JP2010236906A - Water quality evaluation method and device - Google Patents

Water quality evaluation method and device Download PDF

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JP2010236906A
JP2010236906A JP2009082569A JP2009082569A JP2010236906A JP 2010236906 A JP2010236906 A JP 2010236906A JP 2009082569 A JP2009082569 A JP 2009082569A JP 2009082569 A JP2009082569 A JP 2009082569A JP 2010236906 A JP2010236906 A JP 2010236906A
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JP5707670B2 (en
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Norito Ikemiya
範人 池宮
Tatsuo Nagai
達夫 永井
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Kurita Water Industries Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and a device evaluating a water quality of ultrapure water by detecting an amine-based organic substance or the like included in the ultrapure water highly accurately in a short time. <P>SOLUTION: Sample water is circulated as upward flow into a column 3 via a pipe 1 and a valve 2. Particles 4 of a silicon material are filled in the column 3, and a velocity of the upward flow is selected so that the particles 4 of the silicon material form a fluidized bed. Water having contact with the particles 4 of the silicon material is discharged through a pipe 5, a valve 6 and a flowmeter 7. A part of the water is divided by a pipe 8 branched from the pipe 7, and sent out through a flowmeter 10 after measuring a hydrogen concentration by a hydrogen concentration meter 9. A water feeding velocity into the column 3 is set at SV 100-10,000 h<SP>-1</SP>. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は純水（超純水を含む。）の水質を評価する方法及び装置に関する。   The present invention relates to a method and apparatus for evaluating the quality of pure water (including ultrapure water).

ＩＣやメモリーをはじめとする半導体製造工場や液晶パネル製造工場などでは、超純水が大量に使用されている。   A large amount of ultrapure water is used in semiconductor manufacturing plants such as ICs and memories, and liquid crystal panel manufacturing plants.

半導体製造工程においては、半導体デバイスの高精細化が進むに従い、シリコン表面の清浄度の維持、平坦度の維持が重要になってくる。高精細度の半導体を製造する工程においては、超純水が表面のシリコンをわずかでも溶解させると、表面のエッチングに伴う表面荒れが生じ、それに伴い電気特性を低下させるおそれがある。   In the semiconductor manufacturing process, it is important to maintain the cleanliness and flatness of the silicon surface as the semiconductor devices become more precise. In the process of manufacturing a high-definition semiconductor, if ultrapure water dissolves even a small amount of silicon on the surface, surface roughness associated with etching of the surface may occur, and the electrical characteristics may be degraded accordingly.

従って、半導体製造工程においては、シリコン表面荒れを生じさせることがない超純水を使用することが必要であり、超純水がシリコン表面をエッチングする性質を有するか否かを判断することは重要な課題である。   Therefore, in the semiconductor manufacturing process, it is necessary to use ultrapure water that does not cause silicon surface roughness, and it is important to determine whether ultrapure water has the property of etching the silicon surface. It is a difficult task.

超純水中の不純物は、金属などの無機物以外に、有機物があり、全有機性炭素濃度（ＴＯＣ）での管理がなされており、１ｐｐｂ程度以下に保持されている。ＴＯＣとしては、１ｐｐｂ以下であっても、アミン系の有機物が含まれていると、シリコンウエハをエッチングしてしまい、表面の粗さを大きくすることが知られている。また、アミン系の有機物のうちでも、ドデシルアミン、ヘキサデシルアミンあるいはオクタデシルアミンなどのアルキル鎖が長いものほど、エッチング量が多いことが知られている（特許第４０５６４１７号）。このアミン系の不純物は、超純水を製造する際に利用されるアニオン交換樹脂などの溶出物である。半導体工場で新設された超純水設備や、運転を中断した後の再開時に、このようなアミン系の有機物が多く含まれる超純水が排出されることが知られている。   Impurities in ultrapure water include organic substances in addition to inorganic substances such as metals, and are managed at the total organic carbon concentration (TOC), and are maintained at about 1 ppb or less. It is known that even if the TOC is 1 ppb or less, if an amine-based organic substance is contained, the silicon wafer is etched and the surface roughness is increased. Further, among amine-based organic substances, it is known that the longer the alkyl chain such as dodecylamine, hexadecylamine or octadecylamine, the larger the etching amount (Patent No. 4056417). This amine-based impurity is an effluent such as an anion exchange resin used in producing ultrapure water. It is known that ultrapure water containing a large amount of such amine-based organic matter is discharged when the ultrapure water facility newly established in a semiconductor factory or when the operation is resumed after being interrupted.

超純水設備からの超純水が半導体洗浄に用いても良いものかどうかを判定するために、この超純水を用いてウエハを洗浄し、洗浄後のウエハ表面の凹凸を赤外分光法で分析するか原子間力顕微鏡で観察する方法が行われているが、長時間を要すると共に、現場では行いにくい。   In order to determine whether ultrapure water from the ultrapure water facility can be used for semiconductor cleaning, the ultrapure water is used to clean the wafer, and the wafer surface unevenness after cleaning is analyzed by infrared spectroscopy. However, this method requires a long time and is difficult to perform in the field.

特開２００７−１７０８６３には、試料水をシリコン物質と接触させ、該シリコン物質に接触後の試料水に含有されるシリカ濃度に相関する物性値である溶存水素濃度を測定し、該シリコン物質との接触によって上昇した溶存水素濃度に基づいて、試料水の水質を評価する水質評価方法が記載されている。   In JP 2007-170863, sample water is brought into contact with a silicon substance, and the dissolved hydrogen concentration, which is a physical property value correlated with the silica concentration contained in the sample water after contact with the silicon substance, is measured. A water quality evaluation method is described in which the quality of sample water is evaluated based on the dissolved hydrogen concentration increased by the contact.

試料水中にアミン類などのようにシリコンをエッチングし易い物質が混入していると、試料水をシリコン物質に接触させた際にシリコン表面にエッチングが生じ、試料水中にシリコンが溶出する。溶出したシリコンはＯＨ−イオンもしくは水分子と反応し、イオン状シリカ（ケイ酸イオン）（ＳｉＯ３ ２−）になると共に、水素を生成させる。この水素は溶存水素となって水中に存在する。従って、溶存水素濃度はシリカ濃度と相関関係にあるため、溶存水素濃度の上昇をモニタリングすることによって、試料水がシリコンにエッチングを生じさせる水質かどうかを評価することができる。 If a substance that easily etches silicon, such as amines, is mixed in the sample water, etching occurs on the silicon surface when the sample water is brought into contact with the silicon substance, and silicon is eluted in the sample water. The eluted silicon reacts with OH − ions or water molecules to form ionic silica (silicate ions) (SiO 3 2− ) and generate hydrogen. This hydrogen exists in water as dissolved hydrogen. Therefore, since the dissolved hydrogen concentration has a correlation with the silica concentration, it is possible to evaluate whether the sample water is water quality that causes etching in silicon by monitoring the increase in the dissolved hydrogen concentration.

特許第４０５６４１７Patent No. 4056417 特開２００７−１７０８６３JP 2007-170863 A

上記特開２００７−１７０８６３の方法では、試料水をカラムに下向流にて通水しているため、シリコン物質と試料水との反応に時間がかかり、測定時間が長くなる。   In the method disclosed in Japanese Patent Application Laid-Open No. 2007-170863, since the sample water is passed through the column in a downward flow, the reaction between the silicon substance and the sample water takes time and the measurement time becomes long.

また、極めて低い濃度のアミン類（ＴＯＣで０．１ｐｐｂ程度）であってもシリコンの表面エッチングが進行することがあり、検出感度の向上が求められている。   Further, even with extremely low concentrations of amines (about 0.1 ppb in TOC), silicon surface etching may proceed, and improvement in detection sensitivity is required.

本発明は、超純水中に含まれるアミン系の有機物などを短時間で高精度に検出し、超純水の水質を評価できる方法および装置を提供することを目的とする。   An object of this invention is to provide the method and apparatus which can detect the amine organic substance etc. which are contained in ultrapure water with high precision in a short time, and can evaluate the quality of ultrapure water.

請求項１の水質評価方法は、シリコン物質の粒子が充填されたカラムに純水からなる試料水を通水し、通水後の試料水の溶存水素濃度を測定し、該測定値に基づいて試料水の水質を評価する水質評価方法において、該カラムに試料水を上向流で通水することにより流動層を形成すると共に、通水速度をＳＶ１００〜１０，０００ｈ−１とすることを特徴とするものである。 In the water quality evaluation method according to claim 1, sample water made of pure water is passed through a column packed with particles of a silicon substance, the dissolved hydrogen concentration in the sample water after passing is measured, and based on the measured value In the water quality evaluation method for evaluating the quality of sample water, a fluidized bed is formed by passing sample water through the column in an upward flow, and the water flow rate is set to SV100 to 10,000 h −1. It is what.

請求項２の水質評価方法は、請求項１において、純水が下記条件を全て満たす超純水であることを特徴とするものである。
電気比抵抗 ：１８ＭΩ・ｃｍ以上
金属イオン濃度：５ｎｇ／Ｌ以下
残留イオン濃度：１０ｎｇ／Ｌ以下
微粒子数 ：１ｍＬ中に０．１μｍ以上の微粒子５個以下
ＴＯＣ ：０．１〜１０μｇ／Ｌ The water quality evaluation method of claim 2 is characterized in that, in claim 1, the pure water is ultrapure water that satisfies all of the following conditions.
Electrical specific resistance: 18 MΩ · cm or more Metal ion concentration: 5 ng / L or less Residual ion concentration: 10 ng / L or less Number of particles: 5 particles of 0.1 μm or more in 1 mL TOC: 0.1 to 10 μg / L

請求項３の水質評価方法は、請求項１又は２において、シリコン物質が純度９９．９９９９％以上の高純度半導体シリコンであることを特徴とするものである。   The water quality evaluation method of claim 3 is characterized in that, in claim 1 or 2, the silicon substance is high-purity semiconductor silicon having a purity of 99.9999% or more.

請求項４の水質評価方法は、請求項１ないし３のいずれか１項において、シリコン物質が水素終端化されていることを特徴とするものである。   The water quality evaluation method according to claim 4 is characterized in that in any one of claims 1 to 3, the silicon substance is hydrogen-terminated.

請求項５の水質評価方法は、請求項４において、水素終端化する方法が、シリコン物質をオゾン水で洗浄した後にフッ酸で洗浄するものであることを特徴とするものである。   The water quality evaluation method according to claim 5 is characterized in that, in claim 4, the hydrogen termination method is a method in which the silicon substance is washed with ozone water and then washed with hydrofluoric acid.

請求項６の水質評価装置は、シリコン物質の粒子が充填されたカラムと、該カラムに純水からなる試料水を通水する通水手段と、通水後の試料水の溶存水素濃度を測定する手段とを有する水質評価装置において、該通水手段は、該カラムに試料水を上向流で通水することにより流動層を形成すると共に、通水速度をＳＶ１００〜１０，０００ｈ−１とするものであることを特徴とするものである。 The water quality evaluation apparatus according to claim 6 measures a column filled with particles of silicon substance, a water passing means for passing sample water made of pure water through the column, and a dissolved hydrogen concentration of the sample water after passing the water. In the water quality evaluation apparatus, the water passing means forms a fluidized bed by passing sample water through the column in an upward flow, and the water passing speed is set to SV100 to 10,000 h −1 . It is what is characterized by.

請求項７の水質評価装置は、請求項６において、前記シリコン物質が純度９９．９９９９％以上の高純度半導体シリコンであることを特徴とするものである。   The water quality evaluation apparatus according to claim 7 is characterized in that, in claim 6, the silicon substance is high-purity semiconductor silicon having a purity of 99.9999% or more.

本発明によれば、試料水をカラムに上向流にて通水して流動層を形成するので、シリコン物質と試料水との反応が早くなる。そのため、超純水中の極微量のアミン系の有機物を短時間で高精度に検出し、超純水の水質を精度よく評価することができる。   According to the present invention, the sample water is passed through the column in an upward flow to form a fluidized bed, so that the reaction between the silicon substance and the sample water is accelerated. Therefore, a very small amount of amine-based organic matter in ultrapure water can be detected with high accuracy in a short time, and the quality of ultrapure water can be accurately evaluated.

本発明の水質評価方法及び装置は、試料水、特に超純水をシリコン物質と接触させて該超純水中の溶存水素濃度を測定することによって、この超純水がシリコンウエハ表面をエッチングする性質を有するか否かを容易に判定できるので、半導体製造上の不具合の発生防止に極めて有効である。   The water quality evaluation method and apparatus according to the present invention etches a silicon wafer surface by bringing sample water, particularly ultrapure water, into contact with a silicon substance and measuring the dissolved hydrogen concentration in the ultrapure water. Since it can be easily determined whether or not it has properties, it is extremely effective in preventing the occurrence of defects in semiconductor manufacturing.

本発明の評価装置を、超純水製造装置直近、製造装置内、工場への供給配管途上等、任意の位置に設置することにより、水質評価を迅速に実行することが可能となる。従って、本発明は、半導体製造上の不具合の原因及びその発生源の解明に役立ち、解決に大きく寄与する。   By installing the evaluation apparatus of the present invention at an arbitrary position such as the ultrapure water production apparatus immediately, in the production apparatus, or in the middle of supply piping to the factory, it is possible to quickly execute water quality evaluation. Therefore, the present invention is useful for elucidating the cause of a semiconductor manufacturing defect and its source, and greatly contributes to the solution.

本発明方法のフロー図である。It is a flowchart of this invention method. 本発明装置を組み込んだ超純水製造設備のフロー図である。It is a flowchart of the ultrapure water manufacturing equipment incorporating this invention apparatus.

以下、本発明についてさらに詳細に説明する。   Hereinafter, the present invention will be described in more detail.

本発明は、シリコン物質の粒子が充填されたカラムに純水からなる試料水を通水し、通水後の試料水の溶存水素濃度を測定し、該測定値に基づいて試料水の水質を評価する水質評価方法において、該カラムに試料水を上向流で通水することにより流動層を形成すると共に、通水速度をＳＶ１００〜１０，０００ｈ−１とすることを特徴とするものである。 In the present invention, sample water made of pure water is passed through a column filled with particles of a silicon substance, the dissolved hydrogen concentration of the sample water after passing is measured, and the quality of the sample water is determined based on the measured value. In the water quality evaluation method to be evaluated, a fluidized bed is formed by passing sample water through the column in an upward flow, and the water flow rate is set to SV100 to 10,000 h −1. .

前述の通り、特開２００７−１７０８６３には、試料水をシリコン物質と接触させ、該シリコン物質に接触後の試料水に含有される溶存水素濃度を測定し、該シリコン物質との接触によって上昇した溶存水素濃度に基づいて、試料水の水質を評価する水質評価方法が記載されている。   As described above, in Japanese Patent Application Laid-Open No. 2007-170863, sample water is brought into contact with a silicon substance, the concentration of dissolved hydrogen contained in the sample water after contact with the silicon substance is measured, and increased by contact with the silicon substance. A water quality evaluation method for evaluating the quality of sample water based on the dissolved hydrogen concentration is described.

この方法では、試料水中にアミン類などのようにシリコンをエッチングし易い物質が混入していると、試料水をシリコン物質に接触させた際にシリコン表面にエッチングが生じ、試料水中にシリコンが溶出する。溶出したシリコンはＯＨ−イオンもしくは、水分子と反応し、イオン状シリカ（ケイ酸イオン）（ＳｉＯ３ ２−）になると共に、水素を生成させる。この水素は溶存水素となって水中に存在する。従って、溶存水素濃度の上昇をモニタリングすることによって、試料水の水質を評価することができる。 In this method, if a substance that easily etches silicon, such as amines, is mixed in the sample water, etching occurs on the silicon surface when the sample water is brought into contact with the silicon substance, and silicon is eluted in the sample water. To do. The eluted silicon reacts with OH − ions or water molecules to become ionic silica (silicate ions) (SiO 3 2− ) and generate hydrogen. This hydrogen exists in water as dissolved hydrogen. Therefore, the quality of the sample water can be evaluated by monitoring the increase in the dissolved hydrogen concentration.

本発明方法に従って、シリコン物質と接触した後の純水中の溶存水素濃度を測定し、当該物質との接触前の溶存水素濃度と比較すれば、当該物質との接触によって上昇した溶存水素濃度を測定することができる。従って、定期的或いは連続的に溶存水素濃度を測定することにより、純水の水質、特にエッチング性の変動をモニタリングすることができる。また、シリコンへの接触条件を一定のものにすることで、複数種の試料水がシリコンに対して有するエッチング能力を相対的に比較対比することができる。   According to the method of the present invention, when the dissolved hydrogen concentration in pure water after contact with the silicon substance is measured and compared with the dissolved hydrogen concentration before contact with the substance, the dissolved hydrogen concentration increased by contact with the substance Can be measured. Therefore, by measuring the dissolved hydrogen concentration periodically or continuously, the quality of pure water, particularly the change in etching property, can be monitored. Further, by making the contact condition with silicon constant, it is possible to relatively compare and compare the etching ability of a plurality of types of sample water with respect to silicon.

本発明ではシリコンの充填量と通水量との関係が、ＳＶ＝１００〜１０，０００ｈ−１好ましくは２００〜５０００ｈ−１となるように調節し、カラム内に流動層を形成する。ここでＳＶとはＳｐａｃｅ Ｖｅｌｏｃｉｔｙ（空間速度）の略称であり、１時間あたりの通水量をシリコンの充填量で除算した値となる。例えばシリコンの充填量が１２０ｍＬで通水量が６０Ｌ／ｈであれば、ＳＶ＝６０×１，０００／１２０＝５００ｈ−１となる。ＳＶが１００００ｈ−１よりも大きくなると、超純水がシリコンの充填材に接触する時間が短くなり、超純水中のアミン系有機物の検出感度が低くなる。一方、ＳＶが１００ｈ−１を下回ると、水素濃度が飽和状態となるのに極めて長い時間（２４時間以上）を要し、検出時間が長くなる。 Relationship in the present invention the filling quantity and passing water in silicon, SV = 100~10,000h -1 preferably adjusted to be 200~5000h -1, to form a fluidized bed in the column. Here, SV is an abbreviation for Space Velocity (space velocity) and is a value obtained by dividing the amount of water per hour by the amount of silicon filling. For example, if the filling amount of silicon is 120 mL and the water flow rate is 60 L / h, SV = 60 × 1,000 / 120 = 500 h −1 . When the SV is larger than 10,000 h −1 , the time for which the ultrapure water contacts the silicon filler is shortened, and the detection sensitivity of the amine-based organic matter in the ultrapure water is lowered. On the other hand, if SV is less than 100 h −1 , it takes a very long time (24 hours or more) for the hydrogen concentration to reach saturation, and the detection time becomes long.

充填材料のシリコンとしては金属シリコンが用いられる。この金属シリコンとしては、純度が９９％の金属シリコン（純度は２Ｎ、不純物を１％含む）を用いるよりは、純度６Ｎ以上のもの、例えば高純度の半導体ウエハ（９９．９９９９９９９９９％，１１Ｎ）の破砕物あるいは、太陽電池用（９９．９９９９％，６Ｎ以上）に球状に形成されたシリコン（例えば特許第４０７４９３１号に記載のもの）を利用するのが望ましい。   Metal silicon is used as the filling material silicon. As this metal silicon, a metal silicon having a purity of 6N or more, for example, a high-purity semiconductor wafer (99.99999999999%, 11N) is used rather than a metal silicon having a purity of 99% (purity is 2N, including impurities 1%). It is desirable to use crushed material or silicon formed in a spherical shape for solar cells (99.9999%, 6N or more) (for example, the one described in Japanese Patent No. 4074931).

シリコン物質の大きさ（粒径）は、特に制限はないが、０．２ｍｍ〜２．０ｍｍが良く、望ましくは０．２ｍｍ〜１．０ｍｍ程度とする。シリコン物質の形状は、特に制限はない。再溶解して、球形にしたものでも良い。   The size (particle size) of the silicon substance is not particularly limited, but is preferably 0.2 mm to 2.0 mm, and preferably about 0.2 mm to 1.0 mm. The shape of the silicon material is not particularly limited. It may be redissolved into a spherical shape.

シリコンは水素終端化されていることが好ましく、その方法としてまずオゾン水でシリコン表面の有機物を酸化処理し、次いでフッ酸で水素終端化するのが望ましい。オゾン水のオゾン濃度は１ｐｐｍ以上が良く処理時間は３０分程度が良い。フッ酸の濃度は０．５〜１％程度で良く、処理時間は５分程度が良い。   Silicon is preferably hydrogen-terminated, and as a method, it is desirable to first oxidize organic substances on the silicon surface with ozone water and then hydrogen-terminated with hydrofluoric acid. The ozone concentration of ozone water is preferably 1 ppm or more, and the treatment time is preferably about 30 minutes. The concentration of hydrofluoric acid may be about 0.5 to 1%, and the treatment time is about 5 minutes.

シリコン物質を充填するためのカラムとしては、超純水と接触して溶出物を排出しなければ良く、アクリル製でも良く、ポリテトラフルオルエチレン、ＰＦＡ等のフッ素樹脂製でも良い。   The column for filling the silicon substance may be made of an acrylic resin or a fluororesin such as polytetrafluoroethylene or PFA as long as it does not come into contact with ultrapure water to discharge the eluted substance.

水中の溶存水素濃度測定には、各種の溶存水素濃度計を用いることができ、例えば、隔膜電極式溶存水素濃度計が挙げられる。   Various dissolved hydrogen concentration meters can be used for measuring the dissolved hydrogen concentration in water, and examples thereof include a diaphragm electrode type dissolved hydrogen concentration meter.

シリコン充填カラムに試料水の通水を開始した場合、試料水の水質が悪いときにはカラム流出水中の溶存水素濃度がいったん増加するが、水質が良くなると溶存水素濃度が低下する。   When sample water is started to flow through the silicon-filled column, the dissolved hydrogen concentration in the column effluent once increases when the quality of the sample water is poor, but the dissolved hydrogen concentration decreases as the water quality improves.

なお、本発明において、超純水は次の水質を満たすものであることが好ましい。   In the present invention, the ultrapure water preferably satisfies the following water quality.

電気比抵抗 ：１８ＭΩ・ｃｍ以上
金属イオン濃度：５ｎｇ／Ｌ以下
残留イオン濃度：１０ｎｇ／Ｌ以下
微粒子数 ：１ｍＬ中に０．１μｍ以上の微粒子５個以下
ＴＯＣ ：０．１〜１０μｇ／Ｌ Electrical specific resistance: 18 MΩ · cm or more Metal ion concentration: 5 ng / L or less Residual ion concentration: 10 ng / L or less Number of particles: 5 particles of 0.1 μm or more in 1 mL TOC: 0.1 to 10 μg / L

本発明で検知対象となる、シリコン表面荒れを生じさせる不純物としては、アミン類が挙げられる。アミン類のうち特にドデシルアミン、ヘキサデシルアミン、オクタデシルアミンなどのアルキル鎖が長いものは、エッチング量が多いため、本発明方法により精度よく検知することができる。   Examples of impurities that cause silicon surface roughness, which are detection targets in the present invention, include amines. Among amines, those having a long alkyl chain, such as dodecylamine, hexadecylamine, and octadecylamine, can be detected with high accuracy by the method of the present invention because of the large etching amount.

以下、図面を参照して本発明についてさらに詳細に説明する。   Hereinafter, the present invention will be described in more detail with reference to the drawings.

第１図は本発明方法及び装置を示すフロー図である。   FIG. 1 is a flow diagram illustrating the method and apparatus of the present invention.

試料水は、配管１、バルブ２を通ってカラム３に上向流にて通水される。カラム３内にはシリコン物質の粒子４が充填されており、このシリコン物質の粒子４が流動層を形成するように上向流の流速が選定される。シリコン物質の粒子４と接触した水は、配管５、バルブ６、流量計７を通って系外に排出される。この水の一部は、配管７から分岐する配管８によって分取され、水素濃度計９にて水素濃度が測定された後、流量計１０を通って系外に排出される。   The sample water is passed through the pipe 1 and the valve 2 to the column 3 in an upward flow. The column 3 is filled with silicon material particles 4, and the upward flow velocity is selected so that the silicon material particles 4 form a fluidized bed. The water in contact with the silicon substance particles 4 is discharged out of the system through the pipe 5, the valve 6 and the flow meter 7. A part of this water is collected by a pipe 8 branched from the pipe 7, and after the hydrogen concentration is measured by a hydrogen concentration meter 9, the water is discharged out of the system through a flow meter 10.

第２図は、半導体製造工程に適用される超純水設備を示す概略的なフロー図である。   FIG. 2 is a schematic flow diagram showing an ultrapure water facility applied to a semiconductor manufacturing process.

原水は１次純水装置１１で処理された後、サブシステム１２で処理されて超純水となる。この超純水は、ライン１３を介して循環され、その途中で分岐してユースポイント１４に送られる。   The raw water is processed by the primary pure water device 11 and then processed by the subsystem 12 to become ultrapure water. This ultrapure water is circulated through the line 13, branched in the middle thereof, and sent to the use point 14.

超純水は、サブシステム１２から出た直後の地点、ユースポイント１４に送られる直前の地点、及びサブシステム１２に戻る地点で採水用分岐配管１５で分取され、第１図の構成を有した評価装置１６に供給され、評価が行われる。   The ultrapure water is collected by the branch pipe 15 for collecting water at a point immediately after leaving the subsystem 12, a point immediately before being sent to the use point 14, and a point returning to the subsystem 12, and has the configuration shown in FIG. It is supplied to the evaluation device 16 that it has, and evaluation is performed.

以下に、本発明を第２図の超純水製造装置に適用した場合の超純水製造装置の運転方法について説明する。   The operation method of the ultrapure water production apparatus when the present invention is applied to the ultrapure water production apparatus of FIG. 2 will be described below.

［超純水製造装置の新設時及びメンテナンス等で運転を中断した後の再開時］
＜ステップ１＞ サブシステム１２の循環ライン１３からユースポイント１４への供給ラインのバルブを閉めた状態で超純水製造装置の運転を開始又は再開する。評価装置１６のバルブ２を開け、循環ライン１３から分岐した超純水をカラム３に通水する。このとき、評価装置１６における溶存水素濃度の測定値は、予め設定した設定値（許容溶存水素濃度の上限値）を超える。 [When a new ultrapure water production system is installed and when it is restarted after operation has been suspended]
<Step 1> The operation of the ultrapure water production apparatus is started or restarted with the valve of the supply line from the circulation line 13 of the subsystem 12 to the use point 14 closed. The valve 2 of the evaluation device 16 is opened, and ultrapure water branched from the circulation line 13 is passed through the column 3. At this time, the measured value of the dissolved hydrogen concentration in the evaluation device 16 exceeds a preset value (the upper limit value of the allowable dissolved hydrogen concentration).

＜ステップ２＞ その後、時間の経過と共に、評価装置１６における溶存水素濃度測定値が徐々に低下する。この評価装置１６における溶存水素濃度測定値が設定値を下回るまで低下したときには、循環ライン１３を循環する超純水中のシリコン汚染物質の濃度が十分に低減されたと判断し、ユースポイント１４への供給ラインのバルブを開ける。 <Step 2> Thereafter, the dissolved hydrogen concentration measurement value in the evaluation device 16 gradually decreases with time. When the measured dissolved hydrogen concentration in the evaluation device 16 decreases to a value below the set value, it is determined that the concentration of silicon contaminants in the ultrapure water circulating in the circulation line 13 has been sufficiently reduced, and Open the supply line valve.

［超純水製造装置の運転を継続しながらメンテナンスを行う場合］
＜ステップ１＞ 超純水製造装置の運転を継続しながらメンテナンスを行う場合、超純水製造装置の通常運転中に評価装置１６のバルブ２を開け、循環ライン１３から分岐した超純水をカラム３に通水する。評価装置１６における溶存水素濃度の測定値が、予め設定した設定値を超えないことを確認しながら部材更新等のメンテナンスを進めるが、万一設定値を超えた場合には、超純水中のシリコン汚染物質の濃度が高いと判断し、ユースポイント１４への供給ラインのバルブを閉じる。 [When performing maintenance while continuing operation of ultrapure water production equipment]
<Step 1> When performing maintenance while continuing the operation of the ultrapure water production apparatus, the valve 2 of the evaluation device 16 is opened during the normal operation of the ultrapure water production apparatus, and the ultrapure water branched from the circulation line 13 is used as a column. Pass water through 3. While maintaining the measured value of the dissolved hydrogen concentration in the evaluation device 16 to ensure that it does not exceed the preset value, proceed with maintenance such as renewal of the member. It is determined that the concentration of silicon contaminant is high, and the valve of the supply line to the use point 14 is closed.

＜ステップ２＞ メンテナンス終了後、時間の経過と共に、評価装置１６における溶存水素濃度測定値が徐々に低下し、設定値を下回ったときには、循環ライン１３を循環する超純水中のシリコン汚染物質の濃度が十分に低減されたと判断し、ユースポイント１４への供給ラインのバルブを開ける。 <Step 2> When the dissolved hydrogen concentration measurement value in the evaluation device 16 gradually decreases and falls below the set value with the lapse of time after completion of the maintenance, the silicon contaminants in the ultrapure water circulating in the circulation line 13 It is determined that the concentration is sufficiently reduced, and the valve of the supply line to the use point 14 is opened.

以下、実施例、比較例及び参考例について説明する。   Hereinafter, examples, comparative examples, and reference examples will be described.

後述の水質判定時間とは、ウエハを洗浄するのに適当な溶存水素濃度にまで達する全体の時間を表わす。   The water quality determination time described later represents the total time required to reach a dissolved hydrogen concentration appropriate for cleaning the wafer.

［実施例１］
内径２５ｍｍ、高さ７００ｍｍのアクリル製カラム内に半導体高純度シリコンウエハ（純度：１１Ｎ）を破砕し、篩分けして平均粒径約１ｍｍとしたシリコン粒を１２０ｍＬ充填した。なお、シリコン粒は、充填前にオゾン水で３０分洗浄した後に、１％ＨＦ溶液中に５分浸漬して水素終端化を行っている。下記水質の超純水を０．４Ｌ／ｍｉｎとなるように上向流で通水したところシリコン粒子は展開して流動層となった。このときのＳＶは２００ｈ−１であった。カラム流出水中の溶存水素濃度は、隔膜電極式溶存水素計（オービスフェア製）を利用して測定した。 [Example 1]
A semiconductor high-purity silicon wafer (purity: 11N) was crushed in an acrylic column having an inner diameter of 25 mm and a height of 700 mm, and 120 mL of silicon particles having an average particle diameter of about 1 mm were packed by sieving. The silicon grains are washed with ozone water for 30 minutes before filling and then immersed in a 1% HF solution for 5 minutes for hydrogen termination. When ultrapure water having the following water quality was passed in an upward flow at 0.4 L / min, the silicon particles developed and became a fluidized bed. The SV at this time was 200 h- 1 . The dissolved hydrogen concentration in the column effluent was measured using a diaphragm electrode type dissolved hydrogen meter (manufactured by Orbis Fair).

超純水の水質
電気比抵抗 ：１８ＭΩ・ｃｍ以上
金属イオン濃度：５ｎｇ／Ｌ以下
残留イオン濃度：１０ｎｇ／Ｌ以下
微粒子数 ：１ｍＬ中に０．１μｍ以上の微粒子５個以下
ＴＯＣ ：０．１〜１０μｇ／Ｌ Water quality of ultrapure water Electric resistivity: 18 MΩ · cm or more Metal ion concentration: 5 ng / L or less Residual ion concentration: 10 ng / L or less Number of particles: 5 particles of 0.1 μm or more in 1 mL TOC: 0.1 10 μg / L

通水開始から６時間後には溶存水素濃度が６．４５ｐｐｂまで増加したが、その１０時間後に０．２０ｐｐｂ以下となったので、ウエハ洗浄工程への供給を開始した。水質判定に要した時間は１６時間（６＋１０＝１６）であった。   Six hours after the start of water flow, the dissolved hydrogen concentration increased to 6.45 ppb, but after 10 hours it became 0.20 ppb or less, and supply to the wafer cleaning process was started. The time required for water quality determination was 16 hours (6 + 10 = 16).

［実施例２］
太陽電池向けシリコン粒子（純度：６Ｎ、粒径０．５ｍｍ）１２０ｍＬをアクリル製カラムに充填し、ＳＶを５００ｈ−１としたこと以外は実施例１と同等の条件として試験を実施した。なお、このときの通水量は１Ｌ／ｍｉｎである。 [Example 2]
The test was carried out under the same conditions as in Example 1 except that 120 mL of silicon particles for solar cells (purity: 6N, particle size 0.5 mm) were packed in an acrylic column and SV was set to 500 h- 1 . In addition, the amount of water flow at this time is 1 L / min.

通水開始から３時間後には溶存水素濃度が５．４５ｐｐｂまで増加したが、その９時間後に０．２０ｐｐｂ以下となったので、ウエハ洗浄工程への供給を開始した。水質判定に要した時間は１２時間（３＋９＝１２）であった。   Three hours after the start of water flow, the dissolved hydrogen concentration increased to 5.45 ppb, but after 9 hours it became 0.20 ppb or less, and supply to the wafer cleaning process was started. The time required for water quality determination was 12 hours (3 + 9 = 12).

［実施例３］
太陽電池向けシリコン粒子３０ｍＬをアクリルカラムに充填し、ＳＶを２０００ｈ−１としたこと以外は実施例２と同様に試験を実施した。なお、通水量は１Ｌ／ｍｉｎである。 [Example 3]
The test was carried out in the same manner as in Example 2 except that 30 mL of silicon particles for solar cells were filled in an acrylic column and SV was 2000 h- 1 . The water flow rate is 1 L / min.

通水開始から３時間後には溶存水素濃度が３．４５ｐｐｂまで増加したが、その７時間後に０．２０ｐｐｂ以下となったので、ウエハ洗浄工程への供給を開始した。水質判定に要した時間は１０時間（３＋７＝１０）であった。   3 hours after the start of water flow, the dissolved hydrogen concentration increased to 3.45 ppb, but after 7 hours it became 0.20 ppb or less, and supply to the wafer cleaning process was started. The time required for water quality determination was 10 hours (3 + 7 = 10).

［実施例４］
太陽電池向けシリコン粒子２０ｍＬをアクリルカラムに充填し、ＳＶを３０００ｈ−１としたこと以外は実施例２と同様に試験を実施した。なお、通水量は１Ｌ／ｍｉｎである。 [Example 4]
The test was carried out in the same manner as in Example 2 except that 20 mL of silicon particles for solar cells were packed in an acrylic column and SV was set to 3000 h- 1 . The water flow rate is 1 L / min.

通水開始から２時間後には溶存水素濃度が２．４５ｐｐｂまで増加したが、その６時間後に０．２０ｐｐｂ以下となったので、ウエハ洗浄工程への供給を開始した。水質判定に要した時間は８時間（２＋６＝８）であった。   2 hours after the start of water flow, the dissolved hydrogen concentration increased to 2.45 ppb, but after 6 hours it became 0.20 ppb or less, and supply to the wafer cleaning process was started. The time required for water quality determination was 8 hours (2 + 6 = 8).

［比較例１］
実施例１において、超純水をカラムに下向流で通水したこと以外は同等の条件として溶存水素濃度を測定した。通水量は１Ｌ／ｍｉｎであり、ＳＶは５００ｈ−１である。 [Comparative Example 1]
In Example 1, the dissolved hydrogen concentration was measured under the same conditions except that ultrapure water was passed through the column in a downward flow. The amount of water flow is 1 L / min, and SV is 500 h- 1 .

通水開始から６時間後には溶存水素濃度が６．１５ｐｐｂまで増加したが、その１２時間後にはまだ２．００ｐｐｂであり、溶存水素濃度が所定値以下になるにはさらに６時間程度を要した。その結果、水質判定には２４時間以上を要した。そのため、ウエハ洗浄を開始するのに時間がかかり生産性が悪かった。   Six hours after the start of water flow, the dissolved hydrogen concentration increased to 6.15 ppb, but after 12 hours it was still 2.00 ppb, and it took about 6 hours for the dissolved hydrogen concentration to fall below the predetermined value. As a result, it took 24 hours or more for water quality judgment. For this reason, it takes time to start the wafer cleaning, and the productivity is poor.

［参考例１］
９９．９％のシリコン粒子（純度：３Ｎ）６０ｍＬを充填し、ＳＶを１０００ｈ−１としたこと以外は実施例１と同等の条件として試験を実施した。なお、通水量は１Ｌ／ｍｉｎである。 [Reference Example 1]
The test was conducted under the same conditions as in Example 1 except that 60 mL of 99.9% silicon particles (purity: 3N) were filled and SV was set to 1000 h −1 . The water flow rate is 1 L / min.

通水開始から６時間後には溶存水素濃度が２．１５ｐｐｂまで増加したが、その１２時間後にはまだ１．００ｐｐｂであり、溶存水素濃度が所定値以下になるにはさらに６時間程度を要した。その結果、水質判定には２４時間以上を要した。ウエハ洗浄を開始するのに時間がかかり生産性が悪かった。   Six hours after the start of water flow, the dissolved hydrogen concentration increased to 2.15 ppb, but after 12 hours it was still 1.00 ppb, and it took about six hours for the dissolved hydrogen concentration to fall below the predetermined value. As a result, it took 24 hours or more for water quality judgment. It took a long time to start the wafer cleaning, and the productivity was poor.

［参考例２］
９９．９９％のシリコン粒子（純度：４Ｎ）６０ｍＬを充填し、ＳＶを１０００ｈ−１としたこと以外は実施例１と同等の条件として試験を実施した。なお、通水量は１Ｌ／ｍｉｎである。 [Reference Example 2]
The test was carried out under the same conditions as in Example 1 except that 60 mL of 99.99% silicon particles (purity: 4N) were filled and SV was set to 1000 h −1 . The water flow rate is 1 L / min.

通水開始から６時間後には溶存水素濃度が１．７５ｐｐｂまで増加したが、その１２時間後にはまだ０．８５ｐｐｂであり、溶存水素濃度が所定値以下になるにはさらに６時間程度を要した。その結果、水質判定には２４時間以上を要した。そのため、ウエハ洗浄を開始するのに時間がかかり生産性が悪かった。   Six hours after the start of water flow, the dissolved hydrogen concentration increased to 1.75 ppb, but after 12 hours it was still 0.85 ppb, and it took about six hours for the dissolved hydrogen concentration to fall below the predetermined value. As a result, it took 24 hours or more for water quality judgment. For this reason, it takes time to start the wafer cleaning, and the productivity is poor.

［比較例２］
太陽電池用のシリコン粒子（純度：６Ｎ、粒径１．０ｍｍ）４ｍＬを充填すると共に、ＳＶを１５，０００ｈ−１としたこと以外は実施例１と同等の条件として試験を実施した。なお、通水量は１Ｌ／ｍｉｎである。 [Comparative Example 2]
The test was carried out under the same conditions as in Example 1 except that 4 mL of silicon particles for solar cells (purity: 6N, particle size 1.0 mm) were filled, and SV was 15,000 h- 1 . The water flow rate is 1 L / min.

通水開始から６時間後には溶存水素濃度が０．７５ｐｐｂまで増加したが、その１２時間後にはまだ０．５５ｐｐｂであり、溶存水素濃度が所定値以下になるにはさらに６時間程度を要した。その結果、水質判定には２４時間以上を要し、ウエハ洗浄を開始するのに時間がかかり生産性が悪かった。   Six hours after the start of water flow, the dissolved hydrogen concentration increased to 0.75 ppb, but after 12 hours it was still 0.55 ppb, and it took about six hours for the dissolved hydrogen concentration to fall below the predetermined value. As a result, it took 24 hours or more to determine the water quality, and it took time to start the wafer cleaning, and the productivity was poor.

以上より、本発明例（実施例１〜４）によると、水質判定を短時間で行うことができることが認められた。   From the above, according to the present invention examples (Examples 1 to 4), it was confirmed that the water quality determination can be performed in a short time.

３ カラム
４ シリコン粒子
９ 水素濃度計
１４ ユースポイント
１６ 水質評価装置 3 Column 4 Silicon particle 9 Hydrogen concentration meter 14 Use point 16 Water quality evaluation device

Claims (7)

シリコン物質の粒子が充填されたカラムに純水からなる試料水を通水し、通水後の試料水の溶存水素濃度を測定し、該測定値に基づいて試料水の水質を評価する水質評価方法において、
該カラムに試料水を上向流で通水することにより流動層を形成すると共に、通水速度をＳＶ１００〜１０，０００ｈ−１とすることを特徴とする水質評価方法。 Water quality evaluation in which sample water consisting of pure water is passed through a column packed with particles of silicon substance, the dissolved hydrogen concentration of the sample water is measured after passing, and the quality of the sample water is evaluated based on the measured value In the method
A water quality evaluation method characterized by forming a fluidized bed by passing sample water through the column in an upward flow and setting the water flow rate to SV100 to 10,000 h- 1 . 請求項１において、純水が下記条件を全て満たす超純水であることを特徴とする水質評価方法。
電気比抵抗 ：１８ＭΩ・ｃｍ以上
金属イオン濃度：５ｎｇ／Ｌ以下
残留イオン濃度：１０ｎｇ／Ｌ以下
微粒子数 ：１ｍＬ中に０．１μｍ以上の微粒子５個以下
ＴＯＣ ：０．１〜１０μｇ／Ｌ The water quality evaluation method according to claim 1, wherein the pure water is ultrapure water that satisfies all of the following conditions.
Electrical specific resistance: 18 MΩ · cm or more Metal ion concentration: 5 ng / L or less Residual ion concentration: 10 ng / L or less Number of particles: 5 particles of 0.1 μm or more in 1 mL TOC: 0.1 to 10 μg / L 請求項１又は２において、前記シリコン物質が純度９９．９９９９％以上の高純度半導体シリコンであることを特徴とする水質評価方法。   3. The water quality evaluation method according to claim 1, wherein the silicon substance is high-purity semiconductor silicon having a purity of 99.9999% or more. 請求項１ないし３のいずれか１項において、シリコン物質が水素終端化されていることを特徴とする水質評価方法。   4. A water quality evaluation method according to claim 1, wherein the silicon substance is hydrogen-terminated. 請求項４において、水素終端化する方法が、シリコン物質をオゾン水で洗浄した後にフッ酸で洗浄するものであることを特徴とする水質評価方法。   5. The water quality evaluation method according to claim 4, wherein the hydrogen termination method is a method in which the silicon material is washed with ozone water and then washed with hydrofluoric acid. シリコン物質の粒子が充填されたカラムと、該カラムに純水からなる試料水を通水する通水手段と、通水後の試料水の溶存水素濃度を測定する手段とを有する水質評価装置において、
該通水手段は、該カラムに試料水を上向流で通水することにより流動層を形成すると共に、通水速度をＳＶ１００〜１０，０００ｈ−１とするものであることを特徴とする水質評価装置。 In a water quality evaluation apparatus having a column filled with silicon substance particles, a water passage means for passing sample water made of pure water through the column, and a means for measuring the dissolved hydrogen concentration of the sample water after the water flow ,
The water passing means forms a fluidized bed by passing sample water through the column in an upward flow, and sets the water passing speed to SV100 to 10,000 h −1. Evaluation device. 請求項６において、前記シリコン物質が純度９９．９９９９％以上の高純度半導体シリコンであることを特徴とする水質評価装置。   7. The water quality evaluation apparatus according to claim 6, wherein the silicon substance is high-purity semiconductor silicon having a purity of 99.9999% or more.
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