
能である。Furthermore, the present invention has the following usage forms. (1) As the substrate in all the examples, it is possible to use a wiring metal, for example, one having Cu, Al, W, an oxide film, or the like. (2) As the resin in all the examples, a substituted or unsubstituted aromatic ring derivative group can be applied to the phenyl group in the main chain.
【００２６】（３）すべての実施例における樹脂中のフ
ェニル基の置換基としては、種々のものが適用可能であ
るが、特に、比誘電率を低下させるために、フッ素、お
よびフロロアルキル基の置換の適用が可能である。 （４）すべての実施例における樹脂中のフェニル基の置
換基としては、種々のものが適用可能であるが、架橋可
能な置換基の適用が可能である。(3) Various kinds of substituents can be applied to the phenyl group in the resin in all of the examples. Particularly, in order to reduce the relative dielectric constant, fluorine and fluoroalkyl groups can be used. Substitution can be applied. (4) Various kinds of phenyl group substituents in the resin in all the examples are applicable, and crosslinkable substituents are also applicable.
【００２７】（５）すべての実施例における樹脂として
は、主鎖中のケイ素上にフッ素、アルキル基、フロロア
ルキル基の置換されたものの適用が可能である。 （６）すべての実施例における成膜方法は回転塗布法、
浸漬法、吹き付け法、プレス法などの適用が可能であ
る。 （７）すべての実施例において、成膜後のアニールの適
用が可能である。(5) As the resin in all the examples, it is possible to apply a resin in which silicon in the main chain is substituted with fluorine, an alkyl group or a fluoroalkyl group. (6) The film forming method in all the examples is a spin coating method,
A dipping method, a spraying method, a pressing method or the like can be applied. (7) In all the examples, it is possible to apply annealing after film formation.
【００２８】（８）すべての実施例において、成膜の際
に架橋剤の適用が可能である。なお、本発明は上記実施
例に限定されるものではなく、本発明の趣旨に基づいて
種々の変形が可能であり、これらを本発明の範囲から排
除するものではない。(8) In all the examples, it is possible to apply a crosslinking agent during film formation. It should be noted that the present invention is not limited to the above embodiment, and various modifications can be made based on the gist of the present invention, and these are not excluded from the scope of the present invention.
【００２９】[0029]
【発明の効果】以上、詳細に説明したように、本発明の
有機絶縁膜材料によれば、従来の有機絶縁膜材料に比し
て、誘電率の低減を図ることができる。また、簡単な工
程により、有機絶縁膜を形成することができる。As described above in detail, according to the organic insulating film material of the present invention, the dielectric constant can be reduced as compared with the conventional organic insulating film material. Further, the organic insulating film can be formed by a simple process.
Claims (3)
リマー中にフッ素を含むことを特徴とする有機絶縁膜材
料。1. An organic insulating film material having a silicon-aromatic ring bond in the main chain and containing fluorine in the polymer.
とする有機絶縁膜材料。 −ＳｉＲ1 Ｒ2 Ａｒ− ただし、式中Ｒ1 、Ｒ2 はフッ素、アルキル基、フロロ
アルキル基を表わし、同一でも異なっていてもよい。Ａ
ｒは置換、無置換の芳香環誘導基を表わす。2. An organic insulating film material having the structure shown below. —SiR 1 R 2 Ar— However, in the formula, R 1 and R 2 represent fluorine, an alkyl group or a fluoroalkyl group, and may be the same or different. A
r represents a substituted or unsubstituted aromatic ring-derived group.
用い、塗布、加熱により形成することを特徴とする有機
絶縁膜の形成方法。3. A method of forming an organic insulating film, which comprises forming the organic insulating film material according to claim 1 or 2 by coating and heating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10103196A JPH09289205A (en) | 1996-04-23 | 1996-04-23 | Org. insulation film material and forming method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10103196A JPH09289205A (en) | 1996-04-23 | 1996-04-23 | Org. insulation film material and forming method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09289205A true JPH09289205A (en) | 1997-11-04 |
Family
ID=14289814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10103196A Withdrawn JPH09289205A (en) | 1996-04-23 | 1996-04-23 | Org. insulation film material and forming method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09289205A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100504431B1 (en) * | 1998-12-31 | 2005-09-26 | 주식회사 하이닉스반도체 | Low dielectric film formation method using vapor phase silicification process |
| WO2020171054A1 (en) * | 2019-02-20 | 2020-08-27 | Jsr株式会社 | Method for producing semiconductor substrate and composition for producing semiconductor substrate |
-
1996
- 1996-04-23 JP JP10103196A patent/JPH09289205A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100504431B1 (en) * | 1998-12-31 | 2005-09-26 | 주식회사 하이닉스반도체 | Low dielectric film formation method using vapor phase silicification process |
| WO2020171054A1 (en) * | 2019-02-20 | 2020-08-27 | Jsr株式会社 | Method for producing semiconductor substrate and composition for producing semiconductor substrate |
| JPWO2020171054A1 (en) * | 2019-02-20 | 2021-12-16 | Jsr株式会社 | Semiconductor substrate manufacturing method and semiconductor substrate manufacturing composition |
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