JP3721208B2 - Formation method of phosphosilicate glass film by vapor deposition. - Google Patents
Formation method of phosphosilicate glass film by vapor deposition. Download PDFInfo
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- JP3721208B2 JP3721208B2 JP27400894A JP27400894A JP3721208B2 JP 3721208 B2 JP3721208 B2 JP 3721208B2 JP 27400894 A JP27400894 A JP 27400894A JP 27400894 A JP27400894 A JP 27400894A JP 3721208 B2 JP3721208 B2 JP 3721208B2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
- H01L21/02129—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material being boron or phosphorus doped silicon oxides, e.g. BPSG, BSG or PSG
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/14—Other methods of shaping glass by gas- or vapour- phase reaction processes
- C03B19/1415—Reactant delivery systems
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
- H01L21/02216—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/07—Impurity concentration specified
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/20—Doped silica-based glasses doped with non-metals other than boron or fluorine
- C03B2201/28—Doped silica-based glasses doped with non-metals other than boron or fluorine doped with phosphorus
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2207/00—Glass deposition burners
- C03B2207/30—For glass precursor of non-standard type, e.g. solid SiH3F
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2207/00—Glass deposition burners
- C03B2207/30—For glass precursor of non-standard type, e.g. solid SiH3F
- C03B2207/32—Non-halide
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2207/00—Glass deposition burners
- C03B2207/36—Fuel or oxidant details, e.g. flow rate, flow rate ratio, fuel additives
Description
【０００１】
【産業上の利用分野】
本発明は、半導体、フラットディスプレイ、光磁気メモリ、光素子及びセンサー等のデバイスの絶縁保護膜などに利用されるリン珪酸ガラス膜の気相成長による形成法に関する。
【０００２】
【従来の技術】
ＳｉＯ2膜にリンをド−プした形のリン珪酸ガラス(以下、ＰＳＧと略称する)膜は、ＬＳＩ製造プロセスに不可欠な膜であり、表面安定化膜、層間絶縁膜、Ａｌ配線保護膜などに用いられる。ＰＳＧ膜中のＰの効果としてはアルカリゲッタ−、膜の耐クラック性付与、ガラス軟化点の低減などがあげられる。
【０００３】
ＰＳＧ膜の形成法としては化学気相成長(ＣＶＤ)法が用いられ、原料としてＳｉＨ4、ＰＨ3及びＯ2が使用され、下記のような反応によるものが一般的なものである：
ＳｉＨ4＋ＰＨ3＋Ｏ2→ＳｉＯ2＋Ｐ2Ｏ5＋Ｈ2Ｏ
しかしながら、半導体デバイスの微細化、高集積化が進むにつれて配線のアスペクト比が大きくなり、絶縁膜層のステップカバレッジ(段差被覆性)が悪くなって配線間にボイドが生ずる結果となった。
【０００４】
こうした問題点を受けて、現在ではオゾンを酸化剤に用い、Ｓｉソ−スとしてＴＥＯＳ［テトラエトキシシラン：Ｓｉ(ＯＣ2Ｈ5)4］及びＰソ−スとしてトリメチルホスフェイト［ＰＯ(ＯＣＨ3）3］あるいはトリメチルホスファイト［Ｐ(ＯＣＨ3)3］が多く採用されるに至っている。
この原料系で形成されたＰＳＧ膜はステップカバレッジが良好でボイドが生じないことに加え、表面の平坦性が良好であること、ピンホ−ルが無いこと、パ−ティクルの付着が無いことなどの特長を有し、さらに当該原料はＳｉＨ4、ＰＨ3などの水素化物に比べて発火性がないため安全で取り扱い易いといった利点もあり、こうした点が現在実用化されている理由となっている。
【０００５】
【発明が解決しようとする課題】
しかし、半導体デバイスは現在もさらに高集積化、高密度化が進んでいる状況にあり、ＴＥＯＳ、トリメチルホスフェイト等を用いる形成法でもステップカバレッジに限界が生じつつある。そのため、さらに効果的なＰＳＧ膜の形成法が求められている状況にある。
また、ド−プされるリンは、Ｐ2Ｏ3、Ｐ2Ｏ5などの形でＳｉＯ2膜中に３〜５重量％程度含まれているのが一般的であり、リンを高濃度化しようとすると、Ｐ2Ｏ3やＰ2Ｏ5がＳｉＯ2膜から分離する結果となり、一定濃度以上にド−プすることが不可能となっている。
【０００６】
ＰＳＧ膜を層間絶縁膜のリフロ−平坦化に応用する場合には、８重量％以上のリン濃度を必要とし、そのためにはＳｉ−Ｏ−Ｐの安定した結合状態を形成しなければならず、この点からもＰＳＧ膜の形成法の改良が求められている。
【０００７】
従って、本発明の目的は、上記の問題点を解決するべく、分子中にすでにＳｉ−Ｏ−Ｐの結合を含む化合物とオゾンを原料とする気相成長によるＰＳＧ膜の形成法を提供することにある。
【０００８】
【課題を解決するための手段】
即ち、本発明の気相成長によるＰＳＧ膜の形成法は、原料として１分子中にＳｉ−Ｏ−Ｐ結合を有する化合物及びオゾンを使用することを特徴とする。
【０００９】
なお、１分子中にＳｉ−Ｏ−Ｐ結合を有する化合物としては、下記の一般式
【化２】
で示される化合物が好ましい。
【００１０】
また、上記ＰＳＧ膜の形成法に使用される気相成長法としては、化学気相成長(ＣＶＤ)法が好ましい。
【００１１】
本発明方法は絶縁保護膜の形成法として好適なものであり、例えば 半導体、フラットディスプレイ、光磁気メモリ、光素子及びセンサー等のデバイスの絶縁保護膜としてＰＳＧ膜を使用する時に使用することができる。
【００１２】
本発明の気相成長によるＰＳＧ膜の形成法は、Ｓｉ−Ｏ−Ｐ結合を有する化合物の蒸気およびオゾンを常圧にて混合し、加熱した基板にＰＳＧ膜を気相成長させるものである。
【００１３】
本発明のＰＳＧ膜の形成法に原料として用いられるＳｉ−Ｏ−Ｐ結合を有する化合物とは、１分子中にＳｉ−Ｏ−Ｐ結合を１つ以上有する化合物であれば特に限定されない。これに該当する化合物は、例えばアルキル置換シリルホスフェート、アルキル置換シリルホスファイトである。
【００１４】
前記化合物のうち好ましいものは、上記一般式(１)で示される化合物である。一般式(１)において、Ｒ1〜Ｒ5は直鎖または分岐鎖を有するアルキル基であり、それぞれ同一でも異なっても良い。かかるアルキル基としては、メチル、エチル、プロピル、２−プロピル、ブチル、２−ブチル、tert−ブチル、ペンチル、２−ペンチル、tert−ペンチル、ヘキシル、ヘプチル、オクチル等が挙げられる。中でも好ましいアルキル基は炭素数１〜３のアルキル基で、メチル、エチル、プロピル、２−プロピルである。
【００１５】
上記一般式(１)で示される化合物のうち好ましいものとしては、ジメチル(トリメチルシリル)ホスファイト、ジメチル(トリエチルシリル)ホスファイト、ジエチル(トリメチルシリル)ホスファイト、ジイソプロピル(トリメチルシリル)ホスファイト等が挙げられる。
【００１６】
これらの化合物は、一定の蒸気圧を確保するために一定温度に保温し、Ｎ2、Ａｒなどの不活性ガスをキャリアとして吹き込むことにより、該化合物の蒸気含有ガスとして反応チャンバに導入される。このときの基板温度は２５０〜３５０℃とするのが適当である。また、オゾンはＯ2をオゾナイザに通じ、Ｏ2に対して１.５〜７％、好ましくは３〜６％の濃度になるように設定するのが好ましい。なお、ＰＳＧ膜の膜厚は膜成長時間の増減により任意に制御することができる。
【００１７】
本発明方法により得られるＰＳＧ膜は、膜中に安定した結合状態でリンが存在し、また、Ｓｉ／Ｐ濃度比が使用する原料毎に一定であるため、従来品に比べて耐湿性、絶縁耐圧が良好であり、信頼性に優れたものである。
【００１８】
【実施例】
次に実施例を示し、本発明を具体的に説明する。
実施例１
第１図は本発明に用いるＣＶＤ装置の模式的構造図である。図において１ａ〜１ｃは流量計、２ａ〜２ｅはバルブ、３はオゾナイザ−、４は原料の気化室、５はチャンバ、６はディスパ−ジョンヘッド、７はヒ−タ、８は基板のＳｉウエハ、９は排気口である。
まず、原料のジメチル(トリメチルシリル)ホスファイト［Ｍｅ3ＳｉＯＰ(ＯＣＨ3）2］を気化室(4)に充填し、４５℃に保温して蒸気圧を一定にし、また、チャンバ(5)内の基板(8)をヒ−タ(7)で３００℃に加熱した。次に、キャリアガスのＮ2を気化室に３リットル／分で吹き込み、チャンバ内に原料を含むガスを導入した。同時に希釈用ガスとしてＮ2を１８リットル／分で導入し、さらにＯ2ガスをオゾナイザ(3)に通し、オゾン濃度を５％にして導入することによりＳｉウエハ基板上に厚さ１.５μｍのＰＳＧ膜を成長させた。
このようにして得られたＰＳＧ膜中のＰ濃度をＩＣＰ法により測定したところ、１５重量％の高濃度であることが判明した。
また、幅０.２５μｍ、高さ１.２μｍのトレンチに対するステップカバレッジ特性は、第２図ａに示すようにボイドの無い良好なフロ−形状が得られた。
【００１９】
実施例２
原料としてジエチル(トリメチルシリル)ホスファイトを用いる他は実施例１と同様の方法にて、厚さ１.４μｍのＰＳＧ膜を得た。得られたＰＳＧ膜のＰ濃度をＩＣＰ法により測定したところ、１３.５重量％であった。
【００２０】
実施例３
原料としてジエチル(モノメチルジプロピルシリル)ホスファイトを用いる他は実施例１と同様の方法にて、厚さ１.５μｍのＰＳＧ膜を得た。得られたＰＳＧ膜のＰ濃度をＩＣＰ法により測定したところ１３重量％であった。
【００２１】
比較例
原料として、ＳｉソースにＴＥＯＳ及びＰソースにトリメチルホスフェートを用い、気化室をそれぞれ６５℃、６０℃に保温し、チャンバ(5)内の基板(8)をヒ−タ(7)で４００℃に加熱した。次にキャリアガスのＮ2を気化室にそれぞれ３リットル／分、１.５リットル／分で吹き込み、チャンバ内に原料を含むガスを導入した。同時に希釈用ガスとしてＮ2を１８リットル／分で導入し、さらにＯ2ガスをオゾナイザ(3)に通し、オゾン濃度を５％にして導入することによりＳｉウエハ基板上にＰＳＧ膜を成長させた。
このようにして得られたＰＳＧ膜中のＰ濃度をＩＣＰ法測定したところ、４重量％の濃度であった。
また、幅０.２５μｍ、高さ１.２μｍのトレンチに対するステップカバレッジ特性は、第２図ｂに示すようにトレンチ内部にボイドが生ずる結果となった。
【００２２】
【発明の効果】
本発明の効果は、ステップカバレッジ特性が良好で、ＴＥＯＳ系のプロセスより約１００℃低温でＰＳＧ膜が得られる方法を提供することである。また、単一原料からＰＳＧ膜を得ることができ、複数の原料の場合のようにそれぞれの流量比調節の必要がなく、膜製造工程管理が容易な絶縁保護膜製造方法を提供することできる。更に、本発明の方法により、高濃度のＰがド−プでき、ＬＳＩ製造における層間絶縁膜への応用が可能となった。
従って、本発明の気相成長によるＰＳＧ膜の形成法により、信頼性の高い半導体装置の作成が可能となった。
【図面の簡単な説明】
【図１】本発明の実施例に用いるＣＶＤ装置の模式的構造図である。
【図２】実施例と従来法のステップカバレッジの比較図である。
【符号の説明】
１ａ〜１ｃ：流量計
２ａ〜２ｅ：バルブ
３ ：オゾナイザ
４ ：気化室
５ ：チャンバ
６ ：ディスパ−ジョンヘッド
７ ：ヒ−タ
８ ：基板
９ ：排気口[0001]
[Industrial application fields]
The present invention relates to a method of forming a phosphosilicate glass film by vapor deposition used for an insulating protective film of a device such as a semiconductor, a flat display, a magneto-optical memory, an optical element, and a sensor.
[0002]
[Prior art]
A phosphosilicate glass (hereinafter abbreviated as PSG) film in which phosphorus is doped on a SiO 2 film is an indispensable film for an LSI manufacturing process, such as a surface stabilizing film, an interlayer insulating film, an Al wiring protective film, etc. Used for. Examples of the effect of P in the PSG film include an alkali getter, imparting crack resistance to the film, and reducing the glass softening point.
[0003]
A chemical vapor deposition (CVD) method is used as a method for forming the PSG film, SiH 4 , PH 3 and O 2 are used as raw materials, and the following reaction is generally used:
SiH 4 + PH 3 + O 2 → SiO 2 + P 2 O 5 + H 2 O
However, as the semiconductor device is miniaturized and highly integrated, the aspect ratio of the wiring increases, and the step coverage (step coverage) of the insulating film layer deteriorates, resulting in voids between the wirings.
[0004]
In response to these problems, ozone is now used as an oxidizing agent, TEOS [tetraethoxysilane: Si (OC 2 H 5 ) 4 ] as the Si source, and trimethyl phosphate [PO (OCH 3 ) as the P source. 3 ] or trimethyl phosphite [P (OCH 3 ) 3 ] has been widely adopted.
The PSG film formed with this raw material system has good step coverage and no voids, and also has good surface flatness, no pinholes, and no adhesion of particles. In addition, the raw material is advantageous in that it is safe and easy to handle because it is not ignitable as compared with hydrides such as SiH 4 and PH 3 .
[0005]
[Problems to be solved by the invention]
However, semiconductor devices are still being increasingly integrated and densified, and the step coverage is becoming limited even in the formation method using TEOS, trimethyl phosphate, or the like. Therefore, there is a need for a more effective method for forming a PSG film.
The doped phosphorus is generally contained in the SiO 2 film in the form of P 2 O 3 , P 2 O 5 or the like in an amount of about 3 to 5% by weight. Attempts to do so result in the separation of P 2 O 3 and P 2 O 5 from the SiO 2 film, making it impossible to dop above a certain concentration.
[0006]
When the PSG film is applied to the reflow planarization of the interlayer insulating film, a phosphorus concentration of 8% by weight or more is required. For this purpose, a stable bonded state of Si—O—P must be formed, From this point of view, improvement of the method for forming the PSG film is required.
[0007]
Accordingly, an object of the present invention is to provide a method for forming a PSG film by vapor phase growth using a compound containing an Si—O—P bond in the molecule and ozone as raw materials in order to solve the above-mentioned problems. It is in.
[0008]
[Means for Solving the Problems]
That is, the method for forming a PSG film by vapor deposition according to the present invention is characterized in that a compound having a Si—O—P bond in one molecule and ozone are used as raw materials.
[0009]
In addition, as a compound having a Si—O—P bond in one molecule, the following general formula:
The compound shown by these is preferable.
[0010]
Further, as the vapor phase growth method used for forming the PSG film, a chemical vapor deposition (CVD) method is preferable.
[0011]
The method of the present invention is suitable as a method for forming an insulating protective film, and can be used, for example, when a PSG film is used as an insulating protective film for devices such as semiconductors, flat displays, magneto-optical memories, optical elements and sensors. .
[0012]
In the method of forming a PSG film by vapor phase growth according to the present invention, vapor of a compound having a Si—O—P bond and ozone are mixed at normal pressure, and the PSG film is vapor-phase grown on a heated substrate.
[0013]
The compound having a Si—O—P bond used as a raw material in the method for forming a PSG film of the present invention is not particularly limited as long as it is a compound having one or more Si—O—P bonds in one molecule. Examples of such compounds include alkyl-substituted silyl phosphates and alkyl-substituted silyl phosphites.
[0014]
Among the compounds, a compound represented by the general formula (1) is preferable. In the general formula (1), R 1 to R 5 are linear or branched alkyl groups, which may be the same or different. Such alkyl groups include methyl, ethyl, propyl, 2-propyl, butyl, 2-butyl, tert-butyl, pentyl, 2-pentyl, tert-pentyl, hexyl, heptyl, octyl and the like. Among them, preferred alkyl groups are alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, propyl and 2-propyl.
[0015]
Preferable examples of the compound represented by the general formula (1) include dimethyl (trimethylsilyl) phosphite, dimethyl (triethylsilyl) phosphite, diethyl (trimethylsilyl) phosphite, diisopropyl (trimethylsilyl) phosphite and the like.
[0016]
These compounds are kept at a constant temperature in order to ensure a constant vapor pressure, and introduced into the reaction chamber as a vapor-containing gas of the compound by blowing an inert gas such as N 2 or Ar as a carrier. The substrate temperature at this time is suitably 250 to 350 ° C. Further, it is preferable that ozone is set so that O 2 is passed through an ozonizer and the concentration is 1.5 to 7%, preferably 3 to 6% with respect to O 2 . The thickness of the PSG film can be arbitrarily controlled by increasing or decreasing the film growth time.
[0017]
The PSG film obtained by the method of the present invention contains phosphorus in a stable bonding state in the film, and the Si / P concentration ratio is constant for each raw material used. Good withstand voltage and excellent reliability.
[0018]
【Example】
Next, an Example is shown and this invention is demonstrated concretely.
Example 1
FIG. 1 is a schematic structural diagram of a CVD apparatus used in the present invention. In the figure, 1a to 1c are flowmeters, 2a to 2e are valves, 3 is an ozonizer, 4 is a raw material vaporizing chamber, 5 is a chamber, 6 is a dispersion head, 7 is a heater, and 8 is a substrate Si wafer. , 9 are exhaust ports.
First, the raw material dimethyl (trimethylsilyl) phosphite [Me 3 SiOP (OCH 3 ) 2 ] is filled in the vaporization chamber (4), kept at 45 ° C. to keep the vapor pressure constant, and in the chamber (5) The substrate (8) was heated to 300 ° C. with a heater (7). Next, N 2 as a carrier gas was blown into the vaporization chamber at 3 liters / minute, and a gas containing a raw material was introduced into the chamber. At the same time, N 2 was introduced as a dilution gas at a rate of 18 liters / minute, and further O 2 gas was passed through an ozonizer (3) and introduced with an ozone concentration of 5%, so that a thickness of 1.5 μm was formed on the Si wafer substrate. A PSG film was grown.
When the P concentration in the PSG film thus obtained was measured by the ICP method, it was found to be a high concentration of 15% by weight.
Further, as shown in FIG. 2a, the step coverage characteristic for the trench having a width of 0.25 μm and a height of 1.2 μm has a good flow shape without voids.
[0019]
Example 2
A PSG film having a thickness of 1.4 μm was obtained in the same manner as in Example 1 except that diethyl (trimethylsilyl) phosphite was used as a raw material. When the P concentration of the obtained PSG film was measured by the ICP method, it was 13.5% by weight.
[0020]
Example 3
A PSG film having a thickness of 1.5 μm was obtained in the same manner as in Example 1 except that diethyl (monomethyldipropylsilyl) phosphite was used as a raw material. When the P concentration of the obtained PSG film was measured by the ICP method, it was 13% by weight.
[0021]
As comparative materials, TEOS was used as the Si source and trimethyl phosphate was used as the P source, the vaporization chambers were kept at 65 ° C. and 60 ° C., respectively, and the substrate (8) in the chamber (5) was heated to 400 by the heater (7). Heated to ° C. Next, N 2 as a carrier gas was blown into the vaporization chamber at 3 liters / minute and 1.5 liters / minute, respectively, and a gas containing raw materials was introduced into the chamber. At the same time, N 2 was introduced as a dilution gas at a rate of 18 liters / minute, and O 2 gas was passed through an ozonizer (3) and introduced at an ozone concentration of 5% to grow a PSG film on the Si wafer substrate. .
When the P concentration in the PSG film thus obtained was measured by the ICP method, it was 4% by weight.
Further, the step coverage characteristic for a trench having a width of 0.25 .mu.m and a height of 1.2 .mu.m resulted in the formation of voids inside the trench as shown in FIG.
[0022]
【The invention's effect】
The effect of the present invention is to provide a method in which a PSG film is obtained at a temperature lower by about 100 ° C. than a TEOS-based process with good step coverage characteristics. Further, a PSG film can be obtained from a single raw material, and there is no need to adjust the flow rate ratio as in the case of a plurality of raw materials, and an insulating protective film manufacturing method that can easily manage the film manufacturing process can be provided. Furthermore, by the method of the present invention, a high concentration of P can be doped, and application to an interlayer insulating film in LSI manufacturing becomes possible.
Therefore, a highly reliable semiconductor device can be formed by the method of forming a PSG film by vapor deposition according to the present invention.
[Brief description of the drawings]
FIG. 1 is a schematic structural diagram of a CVD apparatus used in an embodiment of the present invention.
FIG. 2 is a comparison diagram of step coverage between an embodiment and a conventional method.
[Explanation of symbols]
1a-1c: Flowmeters 2a-2e: Valve 3: Ozonizer 4: Vaporization chamber 5: Chamber 6: Dispersion head 7: Heater 8: Substrate 9: Exhaust port
Claims (4)
で示される請求項１記載の気相成長によるリン珪酸ガラス膜の形成法。A compound having a Si—O—P bond in one molecule is represented by the following general formula:
The method for forming a phosphosilicate glass film by vapor phase growth according to claim 1, which is represented by the following:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27400894A JP3721208B2 (en) | 1994-11-08 | 1994-11-08 | Formation method of phosphosilicate glass film by vapor deposition. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27400894A JP3721208B2 (en) | 1994-11-08 | 1994-11-08 | Formation method of phosphosilicate glass film by vapor deposition. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08133754A JPH08133754A (en) | 1996-05-28 |
| JP3721208B2 true JP3721208B2 (en) | 2005-11-30 |
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| JP3251554B2 (en) * | 1998-12-04 | 2002-01-28 | キヤノン販売株式会社 | Film forming method and semiconductor device manufacturing method |
| JP2002274871A (en) * | 2001-03-15 | 2002-09-25 | Asahi Denka Kogyo Kk | Method for producing silicate glass layer for optical wave guide and material for cvd used in the same |
| JP5003503B2 (en) * | 2008-01-17 | 2012-08-15 | 三菱電機株式会社 | Method for producing quartz glass and method for producing optical device |
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