JPH04343456A - Manufacture of semiconductor device - Google Patents
Manufacture of semiconductor deviceInfo
- Publication number
- JPH04343456A JPH04343456A JP11612091A JP11612091A JPH04343456A JP H04343456 A JPH04343456 A JP H04343456A JP 11612091 A JP11612091 A JP 11612091A JP 11612091 A JP11612091 A JP 11612091A JP H04343456 A JPH04343456 A JP H04343456A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- gas
- temperature
- oxide film
- film
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000004065 semiconductor Substances 0.000 title claims description 7
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 239000007789 gas Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- 229910000077 silane Inorganic materials 0.000 claims description 11
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 239000011229 interlayer Substances 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 6
- 239000010703 silicon Substances 0.000 abstract description 6
- 238000002230 thermal chemical vapour deposition Methods 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 150000001282 organosilanes Chemical class 0.000 abstract 1
- 238000000280 densification Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、半導体装置の製造方法
に関し、更に詳しくは、例えば多層配線間の層間絶縁膜
として良質のシリコン酸化膜を比較的低温で形成せしめ
る半導体装置の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a semiconductor device, and more particularly, to a method for manufacturing a semiconductor device in which a high-quality silicon oxide film is formed at a relatively low temperature as an interlayer insulating film between, for example, multilayer wiring.
【０００２】0002
【従来の技術】ＬＳＩの集積化が進むにつれて、素子の
最小寸法に対する段差の割合が増大し、しかも配線も多
層化しているので、段差が大きくなると配線の断線や層
間絶縁膜の不良による配線間ショートが問題になってき
ている。従って、層間絶縁膜の平坦化がますます重要に
なってきている。[Background Art] As LSI integration progresses, the ratio of steps to the minimum dimension of the device increases, and wiring also becomes multi-layered. Short circuits are becoming a problem. Therefore, planarization of the interlayer insulating film is becoming increasingly important.
【０００３】従来、半導体装置の製造過程における層間
絶縁膜の形成方法としては、バイアススパッタ法、エッ
チバック法、ＳＯＧ（Ｓｐｉｎ ｏｎ Ｇｌａｓｓ）
塗布法等が提案されており、一部実用化されている。し
かし、従来法にはプラズマを使った場合には、基板にダ
メージを与えるという問題があり、また、ＳＯＧからの
脱ガスで配線不良が発生するという問題があった。そこ
でＴＥＯＳ（テトラエトキシシラン）ソースガスを用い
たＣＶＤ（ＣｈｅｍｉｃａｌＶａｐｏｒ Ｄｅｐｏｓｉ
ｔｉｏｎ） 法が提案されているが、この方法にはＴＥ
ＯＳの熱分解温度が ６００℃以上と高いため、Ａｌを
配線材料とする場合の層間絶縁膜には適用できないとい
う問題がある。この問題を解決するため、ソースガスに
更にオゾンを添加して反応を促進し、 ４００℃程度の
比較的低温で酸化膜を形成し得ることを認めたが、この
方法には、膜質が未だ完全でなく、生成した膜の脱ガス
及び吸湿性の問題があり、更にエッチングレートが異常
に早い部分があって後に巣が出来るという問題があった
。Conventionally, methods for forming interlayer insulating films in the manufacturing process of semiconductor devices include bias sputtering, etchback, and SOG (Spin on Glass).
Coating methods have been proposed and some have been put into practical use. However, in the conventional method, when plasma is used, there is a problem in that it damages the substrate, and there is also a problem in that defective wiring occurs due to degassing from the SOG. Therefore, chemical vapor deposition (CVD) using TEOS (tetraethoxysilane) source gas was developed.
tion) method has been proposed, but this method requires
Since the thermal decomposition temperature of the OS is as high as 600° C. or higher, there is a problem that it cannot be applied to an interlayer insulating film when Al is used as the wiring material. In order to solve this problem, it was found that ozone was further added to the source gas to accelerate the reaction, and an oxide film could be formed at a relatively low temperature of about 400°C, but this method still has insufficient film quality. In addition, there were problems with degassing and hygroscopicity of the formed film, and there was also a problem that there were parts where the etching rate was abnormally high, resulting in the formation of cavities afterwards.
【０００４】0004
【発明が解決しようとする課題】従って、本発明は、前
記した従来の層間絶縁膜の形成方法の問題点を解決して
、基板等がプラズマによるダメージを受けることなく、
例えば ５００℃以下の比較的低温で平坦で緻密な良質
のシリコン酸化膜を形成することのできる半導体装置の
製造方法を提供することを目的とする。SUMMARY OF THE INVENTION Accordingly, the present invention solves the problems of the conventional interlayer insulating film forming method described above, and eliminates damage to the substrate etc. due to plasma.
An object of the present invention is to provide a method for manufacturing a semiconductor device that can form a flat, dense, and high-quality silicon oxide film at a relatively low temperature of, for example, 500° C. or lower.
【０００５】[0005]
【課題を解決するための手段】本発明に従えば、有機シ
ランガスと少なくとも水分子又は水酸基と水素原子をガ
ス状で含んだ雰囲気中で熱ＣＶＤ法のみによってシリコ
ン酸化膜を形成する工程を含んでなることを特徴とする
半導体装置の製造方法が提供される。[Means for Solving the Problems] According to the present invention, the method includes the step of forming a silicon oxide film only by thermal CVD in an atmosphere containing organic silane gas and at least water molecules or hydroxyl groups and hydrogen atoms in gaseous form. A method for manufacturing a semiconductor device is provided.
【０００６】水とＴＥＯＳから加水分解でシラノールが
形成され、これが脱水縮合して酸化膜になることは従来
から知られていた。そこで、本発明者らは先ずケイ素を
シラノール状で基板に堆積させた後、アニールする方法
を試みたが、この方法には時間がかかるのみでなく、成
長した膜はエッチングレートが大きい粗い膜質になるこ
とを認めた。そこで基板温度をあげていった所、ソース
ガスの供給流量に対応した或る温度から膜質の良い、平
坦な膜が得られることを見出した。これは、加水分解と
脱水縮合が同時に起こると共に、水分による酸化も起こ
るためと考えられる。脱水縮合は膜から水酸基ＯＨが抜
け出す反応なので膜質を悪くする。むしろ、水蒸気分圧
を高くして、この脱水反応を抑えて酸化反応をおこさせ
ることによって、又は同時に酸化種を拡散させて酸化さ
せることによって、膜質が向上することを認めた。しか
し、 ３００〜 ５００℃程度の低温では酸化種の拡散
が小さいため、有機基を多く含んだ厚膜が生成し、後で
酸化して安定化しようとしても不可能となるので、中間
反応と同時に酸化も行い、始めから緻密な膜を形成する
のが極めて有効である。更にソースガス中にオゾンを添
加すると、反応が促進されて堆積温度を一層低温化でき
る。この反応の促進は水の不存在下においても起きるが
、この場合には、膜質の向上と緻密化は期待できない。
即ち、加熱された基板周辺に水蒸気、ＯＨ、Ｈ等が存在
することが必要であり、酸化膜の成長と膜の改質は同時
に行なわれなければならない。It has been known for a long time that silanol is formed by hydrolysis from water and TEOS, and that silanol is dehydrated and condensed to form an oxide film. Therefore, the present inventors first tried a method of depositing silicon in the form of silanol on a substrate and then annealing it, but this method was not only time-consuming, but also resulted in a rough film with a high etching rate. I acknowledged that it would happen. When the substrate temperature was raised, it was found that a flat film with good quality could be obtained from a certain temperature corresponding to the supply flow rate of the source gas. This is thought to be because hydrolysis and dehydration condensation occur simultaneously, and oxidation due to moisture also occurs. Since dehydration condensation is a reaction in which hydroxyl groups OH are released from the membrane, it deteriorates the membrane quality. Rather, it has been found that the film quality can be improved by increasing the partial pressure of water vapor to suppress this dehydration reaction and causing an oxidation reaction, or by simultaneously diffusing oxidizing species to cause oxidation. However, at low temperatures of about 300 to 500°C, the diffusion of oxidizing species is small, so a thick film containing many organic groups is formed, and it is impossible to stabilize it by oxidation later. It is extremely effective to form a dense film from the beginning by also performing oxidation. Furthermore, when ozone is added to the source gas, the reaction is promoted and the deposition temperature can be further lowered. This reaction is promoted even in the absence of water, but in this case, improvement in film quality and densification cannot be expected. That is, it is necessary that water vapor, OH, H, etc. exist around the heated substrate, and the growth of the oxide film and the modification of the film must be performed simultaneously.
【０００７】また、ＴＥＯＳ（テトラエトキシシラン）
、ＴＭＯＳ（テトラメトキシシラン）、ＴＭＳ（テトラ
メチルシラン）等の有機シランと酸素、水等を一緒にプ
ラズマ等で励起させると、反応が促進されることが期待
される。しかし、これを実際に試みると、反応が促進さ
れ過ぎて気相反応が主体になり、粒子状の白濁した膜し
か生成しない。分子量の大きい有機シランを安定的に励
起することは難しいが、酸素、水等の酸化種だけを励起
して反応を促進し、膜を緻密化させることは本発明にと
って有効である。更にこの酸化種をパルス的に励起すれ
ば、凹部に酸化膜を埋め込むこともでき、励起パルスオ
フの状態では完全に酸化までは進まない条件にしておけ
ば、有機基を含み流動性を持った状態で流し込み、励起
パルスオンの状態では反応と緻密化が進む条件にするこ
とで完全に平坦で緻密な酸化膜が形成される。オフ状態
で超音波をウェハーに加えると、流動性が増して平坦化
が促進される。この場合にも、有機シランを直接励起す
ると、平坦化と酸化膜の質向上を同時に満足することは
できない。これは、気相で全ての反応が生じてしまうた
め、平坦化を満足させようとすると、基板温度を上げら
れないので膜質が悪くなり、また基板温度を上げると今
度は平坦化が満たせないことになる。[0007] Also, TEOS (tetraethoxysilane)
When organic silanes such as , TMOS (tetramethoxysilane), TMS (tetramethylsilane), and oxygen, water, etc. are excited together with plasma or the like, the reaction is expected to be accelerated. However, when this is actually attempted, the reaction is accelerated too much and the gas phase reaction becomes the main reaction, resulting in only a cloudy particulate film. Although it is difficult to stably excite organic silane having a large molecular weight, it is effective for the present invention to excite only oxidizing species such as oxygen and water to promote the reaction and densify the film. Furthermore, by exciting this oxidizing species in a pulsed manner, it is possible to fill the recess with an oxide film, and if the conditions are such that oxidation does not proceed completely when the excitation pulse is off, the oxidized film will remain in a fluid state containing organic groups. When the excitation pulse is turned on, the reaction and densification proceed under conditions that allow a completely flat and dense oxide film to be formed. Applying ultrasound to the wafer in the off state increases fluidity and promotes planarization. In this case as well, if organic silane is directly excited, planarization and improvement in the quality of the oxide film cannot be achieved at the same time. This is because all reactions occur in the gas phase, so if you try to satisfy planarization, you can't raise the substrate temperature, resulting in poor film quality, and if you raise the substrate temperature, you won't be able to satisfy flattening. become.
【０００８】励起した水、酸素、オゾン、ＯＨ、Ｈなど
をウェハー近傍からウェハーに向かって供給すると、本
発明の効果が更にあがる。ガス状酸化剤の噴射されたウ
ェハー近傍では、圧力上昇により、ウェハー表面とチャ
ンバー内では雰囲気が違うことになり、有機シランガス
がチャンバーを通る時に前段の反応が生じ、酸化剤の圧
力が高いウェハー上で完全な緻密化が行なわれる。The effects of the present invention are further enhanced by supplying excited water, oxygen, ozone, OH, H, etc. toward the wafer from near the wafer. In the vicinity of the wafer where the gaseous oxidant is injected, the pressure rise causes a difference in the atmosphere between the wafer surface and the inside of the chamber, and when the organic silane gas passes through the chamber, the previous reaction occurs, causing Complete densification is performed.
【０００９】ＴＥＯＳ、ＴＭＯＳなどの有機シランをオ
ゾン、水等で前段反応を行なわさせた後に、例えばウェ
ハー近傍に設けたメッシュとウェハー間でプラズマを発
生させると、反応層が明確に二つに分かれるので効果が
あり、電極間隔を小さくすることで気相反応の効果を小
さくできるので、カバレージを悪くすることはない。こ
のようにプラズマにより酸化膜質が向上するメリットは
大きい。[0009] After performing a pre-stage reaction of organic silane such as TEOS or TMOS with ozone, water, etc., if plasma is generated between, for example, a mesh provided near the wafer and the wafer, the reaction layer is clearly divided into two. This is effective, and the effect of gas phase reactions can be reduced by reducing the electrode spacing, so coverage will not deteriorate. In this way, plasma has a great advantage of improving the quality of the oxide film.
【００１０】0010
【実施例】以下、本発明をそのいくつかの実施例に基づ
いて更に詳細に説明するが、本発明の範囲を以下の実施
例に限定するものでないことはいうまでもない。EXAMPLES The present invention will be explained in more detail below based on some examples thereof, but it goes without saying that the scope of the present invention is not limited to the following examples.
【００１１】実施例１
図１を参照して本発明の第一実施例を説明する。この実
施例では水とＴＥＯＳを用いてシリコン酸化膜をシリコ
ン基板上に形成する。水の発生は、恒温槽１の中に配置
した水蒸気発生のシリンダー２から数十トール程度の蒸
気圧に保ち、低差圧マスフローコントローラー（ＭＦＣ
）３により予備加熱室４に所望の量、例えば５０ｓｃｃ
ｍ程度を供給する。同様の装置によりシリンダー５から
ＭＦＣ６を通してＴＥＯＳを、例えば２０ｓｃｃｍ程度
供給する。
更に窒素（Ｎ２ ）又は不活性ガス（例えばＡｒ）を加
えてシャワーノズル７から混合ガスを噴射する。予備加
熱室４では、好ましくは膜が形成しない程度の温度まで
加熱し、前段反応を促進する。好ましくは予備室のガス
圧は２０Ｔｏｒｒ程度（範囲として１〜６０Ｔｏｒｒ）
、温度は ２００℃程度（範囲は １００〜 ３００℃
）とし、反応チャンバーの圧力は、好ましくは ０．１
〜１０Ｔｏｒｒ（範囲は０．０１〜２０Ｔｏｒｒ）にす
る。なお、１０Ｔｏｒｒ以上の圧力で堆積する時は、断
熱膨張による凝集での粒子発生を防止するため、シャワ
ーノズル７での圧力差をなくす必要がある。シリコン基
板８の温度は、好ましくは ４５０℃程度とし、この例
では、シャワーノズル７からのガス噴射の効果で図２に
示した様にシャワーノズルからシリコン基板８近傍で圧
力が上昇する。このパターンは熱分布もほぼ同じである
。このことにより、シリコン基板とその表面上数十μｍ
近傍とで温度分布が発生し、 １００℃程度以上の温度
差が生じる。
このため、基板８上では酸化膜の酸化及び緻密化が同時
に進行すると共に、基板８の極近傍でＴＥＯＳの分解反
応も促進され、低温で緻密なシリコン酸化膜が形成され
る。シリコン酸化膜の成長後、搬送系９を介してロード
ロック室１０のカセット１１に戻すと共に新たなウェハ
ー基板を供給する。Embodiment 1 A first embodiment of the present invention will be described with reference to FIG. In this embodiment, a silicon oxide film is formed on a silicon substrate using water and TEOS. Water is generated from a water vapor generating cylinder 2 placed in a thermostatic chamber 1 at a steam pressure of several tens of torr, and a low differential pressure mass flow controller (MFC) is used to generate water.
) 3 to the preheating chamber 4 in a desired amount, for example 50scc.
About 1000 yen is supplied. Using a similar device, TEOS is supplied from the cylinder 5 through the MFC 6 at a rate of, for example, about 20 sccm. Furthermore, nitrogen (N2) or an inert gas (for example, Ar) is added, and the mixed gas is injected from the shower nozzle 7. In the preheating chamber 4, heating is preferably carried out to a temperature at which no film is formed, thereby promoting the first-stage reaction. Preferably, the gas pressure in the preliminary chamber is about 20 Torr (range 1 to 60 Torr).
, the temperature is around 200℃ (range is 100~300℃)
), and the pressure in the reaction chamber is preferably 0.1
~10 Torr (range 0.01 to 20 Torr). Note that when depositing at a pressure of 10 Torr or more, it is necessary to eliminate the pressure difference at the shower nozzle 7 in order to prevent particle generation due to aggregation due to adiabatic expansion. The temperature of the silicon substrate 8 is preferably about 450° C., and in this example, due to the effect of the gas jet from the shower nozzle 7, the pressure increases near the silicon substrate 8 from the shower nozzle as shown in FIG. This pattern has almost the same heat distribution. This allows the silicon substrate and its surface to be
A temperature distribution occurs in the vicinity, resulting in a temperature difference of approximately 100°C or more. Therefore, the oxidation and densification of the oxide film proceed simultaneously on the substrate 8, and the decomposition reaction of TEOS is also promoted in the very vicinity of the substrate 8, forming a dense silicon oxide film at a low temperature. After the silicon oxide film is grown, the wafer is returned to the cassette 11 in the load lock chamber 10 via the transport system 9 and a new wafer substrate is supplied.
【００１２】このようにして得られた基板上のシリコン
酸化膜はＳＥＭ、エッチレートによって観察したところ
、ラインアンドスペースパターをきれいに埋め込め、ま
たエッチレートも熱酸化膜に近い値を得、非常に平坦で
緻密な良質の膜であった。When the silicon oxide film thus obtained on the substrate was observed by SEM and etch rate, it was found that the line-and-space pattern could be embedded neatly, the etch rate was close to that of a thermal oxide film, and it was extremely flat. The film was dense and of good quality.
【００１３】実施例２
図３を参照して第二実施例を説明する。この例では、ガ
ス供給系は実施例１と同じで、新たに図３に示す様に有
機シランガス以外の酸素、オゾン、水等のガスをウェハ
ー近傍から供給する。チャンバー１２の周辺にドーナツ
状に配置した励起室１３から噴射することによってウェ
ハー近傍での酸化膜の緻密化を更に促進する。更に図４
に示したようにパルス変調された高周波を印加して励起
する。これによりオゾン、イオン、ラジカル等がパルス
的に発生し、この周期に同調して酸化膜の緻密化が起こ
る。更にこの逆位相で流動性物の堆積とマイグレーショ
ンにより平坦化が進行して、平坦かつ高品質の酸化膜が
成長する。この方法によれば、平坦化を促進するため、
基板に超音波発生器１４から超音波を印加する。これに
より、流動性物のマイグレーションが一層盛んになる。
１５はオゾン発生器である。表面流動性を有する膜の堆
積に対して垂直（重力方向）に超音波振動を加えると膜
の重量が見かけ上増加して流動が促進される。Embodiment 2 A second embodiment will be described with reference to FIG. In this example, the gas supply system is the same as in Example 1, and as shown in FIG. 3, gases such as oxygen, ozone, water, etc. other than organic silane gas are newly supplied from near the wafer. The densification of the oxide film near the wafer is further promoted by ejecting from the excitation chamber 13 arranged in a donut shape around the chamber 12. Furthermore, Figure 4
Excite by applying pulse-modulated high frequency as shown in . This generates ozone, ions, radicals, etc. in a pulsed manner, and densification of the oxide film occurs in synchronization with this cycle. Furthermore, flattening progresses due to the deposition and migration of the fluid in this opposite phase, and a flat, high-quality oxide film grows. According to this method, in order to promote flattening,
Ultrasonic waves are applied to the substrate from an ultrasonic generator 14. As a result, the migration of the fluid material becomes more active. 15 is an ozone generator. When ultrasonic vibrations are applied perpendicularly (in the direction of gravity) to a deposited film with surface fluidity, the weight of the film increases apparently and flow is promoted.
【００１４】実施例３
図５を参照して本発明の第三実施例を更に説明する。図
５に示したように、この実施例では、基板１６から５ｍ
ｍ程度離した所に金属（例えばＣｕ製）メッシュ１７を
配置する。このメッシュ１７はガスに対するコンダクタ
ンスが大きく、高周波は漏れないように作製する。シャ
ワー１８のノズルは例えば、図６に示したように、間隔
０．３ｍｍの下に凸のテパー状をしている。これは、
チャンバーとソース供給側との圧力の変化を徐々に行な
うためである。ここで、印加される高周波はパルス状に
行なってもよい。Embodiment 3 A third embodiment of the present invention will be further described with reference to FIG. As shown in FIG. 5, in this embodiment, 5 m from the substrate 16
A metal (for example, made of Cu) mesh 17 is placed at a distance of about m. This mesh 17 has a large conductance with respect to gas and is made so as to prevent leakage of high frequency waves. For example, as shown in FIG. 6, the nozzles of the shower 18 have a downwardly convex tapered shape with an interval of 0.3 mm. this is,
This is to gradually change the pressure between the chamber and the source supply side. Here, the high frequency may be applied in a pulsed manner.
【００１５】本発明の第三実施例に従って、例えばＴＥ
ＯＳ（流量：２０ｓｃｃｍ）並びに水（流量：１００ｓ
ｃｃｍ）、Ｏ２ （流量：５ｓｃｃｍ）、Ａｒ（流量：
１０ｓｃｃｍ）のガスから基板付近温度 ４５０℃でＳ
ｉ基板上に形成させたシリコン酸化膜は、段差部分がな
めらかに埋め込まれ、膜の電気耐圧も５ＭＶ／ｃｍ以上
と高い値を示し、非常に平坦で緻密な良質の膜であった
。According to a third embodiment of the invention, for example TE
OS (flow rate: 20sccm) and water (flow rate: 100s
ccm), O2 (flow rate: 5 sccm), Ar (flow rate:
10 sccm) gas at a temperature near the substrate of 450°C.
In the silicon oxide film formed on the i-substrate, the stepped portions were smoothly filled in, and the film had a high electrical withstand voltage of 5 MV/cm or more, and was a very flat, dense, and high-quality film.
【００１６】実施例４
次に、図７を参照して本発明の第四実施例を更に説明す
る。図７に示したように、この実施例ではウェハー（基
板）１９の近傍に滞留層２０を形成せしめてシリコン酸
化膜を基板上に形成せしめる。この方法では有機シラン
以外のガスのウェハー近傍からの供給室２１より基板１
９を取り囲むようにして供給し、滞留層２０を形成する
。シャワー２２から噴射されたＴＥＯＳ等のガスが滞留
層２０にぶつかり、より一層、基板１９の近傍とシャワ
ー２２付近との圧力差が生じて平坦化と緻密化の同時進
行が効率よく行なわれる。供給室２１よりの水、Ｏ２
などのガスをパルス的に供給すると、膜の流動と酸化が
交互に行なわれるので、より平坦化に効果がある。Embodiment 4 Next, a fourth embodiment of the present invention will be further described with reference to FIG. As shown in FIG. 7, in this embodiment, a retention layer 20 is formed near a wafer (substrate) 19, and a silicon oxide film is formed on the substrate. In this method, a gas other than organic silane is supplied to the substrate 1 from a supply chamber 21 from near the wafer.
9 is supplied to form a retention layer 20. Gas such as TEOS injected from the shower 22 collides with the retention layer 20, further creating a pressure difference between the vicinity of the substrate 19 and the vicinity of the shower 22, so that flattening and densification can proceed efficiently at the same time. Water and O2 from supply chamber 21
When a gas such as the like is supplied in a pulsed manner, the film is alternately flowed and oxidized, which is more effective in flattening the film.
【００１７】[0017]
【発明の効果】以上説明したように、本発明に従えば、
プラズマによるダメージがなく、 ５００℃以下の比較
的低温で平坦でかつ緻密な良質のシリコン酸化膜を形成
できるので、層間絶縁膜の信頼性が著しく向上する。更
に膜にかかる応力も小さいので、多層配線の信頼性も向
上する。従って、本発明によれば多層化がいっそう進み
、何世代も先の集積度を実現することができる。[Effects of the Invention] As explained above, according to the present invention,
Since there is no plasma damage and a flat, dense, high-quality silicon oxide film can be formed at a relatively low temperature of 500° C. or less, the reliability of the interlayer insulating film is significantly improved. Furthermore, since the stress applied to the film is small, the reliability of multilayer wiring is also improved. Therefore, according to the present invention, it is possible to further increase the number of layers and achieve a degree of integration several generations in the future.
【図１】本発明の第一実施例に用いる熱ＣＶＤ装置を示
す図面である。FIG. 1 is a drawing showing a thermal CVD apparatus used in a first embodiment of the present invention.
【図２】本発明の第一実施例におけるガス圧の分布を示
す図面である。FIG. 2 is a drawing showing the gas pressure distribution in the first embodiment of the present invention.
【図３】本発明の第二実施例に用いる熱ＣＶＤ装置の一
部を示す図面である。FIG. 3 is a drawing showing a part of a thermal CVD apparatus used in a second embodiment of the present invention.
【図４】本発明の第二実施例におけるパルス変調された
高周波印加による励起状況を示す図面である。FIG. 4 is a drawing showing an excitation situation by pulse-modulated high frequency application in a second embodiment of the present invention.
【図５】本発明の第三実施例に用いる熱ＣＶＤ装置の一
部を示す図面である。FIG. 5 is a drawing showing a part of a thermal CVD apparatus used in a third embodiment of the present invention.
【図６】本発明の第三実施例に用いるシャワーノズルを
示す図面である。FIG. 6 is a drawing showing a shower nozzle used in a third embodiment of the present invention.
【図７】本発明の第四実施例に用いる熱ＣＶＤ装置の一
部を示す図面である。FIG. 7 is a drawing showing a part of a thermal CVD apparatus used in a fourth embodiment of the present invention.
Claims (8)
は水酸基と水素原子をガス状で含んだ雰囲気中で熱ＣＶ
Ｄ法のみによってシリコン酸化膜を形成する工程を含ん
でなることを特徴とする半導体装置の製造方法。Claim 1: Thermal CV in an atmosphere containing organic silane gas and at least water molecules or hydroxyl groups and hydrogen atoms in gaseous form.
A method for manufacturing a semiconductor device, comprising the step of forming a silicon oxide film only by the D method.
項１に記載の方法。2. The method according to claim 1, wherein ozone is further included in the atmosphere.
又は光等で励起して導入する請求項１又は２に記載の方
法。3. The method according to claim 1, wherein a gas other than organic silane gas is introduced by exciting it with plasma or light.
的に間欠供給すると共に基板に超音波を印加する請求項
３に記載の方法。4. The method according to claim 3, wherein organic silane or other gas is intermittently supplied in pulses and ultrasonic waves are applied to the substrate.
加熱を行なって前段階反応を促進し、更に膜堆積基板側
で反応温度以上にし、かつ、基板側での温度勾配を急に
して、基板付近のガスを滞留させてガス圧を高め、ソー
ス供給側の流れを早くすることを特徴とする請求項１に
記載の方法。5. Performing preheating on the source supply side to a temperature below the film formation temperature to promote the pre-stage reaction, further heating the film deposition substrate side to a temperature above the reaction temperature, and steepening the temperature gradient on the substrate side, The method according to claim 1, characterized in that the gas near the substrate is allowed to stagnate to increase the gas pressure and to speed up the flow on the source supply side.
、このメッシュと基板電極との間でプラズマを発生せし
めることを特徴とする請求項１に記載の方法。6. The method according to claim 1, further comprising arranging a conductive mesh near the substrate and generating plasma between the mesh and the substrate electrode.
ス滞留層へ供給する請求項５に記載の方法。7. The method according to claim 5, wherein a gas other than organic silane is supplied to the gas retention layer near the substrate.
求項５に記載の方法。8. The method according to claim 5, wherein a step is provided surrounding the periphery of the substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11612091A JPH04343456A (en) | 1991-05-21 | 1991-05-21 | Manufacture of semiconductor device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11612091A JPH04343456A (en) | 1991-05-21 | 1991-05-21 | Manufacture of semiconductor device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04343456A true JPH04343456A (en) | 1992-11-30 |
Family
ID=14679194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11612091A Pending JPH04343456A (en) | 1991-05-21 | 1991-05-21 | Manufacture of semiconductor device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04343456A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06168930A (en) * | 1992-11-30 | 1994-06-14 | Nec Corp | Chemical vapor growth, chemical vapor growth device and manufacture of multilayer wiring |
| US5840631A (en) * | 1994-11-28 | 1998-11-24 | Nec Corporation | Method of manufacturing semiconductor device |
| US6352338B1 (en) * | 1992-12-22 | 2002-03-05 | Canon Kabushiki Kaisha | Ink-jet print head, production method thereof, and printing apparatus with the ink-jet print head |
| US6706648B2 (en) | 1995-09-08 | 2004-03-16 | Semiconductor Energy Laboratory Co., Ltd | APCVD method of forming silicon oxide using an organic silane, oxidizing agent, and catalyst-formed hydrogen radical |
| JP2007234709A (en) * | 2006-02-28 | 2007-09-13 | Sanyo Electric Co Ltd | Manufacturing apparatus and manufacturing method of silicon oxide |
| DE102009049283A1 (en) * | 2009-10-13 | 2011-04-14 | Behr Gmbh & Co. Kg | Process for coating at least a part of a basic body |
-
1991
- 1991-05-21 JP JP11612091A patent/JPH04343456A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06168930A (en) * | 1992-11-30 | 1994-06-14 | Nec Corp | Chemical vapor growth, chemical vapor growth device and manufacture of multilayer wiring |
| US6352338B1 (en) * | 1992-12-22 | 2002-03-05 | Canon Kabushiki Kaisha | Ink-jet print head, production method thereof, and printing apparatus with the ink-jet print head |
| US5840631A (en) * | 1994-11-28 | 1998-11-24 | Nec Corporation | Method of manufacturing semiconductor device |
| US6706648B2 (en) | 1995-09-08 | 2004-03-16 | Semiconductor Energy Laboratory Co., Ltd | APCVD method of forming silicon oxide using an organic silane, oxidizing agent, and catalyst-formed hydrogen radical |
| US7491659B2 (en) | 1995-09-08 | 2009-02-17 | Semiconductor Energy Laboratory Co., Ltd. | APCVD method of forming silicon oxide using an organic silane, oxidizing agent, and catalyst-formed hydrogen radical |
| JP2007234709A (en) * | 2006-02-28 | 2007-09-13 | Sanyo Electric Co Ltd | Manufacturing apparatus and manufacturing method of silicon oxide |
| DE102009049283A1 (en) * | 2009-10-13 | 2011-04-14 | Behr Gmbh & Co. Kg | Process for coating at least a part of a basic body |
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