JP2019033187A - Cleaning solvent and manufacturing method of substrate for manufacturing semiconductor device - Google Patents
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Description
本発明は、洗浄溶剤及び半導体装置製造用基板の製造方法に関するものである。 The present invention relates to a cleaning solvent and a method for manufacturing a substrate for manufacturing a semiconductor device.
半導体装置の高性能化は、リソグラフィー技術における光源の短波長化によるパターン寸法の微細化がけん引してきた。しかし、ＡｒＦ光源以降、短波長化の速度が鈍化したため、これに代わるリソグラフィー手法が開発されてきた（特許文献１〜３）。このようなリソグラフィーパターンを基板に転写する方法の一つとして、多層レジスト法がある。この方法は、フォトレジスト膜、即ちレジスト上層膜とエッチング選択性が異なる中間膜、例えばケイ素含有下層膜をレジスト上層膜と被加工基板の間に介在させ、レジスト上層膜にパターンを得た後、上層レジストパターンをドライエッチングマスクとして、ドライエッチングによりレジスト下層膜にパターンを転写し、更に下層レジストパターンをドライエッチングマスクとして、ドライエッチングにより被加工基板にパターンを転写する方法である。 Improvement in the performance of semiconductor devices has been driven by the miniaturization of pattern dimensions due to the shorter wavelength of light sources in lithography technology. However, since the speed of wavelength shortening has slowed since the ArF light source, an alternative lithography method has been developed (Patent Documents 1 to 3). One method for transferring such a lithography pattern onto a substrate is a multilayer resist method. In this method, a photoresist film, that is, an intermediate film having etching selectivity different from that of the resist upper layer film, for example, a silicon-containing lower layer film is interposed between the resist upper layer film and the substrate to be processed, and a pattern is obtained on the resist upper layer film. In this method, the upper resist pattern is used as a dry etching mask, the pattern is transferred to the resist lower layer film by dry etching, and the lower resist pattern is used as the dry etching mask to transfer the pattern to the substrate to be processed by dry etching.
この様な多層レジスト法で使用されるものとして、ケイ素含有膜がよく知られている。例えば、ＣＶＤによるケイ素含有無機膜としては、ＳｉＯ２膜（特許文献４）やＳｉＯＮ膜（特許文献５）等があり、回転塗布により膜を得られるものとしては、ケイ素含有下層膜、所謂ＳＯＧ（スピンオンガラス）膜（特許文献６）や架橋性シルセスキオキサン膜（特許文献７）等がある。ＣＶＤによるケイ素含有無機膜と比較した場合、塗布型のケイ素含有下層膜はプロセス及びコストの点でメリットがある。 Silicon-containing films are well known as those used in such a multilayer resist method. For example, as a silicon-containing inorganic film by CVD, there are an SiO 2 film (Patent Document 4), an SiON film (Patent Document 5), and the like. Spin-on glass) film (Patent Document 6) and cross-linkable silsesquioxane film (Patent Document 7). Compared with a silicon-containing inorganic film formed by CVD, a coating-type silicon-containing underlayer film has advantages in terms of process and cost.
このような半導体装置用の多層膜が形成された半導体装置製造用の基板（ウエハー）を、製造プロセスの関係上、ウエハー搬送用ケースに収納して、製造装置間を搬送しなければならない場合がある。この時、ウエハー端部まで塗布膜が形成されていると、この塗布膜とウエハーケースとが接触し、塗布膜から微小な粉じんが発生する場合がある。この粉じんの発生を防止するため、ウエハー端部の塗布膜を除去する必要がある。 A semiconductor device manufacturing substrate (wafer) on which a multilayer film for such a semiconductor device is formed may be housed in a wafer transfer case and transferred between manufacturing devices due to the manufacturing process. is there. At this time, if the coating film is formed up to the edge of the wafer, the coating film and the wafer case may come into contact with each other, and fine dust may be generated from the coating film. In order to prevent the generation of this dust, it is necessary to remove the coating film on the wafer edge.
上記理由により、ウエハー端部の洗浄は、半導体装置製造プロセスでは一般的に使用されている。しかしながら、ウエハー端部の塗布膜を一般的な洗浄溶剤で洗浄除去すると、塗布膜中への洗浄溶剤の浸透により、本来なら平坦であるはずの洗浄後の塗布膜の端部が盛り上がり、膜厚が厚くなる場合がある。このような厚膜化現象が発生すると、ドライエッチング加工後に厚膜化した塗布膜の一部がウエハー上に残留し、半導体装置の歩留まりの低下の原因となる。 For the above reasons, wafer edge cleaning is commonly used in semiconductor device manufacturing processes. However, if the coating film on the edge of the wafer is removed by washing with a general cleaning solvent, the edge of the coated film after cleaning, which should have been flat, rises due to the penetration of the cleaning solvent into the coating film. May become thicker. When such a thickening phenomenon occurs, a part of the coating film thickened after dry etching remains on the wafer, which causes a reduction in the yield of the semiconductor device.
上述した半導体装置の歩留まり低下を防ぐためには、ウエハー端部の塗布膜を洗浄除去しても、塗布膜が均一な膜厚である必要がある。 In order to prevent the above-described reduction in the yield of the semiconductor device, it is necessary that the coating film has a uniform thickness even if the coating film on the wafer edge is washed away.
本発明は、上記事情に鑑みなされたもので、塗布膜が形成された基板上の端部の塗布膜を洗浄除去する際に適用しても、洗浄後の塗布膜の端部の厚膜化を抑制できる洗浄溶剤、及び該洗浄溶剤を用いた半導体装置製造用基板の製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and even if it is applied when cleaning and removing the coating film at the end portion on the substrate on which the coating film is formed, the end portion of the coating film after cleaning is thickened. An object of the present invention is to provide a cleaning solvent capable of suppressing the above and a method for manufacturing a substrate for manufacturing a semiconductor device using the cleaning solvent.
上記課題を解決するために、本発明では、塗布膜が形成された基板上の端部の前記塗布膜を洗浄除去するための洗浄溶剤であって、下記一般式（Ａ）で示される化合物を含有する洗浄溶剤を提供する。
本発明のような洗浄溶剤であれば、塗布膜が形成された基板上の端部の塗布膜を洗浄除去する際に適用すると、洗浄後の塗布膜の端部の厚膜化を抑制できる。 If the cleaning solvent as in the present invention is applied when cleaning and removing the coating film at the end portion on the substrate on which the coating film is formed, it is possible to suppress the thickening of the end portion of the coating film after cleaning.
また、前記一般式（Ａ）で示される化合物が、常温・常圧で液体であることが好ましい。 Moreover, it is preferable that the compound shown by the said general formula (A) is a liquid at normal temperature and a normal pressure.
このような化合物であれば、洗浄溶剤として容易に使用することが出来る。 Such a compound can be easily used as a cleaning solvent.
また、前記一般式（Ａ）で示される化合物を３０質量％以上含有するものであることが好ましい。 Moreover, it is preferable to contain 30% by mass or more of the compound represented by the general formula (A).
このような洗浄溶剤であれば、塗布膜が形成された基板上の端部の塗布膜を洗浄除去する際、洗浄後の塗布膜の端部の厚膜化をより確実に抑制できる。 With such a cleaning solvent, when the coating film at the end portion on the substrate on which the coating film is formed is cleaned and removed, the thickening of the end portion of the coating film after cleaning can be more reliably suppressed.
また、本発明では、半導体装置製造用基板の製造方法であって、塗布膜を基板上に回転塗布する工程と、前記基板上の端部の塗布膜を下記一般式（Ａ）で示される化合物を含有する洗浄溶剤を用いて洗浄除去する工程と、洗浄除去工程後に得られた塗布膜を１５０℃以上４５０℃以下の温度で１０秒〜３００秒の範囲で熱処理を加えて硬化膜を得る工程とを含む半導体装置製造用基板の製造方法も提供する。
本発明のような半導体装置製造用基板の製造方法であれば、洗浄後の塗布膜の端部の厚膜化を抑制でき、製造プロセスの歩留まりを向上できる。 According to the method for manufacturing a substrate for manufacturing a semiconductor device as in the present invention, it is possible to suppress an increase in the thickness of the end portion of the coated film after cleaning, and to improve the yield of the manufacturing process.
また、前記塗布膜として、ケイ素含有膜を用いることが好ましい。 Moreover, it is preferable to use a silicon-containing film as the coating film.
また、前記ケイ素含有膜として、ポリシロキサンを含有するケイ素含有膜を用いることが好ましい。 Moreover, it is preferable to use a silicon-containing film containing polysiloxane as the silicon-containing film.
また、前記ケイ素含有膜として、ケイ素含有量が１０質量％以上であるケイ素含有膜を用いることが好ましい。 Further, it is preferable to use a silicon-containing film having a silicon content of 10% by mass or more as the silicon-containing film.
このような塗布膜が塗布された基板において、本発明の半導体装置製造用基板の製造方法は好適に用いることが出来る。 In the substrate coated with such a coating film, the method for manufacturing a substrate for manufacturing a semiconductor device of the present invention can be preferably used.
以上のように、本発明の洗浄溶剤であれば、基板上に形成された塗布膜中へ浸透することがないため、塗布膜が塗布されたウエハー端部の不要な塗布膜を洗浄除去する際に用いても、洗浄後の塗布膜の端部に盛り上がり、即ち塗布膜の端部の厚膜化現象が発生しない。結果として、ドライエッチング加工後に厚膜化した塗布膜の一部がウエハー上に残留しないため、被加工基板の欠陥発現を抑制でき、半導体装置製造用基板の製造プロセスの歩留まりを向上できる。また、本発明の半導体装置製造用基板の製造方法であれば、一般式（Ａ）で示される化合物を含有する洗浄溶剤を適用することにより、塗布膜中への洗浄溶剤の浸透が無くなり、洗浄後の塗布膜端部の厚膜化現象は発生しない。そのため、ドライエッチング加工後に厚膜化した塗布膜の一部がウエハー上に残留することはない。その結果として、被加工基板の欠陥発現を抑制でき、半導体装置製造用基板の製造プロセスの歩留まりを向上できる。本発明は、ウエハー上へ回転塗布により形成される有用な回転塗布膜、例えばケイ素含有膜を用いた半導体装置製造用基板の製造方法に好適である。 As described above, the cleaning solvent of the present invention does not penetrate into the coating film formed on the substrate. Therefore, when the unnecessary coating film on the edge of the wafer coated with the coating film is cleaned and removed. Even if it is used, the end of the coated film after washing is raised, that is, the thickening phenomenon at the end of the coated film does not occur. As a result, since a part of the coating film thickened after dry etching does not remain on the wafer, the occurrence of defects in the substrate to be processed can be suppressed, and the yield of the manufacturing process of the substrate for manufacturing a semiconductor device can be improved. Moreover, if it is a manufacturing method of the board | substrate for semiconductor device manufacture of this invention, the penetration of the washing | cleaning solvent in a coating film will be eliminated by applying the washing | cleaning solvent containing the compound shown by general formula (A), and washing | cleaning The thickening phenomenon at the end of the coating film later does not occur. Therefore, a part of the coating film thickened after the dry etching process does not remain on the wafer. As a result, the occurrence of defects in the substrate to be processed can be suppressed, and the yield of the manufacturing process of the semiconductor device manufacturing substrate can be improved. The present invention is suitable for a method of manufacturing a substrate for manufacturing a semiconductor device using a useful spin coating film formed on a wafer by spin coating, for example, a silicon-containing film.
上記のように、塗布膜が形成された基板上の端部の塗布膜を洗浄除去する際に適用しても、洗浄後の塗布膜の端部の厚膜化を抑制できる洗浄溶剤、及び該洗浄溶剤を用いた半導体装置製造用基板の製造方法が求められていた。 As described above, a cleaning solvent that can suppress an increase in the thickness of the edge of the coating film after cleaning, even when applied to the removal of the coating film at the edge of the substrate on which the coating film is formed, and the There has been a demand for a method of manufacturing a substrate for manufacturing a semiconductor device using a cleaning solvent.
本発明者らは、鋭意検討を行った結果、回転塗布による塗布製膜方法、中でもケイ素含有膜の製膜方法において、基板上の端部の不要な塗布膜を溶剤で洗浄除去する際に、洗浄後の塗布膜の盛り上がりが発生しない洗浄溶剤を見出し、本発明を完成させた。 As a result of intensive studies, the inventors of the present invention have performed spin coating to form a coating film, particularly a silicon-containing film, and when removing an unnecessary coating film on the edge of the substrate with a solvent, The present inventors have found a cleaning solvent that does not cause swell of the coated film after cleaning, and completed the present invention.
すなわち、本発明は、塗布膜が形成された基板上の端部の前記塗布膜を洗浄除去するための洗浄溶剤であって、下記一般式（Ａ）で示される化合物を含有する洗浄溶剤である。
以下、本発明について詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
＜洗浄溶剤＞
本発明では、下記一般式（Ａ）で示される化合物を含む洗浄溶剤を、半導体装置製造用基板を製造する際に、塗布膜が形成された基板（ウエハー）上の端部の塗布膜を洗浄除去するための洗浄溶剤として用いる。
In the present invention, a cleaning solvent containing a compound represented by the following general formula (A) is used to clean a coating film at an end on a substrate (wafer) on which a coating film is formed when a substrate for manufacturing a semiconductor device is manufactured. Used as a cleaning solvent for removal.
式中、Ｒは水素原子、芳香族炭化水素、炭素数１〜６のアルキル基、又は極性基である。炭素数１〜６のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、シクロプロピル基、ｎ−ブチル基、ｉ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、シクロブチル基、１−メチル−シクロプロピル基、２−メチル−シクロプロピル基、ｎ−ペンチル基、１−メチル−ｎ−ブチル基、２−メチル−ｎ−ブチル基、３−メチル−ｎ−ブチル基、１，１−ジメチル−ｎ−プロピル基、１，２−ジメチル−ｎ−プロピル基、２，２−ジメチル−ｎ−プロピル基、１−エチル−ｎ−プロピル基、シクロペンチル基、１−メチル−シクロブチル基、２−メチル−シクロブチル基、３−メチル−シクロブチル基、１，２−ジメチル−シクロプロピル基、２，３−ジメチル−シクロプロピル基、１−エチル−シクロプロピル基、２−エチル−シクロプロピル基、ｎ−ヘキシル基、１−メチル−ｎ−ペンチル基、２−メチル−ｎ−ペンチル基、３−メチル−ｎ−ペンチル基、４−メチル−ｎ−ペンチル基、１，１−ジメチル−ｎ−ブチル基、１，２−ジメチル−ｎ−ブチル基、１，３−ジメチル−ｎ−ブチル基、２，２−ジメチル−ｎ−ブチル基、２，３−ジメチル−ｎ−ブチル基、３，３−ジメチル−ｎ−ブチル基、１−エチル−ｎ−ブチル基、２−エチル−ｎ−ブチル基、１，１，２−トリメチル−ｎ−プロピル基、１，２，２−トリメチル−ｎ−プロピル基、１−エチル−１−メチル−ｎ−プロピル基、１−エチル−２−メチル−ｎ−プロピル基、シクロヘキシル基、１−メチル−シクロペンチル基、２−メチル−シクロペンチル基、３−メチル−シクロペンチル基、１−エチル−シクロブチル基、２−エチル−シクロブチル基、３−エチル−シクロブチル基、１，２−ジメチル−シクロブチル基、１，３−ジメチル−シクロブチル基、２，２−ジメチル−シクロブチル基、２，３−ジメチル−シクロブチル基、２，４−ジメチル−シクロブチル基、３，３−ジメチル−シクロブチル基、１−ｎ−プロピル−シクロプロピル基、２−ｎ−プロピル−シクロプロピル基、１−ｉ−プロピル−シクロプロピル基、２−ｉ−プロピル−シクロプロピル基、１，２，２−トリメチル−シクロプロピル基、１，２，３−トリメチル−シクロプロピル基、２，２，３−トリメチル−シクロプロピル基、１−エチル−２−メチル−シクロプロピル基、２−エチル−１−メチル−シクロプロピル基、２−エチル−２−メチル−シクロプロピル基及び２−エチル−３−メチル−シクロプロピル基等が挙げられる。極性基としては、例えば、ニトロ基、シアノ基、スルホ基、カルボキシ基、アシル基、カルバモイル基、エポキシ基、メルカプト基、ヒドロキシ基、ヒドロキシメチル基、ヒドロキシエチル基、アミノ基等が挙げられる。ＸとＹはそれぞれ独立して−ＣＨ２−、−Ｏ−、−ＮＨ−、又は−Ｓ−であり、ｎは１〜６の整数である。 In the formula, R is a hydrogen atom, an aromatic hydrocarbon, an alkyl group having 1 to 6 carbon atoms, or a polar group. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t- Butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n -Butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1 -Methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl Group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl -N-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1, 2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl -Cyclopentyl group, 3-methyl-cyclope Til group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1- i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl- Cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2- Examples thereof include a methyl-cyclopropyl group and a 2-ethyl-3-methyl-cyclopropyl group. Examples of the polar group include nitro group, cyano group, sulfo group, carboxy group, acyl group, carbamoyl group, epoxy group, mercapto group, hydroxy group, hydroxymethyl group, hydroxyethyl group, amino group and the like. X and Y are each independently —CH 2 —, —O—, —NH—, or —S—, and n is an integer of 1 to 6.
また、一般式（Ａ）で示される化合物は、常温・常圧で液体であることが好ましく、具体的にはγ−ブチロラクトン、δ−バレロラクトン、プロピレンカーボネート等が例示できるが、これらに限定されるものではない。 Further, the compound represented by the general formula (A) is preferably liquid at normal temperature and normal pressure, and specific examples include γ-butyrolactone, δ-valerolactone, propylene carbonate and the like, but are not limited thereto. It is not something.
本発明の洗浄溶剤に含まれる一般式（Ａ）で示される化合物の濃度は、３０質量％以上が好ましく、７０質量％以上がより好ましく、９５質量％以上が更に好ましい。 The concentration of the compound represented by the general formula (A) contained in the cleaning solvent of the present invention is preferably 30% by mass or more, more preferably 70% by mass or more, and still more preferably 95% by mass or more.
このような本発明の洗浄溶剤であれば、基板上に形成された塗布膜中へ浸透することがないため、塗布膜が塗布されたウエハー端部の不要な塗布膜を洗浄除去する際に用いても、洗浄後の塗布膜の端部に盛り上がり、即ち洗浄後の塗布膜の端部の厚膜化現象が発生しない。結果として、ドライエッチング加工後に厚膜化した塗布膜の一部がウエハー上に残留しないため、被加工基板の欠陥発現を抑制でき、製造プロセスの歩留まりを向上できる。 Since the cleaning solvent of the present invention does not penetrate into the coating film formed on the substrate, it is used for cleaning and removing an unnecessary coating film on the wafer end coated with the coating film. However, the end of the coated film after cleaning rises, that is, the thickening phenomenon does not occur at the end of the coated film after cleaning. As a result, since a part of the coating film that has been thickened after dry etching does not remain on the wafer, the occurrence of defects in the substrate to be processed can be suppressed, and the yield of the manufacturing process can be improved.
＜半導体装置製造用基板の製造方法＞
また、本発明では、半導体装置製造用基板の製造方法であって、塗布膜を基板上に回転塗布する工程と、前記基板上の端部の塗布膜を下記一般式（Ａ）で示される化合物を含有する洗浄溶剤を用いて洗浄除去する工程と、洗浄除去工程後に得られた塗布膜を１５０℃以上４５０℃以下の温度で１０秒〜３００秒の範囲で熱処理を加えて硬化膜を得る工程とを含む半導体装置製造用基板の製造方法も提供する。以下、各工程について詳しく説明する。
Further, in the present invention, there is provided a method for producing a substrate for manufacturing a semiconductor device, the step of spin-coating a coating film on a substrate, and a compound represented by the following general formula (A): A step of washing and removing using a cleaning solvent containing, and a step of applying a heat treatment to the coating film obtained after the washing and removing step at a temperature of 150 ° C. to 450 ° C. for 10 seconds to 300 seconds to obtain a cured film The manufacturing method of the board | substrate for semiconductor device manufacture containing these is also provided. Hereinafter, each step will be described in detail.
［塗布膜形成工程］
本発明の半導体装置製造用基板の製造方法において、塗布膜はスピンコーター等を用いた常法の回転塗布によって、ウエハー上に形成することができる。
[Coating film forming process]
In the method for manufacturing a substrate for manufacturing a semiconductor device of the present invention, the coating film can be formed on the wafer by conventional spin coating using a spin coater or the like.
塗布膜としては、ケイ素含有膜を用いることが好ましい。ケイ素含有膜材料組成物としては、特に限定されず、ＡｒＦ用ケイ素含有膜材料、ＫｒＦ用ケイ素含有膜材料等を例示することができる。また、例えば、特許文献６や、特許文献８等に挙げられたものを例示することができる。 A silicon-containing film is preferably used as the coating film. It does not specifically limit as a silicon-containing film material composition, The silicon-containing film material for ArF, the silicon-containing film material for KrF, etc. can be illustrated. Further, for example, those listed in Patent Document 6, Patent Document 8, and the like can be exemplified.
なお、ケイ素含有膜としては、ポリシロキサンを含有するケイ素含有膜を用いることが好ましい。 As the silicon-containing film, it is preferable to use a silicon-containing film containing polysiloxane.
また、ケイ素含有膜のケイ素含有量は、１０質量％以上であることが好ましい。 The silicon content of the silicon-containing film is preferably 10% by mass or more.
［塗布膜洗浄除去工程］
ウエハー端部の塗布膜の洗浄除去工程は、塗布膜をウエハー上に回転塗布した後、熱処理工程前に行われる。
[Coating film cleaning removal process]
The process of cleaning and removing the coating film on the wafer edge is performed after the coating film is spin-coated on the wafer and before the heat treatment process.
洗浄除去工程で用いられる洗浄溶剤としては、上述の洗浄溶剤の説明で挙げたものと同様の物を使用する。 As the cleaning solvent used in the cleaning and removing step, the same ones as mentioned in the description of the cleaning solvent are used.
ウエハー端部の塗布膜の洗浄除去する方法としては、特に限定されず、一般的に使用されている洗浄方法を用いることができる。例えば、スピンコーターを用いて上記塗布膜形成後、引き続いて上記洗浄溶剤を基板の端部のみに供給して、端部の塗布膜を除去するようにしてもよいし、塗布膜形成後の基板を回転させながらその端部だけを前記洗浄溶剤に浸漬等により接触させるようにしてもよい。 A method for cleaning and removing the coating film on the edge of the wafer is not particularly limited, and a commonly used cleaning method can be used. For example, after the coating film is formed using a spin coater, the cleaning solvent may be supplied to only the edge of the substrate to remove the coating film on the edge, or the substrate after the coating film is formed. Only the end portion may be brought into contact with the cleaning solvent by immersion or the like.
［熱処理工程］
熱処理工程は、洗浄除去工程後に得られた塗布膜をホットプレート等で加熱することで行われる。また、熱処理工程は１５０℃以上４５０℃以下の温度で１０秒〜３００秒の範囲で行われる。
[Heat treatment process]
The heat treatment step is performed by heating the coating film obtained after the cleaning removal step with a hot plate or the like. Further, the heat treatment step is performed at a temperature of 150 ° C. or higher and 450 ° C. or lower in a range of 10 seconds to 300 seconds.
本発明の半導体装置製造用基板の製造方法は、ウエハー端部の塗布膜を洗浄除去する際、塗布膜中への洗浄溶剤の侵入がないために、洗浄後の塗布膜の端部の盛り上がりは発生しない。その結果として、ドライエッチング加工後に塗布膜の一部がウエハー上に残留しないため、被加工基板の欠陥発現を最小限に抑制することができる。 In the method for manufacturing a substrate for manufacturing a semiconductor device according to the present invention, when the coating film on the wafer edge is cleaned and removed, there is no penetration of the cleaning solvent into the coating film. Does not occur. As a result, since a part of the coating film does not remain on the wafer after dry etching, the occurrence of defects on the substrate to be processed can be minimized.
以下、実施例及び比較例を示して本発明をより具体的に説明するが、本発明は下記の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited to the following Example.
［実施例１］
ケイ素含有レジスト中間層ポリマー（ＳＯＧ−１）として、以下のポリマーのプロピレングリコールエチルエーテル２％溶液を調製した。該ＳＯＧ−１を、東京エレクトロン（株）製クリーントラックＡＣＴ１２を用いてシリコンウエハーに１５００ｒｐｍで回転塗布し、塗布膜を形成した。塗布膜が形成されたシリコンウエハーを回転させたまま、ウエハー端部の塗布膜をγ−ブチロラクトンで７秒間かけ流して外周部から３ｍｍ洗浄除去した後に、２４０℃で６０秒間加熱して、膜厚３８ｎｍの塗布膜（ケイ素含有レジスト中間層）を作製した。得られた塗布膜の中心、端部、及びウエハー端部付近の膜厚を（株）日立ハイテクノロジーズ製電子顕微鏡（Ｓ−４７００）で得られた断面図から測定した。その結果を表１に示す。
As a silicon-containing resist intermediate layer polymer (SOG-1), a 2% solution of propylene glycol ethyl ether in the following polymer was prepared. The SOG-1 was spin-coated on a silicon wafer at 1500 rpm using a clean track ACT12 manufactured by Tokyo Electron Ltd. to form a coating film. While rotating the silicon wafer on which the coating film was formed, the coating film at the wafer edge was washed with γ-butyrolactone for 7 seconds, washed and removed from the outer periphery by 3 mm, and then heated at 240 ° C. for 60 seconds to obtain a film thickness. A 38 nm coating film (silicon-containing resist intermediate layer) was prepared. The film thickness in the vicinity of the center, edge, and wafer edge of the obtained coating film was measured from a cross-sectional view obtained with an electron microscope (S-4700) manufactured by Hitachi High-Technologies Corporation. The results are shown in Table 1.
［実施例２］
ウエハー端部の塗布膜をδ−バレロラクトンで洗浄除去した以外は、実施例１と同様の方法で塗布膜（ケイ素含有レジスト中間層）を作製した。その後、得られた塗布膜の膜厚を実施例１と同様の方法で測定した。その結果を表１に示す。
[Example 2]
A coating film (silicon-containing resist intermediate layer) was produced in the same manner as in Example 1 except that the coating film on the wafer edge was washed and removed with δ-valerolactone. Thereafter, the thickness of the obtained coating film was measured in the same manner as in Example 1. The results are shown in Table 1.
［実施例３］
ウエハー端部の塗布膜をプロピレンカーボネートで洗浄除去した以外は、実施例１と同様の方法で塗布膜（ケイ素含有レジスト中間層）を作製した。その後、得られた塗布膜の膜厚を実施例１と同様の方法で測定した。その結果を表１に示す。
[Example 3]
A coating film (silicon-containing resist intermediate layer) was produced in the same manner as in Example 1 except that the coating film on the wafer edge was washed away with propylene carbonate. Thereafter, the thickness of the obtained coating film was measured in the same manner as in Example 1. The results are shown in Table 1.
［実施例４］
ウエハー端部の塗布膜をγ−ブチロラクトン３０％、プロピレングリコールモノメチルエーテル７０％の混合液で洗浄除去した以外は、実施例１と同様の方法で塗布膜を作製した。その後、得られた塗布膜の膜厚を実施例１と同様の方法で測定した。その結果を表１に示す。
[Example 4]
A coating film was prepared in the same manner as in Example 1 except that the coating film on the edge of the wafer was washed and removed with a mixed solution of 30% γ-butyrolactone and 70% propylene glycol monomethyl ether. Thereafter, the thickness of the obtained coating film was measured in the same manner as in Example 1. The results are shown in Table 1.
［実施例５］
ウエハー端部の塗布膜をδ−バレロラクトン３０％、プロピレングリコールモノメチルエーテル７０％の混合液で洗浄除去した以外は、実施例１と同様の方法で塗布膜を作製した。その後、得られた塗布膜の膜厚を実施例１と同様の方法で測定した。その結果を表１に示す。
[Example 5]
A coating film was produced in the same manner as in Example 1 except that the coating film on the wafer edge was washed and removed with a mixed solution of 30% δ-valerolactone and 70% propylene glycol monomethyl ether. Thereafter, the thickness of the obtained coating film was measured in the same manner as in Example 1. The results are shown in Table 1.
［実施例６］
ウエハー端部の塗布膜をプロピレンカーボネート３０％、プロピレングリコールモノメチルエーテル７０％の混合液で洗浄除去した以外は、実施例１と同様の方法で塗布膜を作製した。その後、得られた塗布膜の膜厚を実施例１と同様の方法で測定した。その結果を表１に示す。
[Example 6]
A coating film was prepared in the same manner as in Example 1 except that the coating film on the wafer edge was washed and removed with a mixed solution of 30% propylene carbonate and 70% propylene glycol monomethyl ether. Thereafter, the thickness of the obtained coating film was measured in the same manner as in Example 1. The results are shown in Table 1.
［比較例１］
ウエハー端部の塗布膜をＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）で洗浄除去した以外は、実施例１と同様の方法で塗布膜を作製した。その後、得られた塗布膜の膜厚を実施例１と同様の方法で測定した。その結果を表１に示す。
[Comparative Example 1]
A coating film was prepared in the same manner as in Example 1 except that the coating film on the wafer edge was washed and removed with PGMEA (propylene glycol monomethyl ether acetate). Thereafter, the thickness of the obtained coating film was measured in the same manner as in Example 1. The results are shown in Table 1.
［比較例２］
ウエハー端部の塗布膜をＰＧＭＥＡ３０％、プロピレングリコールモノメチルエーテル７０％の混合液で洗浄除去した以外は、実施例１と同様の方法で塗布膜を作製した。その後、得られた塗布膜の膜厚を実施例１と同様の方法で測定した。その結果を表１に示す。
[Comparative Example 2]
A coating film was produced in the same manner as in Example 1 except that the coating film on the edge of the wafer was washed and removed with a mixed solution of 30% PGMEA and 70% propylene glycol monomethyl ether. Thereafter, the thickness of the obtained coating film was measured in the same manner as in Example 1. The results are shown in Table 1.
表１に示されるように、本発明の洗浄溶剤でウエハー端部を洗浄した実施例１〜６では、洗浄後の塗布膜端部は厚膜化していなかった。一方、ウエハー端部の洗浄にＰＧＭＥＡを用いた比較例１、２では、洗浄後の塗布膜端部が厚膜化した。これは、ウエハー端部の洗浄時に洗浄液の浸み込みが発生したためだと考えられる。 As shown in Table 1, in Examples 1 to 6 where the wafer edge was cleaned with the cleaning solvent of the present invention, the coated film edge after cleaning was not thickened. On the other hand, in Comparative Examples 1 and 2 in which PGMEA was used for cleaning the wafer edge, the coating film edge after cleaning was thickened. This is thought to be due to the penetration of the cleaning liquid during the cleaning of the wafer edge.
［欠陥検査］
次いで、実施例１〜６、比較例１、２で作製した塗布膜を、後述のエッチング条件（１）でドライエッチングした後、得られたウエハー表面をＫＬＡ−Ｔｅｎｃｏｒ社製暗視野欠陥検査装置ＳＰ２で６０ｎｍ以上の大きさの表面ダスト数を計測した。その結果を表２に示す。
[Defect inspection]
Next, the coating films prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were dry-etched under the etching conditions (1) described below, and the resulting wafer surface was subjected to KLA-Tencor dark field defect inspection apparatus SP2. The number of surface dust having a size of 60 nm or more was measured. The results are shown in Table 2.
（ＣＨＦ３／ＣＦ４系ガスでのエッチング条件（１））
装置：東京エレクトロン（株）製ドライエッチング装置ＴｅｌｉｕｓＳＰ
チャンバー圧力：１０Ｐａ
Ｕｐｐｅｒ／ＬｏｗｅｒＲＦパワー：５００Ｗ／３００Ｗ
ＣＨＦ３ガス流量：５０ｍｌ／ｍｉｎ
ＣＦ４ガス流量：１５０ｍｌ／ｍｉｎ
Ａｒガス流量：１００ｍｌ／ｍｉｎ
処理時間：４０ｓｅｃ
(Etching conditions with CHF 3 / CF 4 gas (1))
Apparatus: Tokyo Electron's dry etching system TeliusSP
Chamber pressure: 10Pa
Upper / LowerRF power: 500W / 300W
CHF 3 gas flow rate: 50 ml / min
CF 4 gas flow rate: 150 ml / min
Ar gas flow rate: 100 ml / min
Processing time: 40 sec
表２に示されるように、本発明の洗浄溶剤でウエハー端部を洗浄した実施例１〜６では、ドライエッチング後のダストの数は１０個以下であった。これは、ウエハー端部の洗浄時に塗布膜への洗浄液の浸み込みが発生せず、ウエハー端部の洗浄後でも、塗布膜端部の膜厚が洗浄前の膜厚と比べ大きな変化が無いことから、続いて適用されたドライエッチングにおいて、均一にドライエッチングされたことで、ドライエッチング残渣が少なかったためだと考えられる。一方、ウエハー端部の洗浄にＰＧＭＥＡを用いた比較例１、２では、ドライエッチング後のダストの数は２００個以上であった。これは、中心部の塗布膜がドライエッチングされる時間で処理しても、厚膜化した塗布膜端部がダストとしてウエハー上に残っているためだと考えられる。 As shown in Table 2, in Examples 1 to 6 where the wafer edge was cleaned with the cleaning solvent of the present invention, the number of dust after dry etching was 10 or less. This is because the cleaning film does not penetrate into the coating film when cleaning the wafer edge, and the film thickness at the coating film edge does not change much compared to the film thickness before cleaning even after cleaning the wafer edge. From this, it is considered that the dry etching residue applied in the subsequent application resulted in less dry etching residue due to uniform dry etching. On the other hand, in Comparative Examples 1 and 2 using PGMEA for cleaning the wafer edge, the number of dust after dry etching was 200 or more. This is considered to be because the thickened coating film edge remains as dust on the wafer even when the coating film in the center is processed for the dry etching time.
以上のことから、本発明であれば、塗布膜が形成された基板上の端部の塗布膜を洗浄除去する際に適用すると、洗浄後の塗布膜の端部の厚膜化を抑制できることが明らかになった。 From the above, if the present invention is applied when cleaning and removing the coating film at the end on the substrate on which the coating film is formed, it is possible to suppress the thickening of the edge of the coating film after cleaning. It was revealed.
なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。 The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.
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