JPH02113525A - Method and apparatus for forming thin film and manufacture of semiconductor device - Google Patents
Method and apparatus for forming thin film and manufacture of semiconductor deviceInfo
- Publication number
- JPH02113525A JPH02113525A JP26618788A JP26618788A JPH02113525A JP H02113525 A JPH02113525 A JP H02113525A JP 26618788 A JP26618788 A JP 26618788A JP 26618788 A JP26618788 A JP 26618788A JP H02113525 A JPH02113525 A JP H02113525A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- substrate
- organic
- forming
- organic functional
- 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
- 239000010409 thin film Substances 0.000 title claims abstract description 83
- 239000004065 semiconductor Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000758 substrate Substances 0.000 claims abstract description 71
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000000524 functional group Chemical group 0.000 claims abstract description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 16
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000004528 spin coating Methods 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000005229 chemical vapour deposition Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 150000003377 silicon compounds Chemical class 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 208000011117 substance-related disease Diseases 0.000 claims 3
- 229910021331 inorganic silicon compound Inorganic materials 0.000 claims 1
- 150000005309 metal halides Chemical class 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 9
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 abstract description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000011368 organic material Substances 0.000 abstract 2
- 239000010408 film Substances 0.000 description 40
- 239000007789 gas Substances 0.000 description 32
- 229910052782 aluminium Inorganic materials 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 13
- 239000011229 interlayer Substances 0.000 description 12
- -1 aluminum Chemical class 0.000 description 11
- 238000000576 coating method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、基板上に薄膜を形成する方法、薄膜を形成す
るための装置、及びこれらを用いた半導体装置の製造方
法に関するものであり、特に、低温で高品質の無機薄膜
を形成するのに好適な方法と装置及び高歩留まり、高信
頼性の半導体装置の製造方法に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method of forming a thin film on a substrate, an apparatus for forming the thin film, and a method of manufacturing a semiconductor device using the same. In particular, the present invention relates to a method and apparatus suitable for forming high-quality inorganic thin films at low temperatures, and a method for manufacturing semiconductor devices with high yield and reliability.
（従来の技術）
従来、低温で無機薄膜を形成する方法として、回転塗布
法や各種のＣＶＤ法、スパッタリング法が用いられてい
た。回転塗布法は、所望の物質を適当な溶媒中に溶解さ
せた溶液を基板上に滴下する工程と、基板を自転させて
溶液を基板上に均一に塗布する工程と、熱処理を加えて
溶液中から溶媒を除去する工程からなる方法であり、ス
ピンオングラス（ＳＯａ）薄膜等の形成に広く用いられ
ている。ＣＶＤ法は、気相中で物質を反応させ、反応生
成物を薄膜として堆積させる方法であり、シリコン酸化
膜やシリコン窒化膜等の絶縁膜やタングステンの選択成
長等に用いられている。スパッタリング法は、薄膜とし
て形成したい物質をイオンで削って所望の物質上に付着
させて薄膜を形成する方法であり、アルミニウム等の金
属薄膜の形成やＣＶＤ法で形成できない物質の薄膜形成
に用いられている。(Prior Art) Conventionally, spin coating methods, various CVD methods, and sputtering methods have been used as methods for forming inorganic thin films at low temperatures. The spin coating method consists of a process in which a solution of a desired substance dissolved in an appropriate solvent is dropped onto a substrate, a process in which the substrate is rotated on its axis to uniformly apply the solution, and a heat treatment is applied to coat the solution in the solution. This method consists of a step of removing the solvent from the substrate, and is widely used for forming spin-on glass (SOa) thin films. The CVD method is a method of reacting substances in a gas phase and depositing a reaction product as a thin film, and is used for selective growth of insulating films such as silicon oxide films and silicon nitride films, and tungsten. The sputtering method is a method of forming a thin film by using ions to scrape the material that you want to form into a thin film and depositing it on the desired material.It is used for forming thin films of metals such as aluminum, and for forming thin films of substances that cannot be formed using the CVD method. ing.
（発明が解決しようとする課題）
回転塗布法を用いると、低温で薄膜形成した場合、薄膜
中に溶媒が残存する。薄膜中に溶媒が残存すると１ｇ膜
形成以降の工程で問題を生じ、製品の歩留まりや信頼性
が低下する。例えば、第１０図に示す半導体装置の第２
層間絶縁膜２０１として。(Problems to be Solved by the Invention) When a spin coating method is used and a thin film is formed at a low temperature, solvent remains in the thin film. If the solvent remains in the thin film, problems will occur in the steps after 1g film formation, and the yield and reliability of the product will decrease. For example, the second part of the semiconductor device shown in FIG.
As an interlayer insulating film 201.
従来の回転塗布法によりシリコン酸化膜を形成すると、
第２層間絶縁膜２０１中に溶媒が残存しているために、
第１アルミ配線ａ （２０２ａ ）と第１アルミ配線ｂ
（２０２ｂ ）の間に漏れ電流が生じる。また、第１
アルミ配線ａ （２０２ａ ）と第２アルミ配線２０３
の間にも漏れ電流が生じる。このような漏れ電流が発生
すると製品は不良となり、製品歩留まりは低下する。ま
た、第２層間絶縁膜２０１中の残存溶媒濃度が高い場合
、第２層間絶縁膜２０１と接している第１アルミ配線２
０２ａ 、 ２０２ｂや第２アルミ配線２０３が腐食す
る。このような配線の腐食は製品の信頼性を低下させる
。２０４はＰ型半導体基板、２０５はフィールド酸化膜
、２０６はゲート酸化膜、２０７はゲート電極、２０８
はｎ型拡散層、２０９は第１層間絶縁膜、２１０はコン
タクトホールであり、２１１はスルーホールである。ま
た、回転塗布法を用いて各種の絶縁膜を形成する場合、
有機官能基を含んだ材料を用いる場合がある。これらの
材料を用いた場合、低温で薄膜を形成すると、有機官能
基が離脱されず膜中に含まれている。この時も、薄膜中
に溶媒が残存する場合と同様に、薄膜形成以後の工程で
問題を生じ、製品の信頼性も低下する。よって、高品質
の無機薄膜を形成するためには、薄ＩＩＩ中の有機物や
有機官能基を除去する必要がある。When a silicon oxide film is formed using the conventional spin coating method,
Because the solvent remains in the second interlayer insulating film 201,
First aluminum wiring a (202a) and first aluminum wiring b
A leakage current occurs between (202b). Also, the first
Aluminum wiring a (202a) and second aluminum wiring 203
Leakage current also occurs between the two. When such leakage current occurs, the product becomes defective and the product yield decreases. In addition, when the concentration of residual solvent in the second interlayer insulating film 201 is high, the first aluminum wiring 2 in contact with the second interlayer insulating film 201
02a, 202b and the second aluminum wiring 203 are corroded. Such wiring corrosion reduces product reliability. 204 is a P-type semiconductor substrate, 205 is a field oxide film, 206 is a gate oxide film, 207 is a gate electrode, 208
209 is an n-type diffusion layer, 209 is a first interlayer insulating film, 210 is a contact hole, and 211 is a through hole. In addition, when forming various insulating films using the spin coating method,
Materials containing organic functional groups may be used. When these materials are used to form a thin film at low temperatures, the organic functional groups are not released and are included in the film. In this case, as in the case where the solvent remains in the thin film, problems occur in the steps after forming the thin film, and the reliability of the product also decreases. Therefore, in order to form a high-quality inorganic thin film, it is necessary to remove organic substances and organic functional groups from Thin III.
高温の熱処理を行うと薄膜中の有機物や有機官能基は除
去可能であるが、高湿の熱処理を行うと膜中にクラック
を生じ、製品の歩留まりが著しく低下する。このため、
薄膜中の有機物や有機官能基を除去する新たな方法が望
まれていた。また１回転塗布法を用いてスピンオングラ
ス（ＳＯＧ）薄膜を形成する場合、従来の方法では膜厚
を厚くすることが困難であった。これは、膜厚が厚くな
ると塗布後の熱処理において膜中にクラックを生じやす
くなるためである。熱処理は溶媒の除去と化学結合の形
成を同時に行っているため１体積収縮と同時に化学結合
の形成をしていることになる。よって、クラックを回避
し、厚膜化を達成するためには、溶媒の除去をした後化
学結合を形成する方法が必要である。High-temperature heat treatment can remove organic substances and organic functional groups in the thin film, but high-humidity heat treatment causes cracks in the film and significantly reduces product yield. For this reason,
A new method for removing organic substances and organic functional groups from thin films has been desired. Furthermore, when forming a spin-on-glass (SOG) thin film using the one-turn coating method, it is difficult to increase the film thickness using conventional methods. This is because as the film thickness increases, cracks are more likely to occur in the film during heat treatment after coating. Since the heat treatment removes the solvent and forms chemical bonds at the same time, it means that the chemical bonds are formed at the same time as one volume shrinks. Therefore, in order to avoid cracks and achieve thicker films, a method of forming chemical bonds after removing the solvent is required.
ＣＶＤ法やスパッタリング法を用いた時にも、′ＯＡ膜
中に有機官能基が含まれている場合がある。Even when CVD or sputtering is used, the OA film may contain organic functional groups.
この場合も回転塗布法の場合と同様に、薄膜中の有機物
や有機官能基を除去する必要がある。高温の熱処理を行
うと薄膜中の有機物や有機官能基は除去可能であるが、
高温の熱処理を行うと薄膜の性質や製造した素子の特性
が変化し、製品の歩留まりが著しく低下する。In this case, as in the case of the spin coating method, it is necessary to remove organic substances and organic functional groups in the thin film. Organic substances and organic functional groups in the thin film can be removed by high-temperature heat treatment, but
When high-temperature heat treatment is performed, the properties of the thin film and the characteristics of the manufactured device change, resulting in a significant drop in product yield.
本発明は、これらの欠点に鑑み種々検討した結果、本発
明を完成するに至ったものである。The present invention was completed as a result of various studies in view of these drawbacks.
（課題を解決するための手段）
本発明は、基板上に有機官能基及び、または有機物を含
む薄膜を形成する工程と、前記基板を超臨界ガスまたは
液化ガスに接触させて前記薄膜中から有機官能基及び、
または有機物を除去する工程を備えてなることを特徴と
する薄膜形成方法と、基板上に溶液を塗布する機構と、
基板を回転させる機構と、基板の温度を制御する機構と
、基板に超臨界ガスまたは液化ガスを接触させる機構を
備えることを特徴とする薄膜形成装置と、半導体基板上
に有機溶媒に溶解したシリコン化合物溶液を回転塗布す
る工程と、前記基板を超臨界ガスまたは液化ガスに接触
させて前記薄膜中から有機溶媒及び、または有機官能基
を除去する工程と、前記基板に熱処理を加える工程を備
えてなることを特徴とする半導体装置の製造方法を提供
するものである。(Means for Solving the Problems) The present invention includes a step of forming a thin film containing an organic functional group and/or an organic substance on a substrate, and a step of bringing the substrate into contact with a supercritical gas or liquefied gas to remove organic matter from the thin film. functional group and
or a method for forming a thin film, the method comprising a step of removing organic matter, and a mechanism for applying a solution onto a substrate;
A thin film forming apparatus comprising a mechanism for rotating a substrate, a mechanism for controlling the temperature of the substrate, and a mechanism for bringing a supercritical gas or liquefied gas into contact with the substrate, and silicon dissolved in an organic solvent on a semiconductor substrate. The method comprises a step of spin-coating a compound solution, a step of bringing the substrate into contact with a supercritical gas or a liquefied gas to remove an organic solvent and/or an organic functional group from the thin film, and a step of applying heat treatment to the substrate. The present invention provides a method for manufacturing a semiconductor device characterized by the following.
（作 用）
有機物質を超臨界ガスまたは液化ガスと接触させると、
有機物質は容易に超臨界ガスまたは液化ガス中に溶解す
る。ここで、液化ガスとは、圧力−温度の状態図におい
て、飽和蒸気圧線以上の圧力状態にあり、大気圧下、常
温ではガス状であるものをいう。超臨界ガスとは、圧力
−温度の状態図において、臨界温度以上、かつ臨界圧力
以上の状態にあるものをいう。一般に、臨界温度は低く
（二酸化炭素：３１℃）、熱処理により有機物質や有機
官能基を除去するよりもはるかに低温で薄膜内の有機物
質や有機官能基を容易に除去することができる。よって
、本発明による方法を用いれば、膜中に不要な有機物や
有機官能基を含まない高品質の無機薄膜を形成すること
ができ、製品の歩留まりや信頼性を飛躍的に増大するこ
とができる。(Function) When organic substances are brought into contact with supercritical gas or liquefied gas,
Organic substances easily dissolve in supercritical or liquefied gases. Here, the liquefied gas refers to a gas that is in a pressure state equal to or higher than the saturated vapor pressure line in a pressure-temperature phase diagram and is gaseous at atmospheric pressure and room temperature. A supercritical gas is a gas that is in a state of a critical temperature or higher and a critical pressure in a pressure-temperature phase diagram. In general, the critical temperature is low (carbon dioxide: 31° C.), and organic substances and organic functional groups within a thin film can be easily removed at a much lower temperature than when organic substances and organic functional groups are removed by heat treatment. Therefore, by using the method according to the present invention, it is possible to form a high-quality inorganic thin film that does not contain unnecessary organic substances or organic functional groups, and it is possible to dramatically increase the yield and reliability of products. .
また、本発明による方法をスピンオングラス（ＳＯＧ）
形成時に用いれば、超臨界ガスまたは液化ガスによる薄
膜中の溶媒除去を行った後熱処理により化学結合を形成
することができるため、クラックの発生を防ぐことがで
き、薄膜の厚膜化を達成することができる。Moreover, the method according to the present invention can be applied to spin-on glass (SOG).
If used during formation, it is possible to form chemical bonds through heat treatment after removing the solvent in the thin film using supercritical gas or liquefied gas, thereby preventing cracks from occurring and achieving thicker thin films. be able to.
また、本発明による装置で薄膜形成や半導体装置の製造
を行うと、回転塗布法における溶液の滴下から溶媒除去
後の熱処理まで全ての工程を一つの装置内で処理できる
ため、高品質の薄膜を迅速に歩留まり高く製造すること
ができる。In addition, when forming thin films and manufacturing semiconductor devices using the apparatus according to the present invention, all steps from dripping the solution in the spin coating method to heat treatment after removing the solvent can be performed in one apparatus, resulting in high-quality thin films. It can be manufactured quickly and with high yield.
（実施例）
本発明の実施例を第１図ないし第９図に基づいて説明す
る。(Example) An example of the present invention will be described based on FIGS. 1 to 9.
実施例１
第１図は、本発明の薄膜形成方法を用いた製造工程の部
分拡大断面図である。同図において、テトラエトキシシ
ラン（Ｓｌ （ＯＣ２Ｈ５） −： Ｔ Ｅ ＯＳ ）
の熱分解反応により、半導体基板１上にシリコン酸化物
の薄膜２を形成する。形成された薄膜２中には、残存の
エトキシ基や、エトキシ基の分解により生じた各種のカ
ルボキシル基が含まれている。半導体基板１をベッセル
３内に設置し、基板温度制御装置４によって温度を５０
〜１００℃に制御する。次に、超臨界状態の二酸化炭素
ガス５を半導体基板１と接触させる。二酸化炭素の圧力
及び温度は、それぞれ７５〜１００気圧、５０〜１００
℃が適当である。Example 1 FIG. 1 is a partially enlarged sectional view of a manufacturing process using the thin film forming method of the present invention. In the same figure, tetraethoxysilane (Sl (OC2H5) -: TEOS)
A thin film 2 of silicon oxide is formed on the semiconductor substrate 1 by the thermal decomposition reaction. The formed thin film 2 contains residual ethoxy groups and various carboxyl groups generated by decomposition of the ethoxy groups. A semiconductor substrate 1 is placed in a vessel 3, and the temperature is set to 50℃ using a substrate temperature control device 4.
Control at ~100°C. Next, carbon dioxide gas 5 in a supercritical state is brought into contact with semiconductor substrate 1 . The pressure and temperature of carbon dioxide are 75 to 100 atmospheres and 50 to 100 atmospheres, respectively.
°C is appropriate.
薄膜２中のエトキシ基やカルボキシル基は、超臨界状態
の二酸化炭素ガス５に溶解し、薄膜２中から離脱される
。このようにして形成した薄膜を用いると、非常に信頼
性の高い半導体装置を製造することができる。The ethoxy groups and carboxyl groups in the thin film 2 are dissolved in the supercritical carbon dioxide gas 5 and released from the thin film 2. By using the thin film formed in this way, a highly reliable semiconductor device can be manufactured.
本実施例においては、薄膜２を形成する方法としてＴＥ
０１の熱分解反応を用いたが、他の有機シリコン化合物
のＣＶＤ法や回転塗布法を用いてもよく、有機金属化合
物、金属ハロゲン化合物のＣＶＤ法を用いてもよい。超
臨界ガスとしては二酸化炭素を用いたが、薄膜２中に含
まれる有機官能基の種類によって他のガスを用いてもよ
い、有機官能基が除去しにくい時は、超臨界ガス中に抽
出助剤を含有させると効果的な場合がある。In this example, TE is used as a method for forming the thin film 2.
Although the thermal decomposition reaction of No. 01 was used, the CVD method or spin coating method of other organosilicon compounds may be used, or the CVD method of organometallic compounds or metal halide compounds may be used. Carbon dioxide was used as the supercritical gas, but other gases may be used depending on the type of organic functional groups contained in the thin film 2. If the organic functional groups are difficult to remove, an extraction aid may be added to the supercritical gas. It may be effective to include agents.
実施例２
第２図は回転塗布法を示す図、第３図は本発明の製造方
法の部分拡大断面図である。第２図において、スピンコ
ータ１０を用いて半導体基板１１上に有機溶剤に溶解し
たシラノール化合物溶液１２を回転塗布し、半導体基板
１１上に薄膜を形成する。第；３図において、半導体基
板１１をベッセル１３内に設置し、基板温度制御装置１
４によって温度を５０〜１００℃に制御する。次に、超
臨界状態の二酸化炭素ガス１５を半導体基板１１と接触
させる。二酸化炭素の圧力及び温度は、それぞれ７５〜
１００気圧、５０〜１００℃が適当である。半導体基板
１１上の薄膜１６内の有機溶剤は、超臨界状態の二酸化
炭素ガス１５中に溶解し、薄膜１６内から除去される。Example 2 FIG. 2 is a diagram showing a spin coating method, and FIG. 3 is a partially enlarged sectional view of the manufacturing method of the present invention. In FIG. 2, a silanol compound solution 12 dissolved in an organic solvent is spin-coated onto a semiconductor substrate 11 using a spin coater 10 to form a thin film on the semiconductor substrate 11. In FIG. 3, the semiconductor substrate 11 is installed in the vessel 13, and the substrate temperature control device 1
4 to control the temperature at 50-100°C. Next, supercritical carbon dioxide gas 15 is brought into contact with semiconductor substrate 11 . The pressure and temperature of carbon dioxide are respectively 75~
A temperature of 100 atm and 50 to 100°C is suitable. The organic solvent in the thin film 16 on the semiconductor substrate 11 is dissolved in the supercritical carbon dioxide gas 15 and removed from the thin film 16 .
次に、基板温度制御装置１４によって半導体基板１１の
温度を４５０℃まで段階的に上昇させる。熱処理条件は
、用いた有機溶剤及び形成する膜の膜厚によって最適な
ものが異なるが、一般に第４図のような時間−温度曲線
が適当と考えられる。この熱処理によりシラノール化合
物の化学結合が形成され、薄膜１６はシリコン酸化膜と
なる。このようにして形成した薄膜を用いると、非常に
信頼性の高い半導体装置を製造することができる。Next, the temperature of the semiconductor substrate 11 is raised stepwise to 450° C. by the substrate temperature control device 14. The optimum heat treatment conditions vary depending on the organic solvent used and the thickness of the film to be formed, but generally a time-temperature curve as shown in FIG. 4 is considered appropriate. Through this heat treatment, chemical bonds of the silanol compounds are formed, and the thin film 16 becomes a silicon oxide film. By using the thin film formed in this way, a highly reliable semiconductor device can be manufactured.
また、本発明による方法を用いると、形成するシリコン
酸化膜厚が厚くなってもクラックを生じにくいため、シ
リコン酸化膜を厚く形成することが可能になる。このよ
うに１回転塗布法によってシリコン酸化膜を厚く形成す
ることができると、金属多層配線を用いた半導体装置を
簡ｊｌ−な製造方法で歩留まり高く製造することができ
る。Further, when the method according to the present invention is used, cracks are less likely to occur even if the silicon oxide film to be formed becomes thicker, so it becomes possible to form a thicker silicon oxide film. If a silicon oxide film can be formed thickly by the one-turn coating method in this way, a semiconductor device using a metal multilayer interconnection can be manufactured with a high yield by a simple manufacturing method.
実施例３
第５図ないし第８図は、本発明の半導体装置の製造方法
の工程を示す部分拡大断面図である。第５図において、
Ｐ型半導体基板１０１上に選択酸化法を用いてフィール
ド酸化ＩＦＪ １０２を形成する。ゲート酸化膜１０３
．ゲート電極１０４を形成し、イオン注入法によりｎ型
拡散層１０５を形成する。第１層間絶縁膜１０６を堆積
し、コンタクトホール１０７を設け、第１アルミ配線１
０８を形成する。次に、実施例２と同様の方法で、ｐ型
半導体基板１０１」―にシラノール化合物溶液を回転塗
布する。第６図において、ｐ型半導体基板１０１をベッ
セル１２０内に設置し、基板温度制御装置１２１によっ
て温度を５０〜１００℃に制御する。次に、超臨界状態
の二酸化炭素ガス１２２をｐ型半導体基板１０１と接触
させる。二酸化炭素の圧力及び温度は、それぞれ７５〜
１００気圧。Embodiment 3 FIGS. 5 to 8 are partially enlarged sectional views showing the steps of the method of manufacturing a semiconductor device of the present invention. In Figure 5,
A field oxidation IFJ 102 is formed on a P-type semiconductor substrate 101 using a selective oxidation method. Gate oxide film 103
．． A gate electrode 104 is formed, and an n-type diffusion layer 105 is formed by ion implantation. A first interlayer insulating film 106 is deposited, a contact hole 107 is formed, and a first aluminum wiring 1 is formed.
08 is formed. Next, in the same manner as in Example 2, a silanol compound solution is spin-coated onto the p-type semiconductor substrate 101''. In FIG. 6, a p-type semiconductor substrate 101 is placed in a vessel 120, and the temperature is controlled at 50 to 100° C. by a substrate temperature control device 121. Next, supercritical carbon dioxide gas 122 is brought into contact with p-type semiconductor substrate 101 . The pressure and temperature of carbon dioxide are respectively 75~
100 atmospheres.
５０〜１００℃が適当である。ｐ型半導体基板１０１上
のシラノール化合物溶液中の有機溶媒は、超臨界二酸化
炭素ガス１２２中に溶解し、シラノール化合物溶液中か
ら除去される。次に、基板温度制御装置１２１によって
半導体基板１０１の温度を４５０°Ｃまで段階的に上昇
させる。最適な熱処理条件は、用いたシラノール化合物
溶液の組成、濃度、塗布厚によって異なるが、一般的に
は第４図のような時間−温度曲線が適当と考えられる。A temperature of 50 to 100°C is suitable. The organic solvent in the silanol compound solution on the p-type semiconductor substrate 101 is dissolved in the supercritical carbon dioxide gas 122 and removed from the silanol compound solution. Next, the temperature of the semiconductor substrate 101 is raised stepwise to 450° C. by the substrate temperature control device 121. Optimal heat treatment conditions vary depending on the composition, concentration, and coating thickness of the silanol compound solution used, but generally a time-temperature curve as shown in FIG. 4 is considered appropriate.
熱処理後のＰ型半導体基板１０１の部分拡大断面図を第
７図に示す。FIG. 7 shows a partially enlarged cross-sectional view of the P-type semiconductor substrate 101 after heat treatment.
熱処理によりシラノール化合物は化学結合を形成し、シ
リコン酸化膜となり、第２層間絶縁膜１２３を形成する
。第８図において、スルーホール１２４を開口し、第２
アルミ配線１２５を形成する。Through heat treatment, the silanol compound forms chemical bonds and becomes a silicon oxide film, forming the second interlayer insulating film 123. In FIG. 8, the through hole 124 is opened and the second
Aluminum wiring 125 is formed.
本発明による方法を用いると、第２層間絶縁膜１２；）
の膜厚が８００ ｎ ｍでも、第２層間絶縁膜１２３中
にクラックは全く生じない。また、第２ＷＪ間絶縁膜１
２：１は回転塗布法を用いて形成しているため、第２層
間絶縁膜１２３上面はなだらかな形状となっている。こ
のため、第２アルミ配線１２５は全く断線を生じない。Using the method according to the invention, the second interlayer insulating film 12;)
Even if the film thickness is 800 nm, no cracks occur in the second interlayer insulating film 123. In addition, the second WJ inter-insulating film 1
2:1 is formed using a spin coating method, so the upper surface of the second interlayer insulating film 123 has a gentle shape. Therefore, the second aluminum wiring 125 does not break at all.
さらに、第２層間絶縁膜１２３中には溶媒が含まれてい
ないため、第１アルミ配線１０８同士や、第１アルミ配
線１０８と第２アルミ配線１２５の漏れ電流はなく、各
アルミ配線の腐食も生じない。Furthermore, since the second interlayer insulating film 123 does not contain a solvent, there is no leakage current between the first aluminum wirings 108 or between the first aluminum wiring 108 and the second aluminum wiring 125, and there is no corrosion of each aluminum wiring. Does not occur.
本実施例においては、薄膜を形成する溶液としてシラノ
ール化合物を用いたが、熱処理後絶縁性を示す他の無機
、有機シリコン化合物を用いてもよい。In this example, a silanol compound was used as the solution for forming the thin film, but other inorganic or organic silicon compounds that exhibit insulation properties after heat treatment may be used.
去施（ｐ１４
第９図に、本発明による薄膜形成装置の−実施例の部分
拡大断面図を示す。同図において、ベッセル１３１内に
円盤状の基板温度制御装置１３２が設置され、基板温度
制御装置１３２は基板回転制御装置１３３によって自転
回数を制御される。基板温度制御装置１３２上方のベッ
セル壁面には、溶液塗布装置１３４が設置され、基板温
度制御装置１３２上に設置された基板１３５七に溶液を
塗布できるようになっている。FIG. 9 shows a partially enlarged sectional view of an embodiment of the thin film forming apparatus according to the present invention. In the same figure, a disk-shaped substrate temperature control device 132 is installed in a vessel 131, The number of rotations of the device 132 is controlled by a substrate rotation control device 133.A solution coating device 134 is installed on the vessel wall above the substrate temperature control device 132, and a solution coating device 134 is installed on the substrate 135 placed on the substrate temperature control device 132. The solution can be applied.
第９図において、基板１３５を基板温度制御装置１３２
上に設置し、温度を５０〜１００℃に制御する。基板回
転制御装置１３３によって基板１３５．基板温度制御装
置１３２を自転させ、溶液塗布袋［１３４から基板１３
５上に溶液を塗布する。次に、ベッセル１３１内に超臨
界ガス１３６を流し、超臨界ガス１３６を基板１３５と
接触させる。塗布した溶液中の有機物は、超臨界ガス１
３６中に溶解し、溶液中の有機物は完全に除去される。In FIG. 9, a substrate 135 is controlled by a substrate temperature control device 132.
and control the temperature at 50-100°C. The substrate rotation control device 133 rotates the substrate 135. The substrate temperature control device 132 is rotated, and the substrate 13 is removed from the solution coating bag [134].
5. Apply the solution on top. Next, a supercritical gas 136 is caused to flow into the vessel 131, and the supercritical gas 136 is brought into contact with the substrate 135. Organic substances in the applied solution are treated with supercritical gas 1
The organic matter in the solution is completely removed.
次に、基板温度制御装置１３２によって基板１３５の温
度を上昇させ、薄膜中の化学結合を形成する。Next, the temperature of the substrate 135 is raised by the substrate temperature control device 132 to form chemical bonds in the thin film.
本発明による装置で薄膜形成や半導体装置の製造を行う
と１回転塗布法における溶液の滴下から溶媒除去後の熱
処理まで全ての工程を一つの装置内で処理できるため、
高品質の薄膜を迅速に歩留まり高く製造することができ
る。When forming thin films and manufacturing semiconductor devices using the apparatus according to the present invention, all steps from dropping the solution in the one-turn coating method to heat treatment after removing the solvent can be performed in one apparatus.
High-quality thin films can be manufactured quickly and with high yield.
（発明の効果）
本発明による方法を用いれば、膜中に不要な有機物や有
機官能基を含まない高品質の無機薄膜を形成することが
でき、製品の歩留まりや信頼性を飛躍的に増大すること
ができる。また、本発明による方法をスピンオングラス
（ＳＯＧ）形成時に用いれば、超臨界ガスまたは液化ガ
スによる薄膜中の溶媒除去を行った後熱処理により化学
結合を形成することができるため、クラックの発生を防
ぐことができ、薄膜の厚膜化を達成することができる。(Effects of the Invention) By using the method of the present invention, it is possible to form a high-quality inorganic thin film that does not contain unnecessary organic substances or organic functional groups in the film, dramatically increasing the yield and reliability of the product. be able to. Furthermore, if the method according to the present invention is used when forming spin-on glass (SOG), chemical bonds can be formed by heat treatment after removing the solvent in the thin film using supercritical gas or liquefied gas, thereby preventing the occurrence of cracks. This makes it possible to increase the thickness of a thin film.
また１本発明による装置でこの薄膜形成を行うと、全て
の工程を一つの装置内で処理できるため、高品質の薄膜
を迅速に安定して製造することができる。また、これら
の方法及び、または装置を用いて半導体装置を製造する
と、高歩留まり。In addition, when this thin film formation is performed using the apparatus according to the present invention, all steps can be performed within one apparatus, so that a high quality thin film can be rapidly and stably manufactured. Furthermore, when semiconductor devices are manufactured using these methods and/or devices, the yield is high.
高信頼性の半導体’ＮＥｔを製造することができ、その
実用的効果は大きい。A highly reliable semiconductor 'NEt' can be manufactured, and its practical effects are significant.
第１図は本発明にかかる薄膜形成方法を用いた一実施例
の工程における部分拡大断面図、第２図は回転塗布法を
示す図、第２３図は別の一実施例における部分拡大断面
図、第４図は一実施例における熱処理における時間−温
度曲線を示す図、第５図ないし第８図は本発明にかかる
半導体装置の製造方法の一実施例の工程における部分拡
大断面図、第９図は本発明にかかる薄膜形成装置の一実
施例の部分拡大断面図、第１０図は従来の回転塗布法を
用いて製造した半導体装置の部分拡大断面図である。
１．１１・・・半導体基板、 ２，１６・・・薄膜、３
、１３．１２０．１３１・・・ベッセル、 ４，１４
゜１２１、１３２・・・基板温度制御装置、 ５，１５
゜１２２・・・超臨界二酸化炭素ガス、１０・・・スピ
ンコータ、１２・・・シラノール化合物溶液、１０１・
・・ｐ型半導体基板、 １０２・・・フィールド酸化膜
、 １０３・・・ゲート酸化膜、 １０４・・・ゲート
電極、 １０５・・・ｎ型拡散層、１０６・・・第１層
聞納Ｍ膜、 １０７・・・コンタクトホール、１０８・
・・第１アルミ配線、 １２３・・・第２層間絶縁膜、
１２４・・・スルーホール、 １２５・・・第２アル
ミ配線、 １３３・・・基板回転制御装置、１３４・・
・溶液塗布装置、 １３５・・・基板、 １３６・・超
臨界ガス。
特許出願人 松下電器産業株式会社
第
図
第
図
第
区
ｏｔ
Ｐ型午導イ：＋１さ≧１シし〔
１０２フィール、ド０シ化方薇！
１０３− テ゛！ト（化升屹
＋０４ ・ケ゛−ト屯控
＋０５・ｎ型ゴあ叡１
＋０６・ オ
＠聞納佐撮
＋０７ コ）タクトホーレ
Ｏ８・ 第１アンレミ亡乙烹に
第
図
第
図
第
図
（ｈｒ）
第
ア
図
第
囚FIG. 1 is a partially enlarged cross-sectional view of a process in an embodiment using the thin film forming method according to the present invention, FIG. 2 is a diagram showing a spin coating method, and FIG. 23 is a partially enlarged cross-sectional view of another embodiment. , FIG. 4 is a diagram showing a time-temperature curve in heat treatment in one embodiment, FIGS. 5 to 8 are partially enlarged cross-sectional views of steps in one embodiment of the method for manufacturing a semiconductor device according to the present invention, and FIG. The figure is a partially enlarged sectional view of one embodiment of the thin film forming apparatus according to the present invention, and FIG. 10 is a partially enlarged sectional view of a semiconductor device manufactured using the conventional spin coating method. 1.11...Semiconductor substrate, 2,16...Thin film, 3
, 13.120.131...Vessel, 4,14
゜121, 132...Substrate temperature control device, 5,15
゜122... Supercritical carbon dioxide gas, 10... Spin coater, 12... Silanol compound solution, 101...
... P-type semiconductor substrate, 102 ... Field oxide film, 103 ... Gate oxide film, 104 ... Gate electrode, 105 ... N-type diffusion layer, 106 ... First layer M film , 107... contact hole, 108...
...first aluminum wiring, 123...second interlayer insulating film,
124...Through hole, 125...Second aluminum wiring, 133...Substrate rotation control device, 134...
- Solution coating device, 135...Substrate, 136...Supercritical gas. Patent applicant: Matsushita Electric Industrial Co., Ltd. 103- Tee! To (Case +04 ・Kate ton +05・N type Goa Ei 1 +06・O@Bunnosa photo +07 ko)Tact hole O8・First enremi dead otsuto diagram diagram diagram diagram (hr) Figure A Prisoner
Claims (11)
膜を形成する工程と、前記基板を超臨界ガスまたは液化
ガスに接触させて前記薄膜中から有機官能基及び、また
は有機物を除去する工程を備えてなることを特徴とする
薄膜形成方法。(1) A step of forming a thin film containing an organic functional group and/or an organic substance on a substrate, and a step of bringing the substrate into contact with a supercritical gas or liquefied gas to remove the organic functional group and/or the organic substance from the thin film. A method for forming a thin film, comprising:
項（１）記載の薄膜形成方法。(2) The thin film forming method according to claim (1), characterized in that a semiconductor is used as the substrate.
する工程として有機シリコン化合物のＣＶＤ法を用いる
ことを特徴とする請求項（１）記載の薄膜形成方法。(3) The thin film forming method according to claim (1), characterized in that the step of forming the thin film containing an organic functional group and/or an organic substance uses a CVD method of an organic silicon compound.
する工程として有機シリコン化合物の回転塗布法を用い
ることを特徴とする請求項（１）記載の薄膜形成方法。(4) The method for forming a thin film according to claim (1), wherein a spin coating method of an organic silicon compound is used as the step of forming the thin film containing an organic functional group and/or an organic substance.
溶媒に溶解した無機シリコン化合物の回転塗布法を用い
ることを特徴とする請求項（１）記載の薄膜形成方法。(5) The thin film forming method according to claim (1), wherein the step of forming the thin film containing an organic substance uses a spin coating method of an inorganic silicon compound dissolved in an organic solvent.
する工程として有機金属化合物または金属ハロゲン化物
のＣＶＤ法を用いることを特徴とする請求項（１）記載
の薄膜形成方法。(6) The thin film forming method according to claim (1), characterized in that the step of forming the thin film containing an organic functional group and/or an organic substance uses a CVD method of an organometallic compound or a metal halide.
いることを特徴とする請求項（１）記載の薄膜形成方法
。(7) The thin film forming method according to claim (1), characterized in that carbon dioxide is used as the supercritical gas or liquefied gas.
ことを特徴とする請求項（１）記載の薄膜形成方法。(8) The method for forming a thin film according to claim (1), wherein the supercritical gas or liquefied gas contains an extraction aid.
除去する工程中もしくは工程終了後に前記基板を加熱す
ることを特徴とする請求項（１）記載の薄膜形成方法。(9) The thin film forming method according to claim (1), wherein the substrate is heated during or after the step of removing organic functional groups and/or organic substances from the thin film.
せる機構と、基板の温度を制御する機構と、基板に超臨
界ガスまたは液化ガスを接触させる機構を備えることを
特徴とする薄膜形成装置。(10) Thin film formation characterized by comprising a mechanism for applying a solution onto a substrate, a mechanism for rotating the substrate, a mechanism for controlling the temperature of the substrate, and a mechanism for bringing supercritical gas or liquefied gas into contact with the substrate. Device.
合物溶液を回転塗布する工程と、前記基板を超臨界ガス
または液化ガスに接触させて前記薄膜中から有機溶媒及
び、または有機官能基を除去する工程と、前記基板に熱
処理を加える工程を備えてなることを特徴とする半導体
装置の製造方法。(11) Spin-coating a silicon compound solution dissolved in an organic solvent onto a semiconductor substrate, and removing the organic solvent and/or organic functional groups from the thin film by bringing the substrate into contact with supercritical gas or liquefied gas. A method for manufacturing a semiconductor device, comprising the steps of: and applying heat treatment to the substrate.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26618788A JPH02113525A (en) | 1988-10-24 | 1988-10-24 | Method and apparatus for forming thin film and manufacture of semiconductor device |
| US07/689,730 US5185296A (en) | 1988-07-26 | 1991-04-24 | Method for forming a dielectric thin film or its pattern of high accuracy on a substrate |
| US07/925,675 US5304515A (en) | 1988-07-26 | 1992-08-07 | Method for forming a dielectric thin film or its pattern of high accuracy on substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26618788A JPH02113525A (en) | 1988-10-24 | 1988-10-24 | Method and apparatus for forming thin film and manufacture of semiconductor device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02113525A true JPH02113525A (en) | 1990-04-25 |
Family
ID=17427464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26618788A Pending JPH02113525A (en) | 1988-07-26 | 1988-10-24 | Method and apparatus for forming thin film and manufacture of semiconductor device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02113525A (en) |
-
1988
- 1988-10-24 JP JP26618788A patent/JPH02113525A/en active Pending
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