JPH04191374A - Production of silicon oxide film by cvd method - Google Patents
Production of silicon oxide film by cvd methodInfo
- Publication number
- JPH04191374A JPH04191374A JP2321462A JP32146290A JPH04191374A JP H04191374 A JPH04191374 A JP H04191374A JP 2321462 A JP2321462 A JP 2321462A JP 32146290 A JP32146290 A JP 32146290A JP H04191374 A JPH04191374 A JP H04191374A
- Authority
- JP
- Japan
- Prior art keywords
- monosilane
- silicon oxide
- oxide film
- tetraethoxysilane
- alkoxysilane
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000000034 method Methods 0.000 title claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical class [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 42
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 19
- 239000000428 dust Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 239000007788 liquid Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000004819 silanols Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
- Silicon Polymers (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ＣＶＤ法（ケミカルペーパーデポジッション
：化学蒸着法）による酸化珪素膜の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing a silicon oxide film by a CVD method (chemical paper deposition: chemical vapor deposition method).
半導体装置製造工程において、酸化珪素膜は、電気的絶
縁体、誘電体、空間充填体、保護膜等として用いられて
いる。この酸化珪素膜の形成方法としては、得られる膜
質が良好なこと、形成速度が早いことから、気体あるい
は気体化した原料を化学反応させて膜を形成するＣＶＤ
法が多用されている。このＣＶＤ法により酸化珪素膜を
形成する際の主原料としては、従来はモノシラン（Ｓｉ
Ｈ４）が用いられていた。In semiconductor device manufacturing processes, silicon oxide films are used as electrical insulators, dielectrics, space fillers, protective films, and the like. The method for forming this silicon oxide film is CVD, which forms a film by chemically reacting gas or gasified raw materials, because the film quality obtained is good and the formation speed is fast.
Laws are widely used. Conventionally, monosilane (Si
H4) was used.
しかし、半導体装置の最小設計寸法が極微細化するにつ
れて、モノシランの性質のいくつかが欠点として見られ
るようになってきた。即ち、凹凸の激しい面上では表面
が平滑な膜を得に＜＜、穴埋め作用も無いこと、ダスト
を生じ易いこと、膜中に水酸基を残し易いことなどであ
る。このため、近時、モノシランに変わる原料として、
モノシランの珪素に結合している水素原子の一部又は全
部を炭素数５以下のアルコキシ基で置き換えたアルコキ
シシラン、特にその中でもテトラエトキシシラン（Ｓ
ｉ （ＯＣ２Ｈｓ ） ４ ）が検討され、実用化され
てきている。However, as the minimum design dimensions of semiconductor devices become extremely fine, some of the properties of monosilane have come to be seen as drawbacks. That is, it is difficult to obtain a film with a smooth surface on a highly uneven surface, there is no hole-filling effect, it is easy to generate dust, and it is easy to leave hydroxyl groups in the film. For this reason, recently, as a raw material to replace monosilane,
Alkoxysilanes in which part or all of the hydrogen atoms bonded to silicon in monosilane are replaced with alkoxy groups having 5 or less carbon atoms, especially tetraethoxysilane (S
i (OC2Hs) 4) has been studied and put into practical use.
しかしながら、このようなアルコキシシランを主原料と
して用いた場合には、基層の種類や表面状態に成膜速度
か依存すること、及び基板温度を比較的高くする必要か
あることか、欠点として挙げられている。However, when such alkoxysilane is used as the main raw material, the disadvantages include that the film formation rate depends on the type and surface condition of the base layer, and that the substrate temperature must be relatively high. ing.
一方、前記モノシランは大気中で直ちに発火する程、補
助原料である酸素と反応しやすい物質であるが、前記テ
トラエトキシシランは、マツチやライターの炎を近イ」
けたくらいでは容易に着火しない程、酸素と反応しにく
い物質であるため、成ｇ操作にあたってはオゾンやプラ
ズマ支援酸素が酸化剤として用いられている。On the other hand, monosilane is a substance that easily reacts with oxygen, an auxiliary raw material, to the extent that it immediately ignites in the atmosphere, but tetraethoxysilane is a substance that is easily ignited by the flame of a matchstick or lighter.
Ozone or plasma-assisted oxygen is used as an oxidizing agent in the oxidizing operation because it is a substance that does not react easily with oxygen, so much so that it does not easily ignite at high temperatures.
そこで本発明者らは、上記モノシランとアルコキシシラ
ンのように性質の異なる原料を用いた反応に注目し、Ｃ
ＶＤ法を用いて、より効率良く成膜することができる酸
化珪素膜の製造方法を開発すべく鋭意研究を重ねた。Therefore, the present inventors focused on a reaction using raw materials with different properties such as the above-mentioned monosilane and alkoxysilane, and
We have conducted extensive research to develop a method for manufacturing silicon oxide films that can be formed more efficiently using the VD method.
〔課題を解決するための手段〕
その結果、アルコキシシランにモノシランかよく溶ける
という事実を発見１−、モノシランとアルコキシシラン
とを併用することにより」−記目的を達成できることを
見出たした。本発明は、かかる知見に基づいて成された
ものである。[Means for Solving the Problem] As a result, it was discovered that monosilane is well soluble in alkoxysilane, and it was discovered that by using monosilane and alkoxysilane together, the object described above can be achieved. The present invention has been made based on this knowledge.
即ち、本発明のＣＶＤ法による酸化珪素膜の製造方法は
、主原料としてアルコキシシランとモノシランとを併用
することを特徴とするものである。That is, the method of manufacturing a silicon oxide film by the CVD method of the present invention is characterized in that alkoxysilane and monosilane are used in combination as main raw materials.
ここで、本発明方法により酸化珪素膜を形成する際の反
応原理を説明する。Here, the reaction principle when forming a silicon oxide film by the method of the present invention will be explained.
まず、モノシランは、加熱された基板の近傍で同時に供
給される酸素出戻応し、ンラノ〜ル（Ｓ ｉ （ＯＨ
） ４ ）になる。このとき反応熱として、１モル当た
り１５１５ｋＪの大量の熱が発生する。このシラノール
は、５０℃以下での昇華蒸気圧より推定した標準沸点が
１１５℃と、揮発性の物質であり、５０℃では不安定で
ある。このシラノールが水と二酸化珪素（Ｓｉｎ２）に
分解するには、］モル当たり約８７ｋＪの反応熱が必要
であり、過剰なエネルギーや脱水環境か無ければ、この
分解が起こりに＜＜、基板上に付着しても再び揮発して
しまうため成膜することが困難である。First, monosilane reacts with oxygen, which is simultaneously supplied in the vicinity of the heated substrate, and reacts with nitrogen (Si(OH)).
) 4) becomes. At this time, a large amount of heat of 1515 kJ per mole is generated as reaction heat. This silanol is a volatile substance with a standard boiling point of 115°C estimated from the sublimation vapor pressure at temperatures below 50°C, and is unstable at 50°C. In order for this silanol to decompose into water and silicon dioxide (Sin2), approximately 87 kJ of reaction heat is required per mole, and in the absence of excess energy or a dehydrating environment, this decomposition will not occur. Even if it adheres, it will volatilize again, making it difficult to form a film.
しかし、前記モノシランの大きな燃焼熱と、この反応が
ＣＶＤ装置の反応室内の亜真空下で行われ、水の蒸気圧
か小さいことから、上記シラノールの分解が進み、基板
上への成膜か可能となる。However, due to the large combustion heat of the monosilane and the fact that this reaction is carried out in a sub-vacuum inside the reaction chamber of the CVD device, and the vapor pressure of water is low, the silanol decomposes and it becomes possible to form a film on the substrate. becomes.
この反応は、気体から固体への変化であるので、基板表
面に付着した反応生成物の流動は起こり難く、穴埋め効
果は全く期待てきない。また、シラノールが完全に分解
した後の反応生成物は、基板着床蒸気圧等の基板上での
分子移動能力かないので緻密な膜にならずに粉状になっ
てしまう。従って、基板上への成膜は、シラノールか半
分解状態で基板上に着床し、分解が進んで膜状に固体化
することによって行われる。また、このとき生成して固
体中に閉し込められた水酸基は離脱し難く、固体中に残
存することになる。即ち、モノシランの持つ大きな生成
エネルギーかむしろ欠点として作用する条件となる。Since this reaction is a change from gas to solid, it is difficult for the reaction product attached to the substrate surface to flow, and no hole-filling effect can be expected. Furthermore, the reaction product after the silanol is completely decomposed does not have the ability to move molecules on the substrate, such as the vapor pressure on the substrate, so it does not form a dense film but becomes powder. Therefore, a film is formed on a substrate by depositing the silanol on the substrate in a half-decomposed state, progressing to decomposition, and solidifying into a film. Furthermore, the hydroxyl groups generated at this time and trapped in the solid are difficult to leave and remain in the solid. In other words, the large production energy of monosilane is a condition that acts as a disadvantage.
一方のアルコキシシランは、前述のように、モノシラン
の珪素に結合している水素原子の一部又は全部を炭素数
５以下のアルコキシ基で置き換えたもので、本発明に用
いるアルコキシシランとしては、前記テトラエトキシシ
ランを初めとして、トリエトキシシラン、テトライソプ
ロポキシンラン、テトラセカンダリブトキシシラン等各
種のものを挙げることかできる。As mentioned above, one alkoxysilane is a monosilane in which part or all of the hydrogen atoms bonded to silicon are replaced with an alkoxy group having 5 or less carbon atoms. In addition to tetraethoxysilane, there may be mentioned various types such as triethoxysilane, tetraisopropoxinlan, and tetrasecandabutoxysilane.
このようなアルコキシシランの代表としてテトラエトキ
シシランと酸素との反応を考えてみると、この反応でテ
トラエトキシシラン１モル当たり、９１３ｋＪの反応熱
が発生するとともに、シラノール、アセトアルデヒド、
エタノールが生成することが考えられる。しかしこの反
応は、−度に起こるのではなく、テトラエトキシシラン
の側鎖が取れて水酸基に変わるのに大きな活性化エネル
ギーが必要であり、これによって反応が律速される。Considering the reaction between tetraethoxysilane and oxygen, which is a typical example of such alkoxysilane, this reaction generates 913 kJ of reaction heat per mole of tetraethoxysilane, and also produces silanol, acetaldehyde,
It is possible that ethanol is generated. However, this reaction does not occur instantaneously, and a large amount of activation energy is required to remove the side chain of tetraethoxysilane and convert it into a hydroxyl group, which limits the rate of the reaction.
さらに、水酸基を持った中間分解物は５ｉ−０−３ｉの
シロキサン結合により縮合して高分子化する。この縮合
体は、分子量数十万以上になるまでは低揮発性、低粘性
率の液体であることを知見した。Further, the intermediate decomposition product having a hydroxyl group is condensed through a 5i-0-3i siloxane bond to form a polymer. It was found that this condensate is a liquid with low volatility and low viscosity until the molecular weight reaches several hundred thousand or more.
即ち、ＣＶＤ法におけるテトラエトキシシランの成膜反
応は、気体から液体に変化した後、該液体が固体化する
ことにより行われる。従って、水酸基の離脱もかなりの
程度まで液相中で行われ、モノシランのように固体化し
た後に水酸基が離脱する必要性は比較的小さくて済む。That is, the film-forming reaction of tetraethoxysilane in the CVD method is performed by changing from gas to liquid and then solidifying the liquid. Therefore, the elimination of hydroxyl groups is also carried out to a considerable extent in the liquid phase, and there is relatively little need for the elimination of hydroxyl groups after solidification as in the case of monosilane.
即ち、反応条件を工夫することによって、水酸基の残存
量を少なくすることが可能である。That is, by modifying the reaction conditions, it is possible to reduce the amount of remaining hydroxyl groups.
それたけてなく、基板表面に流動性の大きな液体を存在
させることができるので、穴埋め効果等の平坦化が期待
てきる。しかし、ロウに水が濡れないのと同じように、
表面エネルギーの大きく異なる固体表面には液体の濡れ
が悪くなる。In addition, since a highly fluid liquid can be present on the substrate surface, it is expected to have a flattening effect such as filling holes. However, just as water does not get wet with wax,
Solid surfaces with greatly different surface energies have poor wettability with liquids.
ところが、このテトラエトキシシランにおける不都合は
、前記モノシランの持つ大きな反応エネルギーと、本発
明者らか知見したアルコキシシランにモノシランがよく
溶けるという事実により解決が可能となった。即ち、テ
トラエトキシシラン等のアルコキシシランを主原料とす
るＣＶＤ装置内に、モノシランを同時に、あるいは時間
をずらせて導入すると、モノシランは、不安定な分子状
態と、容易に分解して発生する発生期の水素の還元作用
との働きにより、基板選択性の小さな酸化珪素の分子膜
を形成する。生成した酸化珪素膜は、テトラエトキシシ
ランから生成した液体と良く馴染み、液体の基板選択性
も無くすことができる。However, this disadvantage of tetraethoxysilane can be overcome by the large reaction energy of monosilane and the fact that monosilane is well soluble in alkoxysilane, which the present inventors have discovered. In other words, if monosilane is introduced simultaneously or at different times into a CVD device that uses alkoxysilane such as tetraethoxysilane as its main raw material, monosilane will be in an unstable molecular state and will easily decompose during the generation phase. A molecular film of silicon oxide with low substrate selectivity is formed by the reduction action of hydrogen. The produced silicon oxide film is compatible with the liquid produced from tetraethoxysilane, and the substrate selectivity of the liquid can also be eliminated.
従って、アルミニウム配線等の表面とテトラエトキシシ
ランとが馴染まず、満足な酸化珪素膜を得ることができ
なかったか、馴染みの良いモノシランと併用することに
より、アルミニウム配線等の上でもテトラエトキシシラ
ンによる酸化珪素膜が形成できるなど、基板選択性の顕
著な改善が可能となった。Therefore, tetraethoxysilane is not compatible with the surface of aluminum wiring, etc., making it impossible to obtain a satisfactory silicon oxide film, or by using it together with monosilane, which has good compatibility, tetraethoxysilane oxidizes even on aluminum wiring, etc. It has become possible to significantly improve substrate selectivity, including the ability to form a silicon film.
また、モノシランは、テトラエトキシシランの縮合した
液体中に溶けるので、反応時に生成した水を液相中に放
出することができる。さらにテトラエトキシシラン及び
その縮合物は、前記水の存在で、生成したエタノール等
を放出して縮合が進むとともに、モノシランの放出エネ
ルギーがテトラエトキシシランの活性化エネルギーの供
給源としても働くので、基板の加熱温度を低下させるこ
とが可能となる。Moreover, since monosilane dissolves in the condensed liquid of tetraethoxysilane, water produced during the reaction can be released into the liquid phase. Furthermore, in the presence of water, tetraethoxysilane and its condensates release generated ethanol, etc., and condensation progresses, and the released energy of monosilane also serves as a source of activation energy for tetraethoxysilane, so It becomes possible to lower the heating temperature.
換言すれば、テトラエトキシシランの中でのモノシラン
は、モノシラン単独の時と異なり、シラノールを形成し
易く、かつ液相反応になる。このことにより、モノシラ
ンの欠点の原因と考えられる性質は長所となり、テトラ
エトキシシランの欠点を補うように作用し、両者の相乗
効果により、優れた酸化珪素膜を形成することが可能と
なる。In other words, monosilane in tetraethoxysilane easily forms silanol and undergoes a liquid phase reaction, unlike monosilane alone. As a result, the properties that are thought to be the cause of the drawbacks of monosilane become advantages, and act to compensate for the drawbacks of tetraethoxysilane, and the synergistic effect of the two makes it possible to form an excellent silicon oxide film.
また、アルコキシシランとモノシランとの混合比は、Ｃ
ＶＤ法の操作条件や装置構成、得られる酸化珪素膜に要
求される平坦化等の各種の条件等により異なるが、例え
ば、アルコキシシランとしてテトラエトキシシランを用
いた場合には、テトラエトキシシラン１モルに対して、
モノシランが０．５モル以下、千分の１モル以上である
ことが望ましい。即ち、モノシラン１分子から２分子の
水ができ、テトラエトキシシラン１分子は２分子の水で
エタノールを放出して酸化珪素となるが、テトラエトキ
シシランの縮合速度を上げ過ぎると平坦化が困難になる
ことと、水酸基の残量をできるだけ少なくすることを考
慮すると、テトラエトキシシラン１モルに対してモノシ
ランを０．５モル以下とするべきてあり、また、モノシ
ランに、テトラエトキシシランの触媒的効果を期待し、
膜の平坦化を重視する見地からは、テトラエトキシシラ
ン１モルに対してモノシランが千分の１モル以上である
ことが目安になる。In addition, the mixing ratio of alkoxysilane and monosilane is C
Although it varies depending on various conditions such as the operating conditions and equipment configuration of the VD method and the flattening required for the resulting silicon oxide film, for example, when tetraethoxysilane is used as the alkoxysilane, 1 mol of tetraethoxysilane is used. For,
It is desirable that the amount of monosilane is 0.5 mol or less, and 1/1000 mol or more. In other words, one molecule of monosilane produces two molecules of water, and one molecule of tetraethoxysilane releases ethanol with two molecules of water to become silicon oxide, but if the condensation rate of tetraethoxysilane is increased too much, flattening becomes difficult. Considering that the remaining amount of hydroxyl groups should be as small as possible, the amount of monosilane should be 0.5 mol or less per 1 mol of tetraethoxysilane. expecting,
From the viewpoint of placing importance on flattening the film, a guideline is that monosilane should be at least 1/1000 mole per mole of tetraethoxysilane.
尚、アルコキシシランとモノシランとを、時間をずらせ
て装置に導入する場合には、モノシランにより形成され
る基板上の酸化珪素膜の厚さが、１００ｎｓ程度を限度
とすべきである。これは、前記モノシランにおける固体
中の拡散により水酸基を放出できる限界厚さであり、こ
れ以上の厚さにすると残存水酸基の量が多くなり好まし
くない。Note that when alkoxysilane and monosilane are introduced into the device at different times, the thickness of the silicon oxide film on the substrate formed by monosilane should be limited to about 100 ns. This is the limit thickness at which the monosilane can release hydroxyl groups by diffusion in the solid, and if the thickness is greater than this, the amount of residual hydroxyl groups will increase, which is not preferable.
以下、本発明の実施例及び比較例を説明する。 Examples and comparative examples of the present invention will be described below.
実施例１
５００ Ｐ ａ （３，７５Ｔｏｒｒ）の反応室内に設
置した半導体基板を約３５０℃に加熱するとともに、モ
ノシラン、テトラエトキシシラン、オゾンを流量比率で
１〜２：２０：４０となるように供給して成膜を行った
。その結果、平坦性に優れ、水酸基残存量の少ない優れ
た酸化珪素膜を得ることかできた。Example 1 A semiconductor substrate placed in a 500 Pa (3.75 Torr) reaction chamber was heated to about 350°C, and monosilane, tetraethoxysilane, and ozone were mixed at a flow rate of 1 to 2:20:40. The film was formed by supplying it. As a result, an excellent silicon oxide film with excellent flatness and a small amount of residual hydroxyl groups could be obtained.
比較例１
１００〜５００ Ｔｏｒｒの反応室内に設置した半導体
基板を約３５０℃に加熱するとともに、モノシランと酸
素をモル流量比率で５＝２０となるように供給して成膜
を行った。その結果、得られた酸化珪素膜は実施例１に
比べて平坦性が劣り、水酸基残存量も多かった。Comparative Example 1 A semiconductor substrate placed in a reaction chamber at 100 to 500 Torr was heated to about 350° C., and monosilane and oxygen were supplied at a molar flow rate ratio of 5=20 to form a film. As a result, the obtained silicon oxide film was inferior in flatness compared to Example 1, and had a large amount of residual hydroxyl groups.
比較例２
１００〜５００ Ｔｏｒｒの反応室内に設置した半導体
基板を約５００℃に加熱するとともに、テトラエトキシ
シランとオゾンとの流量比率を１；２となるように供給
して成膜を行ったが、基板面上の二酸化珪素膜厚は、シ
リコン面上に比べて薄く、不満足であった。Comparative Example 2 A semiconductor substrate placed in a reaction chamber at 100 to 500 Torr was heated to about 500°C, and a film was formed by supplying tetraethoxysilane and ozone at a flow rate ratio of 1:2. The thickness of the silicon dioxide film on the substrate surface was thinner than that on the silicon surface, which was unsatisfactory.
以上説明したように、本発明の酸化珪素膜の製造方法は
、主原料としてアルコキシシランとモノシランとを併用
するから、基板選択性がなく、平坦化の特性も良い酸化
珪素膜を、より低い温度で、かつダスト発生か起こりに
くい条件下で製造することが可能となる。As explained above, since the method for manufacturing a silicon oxide film of the present invention uses alkoxysilane and monosilane together as the main raw materials, it is possible to produce a silicon oxide film without substrate selectivity and with good planarization characteristics at a lower temperature. This makes it possible to manufacture the product under conditions where dust generation is unlikely to occur.
Claims (2)
用することを特徴とするＣＶＤ法による酸化珪素膜の製
造方法。1. A method for producing a silicon oxide film by a CVD method, characterized in that alkoxysilane and monosilane are used in combination as main raw materials.
り、該テトラエトキシシランとモノシランとの混合比が
、テトラエトキシシラン１モルに対して、モノシランが
０．５モル以下、千分の１モル以上であることを特徴と
する請求項１記載のＣＶＤ法による酸化珪素膜の製造方
法。2. The alkoxysilane is tetraethoxysilane, and the mixing ratio of the tetraethoxysilane and monosilane is 0.5 mol or less and 1/1000 mol or more of monosilane per 1 mol of tetraethoxysilane. A method for manufacturing a silicon oxide film by a CVD method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2321462A JPH04191374A (en) | 1990-11-26 | 1990-11-26 | Production of silicon oxide film by cvd method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2321462A JPH04191374A (en) | 1990-11-26 | 1990-11-26 | Production of silicon oxide film by cvd method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04191374A true JPH04191374A (en) | 1992-07-09 |
Family
ID=18132840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2321462A Pending JPH04191374A (en) | 1990-11-26 | 1990-11-26 | Production of silicon oxide film by cvd method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04191374A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6830786B2 (en) | 1997-05-21 | 2004-12-14 | Nec Corporation | Silicon oxide film, method of forming the silicon oxide film, and apparatus for depositing the silicon oxide film |
| US7902549B2 (en) | 2002-05-17 | 2011-03-08 | Samsung Electronics Co., Ltd. | Deposition method of insulating layers having low dielectric constant of semiconductor device, a thin film transistor substrate using the same and a method of manufacturing the same |
-
1990
- 1990-11-26 JP JP2321462A patent/JPH04191374A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6830786B2 (en) | 1997-05-21 | 2004-12-14 | Nec Corporation | Silicon oxide film, method of forming the silicon oxide film, and apparatus for depositing the silicon oxide film |
| US7902549B2 (en) | 2002-05-17 | 2011-03-08 | Samsung Electronics Co., Ltd. | Deposition method of insulating layers having low dielectric constant of semiconductor device, a thin film transistor substrate using the same and a method of manufacturing the same |
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