JPS60245138A - Forming method of silicon oxide film - Google Patents
Forming method of silicon oxide filmInfo
- Publication number
- JPS60245138A JPS60245138A JP59100997A JP10099784A JPS60245138A JP S60245138 A JPS60245138 A JP S60245138A JP 59100997 A JP59100997 A JP 59100997A JP 10099784 A JP10099784 A JP 10099784A JP S60245138 A JPS60245138 A JP S60245138A
- Authority
- JP
- Japan
- Prior art keywords
- oxide film
- film
- silicon oxide
- resin
- forming
- 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.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
- H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 ２ ベー。[Detailed description of the invention] Industrial applications 2 Bae.
本発明は、シリコン酸化膜の形成方法に関するもので、
より詳しくは、シリコン樹脂を光化学反応により分解し
、酸化し直接シリコン酸化膜に変換するもので、半導体
装置の絶縁膜、保護膜および多層配線の層間絶縁膜など
に使用されているシリコン酸化膜の形成方法を提供する
ものである。The present invention relates to a method for forming a silicon oxide film,
More specifically, it decomposes silicon resin through a photochemical reaction, oxidizes it, and directly converts it into a silicon oxide film. A forming method is provided.
従来例の構成とその問題点
従来のシリコン酸化膜（以下酸化膜）形成方法としては
、■シリコン基板を高温酸化雰囲気中で酸化する方法（
基板の変質による膜形成法）、■シランガス等と酸化性
ガスの混合気体を熱、光、プラズマ等で化学反応をおこ
させ膜を形成する方法（基板への堆積による膜形成）、
■樹脂を塗布し熱処理により酸化する方法（変質による
膜形成）などが挙げられる。Structure of conventional example and its problems Conventional methods for forming silicon oxide films (hereinafter referred to as oxide films) include: ■ A method of oxidizing a silicon substrate in a high-temperature oxidizing atmosphere (
(Film formation method by altering the quality of the substrate), ■Method of forming a film by causing a chemical reaction with a mixture of silane gas, etc. and oxidizing gas using heat, light, plasma, etc. (Film formation by deposition on the substrate),
■Method of applying resin and oxidizing it by heat treatment (film formation by alteration).
本発明は、前述の■に係わるもので、その従来例として
は以下の二つがある。The present invention relates to the above-mentioned item (1), and there are the following two conventional examples thereof.
（１） オルガノシロキサン樹脂またはシリコン樹脂に
エネルギー線を照射し、現像しパターン形成後に、加熱
し樹脂を酸化硬化する方法（特開３ハ、。(1) A method in which organosiloxane resin or silicone resin is irradiated with energy rays, developed to form a pattern, and then heated to oxidize and harden the resin (JP-A-3-C).
昭５７−５９３５８号）。No. 57-59358).
（ＩＩ） ジメチルンロキザン重合体（シリコンオイル
）にＡｒＦレーザーを照射し酸化膜を形成する方法（応
用物理学会予稿・１９８４春・１Ｐ−に−５）
このような従来技術においては、次の問題点を有してい
る。（Ｔ）の技術においては、エネルギー線を照射し現
像を行なうため、現像液によるクラックが発生する。そ
のため、膜厚を１．２μｍ以」−に形成することは困難
である。さらに、パターン形成後の加熱硬化時に体積収
縮によるクラックか発生する。(II) A method of forming an oxide film by irradiating dimethylronoxane polymer (silicon oil) with ArF laser (Proceedings of Japan Society of Applied Physics, Spring 1984, 1P-5) In such conventional technology, the following problem is solved. It has points. In the technique (T), since development is performed by irradiating energy rays, cracks occur due to the developer. Therefore, it is difficult to form a film with a thickness of 1.2 μm or more. Furthermore, cracks occur due to volume shrinkage during heat curing after pattern formation.
（ｎ）の技術においては、（Ｉ）の技術の欠点はないが
シリコンオイルを用いることは、オイル状であるため、
ＡｒＦレーザー光による部分加熱により一部気化蒸発し
、膜ベリの原因となる。さらに、その流動性のため、塗
布膜厚を均一に保つことが困難となる。Although the technology (n) does not have the drawbacks of the technology (I), the use of silicone oil is oil-like, so
Due to partial heating by the ArF laser beam, a portion of the film evaporates and evaporates, causing film burrs. Furthermore, its fluidity makes it difficult to maintain a uniform coating thickness.
発明の目的
本発明は、前述の技術課題を解決するためになされたも
ので、半導体装置の絶縁膜や保護膜として有用な酸化膜
を均一性良く、安定に形成する方法を提供することを目
的とするものである。Purpose of the Invention The present invention has been made in order to solve the above-mentioned technical problems, and its purpose is to provide a method for stably forming an oxide film with good uniformity, which is useful as an insulating film or a protective film for semiconductor devices. That is.
発明の構成
本発明はシリコン樹脂（高分子量のシリコン化合物）を
溶媒に溶解し基板に塗布し、加熱し溶媒を除去する。そ
の後に、シリコン樹脂を酸化性雰囲気中で、たとえば５
ｉ−Ｃの結合を分解するエネルギーを持つ波長の光を選
択的に照射し、結合を切断する。結合切断後、酸化性雰
囲気により、Ｓｉ の酸化を進行させる。Structure of the Invention In the present invention, silicone resin (high molecular weight silicon compound) is dissolved in a solvent, applied to a substrate, and heated to remove the solvent. Thereafter, the silicone resin is heated in an oxidizing atmosphere, for example,
Selective irradiation with light having a wavelength that has the energy to break down the i-C bond breaks the bond. After bond cleavage, Si 2 is oxidized in an oxidizing atmosphere.
実施例の説明
捷ず、この技術的背景を詳しく説明する。結合エネルギ
ー以上の光子エネルギーをもつ波長の光を結合に照射す
れば、結合が切断する。この時の波長の選択としては、
切断したい結合と、のこしたい結合および生成物の結合
の中間のエネルギーをもつ波長の光が良い。具体的には
、シリコン樹脂がＳ ＩＣＨ３の基を有する場合を説明
する。The technical background will be explained in detail without giving details of the embodiments. If a bond is irradiated with light of a wavelength that has a photon energy greater than the bond energy, the bond will be broken. At this time, the wavelength selection is as follows:
It is best to use light with a wavelength that is intermediate in energy between the bond you want to break, the bond you want to preserve, and the product bond. Specifically, a case where the silicone resin has a SICH3 group will be explained.
５ｔ−００結合エネルギーは１９１１ｅａｌ ／ｍｏｌ
で有６ベー／
す、５ｔ−Ｃのそれは１ｏ４１ａＩＩ／ｍＯ１で有り、
Ｃ−Ｈのそれは８１７ ／１ｎｏｌである。この時、Ｓ
ｌ−〇と５ｔ−Ｃの中間の光子エネルギーを持つ波長の
光により容易に分解がおこる。この反応によりメチル基
がＳｉより解離し、５ｉ−ｏの結合はのこる。この時に
この反応を酸化性雰囲気下で行なうことによりＳｉが酸
化され、酸化膜として形成される。5t-00 binding energy is 1911eal/mol
That of 5t-C is 1o41aII/mO1,
That of C-H is 817/1nol. At this time, S
Decomposition occurs easily with light having a wavelength of photon energy between l-0 and 5t-C. This reaction causes the methyl group to dissociate from Si, leaving the 5i-o bond. At this time, by performing this reaction in an oxidizing atmosphere, Si is oxidized and an oxide film is formed.
酸化を促進する一例として、酸素の場合を考えると、酸
素の結合エネルギー以上の有する波長の光を併用するこ
とはさらに有効となる。次式に示０２→ Ｏ・ ＋Ｏ・
（１８４，９ｎｍ）す過程を経て、生成される酸素ラ
ジカルが酸化膜形成に有効に作用する。本発明の化学反
応過程の一例を次式に示す
Ｈ３
６・、−７
この技術において、シリコン樹脂を用いることは基板塗
布時の平坦性をにげるとともに、溶媒除去後は流動性が
ないため、均一に膜を形成することが可能となる。この
シリコン樹脂は、ラダーシリコン捷たは、オルガノシロ
キザン樹脂が反応性。Considering the case of oxygen as an example of promoting oxidation, it is even more effective to use light having a wavelength higher than the binding energy of oxygen. The following formula shows 02→ O・ +O・
(184,9 nm) The oxygen radicals generated effectively act on the formation of an oxide film. An example of the chemical reaction process of the present invention is shown by the following formula: It becomes possible to form a film on This silicone resin is reactive with ladder silicone resin or organosiloxane resin.
塗布時の膜性能から特に有効である。It is particularly effective in terms of film performance during coating.
さらに、この技術を用いて得られる膜は、光照射部は酸
化膜に変質しており、光来照射部はシリコン樹脂そのま
まである。従って、現像時に現像液に対する溶解性が、
まったく異るため、形成膜に現像液による悪影響（クラ
ック発生など）は生じない。腫だ光のみで直接酸化膜化
をはかるため、熱処理をする必要がなく工程が簡略であ
る。Furthermore, in the film obtained using this technique, the light irradiated area is transformed into an oxide film, and the light irradiated area remains as silicone resin. Therefore, the solubility in the developer during development is
Since they are completely different, the developing solution does not have any adverse effects (such as cracking) on the formed film. Since the oxidation film is directly formed using only flashlight, there is no need for heat treatment and the process is simple.
本発明の一実施例を第１図〜第４図を用いて説明する。An embodiment of the present invention will be described using FIGS. 1 to 4.
第１図において、シリコン半導体等の基板１上に厚さ約
２．０μｍのラダーシリコン（ＪＳＲ製）層２が形成さ
れている。これは、ラダーシリコンの酢酸ノルマルブチ
ル溶液を塗布し、乾燥することにより得られる。In FIG. 1, a ladder silicon (manufactured by JSR) layer 2 having a thickness of approximately 2.0 μm is formed on a substrate 1 made of silicon semiconductor or the like. This is obtained by applying a n-butyl acetate solution of ladder silicon and drying it.
次に、第２図に示す様に、ＡｒＦエキシマレ−ザ７１＼
−２
−３を空気中で選択的に照射した。選択照射部分に、第
３図に示すごとく、シリコン酸化膜部分４が形成される
。その後、酸化膜部分４以外を現像液酢酸ノルマルブチ
ルで除去し、第４図に示すごとく、酸化膜４のパターン
を形成した。形成した酸化膜は、膜厚２μｍ以上でも、
クラフクの発生がなく緻密な膜が形成されることがわか
った。Next, as shown in Fig. 2, the ArF excimer laser 71\
-2 -3 was selectively irradiated in air. As shown in FIG. 3, a silicon oxide film portion 4 is formed in the selectively irradiated portion. Thereafter, the portion other than the oxide film portion 4 was removed using a developer solution, n-butyl acetate, to form a pattern of the oxide film 4 as shown in FIG. Even if the formed oxide film has a thickness of 2 μm or more,
It was found that a dense film was formed without the occurrence of cracks.
発明の効果
本発明で得られる酸化膜は、熱反応で得られる膜と比較
して、緻密であるとともに、形成方法において、シリコ
ン樹脂パターン形成と同時に酸化膜化が可能であること
から工程の簡略化がはかれる。本発明は半導体装置の保
護膜、絶縁膜および多層配線の層間絶縁膜に有用である
だけでなく、従来からシリコン酸化膜を用いている電子
デバイス（たとえば、化合物半導体や液晶配向膜なと）
にも同様に有効である。Effects of the Invention The oxide film obtained by the present invention is denser than the film obtained by thermal reaction, and the process is simplified because the oxide film can be formed at the same time as the silicone resin pattern is formed. The transformation is measured. The present invention is useful not only for protective films, insulating films, and interlayer insulating films for multilayer interconnects in semiconductor devices, but also for electronic devices that have conventionally used silicon oxide films (for example, compound semiconductors and liquid crystal alignment films).
It is equally valid for
第１図〜第４図は、本発明の一実施例のシリコン酸化膜
を形成する工程の断面説明図である。
１・・・・・・基板、２・・・・・・シリコン樹脂膜、
３・・・・・エキシマレーザー光、４・・・・・・シリ
コン酸化膜。
代理人の氏名 弁理士 中 尾 敏 男 はが１名第１
図
第４図
ト
ぺ1 to 4 are cross-sectional explanatory views of the process of forming a silicon oxide film according to an embodiment of the present invention. 1...Substrate, 2...Silicon resin film,
3...Excimer laser light, 4...Silicon oxide film. Name of agent: Patent attorney Toshio Nakao (1st person)
Figure 4 Tope
Claims (4)
に際し、酸化性雰囲気中で、光照射によりシリコン樹脂
を酸化することを特徴とするシリコン酸化ｉ匍成方法。(1) A method for forming a silicon oxide film, which is characterized in that when forming a silicon oxide film from a silicon resin, the silicon resin is oxidized by light irradiation in an oxidizing atmosphere.
ガノシロキサン樹脂であることを特徴とする特許請求の
範囲第１項記載のシリコン酸化膜の形成方法。(2) The method for forming a silicon oxide film according to claim 1, wherein the silicone resin is ladder silicon or organosiloxane resin.
特許請求の範囲第１項記載のシリコン酸化膜の形成方法
。(3) The method for forming a silicon oxide film according to claim 1, wherein the light has two or more wavelengths.
択的に照射することを特徴とする特許請求の範囲第１項
記載のシリコン酸化膜の形成方法。(4) The method for forming a silicon oxide film according to claim 1, characterized in that light of a wavelength effective for activating the oxidizing atmosphere is selectively irradiated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59100997A JPS60245138A (en) | 1984-05-18 | 1984-05-18 | Forming method of silicon oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59100997A JPS60245138A (en) | 1984-05-18 | 1984-05-18 | Forming method of silicon oxide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60245138A true JPS60245138A (en) | 1985-12-04 |
Family
ID=14288934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59100997A Pending JPS60245138A (en) | 1984-05-18 | 1984-05-18 | Forming method of silicon oxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60245138A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6310527A (en) * | 1986-07-02 | 1988-01-18 | Hitachi Ltd | Manufacture of semiconductor device |
| WO2004102274A3 (en) * | 2003-05-12 | 2005-09-09 | Micron Technology Inc | Use of spin-on, photopatternable, interplayer dielectric materials and intermediate semiconductor device structure utilizing the same |
-
1984
- 1984-05-18 JP JP59100997A patent/JPS60245138A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6310527A (en) * | 1986-07-02 | 1988-01-18 | Hitachi Ltd | Manufacture of semiconductor device |
| WO2004102274A3 (en) * | 2003-05-12 | 2005-09-09 | Micron Technology Inc | Use of spin-on, photopatternable, interplayer dielectric materials and intermediate semiconductor device structure utilizing the same |
| US8486612B2 (en) | 2003-05-12 | 2013-07-16 | Micron Technology, Inc. | Methods of forming intermediate semiconductor device structures using spin-on, photopatternable, interlayer dielectric materials |
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