JP2017138226A - Fine particle capturing device and fine particle measuring method - Google Patents
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Abstract
Description
本発明は、微粒子捕捉装置および微粒子測定方法に関する。 The present invention relates to a fine particle capturing apparatus and a fine particle measurement method.
半導体デバイスや液晶デバイスの製造プロセスでは、不純物が高度に除去された超純水などの液体を用いて、半導体ウエハやガラス基板の洗浄が行われている。このようなウエット洗浄に使用される液体に含まれる微粒子は、デバイスの歩留まりを低下させる直接の原因となるため、その濃度が厳しく管理されている。 In a manufacturing process of a semiconductor device or a liquid crystal device, a semiconductor wafer or a glass substrate is cleaned using a liquid such as ultrapure water from which impurities are highly removed. Since the fine particles contained in the liquid used for such wet cleaning directly cause a decrease in device yield, the concentration thereof is strictly controlled.
近年、半導体デバイスの高集積化・微細化が急激に進んでおり、例えば、「国際半導体技術ロードマップ（ＩＴＲＳ）２０１３」によれば、ＤＲＡＭ（Ｄｙｎａｍｉｃ Ｒａｎｄｏｍ Ａｃｃｅｓｓ Ｍｅｍｏｒｙ）のハーフピッチ寸法は、２０２４年に１１ｎｍに達すると予想されている。これに伴い、問題となる微粒子のサイズ（粒径）もさらに小さくなることが予想され、現状よりもさらに小さい粒径の微粒子を管理することが求められる可能性がある。 In recent years, high integration and miniaturization of semiconductor devices have been progressing rapidly. For example, according to “International Semiconductor Technology Roadmap (ITRS) 2013”, the half pitch dimension of DRAM (Dynamic Random Access Memory) is 2024. It is expected to reach 11 nm. Along with this, the size (particle diameter) of the problematic fine particles is expected to be further reduced, and there is a possibility that it is required to manage fine particles having a smaller particle diameter than the current state.
半導体デバイスの高集積化・微細化が進む中、半導体ウエハの洗浄には、超純水の他、アルコールなどの有機溶媒も多く用いられている。このような溶液の場合、上述の（微粒子の粒径に関する）要求を保証するためには、微粒子の発生源を特定して対策を講ずることが必要になる。微粒子の発生源を特定するためには、溶液に含まれる微粒子の組成を把握することが有効である。また、微粒子の組成を把握することは、不意のトラブル時にその原因を特定するためにも非常に有効な手段である。 As semiconductor devices are highly integrated and miniaturized, organic solvents such as alcohol are often used for cleaning semiconductor wafers in addition to ultrapure water. In the case of such a solution, in order to guarantee the above-mentioned requirements (related to the particle size of the fine particles), it is necessary to identify the source of the fine particles and take measures. In order to identify the generation source of the fine particles, it is effective to grasp the composition of the fine particles contained in the solution. In addition, grasping the composition of the fine particles is a very effective means for identifying the cause in case of unexpected trouble.
溶液中の微粒子の組成分析を行う方法として、特許文献１には、金属を主成分とするフィルタに溶液を通して微粒子を捕捉し、捕捉した微粒子を走査型電子顕微鏡（ＳＥＭ）とエネルギー分散型Ｘ線分析装置（ＥＤＸ）とを用いて組成分析する方法が開示されている。 As a method for performing composition analysis of fine particles in a solution, Patent Document 1 discloses that fine particles are captured through a solution through a metal-based filter, and the captured fine particles are scanned with an electron microscope (SEM) and energy dispersive X-ray. A method of composition analysis using an analyzer (EDX) is disclosed.
上述した方法において、特に半導体ウエハのウエット洗浄用の微粒子濃度が低く管理された溶液を対象とする場合、同じ通液量ではフィルタに捕捉される微粒子が少ないため、ＳＥＭでフィルタ上の微粒子を探し出すのは容易ではない。このような場合でも、例えば数十〜数百リットル程度の大量の溶液をフィルタに通すことで、フィルタ上に捕捉される微粒子が多くなり、ＳＥＭで観察した際にも容易に粒子を探し出すことが可能になる。しかしながら、このような大量の通液を行うことは、現実的な方法ではなく、有機溶媒を対象とする場合には、安全上困難である。 In the above-described method, particularly when a solution in which the concentration of fine particles for wet cleaning of a semiconductor wafer is controlled is a target, the amount of fine particles captured by the filter is small with the same flow rate, and therefore the fine particles on the filter are searched for by SEM. It's not easy. Even in such a case, for example, by passing a large amount of solution of about several tens to several hundreds of liters through the filter, the amount of fine particles trapped on the filter increases, and particles can be easily found even when observed with an SEM. It becomes possible. However, conducting such a large amount of liquid is not a practical method and is difficult for safety when an organic solvent is used.
そこで、本発明の目的は、少ない通液量で液体に含まれる微粒子を効率的に捕捉する微粒子捕捉装置を提供することである。また、本発明の目的は、この微粒子捕捉装置を用いた微粒子測定方法も提供することである。 Therefore, an object of the present invention is to provide a fine particle capturing apparatus that efficiently captures fine particles contained in a liquid with a small amount of liquid flow. Another object of the present invention is to provide a fine particle measuring method using this fine particle capturing apparatus.
上述した目的を達成するために、本発明の微粒子捕捉装置は、液体に含まれる微粒子を捕捉する微粒子捕捉装置であって、ろ過膜を含むろ過手段を有している。ろ過手段は、ろ過手段に流入した液体がろ過膜の一部に通液されるように構成されている。 In order to achieve the above-described object, the particulate trapping device of the present invention is a particulate trapping device that traps particulates contained in a liquid, and has a filtering means including a filtration membrane. The filtering means is configured such that the liquid flowing into the filtering means is passed through a part of the filtration membrane.
また、本発明の微粒子測定方法は、液体に含まれる微粒子を測定する微粒子測定方法であって、ろ過膜の一部に液体を通液して微粒子を捕捉する工程と、捕捉された微粒子の組成を分析する工程と、を含んでいる。 The fine particle measurement method of the present invention is a fine particle measurement method for measuring fine particles contained in a liquid, the step of capturing the fine particles by passing the liquid through a part of the filtration membrane, and the composition of the captured fine particles. Analyzing the process.
このような微粒子捕捉装置および微粒子測定方法では、ろ過膜の一部で集中的に微粒子を捕捉するようになっているため、微粒子濃度が低く管理された溶液の場合でも、溶液中の微粒子を少ない通液量で効率的に捕捉して測定することが可能になる。 In such a particulate trap and particulate measuring method, particulates are intensively captured by a part of the filtration membrane, so even in the case of a solution whose particulate concentration is controlled to be low, there are few particulates in the solution. It is possible to efficiently capture and measure by the amount of liquid flow.
以上、本発明によれば、少ない通液量で液体に含まれる微粒子を効率的に捕捉する微粒子捕捉装置と、それを用いた微粒子測定方法を提供することができる。 As described above, according to the present invention, it is possible to provide a fine particle capturing apparatus that efficiently captures fine particles contained in a liquid with a small amount of liquid flow, and a fine particle measurement method using the same.
以下、図面を参照して、本発明の実施の形態について説明する。 Embodiments of the present invention will be described below with reference to the drawings.
まず、図１を参照して、本発明の一実施形態による微粒子捕捉装置の構成について説明する。図１は、本実施形態の微粒子捕捉装置の構成を示す概略図である。 First, with reference to FIG. 1, the structure of the fine particle trapping apparatus according to an embodiment of the present invention will be described. FIG. 1 is a schematic view showing the configuration of the particulate trapping apparatus of the present embodiment.
なお、以下では、本実施形態の微粒子捕捉装置が対象とする好適な液体として、有機溶媒を主成分とする溶液（以下、単に「溶液」ともいう）を例示するが、本発明の微粒子捕捉装置は、他の液体、例えば純水や超純水にも好適に適用可能であることに留意されたい。本実施形態で対象となる有機溶媒としては、例えば、アセトン、メチルエチルケトン、酢酸−ｎ−ブチル、メチルイソプチルケトン、メタノール、エタノール、イソプロピルアルコール（ＩＰＡ）、プロピレングリコール１−モノメチルエーテル２−アセタート（ＰＧＭＥＡ）、酢酸エチル、酢酸イソペンチル、シクロヘキサノン、Ｎ−メチル−２−ピリジノン、γ−ブチロラクトン、エチレングリコール、ジメチルエーテルなどが挙げられる。 In the following, a solution containing an organic solvent as a main component (hereinafter, also simply referred to as “solution”) is exemplified as a suitable liquid targeted by the particulate trapping apparatus of the present embodiment. However, the particulate trapping apparatus of the present invention is exemplified. It should be noted that can be suitably applied to other liquids such as pure water and ultrapure water. Examples of the organic solvent to be used in this embodiment include acetone, methyl ethyl ketone, n-butyl acetate, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol (IPA), propylene glycol 1-monomethyl ether 2-acetate (PGMEA). ), Ethyl acetate, isopentyl acetate, cyclohexanone, N-methyl-2-pyridinone, γ-butyrolactone, ethylene glycol, dimethyl ether and the like.
微粒子捕捉装置１は、試料である溶液をろ過して、溶液中の微粒子を捕捉するためのろ過装置（ろ過手段）１０を有している。ろ過装置１０は、ろ過膜１１と、ろ過膜１１を内部に収容して保持するホルダ１２とを有し、溶液が流入口１０ａから内部に流入してろ過膜１１に通液され、ろ過膜１１に通液された溶液が流出口１０ｂから流出するように構成されている。これにより、ろ過装置１０は、溶液中の微粒子をろ過膜１１上に捕捉することができる。 The fine particle capture device 1 has a filtration device (filtering means) 10 for filtering a solution as a sample and capturing fine particles in the solution. The filtration device 10 includes a filtration membrane 11 and a holder 12 that accommodates and holds the filtration membrane 11 therein, and the solution flows into the inside through the inlet 10a and is passed through the filtration membrane 11. The solution passed through the outlet 10 is configured to flow out from the outlet 10b. Thereby, the filtration apparatus 10 can capture the fine particles in the solution on the filtration membrane 11.
ろ過膜１１は、単一の材料からなる平膜である。ろ過膜１１の材料は、特定の材料に限定されるものではないが、耐溶剤性の観点から、無機材料であることが好ましい。そのような材料としては、例えば、アルミニウム、チタン、ケイ素、ジルコニウム、ステンレス、ニッケル、銅、パラジウム、白金、炭素などの金属を主成分とする材料、ゼオライト、セラミックが挙げられるが、金属を主成分とする材料、特に溶液との活性が少ない金属酸化物が好適に用いられる。金属酸化膜を用いる場合、耐溶剤性を向上させるために、８００℃以上に加熱した結晶性が高いものを用いることが好ましい。なお、耐溶剤性を有しているものであれば、無機材料の他、有機材料を用いることもできる。そのような材料としては、例えば、ポリプロピレン（ＰＰ）、ポリエチレン（ＰＥ）、ポリカーボネート（ＰＣ）、ポリ塩化ビニル（ＰＶＣ）、酢酸セルロース（ＣＡ）、４フッ化エチレン（ＰＴＦＥ）、テトラフルオロエチレン・パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体（ＦＥＰ）、テトラフルオロエチレン・エチレン共重合体（ＥＴＦＥ）、ポリビニリデンフルオライド（ＰＶＤＦ）、ポリクロロトリフルオロエチレン（ＰＣＴＦＥ）、クロロトリフルオエチレン・エチレン共重合体（ＥＣＴＦＥ）、ポリアクリロニトリル（ＰＡＮ）、ポリイミド（ＰＩ）、ポリスルホン（ＰＳ）、ポリエーテルスルホン（ＰＥＳ）、ポリエチレンテレフタレート（ＰＥＴ）が挙げられる。ここで、耐溶剤性とは、有機溶媒に対する耐性を意味し、有機溶媒に対して腐食や変質を起こさない性質を意味する。 The filtration membrane 11 is a flat membrane made of a single material. The material of the filtration membrane 11 is not limited to a specific material, but is preferably an inorganic material from the viewpoint of solvent resistance. Examples of such materials include materials containing metals such as aluminum, titanium, silicon, zirconium, stainless steel, nickel, copper, palladium, platinum, and carbon, zeolites, and ceramics. A metal oxide having a low activity with a material, particularly a solution, is preferably used. In the case of using a metal oxide film, it is preferable to use a film having high crystallinity heated to 800 ° C. or higher in order to improve solvent resistance. In addition, as long as it has solvent resistance, an organic material other than an inorganic material can also be used. Examples of such materials include polypropylene (PP), polyethylene (PE), polycarbonate (PC), polyvinyl chloride (PVC), cellulose acetate (CA), tetrafluoroethylene (PTFE), and tetrafluoroethylene parsene. Fluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene ( PCTFE), chlorotrifluoroethylene-ethylene copolymer (ECTFE), polyacrylonitrile (PAN), polyimide (PI), polysulfone (PS), polyethersulfone (PES), polyethylene terephthalate (PE) ), And the like. Here, the solvent resistance means resistance to an organic solvent and means a property that does not cause corrosion or alteration to the organic solvent.
ろ過膜１１の上流側の表面（以下、「上面」という）における孔径は、捕捉対象とする微粒子の種類に応じて適宜選択することができ、例えば１０〜２００ｎｍ程度である。ろ過膜１１の上面で捕捉した微粒子をエネルギー分散型Ｘ線分析装置（ＥＤＸ）で組成分析する場合、ろ過膜１１の孔径が上面からある程度の深さまで均一でないと、ろ過膜１１によるバックグラウンドの影響が大きくなってしまう。このような影響を最小限に抑えるために、ろ過膜１１は、上面から膜厚方向に４００ｎｍ以上の均一な孔径を有していることが好ましく、５００ｎｍ以上の均一な孔径を有していることがさらに好ましい。また、ろ過膜１１が上面から膜厚方向に１μｍを超えて均一な孔径を有していると、孔径のサイズによっては、ろ過抵抗が大きくなり、ろ過時間が長くなってしまう場合がある。そのため、ろ過膜１１は、その上面の孔径が小さく、特に５０ｎｍ以下の場合には、膜厚方向に１μｍ以下の均一な孔径を有していることが好ましい。ろ過膜１１の製造方法としては、特定の方法に限定されるものではないが、金属を主成分とする材料を用いる場合、均一な孔径を形成することができる点で、陽極酸化による方法が好ましい。その場合、ろ過膜１１としては、特にアルミニウムを陽極酸化して得られるアルミナ膜がより好ましい。 The pore diameter on the upstream surface (hereinafter referred to as “upper surface”) of the filtration membrane 11 can be appropriately selected according to the type of fine particles to be captured, and is, for example, about 10 to 200 nm. When the composition of the fine particles captured on the upper surface of the filtration membrane 11 is analyzed by an energy dispersive X-ray analyzer (EDX), if the pore diameter of the filtration membrane 11 is not uniform from the upper surface to a certain depth, the influence of the background by the filtration membrane 11 Will become bigger. In order to minimize such influence, the filtration membrane 11 preferably has a uniform pore diameter of 400 nm or more in the film thickness direction from the upper surface, and has a uniform pore diameter of 500 nm or more. Is more preferable. Moreover, when the filtration membrane 11 has a uniform pore diameter exceeding 1 μm in the film thickness direction from the upper surface, depending on the size of the pore diameter, the filtration resistance may increase and the filtration time may be prolonged. Therefore, it is preferable that the filtration membrane 11 has a uniform pore diameter of 1 μm or less in the film thickness direction when the pore diameter of the upper surface is small, particularly when it is 50 nm or less. The method for producing the filtration membrane 11 is not limited to a specific method, but when a material containing a metal as a main component is used, an anodic oxidation method is preferable in that a uniform pore diameter can be formed. . In that case, the filtration membrane 11 is particularly preferably an alumina membrane obtained by anodizing aluminum.
ホルダ１２の材料としては、溶液の望ましくない汚染を抑制するために、耐溶剤性を有する材料から形成されていることが好ましい。そのような材料としては、例えば、ポリプロピレン（ＰＰ）、ポリエチレン（ＰＥ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリテトラフルオロエチレンなどのフッ素系樹脂、ナイロン、ポリエーテルエーテルケトン（ＰＥＥＫ）が挙げられるが、幅広い有機溶媒に対する耐性を有している点で、ＰＰ、ＰＥ、ＰＥＴ、フッ素系樹脂が特に好適に用いられる。 The material of the holder 12 is preferably made of a solvent-resistant material in order to suppress undesirable contamination of the solution. Examples of such materials include fluorine resins such as polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), and polytetrafluoroethylene, nylon, and polyether ether ketone (PEEK). PP, PE, PET, and fluororesin are particularly preferably used because they have resistance to organic solvents.
また、微粒子捕捉装置１は、ろ過装置１０に供給する溶液を収容する供給タンク２と、ろ過装置１０からの溶液を収容する廃液タンク３とを有している。供給タンク２は、加圧可能な容器であり、供給タンク２にガスを導入するガス導入管４と、流入口１０ａを通じてろ過装置１０に溶液を供給する溶液供給管５とに接続されている。供給タンク２内の溶液は、ガス導入管４を通じて導入されるガスにより供給タンク２を加圧することで、溶液供給管５を通じてろ過装置１０に供給されるようになっている。供給タンク２に導入されるガスとしては、窒素やアルゴンなどの不活性ガスを用いることが好ましい。廃液タンク３は、流出口１０ｂを通じてろ過装置１０からの溶液を回収する廃液回収管６に接続されている。廃液タンク３には、廃液量を容易に把握することができるように、目盛りなどの計量手段が設けられていることが好ましい。 Further, the particulate trap 1 has a supply tank 2 that stores a solution to be supplied to the filtration device 10 and a waste liquid tank 3 that stores a solution from the filtration device 10. The supply tank 2 is a container that can be pressurized, and is connected to a gas introduction pipe 4 that introduces gas into the supply tank 2 and a solution supply pipe 5 that supplies a solution to the filtration device 10 through an inflow port 10a. The solution in the supply tank 2 is supplied to the filtration device 10 through the solution supply pipe 5 by pressurizing the supply tank 2 with the gas introduced through the gas introduction pipe 4. As the gas introduced into the supply tank 2, an inert gas such as nitrogen or argon is preferably used. The waste liquid tank 3 is connected to a waste liquid recovery pipe 6 that recovers the solution from the filtration device 10 through the outlet 10b. The waste liquid tank 3 is preferably provided with measuring means such as a scale so that the amount of waste liquid can be easily grasped.
供給タンク２は、耐圧性の材料および構造からなることが好ましく、特にステンレス鋼（ＳＵＳ）や金属酸化物などから形成されていることが好ましい。さらに、供給タンク２内の溶液と接触する接液部は、耐溶剤性を有する材料から形成されていることが好ましく、特にＰＰ、ＰＥＴ、フッ素系樹脂から形成されていることが好ましい。 The supply tank 2 is preferably made of a pressure-resistant material and structure, and particularly preferably made of stainless steel (SUS) or metal oxide. Furthermore, the liquid contact portion that comes into contact with the solution in the supply tank 2 is preferably formed from a solvent-resistant material, and is particularly preferably formed from PP, PET, or a fluororesin.
なお、図示した実施形態では、加圧容器としての供給タンク２に直接溶液を充填して圧送する方法を用いているが、加圧容器を用いて溶液を圧送する方法としては、これに限定されるものではない。例えば、溶液が充填されたボトルを加圧容器内に収容し、ボトルごと加圧して溶液を圧送する方法を用いることもできる。加圧容器内の溶液を直接加圧する方法では、加圧容器に溶液を充填する際に溶液が汚染されたり、加圧容器から溶液中に汚染物質が混入したりする可能性があるが、ボトルごと加圧する方法は、このような可能性を排除できる点で好ましい。また、ボトルごと加圧する方法は、加圧容器が直接溶液に接触することがないため、上述した加圧容器の接液部の材料を考慮する必要がない点でも好ましい。溶液を充填するボトルは、耐溶剤性を有する材料から形成されていることが好ましく、特にＰＰ、ＰＥ、ＰＥＴ、フッ素系樹脂から形成されていることが好ましい。 In the illustrated embodiment, a method is used in which the supply tank 2 serving as a pressurized container is directly filled with a solution and pumped, but the method of pumping a solution using a pressurized container is not limited thereto. It is not something. For example, it is possible to use a method in which a bottle filled with a solution is accommodated in a pressurized container, and the solution is pressurized by feeding the bottle together. In the method of directly pressurizing the solution in the pressurized container, there is a possibility that the solution is contaminated when the pressurized container is filled with the solution, or contaminants may be mixed into the solution from the pressurized container. The pressurizing method is preferable in that it can eliminate such a possibility. Further, the method of pressurizing the entire bottle is preferable in that the pressurized container does not directly contact the solution, and therefore it is not necessary to consider the material of the liquid contact part of the pressurized container described above. The bottle filled with the solution is preferably formed from a material having solvent resistance, and particularly preferably formed from PP, PE, PET, or a fluorine-based resin.
溶液供給管５は、ホルダ１２と同様に、耐溶剤性を有する材料から形成されていることが好ましく、特にＰＰ、ＰＥ、ＰＥＴ、フッ素系樹脂から形成されていることが好ましい。廃液タンク３の材料としても、耐溶剤性の観点から、ホルダ１２と同様の材料であることが好ましく、特にＰＰ、ＰＥ、ＰＥＴ、フッ素系樹脂が好適に用いられる。なお、ガスを通じた汚染物質の混入も抑制するために、ガス導入管４には、ゴミや湿度、その他の不純物を除去するためのフィルタや触媒が設置されていることが好ましい。 As with the holder 12, the solution supply pipe 5 is preferably formed from a material having solvent resistance, and is particularly preferably formed from PP, PE, PET, or a fluorine-based resin. The material of the waste liquid tank 3 is also preferably the same material as that of the holder 12 from the viewpoint of solvent resistance, and in particular, PP, PE, PET, and fluorine resin are preferably used. In order to suppress contamination of contaminants through the gas, the gas introduction pipe 4 is preferably provided with a filter and a catalyst for removing dust, humidity, and other impurities.
試料である溶液をろ過装置１０に供給する方法としては、安全面および溶液への汚染物質の混入を大幅に抑制できる点で、上述した加圧容器を用いて圧送する方法が特に好ましいが、これに限定されるものではない。例えば、溶液（有機溶媒）の製造プラントなどから分岐した配管から直接供給する方法、タンク内の溶液をポンプで圧送する方法、廃液タンク３を密閉容器として真空ポンプに接続して減圧ろ過を行う方法などを用いることができる。 As a method of supplying the sample solution to the filtration device 10, the method of pumping using the above-described pressurized container is particularly preferable in terms of safety and the possibility of significantly suppressing contamination of the solution. It is not limited to. For example, a method of directly supplying from a pipe branched from a solution (organic solvent) production plant, a method of pumping the solution in the tank with a pump, a method of performing vacuum filtration by connecting the waste liquid tank 3 as a sealed container to a vacuum pump Etc. can be used.
次に、図２を参照して、本実施形態のろ過装置の構成について説明する。図２（ａ）は、本実施形態のろ過装置の分解斜視図であり、図２（ｂ）は、ろ過膜の部分を上流側から見た平面図である。 Next, with reference to FIG. 2, the structure of the filtration apparatus of this embodiment is demonstrated. Fig.2 (a) is an exploded perspective view of the filtration apparatus of this embodiment, FIG.2 (b) is the top view which looked at the part of the filtration membrane from the upstream.
本実施形態では、ろ過膜１１の上面に、開口部１３ａを有する被覆シート（シート部材）１３が接着されている。これにより、被覆シート１３は、ろ過膜１１の上面の一部を露出させ、その露出させた部分のみに溶液を通液させることができるようになっている。その結果、本実施形態のろ過装置１０では、溶液中の微粒子をろ過膜１１の上面の露出した部分で集中的に捕捉することができ、少ない通液量で微粒子を効率的に捕捉することが可能になる。したがって、本実施形態のろ過装置１０は、微粒子濃度が低い溶液、特に１０００００個／ｍｌ以下の微粒子濃度の溶液に非常に有効である。 In the present embodiment, a cover sheet (sheet member) 13 having an opening 13 a is bonded to the upper surface of the filtration membrane 11. Thereby, the covering sheet 13 exposes a part of the upper surface of the filtration membrane 11 and allows the solution to pass through only the exposed portion. As a result, in the filtration device 10 of the present embodiment, the fine particles in the solution can be intensively captured at the exposed portion of the upper surface of the filtration membrane 11, and the fine particles can be efficiently captured with a small amount of liquid flow. It becomes possible. Therefore, the filtration device 10 of this embodiment is very effective for a solution having a low particle concentration, particularly a solution having a particle concentration of 100000 particles / ml or less.
被覆シート１３の材料は、特定の材料に限定されるものではないが、耐溶剤性を有するものであることが好ましい。そのような材料としては、例えば、ポリプロピレン（ＰＰ）、ポリエチレン（ＰＥ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリテトラフルオロエチレンなどのフッ素系樹脂、ナイロン、ポリエーテルエーテルケトン（ＰＥＥＫ）が挙げられるが、幅広い有機溶媒に対する耐性を有している点で、ＰＰ、ＰＥ、ＰＥＴ、フッ素系樹脂が好適に用いられる。 The material of the covering sheet 13 is not limited to a specific material, but preferably has a solvent resistance. Examples of such materials include fluorine resins such as polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), and polytetrafluoroethylene, nylon, and polyether ether ketone (PEEK). PP, PE, PET, and fluororesin are preferably used because they have resistance to organic solvents.
被覆シート１３のろ過膜１１への接着方法としては、いくつかの方法が考えられる。例えば、エポキシ樹脂などの有機系接着剤を用いる方法が考えられるが、この方法は、溶媒の影響により接着剤の溶出や溶解の可能性が高いため、好ましくない。また、無機系接着剤を用いる方法も、無機系接着剤が微視的には粒子の集合体であるため、粒子の発生源となる可能性が非常に高く、好ましくない。このような観点から、被覆シート１３は、熱溶着によってろ過膜１１に接着されていることが特に好ましい。 Several methods can be considered as a method of adhering the covering sheet 13 to the filtration membrane 11. For example, a method using an organic adhesive such as an epoxy resin is conceivable. However, this method is not preferable because the adhesive is likely to be eluted and dissolved under the influence of a solvent. Also, a method using an inorganic adhesive is not preferable because the inorganic adhesive is an aggregate of particles microscopically and is very likely to become a particle generation source. From such a viewpoint, it is particularly preferable that the covering sheet 13 is bonded to the filtration membrane 11 by heat welding.
被覆シート１３の開口部１３ａの大きさ（すなわち、ろ過膜１１のろ過面積）は、溶液の必要通液量や、ろ過膜１１の上面に捕捉した微粒子を走査型電子顕微鏡（ＳＥＭ）で観測する際の効率などを考慮すると、１０ｍｍ２以上１３２ｍｍ２未満であることが好ましく、１０ｍｍ２以上８０ｍｍ２以下であることがより好ましく、１０ｍｍ２以上５０ｍｍ２以下であることがさらに好ましい。なお、被覆シート１３の開口部１３ａの形状は、図示した円形に限定されるものではなく、他の幾何形状であってもよい。 The size of the opening 13a of the covering sheet 13 (that is, the filtration area of the filtration membrane 11) is measured with a scanning electron microscope (SEM) for the required liquid flow rate of the solution and fine particles captured on the upper surface of the filtration membrane 11. considering efficiency, etc. upon, is preferably less than 10 mm 2 or more 132 mm 2, more preferably 10 mm 2 or more 80 mm 2 or less, and more preferably 10 mm 2 or more 50 mm 2 or less. The shape of the opening 13a of the covering sheet 13 is not limited to the illustrated circle, and may be another geometric shape.
本実施形態では、図示したように、ろ過膜１１および被覆シート１３を収容するホルダ１２は、流入口１０ａが設けられた上部プレート１４と、流出口１０ｂが設けられた下部プレート１５とから構成されているが、ホルダ１２の構成は、これに限定されるものではない。 In the present embodiment, as illustrated, the holder 12 that accommodates the filtration membrane 11 and the covering sheet 13 includes an upper plate 14 provided with an inflow port 10a and a lower plate 15 provided with an outflow port 10b. However, the configuration of the holder 12 is not limited to this.
ろ過膜１１および被覆シート１３は、ホルダ１２に収容される前に、洗浄されていることが好ましい。その洗浄方法としては、特定の方法に限定されるものではないが、浸漬方式や枚葉方式、膜面に洗浄液を直接打ち当てる打ち当て方式などの方法と、メガソニック洗浄やウルトラソニック洗浄とを組み合わせたものを用いることが好ましい。また、用いる洗浄液は、超純水や水素水、酸素水に、アルカリや界面活性剤、過酸化水素などを添加したものが好適である。 The filtration membrane 11 and the covering sheet 13 are preferably washed before being accommodated in the holder 12. The cleaning method is not limited to a specific method, but includes a dipping method, a single-wafer method, a striking method in which the cleaning liquid is directly applied to the film surface, megasonic cleaning, and ultrasonic cleaning. It is preferable to use a combination. The cleaning liquid to be used is preferably one obtained by adding an alkali, a surfactant, hydrogen peroxide or the like to ultrapure water, hydrogen water, or oxygen water.
通液によるろ過膜１１の変形や破損を抑制するために、図示していないが、ろ過膜１１の下流側、すなわちろ過膜１１と下部プレート１５との間に、ろ過膜１１を支持するメッシュが配置されていてもよい。この場合、メッシュは、ろ過膜１１と共に被覆シート１３に熱溶着によって接着されていてもよく、ろ過膜１１と下部プレート１５との間に単に載置されているだけでもよい。溶液を通すものであって耐溶剤性を有しているものであれば、メッシュの材料や形態に特に制限はない。溶液の汚染を考慮すると、メッシュの材料としては、ろ過膜１１と同様の材料や、ＳＵＳ、フッ素系樹脂、ＰＰ、ＰＥ、ＰＥＴなどが好適に用いられる。また、通液時の圧力損失と操作性の観点から、メッシュの厚みは、０．１〜１ｍｍであることが好ましく、より好ましくは０．１〜０．５ｍｍである。 In order to suppress deformation and breakage of the filtration membrane 11 due to liquid passage, although not shown, a mesh supporting the filtration membrane 11 is provided downstream of the filtration membrane 11, that is, between the filtration membrane 11 and the lower plate 15. It may be arranged. In this case, the mesh may be bonded to the covering sheet 13 together with the filtration membrane 11 by thermal welding, or may simply be placed between the filtration membrane 11 and the lower plate 15. There is no particular limitation on the mesh material and form as long as it is a solution-permeable material and has solvent resistance. In consideration of the contamination of the solution, as the mesh material, the same material as the filter membrane 11, SUS, fluorine resin, PP, PE, PET, or the like is preferably used. In addition, from the viewpoint of pressure loss during operation and operability, the mesh thickness is preferably 0.1 to 1 mm, and more preferably 0.1 to 0.5 mm.
また、被覆シート１３と上部プレート１４との間には、図示していないが、流入口１０ａとろ過膜１１との間をシールするＯリングなどのシール部材が配置されている。本実施形態において、ろ過膜１１の上面に被覆シート１３が設けられていることは、ろ過膜１１として無機材料からなる膜を用いる場合、シール部材による膜の破損も抑制できる点でも有利である。 Further, although not shown, a sealing member such as an O-ring that seals between the inflow port 10a and the filtration membrane 11 is disposed between the covering sheet 13 and the upper plate 14. In the present embodiment, the provision of the covering sheet 13 on the upper surface of the filtration membrane 11 is advantageous in that when a membrane made of an inorganic material is used as the filtration membrane 11, damage to the membrane due to the sealing member can be suppressed.
ろ過膜１１の上面の一部を露出させる形態は、上述した被覆シート１３を用いるものに限定されるものではない。被覆シート１３の代わりに、例えば液状ガスケットを用いることもできる。液状ガスケットは、ろ過膜１１とホルダ１２とに密着し、流入口１０ａから供給される溶液がろ過膜１１と液状ガスケットとの密着部に流入しないように構成されていればよい。液状ガスケットの材料に特に制限はないが、耐溶剤性の観点から、フッ素系液状ガスケットを用いることが好ましい。 The form in which a part of the upper surface of the filtration membrane 11 is exposed is not limited to that using the covering sheet 13 described above. For example, a liquid gasket can be used instead of the covering sheet 13. The liquid gasket should just be comprised so that it may contact | adhere to the filtration membrane 11 and the holder 12, and the solution supplied from the inflow port 10a may not flow into the contact | adherence part of the filtration membrane 11 and liquid gasket. The material of the liquid gasket is not particularly limited, but a fluorine-based liquid gasket is preferably used from the viewpoint of solvent resistance.
なお、少ない通液量で微粒子を効率的・集中的に捕捉するという観点からは、ろ過膜の上面の一部を露出させる形態の他に、通液面積を小さくするという意味で、サイズの小さいろ過膜を使用することも考えられる。しかしながら、ろ過膜のサイズが小さいと、操作性が悪く、操作由来の微粒子がろ過膜に付着する可能性が非常に高くなる。また、微小なろ過膜やそれを保持するホルダは、市場のニーズが少ないため、容易に手に入るものではない。これに対し、本実施形態のように、ろ過膜の一部のみに通液する方法によれば、通液部分以外の面積が広く確保されているため、操作性も良く、操作由来の微粒子による汚染を抑制することができる。また、市販のろ過膜およびホルダを用いることができるため、安価に実現できる点でも有利である。 In addition, from the viewpoint of efficiently and intensively capturing fine particles with a small amount of liquid flow, in addition to a form in which a part of the upper surface of the filtration membrane is exposed, the size is small in the sense of reducing the liquid flow area. It is also conceivable to use a filtration membrane. However, when the size of the filtration membrane is small, the operability is poor, and the possibility that the fine particles derived from the operation adhere to the filtration membrane becomes very high. Further, a minute filtration membrane and a holder for holding the membrane are not easily available because there are few market needs. On the other hand, according to the method of passing through only a part of the filtration membrane as in this embodiment, the area other than the liquid passing part is widely secured, so that the operability is good and the operation-derived fine particles are used. Contamination can be suppressed. Moreover, since a commercially available filtration membrane and holder can be used, it is advantageous in that it can be realized at low cost.
ここで、図１を参照して、本実施形態の微粒子捕捉装置を用いた微粒子測定方法について簡単に説明する。 Here, with reference to FIG. 1, the particle measuring method using the particle capturing apparatus of the present embodiment will be briefly described.
まず、ガス導入管４を通じた不活性ガス（窒素など）の導入により、供給タンク２を加圧し、供給タンク２内の溶液を溶液供給管５からろ過装置１０に供給する。こうして供給された溶液はろ過膜１１の一部に通液され、その部分に溶液中の微粒子が捕捉される。溶液をろ過膜１１で一定量ろ過した後、不活性ガスの導入を停止して、ろ過装置１１への溶液の供給を停止する。次に、清浄度の高い雰囲気中でろ過装置１０（ホルダ１２）からろ過膜１１を取り出し、取り出したろ過膜１１を十分に乾燥させた後、ＳＥＭで観測して、ろ過膜１１に捕捉した微粒子を計数する。それと同時に、ＥＤＸを用いて、ろ過膜１１に捕捉した微粒子の組成分析を行う。実際には、この微粒子の組成分析結果から、ろ過膜１１のみの組成分析結果を差し引くことで、捕捉した微粒子の組成を特定する。本実施形態では、ろ過膜１１の一部で集中的に微粒子を捕捉できるため、ＳＥＭの観測効率とＥＤＸの分析感度を共に向上させることができる。 First, the supply tank 2 is pressurized by introducing an inert gas (such as nitrogen) through the gas introduction pipe 4, and the solution in the supply tank 2 is supplied from the solution supply pipe 5 to the filtration device 10. The solution thus supplied is passed through a part of the filtration membrane 11, and the fine particles in the solution are captured by that part. After a certain amount of solution is filtered through the filter membrane 11, the introduction of the inert gas is stopped, and the supply of the solution to the filtration device 11 is stopped. Next, the filtration membrane 11 is taken out from the filtration device 10 (holder 12) in an atmosphere with a high degree of cleanness, and the taken-out filtration membrane 11 is sufficiently dried, and then observed with an SEM and captured by the filtration membrane 11 Count. At the same time, composition analysis of the fine particles trapped on the filtration membrane 11 is performed using EDX. Actually, the composition of the captured fine particles is specified by subtracting the composition analysis result of only the filtration membrane 11 from the composition analysis result of the fine particles. In the present embodiment, since fine particles can be intensively captured by a part of the filtration membrane 11, both the SEM observation efficiency and the EDX analysis sensitivity can be improved.
次に、具体的な実施例を挙げて、本発明をより詳細に説明する。 Next, the present invention will be described in more detail with reference to specific examples.
（実施例１）
本実施例では、図１に示す微粒子捕捉装置および図２に示すろ過装置を用いて、溶液中の微粒子を捕捉した。ろ過膜として、上面での孔径が１００ｎｍ、その孔深さが２５μｍの、Ａｌを主成分とする膜を用いた。被覆シートとして、開口部の面積が２０ｍｍ２のＰＥＴシートをろ過膜に熱溶着したものを用い、ホルダとして、ＰＦＡ製のホルダを用いた。ろ過する溶液としては、粒径１２３ｎｍのポリスチレンラテックス（ＰＳＬ）を１０個／ｍｌ添加したイソプロピルアルコール（ＩＰＡ）を用い、０．２ＭＰａの窒素ガスを用いて、ろ過装置に７２０ｍｌ通液した。
Example 1
In this example, fine particles in the solution were captured using the fine particle capturing apparatus shown in FIG. 1 and the filtration apparatus shown in FIG. As the filtration membrane, a membrane mainly composed of Al having a pore diameter of 100 nm on the upper surface and a pore depth of 25 μm was used. As a covering sheet, a PET sheet having an opening area of 20 mm 2 thermally welded to a filtration membrane was used, and a PFA holder was used as a holder. As a solution to be filtered, isopropyl alcohol (IPA) added with 10 polystyrene latex (PSL) having a particle size of 123 nm / ml was used, and 720 ml was passed through a filtration device using 0.2 MPa nitrogen gas.
そして、こうして捕捉した微粒子（ＰＳＬ粒子）を、走査型電子顕微鏡（ＳＥＭ）を用いて観測した。ＳＥＭの観測倍率は１００００倍とし、観測視野数は５００視野とした。 The captured fine particles (PSL particles) were observed using a scanning electron microscope (SEM). The observation magnification of SEM was 10,000 times, and the number of observation fields was 500.
（実施例２）
ろ過膜として、上面での孔径が１０ｎｍ、その孔深さが５００ｎｍの膜を用い、溶液に添加した粒子を平均粒子径１０ｎｍのＳｉ粒子（１０００個／ｍｌ）とし、ろ過装置への通液量を２００ｍｌとした以外、実施例１と同様の条件で微粒子の捕捉と観測を行った。
(Example 2)
As a filtration membrane, a membrane having a pore diameter of 10 nm on the upper surface and a pore depth of 500 nm is used. The particles added to the solution are Si particles (1000 particles / ml) having an average particle diameter of 10 nm, and the amount of liquid passing through the filtration device The microparticles were captured and observed under the same conditions as in Example 1 except that the amount was 200 ml.
（実施例３）
溶液に添加した粒子を平均粒子径１００ｎｍのＳｉ粒子（１００個／ｍｌ）とした以外、実施例１と同様の条件で微粒子の捕捉と観測を行った。
(Example 3)
Fine particles were captured and observed under the same conditions as in Example 1 except that the particles added to the solution were Si particles (100 particles / ml) having an average particle diameter of 100 nm.
（実施例４）
被覆シートとして、ポリ塩化ビニル（ＰＶＣ）シールをアクリル系粘着剤でろ過膜に接着したものを用いた以外、実施例３と同様の条件で微粒子の捕捉と観測を行った。
Example 4
Fine particles were captured and observed under the same conditions as in Example 3 except that a polyvinyl chloride (PVC) seal adhered to the filtration membrane with an acrylic adhesive was used as the covering sheet.
（実施例５）
溶液をプロピレングリコール１−モノメチルエーテル２−アセタート（ＰＧＭＥＡ）とした以外、実施例３と同様の条件で微粒子の捕捉と観測を行った。
(Example 5)
Fine particles were captured and observed under the same conditions as in Example 3 except that the solution was propylene glycol 1-monomethyl ether 2-acetate (PGMEA).
（実施例６）
被覆シートとして、ＰＥＴシールをシリコン系粘着剤でろ過膜に接着したものを用いた以外、実施例５と同様の条件で微粒子の捕捉と観測を行った。
(Example 6)
Fine particles were captured and observed under the same conditions as in Example 5 except that the coated sheet used was a PET seal adhered to the filtration membrane with a silicon adhesive.
（実施例７）
被覆シートとして、ＰＥＴシートを主成分がアルミナである耐熱性無機系接着剤でろ過膜に接着したものを用いた以外、実施例５と同様の条件で微粒子の捕捉と観測を行った。
(Example 7)
Fine particles were captured and observed under the same conditions as in Example 5 except that the coated sheet was a PET sheet adhered to the filtration membrane with a heat-resistant inorganic adhesive whose main component was alumina.
（比較例）
被覆シートの開口部の面積を１３２ｍｍ２とし、ろ過装置への通液量を８２０ｍｌとした以外、実施例１と同様の条件で微粒子の捕捉と観測を行った。
(Comparative example)
Fine particles were captured and observed under the same conditions as in Example 1 except that the area of the opening of the covering sheet was 132 mm 2 and the liquid flow rate through the filtration device was 820 ml.
表１に、実施例１および比較例における、ＳＥＭによる検出粒子数とそこから算出された溶液の粒子濃度の結果を示す。 Table 1 shows the number of detected particles by SEM and the particle concentration of the solution calculated therefrom in Example 1 and Comparative Example.
また、粒子濃度については、検出された粒子数からポアソン分布を用いて算出されるため、検出される粒子数が多くなるほど、その相対誤差は小さくなるが、このことは、実施例１において算出された粒子濃度がより信頼性の高い値であることを意味している。なお、比較例では、算出される粒子濃度の相対誤差を６０％以下とするため、すなわち、粒子濃度を高い信頼性で算出するためには、１０個以上の粒子数を検出する必要があり、そのためには１５００視野以上の観察が必要となる。これには、多くの時間を要するため、この点でも、実施例１がより良好である。 Further, since the particle concentration is calculated from the number of detected particles using the Poisson distribution, the relative error becomes smaller as the number of detected particles increases. This is calculated in the first embodiment. This means that the particle concentration is a more reliable value. In the comparative example, in order to set the relative error of the calculated particle concentration to 60% or less, that is, in order to calculate the particle concentration with high reliability, it is necessary to detect the number of particles of 10 or more. For that purpose, it is necessary to observe over 1500 fields of view. Since this takes a lot of time, the first embodiment is better in this respect as well.
次に、表２に、実施例２〜７におけるＳＥＭの観測結果、具体的には、溶液通液後のろ過膜の表面の様子および被覆シートとの接着状態を観測した結果を示す。 Next, Table 2 shows the observation results of SEM in Examples 2 to 7, specifically, the results of observing the state of the surface of the filtration membrane after passing through the solution and the adhesion state with the covering sheet.
表２から、被覆シートの接着方法については、有機溶媒を主成分とする溶液を対象とする場合、実施例２，３，５の熱溶着を用いる方法が優位であることが確認された。実施例２，３，５では、エネルギー分散型Ｘ線分析装置（ＥＤＸ）を用いた組成分析を行ったところ、ろ過膜に捕捉された粒子がＩＰＡに含まれるＳｉ粒子であることが確認された。一例として、実施例２におけるろ過膜のＳＥＭ写真と観測した粒子のＥＤＸスペクトルを、それぞれ図３（ａ）および図３（ｂ）に示す。 From Table 2, it was confirmed that the method using the thermal welding of Examples 2, 3, and 5 is superior when the solution having the organic solvent as a main component is used as the method for adhering the covering sheet. In Examples 2, 3 and 5, when composition analysis was performed using an energy dispersive X-ray analyzer (EDX), it was confirmed that the particles captured by the filtration membrane were Si particles contained in IPA. . As an example, the SEM photograph of the filtration membrane in Example 2 and the observed EDX spectrum of the particles are shown in FIGS. 3 (a) and 3 (b), respectively.
１ 微粒子捕捉装置
２ 供給タンク
３ 廃液タンク
４ ガス導入管
５ 溶液供給管
６ 廃液回収管
１０ ろ過装置
１０ａ 流入口
１０ｂ 流出口
１１ ろ過膜
１２ ホルダ
１３ 被覆シート
１３ 開口部
１４ 上部プレート
１５ 下部プレート
DESCRIPTION OF SYMBOLS 1 Fine particle capture apparatus 2 Supply tank 3 Waste liquid tank 4 Gas introduction pipe 5 Solution supply pipe 6 Waste liquid collection pipe 10 Filtration apparatus 10a Inlet 10b Outlet 11 Filtration membrane 12 Holder 13 Cover sheet 13 Opening 14 Upper plate 15 Lower plate
Claims (10)
ろ過膜を含むろ過手段を有し、前記ろ過手段は、該ろ過手段に流入した前記液体が前記ろ過膜の一部に通液されるように構成されている、微粒子捕捉装置。 A fine particle capturing apparatus for capturing fine particles contained in a liquid,
A particulate trapping device comprising filtration means including a filtration membrane, wherein the filtration means is configured such that the liquid flowing into the filtration means is passed through a part of the filtration membrane.
ろ過膜の一部に前記液体に通液して前記微粒子を捕捉する工程と、
前記捕捉された微粒子の組成を分析する工程と、
を含む、微粒子測定方法。 A fine particle measurement method for measuring fine particles contained in a liquid,
Passing the liquid through a part of the filtration membrane and capturing the fine particles;
Analyzing the composition of the captured particulates;
A method for measuring fine particles.
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