JP4839968B2 - Resist removing composition and resist removing method - Google Patents
Resist removing composition and resist removing method Download PDFInfo
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- JP4839968B2 JP4839968B2 JP2006159572A JP2006159572A JP4839968B2 JP 4839968 B2 JP4839968 B2 JP 4839968B2 JP 2006159572 A JP2006159572 A JP 2006159572A JP 2006159572 A JP2006159572 A JP 2006159572A JP 4839968 B2 JP4839968 B2 JP 4839968B2
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Description
本発明は、レジスト除去用組成物に関する。さらには、半導体デバイスやフラットパネルディスプレー等に使用されるレジストを選択的に除去できる組成物に関するものである。 The present invention relates to a resist removal composition. Furthermore, it is related with the composition which can selectively remove the resist used for a semiconductor device, a flat panel display, etc.
レジストは、半導体やフラットパネルディスプレー等の製造に欠かせないものである。このレジストを除去するため、硫酸と過酸化水素の混合物（ＳＰＭ）やアミンを含む溶媒が一般に使用されている。中でも半導体の基板工程に使用されるレジストは、砒素が高濃度で注入されており、非常に除去し難くなっている。このレジストを除去するために、現在は、ＳＰＭを使用している。ところが、近年、半導体の微細化に伴い、シリコン部分のわずかな酸化、あるいはシリコン酸化膜（以下、酸化膜と称す）へのわずかなダメージも、半導体デバイスの製造には致命的になってきている。現在、最も多用されているＳＰＭは、過酸化水素という酸化剤を含み、しかも酸化膜へのダメージがあるため、最先端の微細化された半導体の製造には適用できなくなってきている。 The resist is indispensable for manufacturing semiconductors and flat panel displays. In order to remove the resist, a mixture containing sulfuric acid and hydrogen peroxide (SPM) or an amine is generally used. In particular, a resist used in a semiconductor substrate process is implanted with a high concentration of arsenic and is very difficult to remove. Currently, SPM is used to remove the resist. However, in recent years, with the miniaturization of semiconductors, slight oxidation of a silicon portion or slight damage to a silicon oxide film (hereinafter referred to as an oxide film) has become fatal for the manufacture of semiconductor devices. . At present, the most frequently used SPM contains an oxidizing agent called hydrogen peroxide and has a damage to an oxide film, so that it cannot be applied to the manufacture of the most advanced miniaturized semiconductors.
一方、硫酸を用いたレジスト剥離液として、硫酸及び有機ニトリルからなるレジスト剥離液が開示されているが、半導体の基板工程で使用される砒素が高濃度に注入されたレジストにおいては、除去が困難であった（例えば、特許文献１参照）。 On the other hand, a resist stripping solution composed of sulfuric acid and an organic nitrile is disclosed as a resist stripping solution using sulfuric acid, but it is difficult to remove in a resist in which arsenic used in a semiconductor substrate process is implanted at a high concentration. (For example, see Patent Document 1).
本発明の目的は、上記の課題に鑑みて、酸化剤を含まず、しかも酸化膜にダメージを与えず、砒素が注入されたレジストを除去する組成物を提供することにある。 In view of the above problems, an object of the present invention is to provide a composition for removing a resist into which arsenic has been implanted without containing an oxidizing agent and damaging an oxide film.
本発明者らは、レジスト除去について鋭意検討した結果、硫酸及び可溶性ケイ素化合物を含んでなるレジスト除去用組成物が、酸化剤を含まず、しかも他の半導体材料、特に酸化ケイ素にダメージを与えることなく、レジストを除去できることを見出し、本発明を完成させるに至った。 As a result of intensive studies on resist removal, the present inventors have found that a resist removal composition containing sulfuric acid and a soluble silicon compound does not contain an oxidizing agent and damages other semiconductor materials, particularly silicon oxide. Thus, the present inventors have found that the resist can be removed and have completed the present invention.
すなわち、本発明は、硫酸及び可溶性ケイ素化合物を含んでなるレジスト除去用組成物、及びそれを用いたレジストの除去方法に関する。 That is, the present invention relates to a resist removal composition comprising sulfuric acid and a soluble silicon compound, and a resist removal method using the same.
以下に、本発明をさらに詳細に説明する。 The present invention is described in further detail below.
本発明のレジスト除去用組成物の必須成分は、硫酸及び可溶性ケイ素化合物である。 The essential components of the resist removal composition of the present invention are sulfuric acid and a soluble silicon compound.
本発明のレジスト除去用組成物は硫酸を必須成分とするが、使用する硫酸には特に制限はなく、一般に流通している硫酸を使用することができる。硫酸には電子材料に適した、金属分の少ないグレードがあるが、これを使用することが好ましい。 Although the resist removal composition of the present invention contains sulfuric acid as an essential component, the sulfuric acid used is not particularly limited, and generally available sulfuric acid can be used. Sulfuric acid has a low metal content suitable for electronic materials, but it is preferable to use this.
硫酸の濃度は濃いものが好ましく、濃硫酸が最も好ましい。水が混入するとレジスト除去能力が低下する。 A concentrated sulfuric acid is preferable, and concentrated sulfuric acid is most preferable. When water is mixed in, the resist removing ability is lowered.
本発明のレジスト除去用組成物は、可溶性ケイ素化合物が必須成分であり、ケイ酸、ケイ酸塩、ヘキサフルオロケイ酸、ヘキサフルオロケイ酸塩が特に好ましいが、それ以外の可溶性ケイ素化合物を使用しても一向に差し支えない。例えば、燐酸で窒化ケイ素をエッチングした場合、燐酸中にケイ素化合物が溶解していることが知られているが、このケイ素化合物を含む燐酸を、本発明のレジスト除去用組成物に使用することも可能である。ケイ酸塩、ヘキサフルオロケイ酸塩としては、アンモニウム塩が好ましい。ケイ酸、ケイ酸塩は、ケイ素酸化物などを硫酸に添加し、加熱して溶解させたものを使用しても良い。ヘキサフルオロケイ酸、ヘキサフルオロケイ酸塩は、工業的に流通しているものを使用しても良いし、ケイ酸にフッ化水素酸を反応させ、さらにこれを塩にしても良い。 In the resist removal composition of the present invention, a soluble silicon compound is an essential component, and silicic acid, silicate, hexafluorosilicate, and hexafluorosilicate are particularly preferable, but other soluble silicon compounds are used. But it does n’t matter. For example, when silicon nitride is etched with phosphoric acid, it is known that a silicon compound is dissolved in phosphoric acid. Phosphoric acid containing this silicon compound may also be used in the resist removal composition of the present invention. Is possible. As the silicate and hexafluorosilicate, ammonium salts are preferable. Silicic acid and silicate may be those obtained by adding silicon oxide or the like to sulfuric acid and dissolving it by heating. Hexafluorosilicic acid and hexafluorosilicate may be commercially available, or may be hydrolyzed with silicic acid and further salted.
本発明のレジスト除去用組成物における可溶性ケイ素化合物の濃度は、０．０００１〜０．５重量％、特に０．００１〜０．１重量％が好ましい。０．０００１重量％未満では、酸化膜のダメージを抑制することができず、０．５重量％以上ではレジスト除去能力が低下する。 The concentration of the soluble silicon compound in the resist removal composition of the present invention is preferably 0.0001 to 0.5% by weight, particularly preferably 0.001 to 0.1% by weight. If the amount is less than 0.0001% by weight, damage to the oxide film cannot be suppressed. If the amount is 0.5% by weight or more, the resist removing ability is lowered.
本発明のレジスト除去用組成物は、燐酸及び／又はアミン化合物をさらに含んでなることが好ましい。燐酸及びアミン化合物は、金属成分とキレートを形成し、金属成分の基板への付着を抑制することができる。 The resist removing composition of the present invention preferably further comprises phosphoric acid and / or an amine compound. Phosphoric acid and an amine compound can form a chelate with a metal component and suppress adhesion of the metal component to the substrate.
本発明に用いることができる燐酸としては、オルトリン酸、メタリン酸、ポリリン酸及びその塩が挙げられ、アミン化合物としては、エチレンジアミン、ジエチレントリアミン等のエチレンアミン類及びその塩が挙げられる。これらのうち、特にオルトリン酸が好ましい。 Examples of phosphoric acid that can be used in the present invention include orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, and salts thereof, and examples of the amine compound include ethyleneamines such as ethylenediamine and diethylenetriamine, and salts thereof. Of these, orthophosphoric acid is particularly preferable.
本発明のレジスト除去用組成物は、半導体デバイス、フラットパネルディスプレー等の製造で使用されるレジストの除去に対して、優れた性能を発揮する。その中でも特に、ＳＰＭでレジストを除去していた工程に適用することができる。具体的には、半導体の基板工程において、砒素を高濃度でドープしたレジストを除去するのに有効である。 The composition for removing a resist of the present invention exhibits excellent performance for removing a resist used in the production of semiconductor devices, flat panel displays and the like. In particular, the present invention can be applied to a process in which the resist is removed by SPM. Specifically, it is effective for removing a resist doped with arsenic at a high concentration in a semiconductor substrate process.
本発明のレジスト除去用組成物を使用する際の温度は、２０〜１８０℃、好ましくは８０〜１６０℃である。１８０℃を超える温度では、酸化膜へのダメージが発生し易く、２０℃未満の温度では、工業的に満足できる速度でレジストを除去することが難しい。 The temperature at the time of using the resist removing composition of the present invention is 20 to 180 ° C, preferably 80 to 160 ° C. When the temperature exceeds 180 ° C., damage to the oxide film is likely to occur, and when the temperature is less than 20 ° C., it is difficult to remove the resist at an industrially satisfactory rate.
本発明のレジスト除去用組成物を使用し、レジストを除去する際、超音波などを使用し、除去速度を促進させても良い。 When the resist removing composition of the present invention is used and the resist is removed, ultrasonic waves or the like may be used to accelerate the removal rate.
本発明のレジスト除去用組成物によれば、シリコンの酸化、酸化膜へのダメージが無く、レジストを除去できるため、微細化された半導体を製造することが可能となる。 According to the composition for removing a resist of the present invention, since the resist can be removed without oxidizing silicon and damaging the oxide film, a miniaturized semiconductor can be manufactured.
本発明を以下の実施例によりさらに詳細に説明するが、本発明はこれらに限定されるものではない。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
実施例１
濃硫酸にヘキサフルオロケイ酸を０．０２５重量％添加したレジスト除去液を調製した。この除去液を１５０℃に加熱し、これに、砒素を１０１６ドープしたＫｒＦレジストを成膜したシリコンウエハを５分間浸漬した。５分後にはレジストは完全に除去されていた。
Example 1
A resist removal solution was prepared by adding 0.025% by weight of hexafluorosilicic acid to concentrated sulfuric acid. The removal liquid was heated to 0.99 ° C., this was a silicon wafer was formed a KrF resist was 10 16 doped with arsenic for 5 minutes. After 5 minutes, the resist was completely removed.
また、同じ組成の液に、熱酸化で形成された酸化膜を成膜したシリコンウエハを１５０℃で浸漬した。５分間での酸化膜のダメージは０．８オングストロームであった。 In addition, a silicon wafer on which an oxide film formed by thermal oxidation was formed was immersed in a liquid having the same composition at 150 ° C. The damage of the oxide film in 5 minutes was 0.8 angstrom.
実施例２
濃硫酸に酸化膜を成膜したシリコンウエハを浸漬し、１５０℃で１時間加熱し、濃硫酸にシリコン化合物を溶解させた。このようにして調製したレジスト除去液を８０℃にし、これに砒素を１０１４ドープしたｉ線レジストを成膜したシリコンウエハを１時間浸漬したところ、レジストは完全に除去されていた。
Example 2
A silicon wafer having an oxide film formed on concentrated sulfuric acid was immersed and heated at 150 ° C. for 1 hour to dissolve the silicon compound in concentrated sulfuric acid. Thus the resist removing solution, prepared at 80 ° C., which at the silicon wafer was formed a 10 14 doped i-line resist arsenic was immersed for 1 hour, the resist had been completely removed.
また、同じ組成の液に、熱酸化で形成された酸化膜を成膜したシリコンウエハを８０℃で浸漬した。１時間での酸化膜のダメージは０．２オングストロームであった。 In addition, a silicon wafer on which an oxide film formed by thermal oxidation was formed was immersed in a liquid having the same composition at 80 ° C. The damage to the oxide film in 1 hour was 0.2 angstrom.
比較例１
濃硫酸を１５０℃に加熱し、これに、砒素を１０１６ドープしたＫｒＦレジストを成膜したシリコンウエハを５分間浸漬した。５分後にはレジストは完全に除去されていた。
Comparative Example 1
Concentrated sulfuric acid was heated to 150 ° C., and a silicon wafer on which a KrF resist doped with 10 16 arsenic was formed was immersed in this for 5 minutes. After 5 minutes, the resist was completely removed.
また、同じ組成の液に、熱酸化で形成された酸化膜を成膜したシリコンウエハを１５０℃で浸漬した。５分間での酸化膜のダメージは１０オングストロームであった。
In addition, a silicon wafer on which an oxide film formed by thermal oxidation was formed was immersed in a liquid having the same composition at 150 ° C. The damage to the oxide film in 5 minutes was 10 angstroms.
Claims (6)
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| JP2006159572A JP4839968B2 (en) | 2006-06-08 | 2006-06-08 | Resist removing composition and resist removing method |
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| JP4839968B2 true JP4839968B2 (en) | 2011-12-21 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5017985B2 (en) * | 2006-09-25 | 2012-09-05 | 東ソー株式会社 | Resist removing composition and resist removing method |
| JP5565551B2 (en) * | 2009-07-29 | 2014-08-06 | 石原ケミカル株式会社 | Resist remover |
| JP5836906B2 (en) * | 2012-04-26 | 2015-12-24 | 東京エレクトロン株式会社 | Substrate processing apparatus and substrate processing method |
| JP5832397B2 (en) * | 2012-06-22 | 2015-12-16 | 東京エレクトロン株式会社 | Substrate processing apparatus and substrate processing method |
| WO2015095726A1 (en) * | 2013-12-20 | 2015-06-25 | Entegris, Inc. | Use of non-oxidizing strong acids for the removal of ion-implanted resist |
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| JP4614415B2 (en) * | 2000-08-30 | 2011-01-19 | フアインポリマーズ株式会社 | Resist residue remover |
| DE10227867A1 (en) * | 2002-06-22 | 2004-01-08 | Merck Patent Gmbh | Composition for removing sidewall residues |
| JP4270544B2 (en) * | 2003-03-06 | 2009-06-03 | 花王株式会社 | Release agent composition |
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