JP5446487B2 - Method for producing composition for immersion exposure and composition for immersion exposure - Google Patents
Method for producing composition for immersion exposure and composition for immersion exposure Download PDFInfo
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- JP5446487B2 JP5446487B2 JP2009139584A JP2009139584A JP5446487B2 JP 5446487 B2 JP5446487 B2 JP 5446487B2 JP 2009139584 A JP2009139584 A JP 2009139584A JP 2009139584 A JP2009139584 A JP 2009139584A JP 5446487 B2 JP5446487 B2 JP 5446487B2
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- 238000007654 immersion Methods 0.000 title claims description 92
- 239000000203 mixture Substances 0.000 title claims description 77
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000007872 degassing Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 description 10
- 229920002120 photoresistant polymer Polymers 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000001165 gas chromatography-thermal conductivity detection Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007687 exposure technique Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- -1 methyl-3-trifluoromethyl-butyl Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
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- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Description
本発明は、液浸露光におけるパターン欠陥等の品質不良を減少させるために、溶存気体量を減少させた液浸露光用組成物を得ることが出来る液浸露光用組成物の製造方法と、それによって得られる液浸露光用組成物に関する。 The present invention relates to a method for producing an immersion exposure composition capable of obtaining an immersion exposure composition in which the amount of dissolved gas is reduced in order to reduce quality defects such as pattern defects in immersion exposure, and It is related with the composition for immersion exposure obtained by these.
半導体素子等の電子デバイスを製造するに際し、投影光学系を介して、フォトマスクとしてのレチクルのパターンをフォトレジストが塗布されたウェハ上の各ショット領域に転写する、ステッパー型、又は、ステップアンドスキャン方式の、投影露光装置が使用されている。 When manufacturing electronic devices such as semiconductor elements, a stepper type or step-and-scan method that transfers a reticle pattern as a photomask to each shot area on a wafer coated with photoresist via a projection optical system A projection exposure apparatus of the type is used.
このような投影露光装置においては、電子デバイスの小型化、高集積化に伴う電子デバイスの回路の微細化に対応すべく、投影光学手段の解像度を向上させていく必要がある。そして、投影光学手段の解像度は、使用する露光波長を短くする程、又、投影光学手段の開口数が大きい程、高くなるものであるから、回路の微細化に伴って、露光装置で使用される露光波長は、年々、短波長化してきており、投影光学手段の開口数も増大してきている。又、露光を行う際には、解像度と同様に、焦点深度も重要となる。ここで、ウェハと投影露光装置のレンズとの空間が空気又は窒素で満たされている場合には、解像度Ｒ及び焦点深度δは、それぞれ、（ｉ）式、（ｉｉ）式で表される。（ｉ）式、（ｉｉ）式において、λは露光波長、ＮＡ（Ｎｕｍｅｒｉｃａｌ Ａｐｅｒｔｕｒｅ）は投影光学系の開口数、ｋ１、ｋ２はプロセス係数である。
Ｒ＝ｋ１・λ／ＮＡ （ｉ）
δ＝ｋ２・λ／ＮＡ２ （ｉｉ）
In such a projection exposure apparatus, it is necessary to improve the resolution of the projection optical means in order to cope with the miniaturization of the circuit of the electronic device accompanying the miniaturization and high integration of the electronic device. The resolution of the projection optical means becomes higher as the exposure wavelength to be used is shortened or the numerical aperture of the projection optical means is larger. The exposure wavelength that has been shortened year by year, and the numerical aperture of projection optical means has also increased. In addition, when performing exposure, the depth of focus is important as well as the resolution. Here, when the space between the wafer and the lens of the projection exposure apparatus is filled with air or nitrogen, the resolution R and the depth of focus δ are expressed by equations (i) and (ii), respectively. In equations (i) and (ii), λ is an exposure wavelength, NA (Numerical Aperture) is the numerical aperture of the projection optical system, and k1 and k2 are process coefficients.
R = k1 · λ / NA (i)
δ = k 2 · λ / NA 2 (ii)
これに対し、ウェハと投影露光装置のレンズとの空間が屈折率ｎの媒体で満たされると、解像度Ｒ及び焦点深度δは、それぞれ、（ｉｉｉ）式、（ｉｖ）式で表されるものとなる。
Ｒ＝ｋ１・（λ／ｎ）ＮＡ （ｉｉｉ）
δ＝ｋ２・ｎλ／ＮＡ２ （ｉｖ）
On the other hand, when the space between the wafer and the lens of the projection exposure apparatus is filled with a medium having a refractive index n, the resolution R and the depth of focus δ are expressed by equations (iii) and (iv), respectively. Become.
R = k1 · (λ / n) NA (iii)
δ = k2 · nλ / NA 2 (iv)
例えば、波長１９３ｎｍのＡｒＦを用いたプロセスで、媒体として水（純水）を使用すると、波長１９３ｎｍの光の水中での屈折率ｎは１．４４であるから、空気又は窒素を媒体とする露光時と比較して、解像度Ｒは６９．４％（Ｒ＝ｋ１・（λ／１．４４）ＮＡ）、焦点深度は１４４％（δ＝ｋ２・１．４４λ／ＮＡ２）となる。 For example, when water (pure water) is used as a medium in a process using ArF with a wavelength of 193 nm, the refractive index n of water with a wavelength of 193 nm in water is 1.44. Compared to the time, the resolution R is 69.4% (R = k1 · (λ / 1.44) NA), and the focal depth is 144% (δ = k2 · 1.44λ / NA 2 ).
このように、ウェハと投影露光装置のレンズとの空間を屈折率ｎの媒体で満たし、露光に用いる放射線の波長を短波長化して、微細なパターンを転写可能とする露光技術を、液浸露光（液浸露光方法）という。この液浸露光は、デザインルールが、９０ｎｍから６５ｎｍへ、更には４５ｎｍへと、微細化する電子デバイスの製造においては、必須の技術と考えられ、それに使用する投影露光装置が知られている（例えば、特許文献１を参照）。又、水よりも屈折率が大きく、優れた透過性を有する液浸露光用液体も提案されている（特許文献２参照）。 In this way, the exposure technique that fills the space between the wafer and the lens of the projection exposure apparatus with a medium having a refractive index n, shortens the wavelength of the radiation used for exposure, and enables transfer of a fine pattern is applied by immersion exposure. (Immersion exposure method). This immersion exposure is considered an indispensable technique in the manufacture of electronic devices that are miniaturized from 90 nm to 65 nm in design rule, and further to 45 nm, and a projection exposure apparatus used therefor is known ( For example, see Patent Document 1). In addition, a liquid for immersion exposure having a higher refractive index than water and excellent transparency has been proposed (see Patent Document 2).
ところで、液浸露光においては、ウェハ上に塗布・形成されたフォトレジストと投影露光装置のレンズは、それぞれ媒体（液浸媒体ともいう）と接触する。そのため、フォトレジストに液浸媒体が浸透し、フォトレジストの解像度が低下することがある。又、フォトレジストを構成する成分が液浸媒体へ溶出することにより、投影露光装置のレンズの表面を汚染することもある。 By the way, in immersion exposure, the photoresist applied and formed on the wafer and the lens of the projection exposure apparatus are in contact with a medium (also referred to as an immersion medium). Therefore, the immersion medium may penetrate into the photoresist, and the resolution of the photoresist may be reduced. Further, the components constituting the photoresist may elute into the immersion medium, thereby contaminating the lens surface of the projection exposure apparatus.
このような事情の下、フォトレジストと液浸媒体（例えば、水）とを遮断するために、フォトレジスト（膜）の上に、スピン塗布によって上層膜を形成する技術が知られており、十分な透過性を有し、現像液であるアルカリ液に容易に溶解する、上層膜が開示されている（例えば、特許文献３を参照）。又、上層膜を使用しなくても、液浸露光において、液浸媒体である水に溶出し難いレジスト樹脂組成物が提案されている（例えば、特許文献４を参照）。 Under such circumstances, a technique for forming an upper layer film on the photoresist (film) by spin coating is known in order to block the photoresist and the immersion medium (for example, water). An upper layer film is disclosed which has excellent permeability and can be easily dissolved in an alkali solution as a developer (see, for example, Patent Document 3). In addition, a resist resin composition that does not easily dissolve in water as an immersion medium in immersion exposure without using an upper layer film has been proposed (see, for example, Patent Document 4).
しかしながら、従来、例えば、上層膜を形成すべく、上層膜を形成するための組成物を、ウェハ上のフォトレジストの更に上にスピン塗布しようとすると、その組成物に溶け込んでいた気体から気泡が発生する、という問題があった。通常、塗布前に、上層膜を形成するための組成物をフィルタで濾過するが、この気泡は、このフィルタを通過する際に生じる圧力変動によって前記組成物内から分離したものと考えられた。このような気泡はフォトレジストに付着し、パターン欠陥等の原因となる。又、溶存酸素や、酸素に１９３ｎｍの光を照射した時に生じるオゾンは、１９３ｎｍの光を強く吸収するため、液浸媒体の透過率に大きな影響を与える。 However, conventionally, for example, in order to form an upper layer film, when a composition for forming the upper layer film is spin-coated on the photoresist on the wafer, bubbles are generated from the gas dissolved in the composition. There was a problem that it occurred. Usually, the composition for forming the upper layer film is filtered with a filter before coating, but it was considered that the bubbles were separated from the composition by the pressure fluctuation generated when passing through the filter. Such bubbles adhere to the photoresist and cause pattern defects and the like. In addition, dissolved oxygen and ozone generated when 193 nm light is irradiated to oxygen strongly absorbs 193 nm light, and thus greatly affects the transmittance of the immersion medium.
本発明は、このような問題に対処するためになされたものであって、本発明の課題は、（液浸露光用）組成物から気体の発生を抑制する手段を提供することである。研究が重ねられた結果、以下の手段によって上記課題を解決し得ることを見出し、本発明を完成するに至った。 The present invention has been made to cope with such problems, and an object of the present invention is to provide means for suppressing generation of gas from a composition (for immersion exposure). As a result of repeated research, it has been found that the above-mentioned problems can be solved by the following means, and the present invention has been completed.
即ち、先ず、本発明によれば、樹脂成分と溶剤とを含む液浸露光用組成物をフィルタで濾過する工程Ａと、液浸露光用組成物の溶存気体を脱気する工程Ｂと、工程Ａ及び工程Ｂを終えた後に液浸露光用組成物を充填する工程Ｃと、を有する液浸露光用組成物の製造方法が提供される。 That is, first, according to the present invention, the step A of filtering the immersion exposure composition containing the resin component and the solvent, the step B of degassing the dissolved gas of the immersion exposure composition, and the step There is provided a method for producing an immersion exposure composition comprising the step C of filling the immersion exposure composition after the completion of the step A and the process B.
液浸露光用組成物とは、上層膜を形成するための組成物（液浸露光用上層膜形成組成物ともいう）、液浸媒体である水に溶出し難いレジスト樹脂組成物（液浸露光用感放射線性樹脂組成物、又は液浸露光用レジスト樹脂組成物ともいう）、及び液浸媒体（液浸露光用液体ともいう）を指す。液浸露光用上層膜形成用組成物の溶剤は、１価のアルコール類又は鎖状飽和炭化水素類であり、その混合物でもよい。 The composition for immersion exposure is a composition for forming an upper layer film (also referred to as an upper layer film forming composition for immersion exposure), a resist resin composition that is difficult to elute in water as an immersion medium (immersion exposure). Radiation sensitive resin composition, or resist resin composition for immersion exposure), and immersion medium (also referred to as immersion exposure liquid). The solvent of the composition for forming an upper layer film for immersion exposure is a monohydric alcohol or a chain saturated hydrocarbon, and may be a mixture thereof.
工程Ａにおいて使用されるフィルタは、その材料がＰＥ、ＰＴＦＥ、アミド系合成繊維等であるものが好ましい。 The filter used in the step A is preferably a material whose material is PE, PTFE, amide synthetic fiber or the like.
工程Ｂにおいて脱気する手段としては、超音波脱気法、気体透過膜による脱気法、減圧脱気法等があるが、生産性、コストの面から、減圧脱気法が好ましい。 As means for degassing in the step B, there are an ultrasonic degassing method, a degassing method using a gas permeable membrane, a vacuum degassing method, etc., but a vacuum degassing method is preferable from the viewpoint of productivity and cost.
工程Ｃにおいて、充填する先は容器等である。この容器等は、気体が通過し難い材料で構成されることが好ましい。 In Step C, the filling destination is a container or the like. The container or the like is preferably made of a material that is difficult for gas to pass through.
本発明に係る液浸露光用組成物の製造方法においては、上記工程Ａが、循環する閉鎖系内において、不活性ガス雰囲気で、行われることが好ましい。 In the method for producing an immersion exposure composition according to the present invention, the step A is preferably performed in an inert gas atmosphere in a circulating closed system.
循環する閉鎖系は、タンク、配管、弁、ポンプ等で構築することが出来る。不活性ガスは、例えば、窒素ガス、アルゴンガスである。不活性ガス雰囲気は、閉鎖系を不活性ガスで満たし、一定圧力を保持することによって実現される。 A circulating closed system can be constructed with tanks, piping, valves, pumps, and the like. The inert gas is, for example, nitrogen gas or argon gas. An inert gas atmosphere is achieved by filling the closed system with inert gas and maintaining a constant pressure.
本発明に係る液浸露光用組成物の製造方法においては、上記工程Ｂにおいて、液浸露光用組成物をタンク内に貯蔵し、そのタンク内を０．０９ＭＰａ以下に減圧にして攪拌することによって、液浸露光用組成物の溶存気体を脱気することが好ましい。この場合において、（工程Ｂの後の）工程Ｃにおいて、タンク内の圧力が常圧以下であることが好ましい。 In the method for producing an immersion exposure composition according to the present invention, in step B, the immersion exposure composition is stored in a tank, and the inside of the tank is reduced to 0.09 MPa or less and stirred. It is preferable to degas the dissolved gas of the composition for immersion exposure. In this case, in step C (after step B), the pressure in the tank is preferably not more than normal pressure.
工程Ｂにおいてタンク内を０．０９ＭＰａ以下に減圧にする場合、その圧力は、その０．０９ＭＰａ以下で保持することが好ましく、更には０．０５ＭＰａ以下で保持することが、より好ましい。タンク内の圧力が０．０９ＭＰａより高いと、脱気効果が低くなるおそれがある。 When the pressure in the tank is reduced to 0.09 MPa or less in Step B, the pressure is preferably maintained at 0.09 MPa or less, more preferably 0.05 MPa or less. When the pressure in the tank is higher than 0.09 MPa, the deaeration effect may be lowered.
（工程Ｂの後の）工程Ｃにおいて、タンク内の圧力は減圧することが、より好ましい。 In step C (after step B), the pressure in the tank is more preferably reduced.
次に、本発明によれば、溶存酸素量が１５ｐｐｍ以下、溶存窒素量が１５０ｐｐｍ以下である、上記した何れかの液浸露光用組成物の製造方法で製造された液浸露光用組成物が提供される。溶存酸素量、溶存窒素量は、例えば、ガスクロマトグラフで測定することが出来る。 Next, according to the present invention, there is provided an immersion exposure composition produced by any one of the above-described methods for producing an immersion exposure composition, wherein the dissolved oxygen content is 15 ppm or less and the dissolved nitrogen content is 150 ppm or less. Provided. The amount of dissolved oxygen and the amount of dissolved nitrogen can be measured by, for example, a gas chromatograph.
本発明に係る液浸露光用組成物の製造方法は、樹脂成分と溶剤とを含む液浸露光用組成物の溶存気体を脱気する工程Ｂを有するので、液浸露光用組成物の溶存気体量を減少させることが出来る。従って、本発明に係る液浸露光用組成物の製造方法によって得られる液浸露光用組成物は、液浸露光に使用されたときに、気泡の発生が起こり難い。 Since the manufacturing method of the composition for immersion exposure according to the present invention includes the step B of degassing the dissolved gas of the composition for immersion exposure containing a resin component and a solvent, the dissolved gas of the composition for immersion exposure The amount can be reduced. Therefore, when the composition for immersion exposure obtained by the method for producing a composition for immersion exposure according to the present invention is used for immersion exposure, bubbles are hardly generated.
本発明に係る液浸露光用組成物の製造方法は、好ましくは、工程Ｂにおいて、液浸露光用組成物をタンク内に貯蔵し、そのタンク内を減圧にして攪拌することによって、液浸露光用組成物の溶存気体を脱気するので、液浸露光用組成物の溶存気体量を、十分に減少させることが出来る。従って、本発明に係る液浸露光用組成物の製造方法によって得られる液浸露光用組成物は、液浸露光に使用されたときに、気泡の発生が起こり難い。 In the method for producing a composition for immersion exposure according to the present invention, preferably, in step B, the composition for immersion exposure is stored in a tank, and the inside of the tank is depressurized and stirred to obtain a liquid immersion exposure. Since the dissolved gas in the composition is degassed, the amount of dissolved gas in the composition for immersion exposure can be sufficiently reduced. Therefore, when the composition for immersion exposure obtained by the method for producing a composition for immersion exposure according to the present invention is used for immersion exposure, bubbles are hardly generated.
本発明に係る液浸露光用組成物の製造方法は、工程Ａ及び工程Ｂを終えた後に液浸露光用組成物を充填する工程Ｃを有し、好ましくは、（工程Ｂの後の）工程Ｃにおいて、タンク内の圧力が常圧以下であるので、充填時に、液浸露光用組成物に気体が、再度、溶け込むことがなく、溶存気体を減少させたまま、少なくとも増加を抑制して、液浸露光用組成物を充填することが出来る。 The manufacturing method of the composition for immersion exposure according to the present invention includes the step C of filling the composition for immersion exposure after finishing the step A and the step B, preferably (after the step B). In C, since the pressure in the tank is equal to or lower than normal pressure, at the time of filling, the gas does not dissolve again in the immersion exposure composition, and at least the increase is suppressed while the dissolved gas is reduced, The composition for immersion exposure can be filled.
本発明に係る液浸露光用組成物は、溶存酸素量が１５ｐｐｍ以下、溶存窒素量が１５０ｐｐｍ以下であるので、フォトレジストの上にスピン塗布する際に、気泡も発生し難く、その結果、液浸露光において、パターン欠陥等の品質不良が低減される。 Since the composition for immersion exposure according to the present invention has a dissolved oxygen content of 15 ppm or less and a dissolved nitrogen content of 150 ppm or less, bubbles are hardly generated when spin-coated on a photoresist. In immersion exposure, quality defects such as pattern defects are reduced.
以下、本発明の実施の形態について、図面を参酌しながら説明するが、本発明はこれらに限定されて解釈されるべきものではなく、本発明の範囲を逸脱しない限りにおいて、当業者の知識に基づいて、種々の変更、修正、改良を加え得るものである。図面は、好適な本発明の実施の形態を表すものであるが、本発明は図面に表される態様や図面に示される情報により制限されない。本発明を実施し又は検証する上では、本明細書中に記述されたものと同様の手段若しくは均等な手段が適用され得るが、好適な手段は以下に記述される手段である。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention should not be construed as being limited to these embodiments, and the knowledge of those skilled in the art can be obtained without departing from the scope of the present invention. Various changes, modifications and improvements can be made based on this. The drawings show preferred embodiments of the present invention, but the present invention is not limited by the modes shown in the drawings or the information shown in the drawings. In practicing or verifying the present invention, means similar to or equivalent to those described in the present specification can be applied, but preferred means are those described below.
本発明に係る液浸露光用組成物の製造方法は、樹脂成分と溶剤とを含む液浸露光用組成物をフィルタで濾過する工程Ａと、樹脂成分と溶剤とを含む液浸露光用組成物の溶存気体を脱気する工程Ｂと、工程Ａ及び工程Ｂを終えた後に液浸露光用組成物を充填する工程Ｃと、を有するものであるが、このような本発明に係る液浸露光用組成物の製造方法は、例えば、図１に示される閉鎖系の装置によって実施することが出来る。 The method for producing an immersion exposure composition according to the present invention includes a step A for filtering an immersion exposure composition containing a resin component and a solvent, and a composition for immersion exposure containing a resin component and a solvent. Step B for degassing the dissolved gas and Step C for filling the immersion exposure composition after Step A and Step B have been completed. Such immersion exposure according to the present invention The manufacturing method of the composition for an application can be implemented, for example, by a closed system apparatus shown in FIG.
図１は、本発明に係る液浸露光用組成物の製造方法に用いられる装置の一例を示し、その構成を示すフロー図である。この装置は、タンク１、ポンプ５、流量計２、及びフィルタ３、並びにこれらを閉鎖的に結んで循環する配管６及びそれに付帯する図示しない弁等で構成される。循環する閉鎖系は、これらタンク１、ポンプ５、流量計２、フィルタ３、配管６、弁等で構築される。又、この装置は、配管６から分岐する配管７及びそれに付帯する図示しない弁等、並びに充填先の容器４を備えている。
FIG. 1 is a flow chart showing an example of an apparatus used in the method for producing a composition for immersion exposure according to the present invention and showing the configuration thereof. This apparatus includes a tank 1, a
図１に示される装置を用いて、配管７は遮断し、液浸露光用組成物を配管６で（図１中の矢印方向に）循環させれば、液浸露光用組成物はフィルタ３で濾過される。又、液浸露光用組成物をタンク１内に貯蔵し、そのタンク１内を減圧にして攪拌することによって、液浸露光用組成物の溶存気体を脱気することが出来る。そして、タンク１の前で配管６を遮断し、配管７を通じさせることで、液浸露光用組成物を容器４へ充填することが出来る。
If the apparatus shown in FIG. 1 is used, the
以下、本発明を実施例に基づいて更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples.
（実施例１）図１に示される装置を使用した。フィルタ３として、ＰＥフィルタ（０．０３μｍ、濾過面積２．２ｍ２）を用い、液浸露光用組成物としては、２−メチル−アクリル酸４，４，４−トリフルオロ−３−ヒドロキシ−１−メチル−３−トリフルオロメチル−ブチル重合体、Ｍｗ１０５００を、４質量％含む４−メチル−２−ペンタノールを用いた。
Example 1 The apparatus shown in FIG. 1 was used. A PE filter (0.03 μm, filtration area 2.2 m 2 ) was used as the
２００Ｌ（リットル）の液浸露光用組成物をタンク１に仕込み、常圧下で、ポンプ５によって、１２０Ｌ／ｈｒの流量で循環させ、濾過を行った。そして、循環を止め、タンク１内の液浸露光用組成物を攪拌するとともに、タンク１内の圧力を０．０５ＭＰａにし、４時間保持して、脱気を行った。その後、窒素ガスを使用してタンク１内を常圧に戻し、常圧下で、液浸露光用組成物を容器４へ充填した。容器４に充填した液浸露光用組成物の酸素量と窒素量を、ガスクロマトグラフィ（島津製作所社製、ＧＣ−ＴＣＤ）により測定したところ、溶存酸素量は１ｐｐｍ、溶存窒素量は１１０ｐｐｍであった。
200 L (liter) of the composition for immersion exposure was charged into the tank 1 and circulated at a flow rate of 120 L / hr by the
（実施例２）液浸露光用組成物として、２−メチル−アクリル酸４，４，４−トリフルオロ−３−ヒドロキシ−１−メチル−３−トリフルオロメチル−ブチルとビニルスルホン酸の共重合体、Ｍｗ９０００を、４質量％含む４−メチル−２−ペンタノールを用いた。それ以外は、実施例１と同様にして、図１に示される装置及びフィルタを使用し、実施例１と同様にして、濾過、脱気、充填工程を実施し、充填した液浸露光用組成物の酸素量と窒素量を、ガスクロマトグラフィ（島津製作所社製、ＧＣ−ＴＣＤ）により測定した。結果は、溶存酸素量が２ｐｐｍ、溶存窒素量は１２０ｐｐｍであった。
(Example 2) Copolymerization of 2-methyl-
（比較例１）実施例１と同じ装置、フィルタ、液浸露光用組成物を使用した。２００Ｌの液浸露光用組成物をタンク１に仕込み、常圧下で、ポンプ５によって、１００Ｌ／ｈｒの流量で循環させ、濾過を行った。その後、タンク１内の圧力を０．１５ＭＰａにして、液浸露光用組成物を容器４へ充填した。容器４に充填した液浸露光用組成物の酸素量と窒素量を、ガスクロマトグラフィ（島津製作所社製、ＧＣ−ＴＣＤ）により測定したところ、溶存酸素量は１７ｐｐｍ、溶存窒素量は２２０ｐｐｍであった。
Comparative Example 1 The same apparatus, filter, and immersion exposure composition as in Example 1 were used. 200 L of the immersion exposure composition was charged into the tank 1 and circulated at a flow rate of 100 L / hr by the
本発明に係る液浸露光用組成物の製造方法は、本発明に係る液浸露光用組成物を製造する手段として利用される。本発明に係る液浸露光用組成物は、半導体素子等の電子デバイスを製造するに際して行われる液浸露光に、好適に利用される。 The method for producing an immersion exposure composition according to the present invention is used as a means for producing the immersion exposure composition according to the present invention. The composition for immersion exposure according to the present invention is suitably used for immersion exposure performed in the production of electronic devices such as semiconductor elements.
１：タンク、２：流量計、３：フィルタ、４：容器、５：ポンプ、６：（循環）配管、７：（分岐）配管。 1: tank, 2: flow meter, 3: filter, 4: container, 5: pump, 6: (circulation) piping, 7: (branch) piping.
Claims (4)
前記液浸露光用組成物の溶存気体を脱気する工程Ｂと、
前記工程Ａ及び工程Ｂを終えた後に前記液浸露光用組成物を充填する工程Ｃと、
を有し、
前記工程Ａが、循環する閉鎖系内において、不活性ガス雰囲気で、行われる液浸露光用組成物の製造方法。 A step A of filtering a composition for immersion exposure containing a resin component and a solvent with a filter;
Step B for degassing the dissolved gas of the immersion exposure composition;
Step C after filling the composition for immersion exposure after finishing Step A and Step B;
I have a,
A method for producing a composition for immersion exposure , wherein the step A is carried out in an inert gas atmosphere in a circulating closed system .
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