JP4419315B2 - Substrate cleaning method and substrate cleaning apparatus - Google Patents
Substrate cleaning method and substrate cleaning apparatus Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、弗化アンモニウムを含む水溶液を洗浄液として用いた基板洗浄方法及び基板洗浄装置に関するものであり、洗浄の均一安定処理、並びに洗浄液の使用量の削減を目的として開発された新規な基板洗浄方法及び基板洗浄装置に関するものである。
【０００２】
【従来技術】
弗化アンモニウム水溶液（弗化水素酸とアンモニアとの任意混合液や界面活性剤を含有するもの等も含む。）は、弗化水素酸等と混合することにより、半導体（主にシリコン酸化膜）基板やガラス基板の洗浄やエッチングを目的として、半導体やＬＣＤ製造工程で多用されている。
【０００３】
これら分野では、製品の軽量化、小型化、低消費電力化を目的として、より集積度の高い微細加工技術が求められている。このため、弗化アンモニウム水溶液や同水溶液と弗化水素酸との混合液による基板の洗浄においても、より精度の高い処理が望まれている。
【０００４】
【発明が解決しようとする課題】
ところで、上記洗浄やエッチングにおいては、洗浄液中の薬品成分（ＮＨ４Ｆ、ＨＦ）や水分が時間経過とともに変化（蒸発）するため、これによりシリコン酸化膜やガラス基板に対するエッチングレートが変化（増加）するという問題点を有している。
【０００５】
これは、使用中に洗浄液中の弗酸成分の濃度が時間経過とともに徐々に増加することによるものであるが、現状では、洗浄液の液交換を頻繁に行うことにより、洗浄液中の各種成分濃度の変化に対する処置を講じていた。
【０００６】
しかしながら、この対策では非常に多量の該洗浄液を使用することになり［特に弗化アンモニウム含有洗浄液は数十％（例えば４０重量％程度）の高濃度の状態で使用されるため、通常数％程度の濃度で使用される他の洗浄液と比べて１回当たりの液交換で消費される薬品量は多くなる。］、これに伴い、弗化アンモニウムや弗化水素酸の使用量（薬品経費）が増加することになる。
【０００７】
また、洗浄液が使用済みとなった場合、図４に示すような排水処理が必要となるが、この場合、多量の資源（排水処理剤）が消費され、これに伴い多量の廃棄物（排水と汚泥）を発生することになる（図５参照）。
【０００８】
図４は、洗浄液の廃液処理工程を説明するものであり、洗浄槽８１から生じた廃液は、ｐＨ調整槽８２に運ばれ、ここで例えば２０％水酸化カルシウム液で中和される。次に、廃液は、凝沈槽８３に運ばれ、硫酸アルミニウム等の薬品により凝沈し、続いて凝集槽８４にてポリアクリルアミド系凝集剤等の高分子凝集剤により凝集・沈殿し、その後は下水や汚泥となって排出される。
【０００９】
前記処理工程では、図５に示すように、４０％弗化アンモニウム水溶液１ｋｇに対し、２０％水酸化カルシウム２．０ｋｇ、８％硫酸アルミニウム０．３ｋｇ、高分子凝集剤１．６ｋｇを必要とし、固形分７０％汚泥２．６ｋｇ、下水排水２．３ｋｇが生じる。
【００１０】
近年、地球環境問題は世界的な関心事となってきており、半導体やＬＣＤ等の基板製造時の環境負荷が問題視されるようになってきた昨今、洗浄液に関しても単にコストダウンの目的だけではなく、省資源や廃棄物の低減、環境浄化等の環境保全面での対応が社会的に強く求められるようになってきている。
【００１１】
本発明は、このような従来の実情に鑑みて提案されたものであり、均一安定な基板洗浄が可能であり、省資源化、廃棄物低減化等を可能とする基板洗浄方法、基板洗浄装置を提供することを目的とする。
【００１２】
【課題を解決するための手段】
上述の目的を達成するために、本発明の基板洗浄方法は、弗化アンモニウムを含む水溶液を洗浄液として基板の洗浄を行う際に、上記洗浄液中のＨＦの濃度を測定し、測定結果が０．０５〜０．１重量％の範囲を下回った場合にはＨＦ成分を補充し、測定結果が０．０５〜０．１重量％の範囲を上回った場合にはアンモニア成分を補充し、上記ＨＦの濃度を上記０．０５〜０．１重量％の範囲に維持する。
【００１３】
また、本発明の基板洗浄装置は、弗化アンモニウムを含む水溶液を洗浄液として基板の洗浄を行う基板洗浄装置において、上記洗浄液を収容する基板洗浄処理槽と、上記洗浄液中のＨＦの濃度を測定する濃度測定手段と、上記濃度測定手段における測定結果が０．０５〜０．１重量％の範囲を下回った場合にはＨＦ成分を補充し、測定結果が０．０５〜０．１重量％の範囲を上回った場合にはアンモニア成分を補充し、上記ＨＦの濃度を０．０５〜０．１重量％の範囲に維持する補充手段とを備えるものである。
【００１４】
弗化アンモニウム水溶液や、弗化アンモニウム水溶液と弗化水素酸との混合液を洗浄液として基板の洗浄やエッチングを行う際に、洗浄液の使用時間の経過と共に洗浄液中の各種薬品成分の濃度が変化する。
【００１５】
本発明では、洗浄液中の所定の成分の濃度を測定し、測定結果が設定範囲を外れたときに洗浄液に必要な成分を補充し、当該成分濃度を是正する。これにより、基板の洗浄処理が均一安定化（エッチング量の均一化）される。
【００１６】
それとともに、洗浄液の液交換頻度の低減が図られ洗浄液の使用量が削減され、さらには洗浄液を排水処理するために必要とされる薬品の使用量の低減、排水処理により排出される排水と汚泥の発生量の低減が可能となる。
【００１７】
すなわち、本発明によれば、基板の洗浄処理の均一安定化が達成され、洗浄液の使用量の低減や排出量の低減が実現される。
【００１８】
【発明実施の形態】
以下、本発明を適用した基板洗浄方法や基板洗浄装置について、図面を参照しながら詳細に説明する。
【００１９】
本発明は、弗化アンモニウム水溶液、あるいは弗化アンモニウム水溶液と弗化水素酸との混合液を洗浄液とする基板洗浄（あるいはエッチング）において、洗浄液中の各種成分濃度の変化に応じて、洗浄液に水、アンモニア、アンモニア水、弗化アンモニウム水溶液等の必要成分を補充し、これを是正すると共に、洗浄液の累積使用時間に応じて洗浄液の液交換を行い、常に一定の濃度の洗浄液で洗浄を行うものである。
【００２０】
図１は、弗化アンモニウムと弗化水素の混合液に関して、時間経過と熱酸化膜に対するエッチングレートとの関係を示したものである。洗浄液の組成は、ＮＨ４ Ｆ（４０％）／ＨＦ（５０％）＝４００／１であり、洗浄液の温度は２５℃、熱酸化膜はＳｉＯ２ である。
【００２１】
この図１より、時間経過とともに熱酸化膜に対するエッチングレートが大幅に増加していることがわかる。
【００２２】
このように、上記洗浄液を用いた基板洗浄においては、刻一刻とエッチングレートが変化していることになるが、このエッチングレートと経過時間との間には非常に高い相関関係（比例関係）がある。これは、洗浄液中の水分や薬品（ＮＨ４ Ｆ、ＨＦ）成分が時間経過とともに変化（蒸発）していること、具体的には洗浄液中の水分やアンモニア成分が一定の比率で蒸発しており、洗浄液中のＨＦ成分（熱酸化膜をエッチングに起因する直接的な成分）濃度が一定比率で増加していることを意味している。
【００２３】
図２は、洗浄液中のＨＦ濃度の時間経過による変化を示したものであるが、時間経過とともにＨＦの濃度は一定の比率で増加していることがわかる。
【００２４】
以上のことより、弗化アンモニウム水溶液や弗化水素酸混合液による基板の洗浄（エッチング）処理には、洗浄液中のＨＦ濃度を均一且つ安定に維持することが必要となる。
【００２５】
そこで、本発明においては、図３に示すような洗浄システムにより、洗浄液中のＨＦ濃度を設定範囲内に維持するようにしている。
【００２６】
この洗浄システムでは、定期的に洗浄液の濃度測定を行い、この測定結果に基づいて以後の操作を行う。
【００２７】
ここでは、ＨＦ濃度を測定対象とする洗浄システムを例にして説明する。
【００２８】
上記の通り、ＨＦ濃度は時間経過に伴って次第に変化するので、本洗浄システムでは、定期的（例えば６×ｎ時間毎：ｎは８未満の整数）にＨＦ濃度を濃度測定機により測定する。
【００２９】
ここで、洗浄液中の構成成分（例えばＨＦ）の濃度を測定する方法としては、所定の波長の吸光度や赤外・紫外吸収スペクトル、屈折率、比重、透過率、電導率等の測定を用いても良いし、カールフィシャーの水分濃度測定計や液体（イオン）クロマトグラフィー等の測定機を用いても良い。
【００３０】
この濃度測定において、ＨＦ濃度が設定範囲内、例えばＨＦ濃度が０．０５〜０．１重量％の範囲内に入っている場合には、洗浄処理を実施する。
【００３１】
そして、所定に期間使用して、液交換の時期がきたら、洗浄槽内の洗浄液を全て交換する。ここでは、液交換の時期を４８時間経過後とした。
【００３２】
液交換を実施した場合には、所定の時間後、例えば１０分後に上記濃度測定を行う。
【００３３】
また、液交換の時期が来るまでは、継続的に洗浄を実施するが、濃度測定後の時間をカウントし、所定の時間（例えば６×ｎ時間毎：ｎは８未満の整数）が経過した後には、再度濃度測定を行い、ＨＦ濃度を確認する。
【００３４】
なお、上記フローにおいて、液交換時期の確認と濃度測定後の経過時間の確認は、どちらが先でも良い。
【００３５】
一方、上記濃度測定において、ＨＦ濃度が設定範囲を外れている場合、例えばＨＦ濃度が０．０５〜０．１重量％の範囲から外れた場合には、これを是正するための成分を洗浄液中に補充する。
【００３６】
例えば、測定したＨＦ濃度が上記設定範囲を上回った場合には、アンモニア成分を洗浄液中に補充して、ＨＦ濃度を下げる。
【００３７】
このとき、ＨＦの設定濃度と測定濃度の差分のモル数に対応するアンモニアを供給すれば、ＨＦ濃度を上記設定範囲内に戻すことができる。
【００３８】
具体的には、
［測定時のＨＦ濃度（重量％）−ＨＦの設定濃度（重量％）］×（アンモニアの分子量／ＨＦの分子量）×洗浄液の全重量
なる式で表される量のアンモニア成分を含むアンモニアガス、あるいはアンモニア水を洗浄液に供給する。
【００３９】
アンモニア成分を補充すると、ＨＦが中和されて弗化アンモニウムとなり、その結果、洗浄液中のＨＦ濃度が抑えられる。アンモニア水の場合には、希釈による効果と中和による効果の両者が期待できる。
【００４０】
逆に、測定したＨＦ濃度が上記設定範囲を下回った場合には、ＨＦ成分を洗浄液中に補充して、ＨＦ濃度を上げる。
【００４１】
このとき、ＨＦの設定濃度と測定濃度の差分のＨＦ成分を供給すれば、ＨＦ濃度を上記設定範囲内に戻すことができる。
【００４２】
具体的には、
［測定時のＨＦ濃度（重量％）−ＨＦの設定濃度（重量％）］×洗浄液の全重量なる式で表される量のＨＦ成分、例えばＨＦガスや弗化水素酸を洗浄液に供給する。
【００４３】
なお、この洗浄システムにおいては、何度濃度測定を行ってもＨＦ濃度が設定濃度範囲内に入らない場合、エラー通報を行い、作業を一時中止にするようになっている。例えば、ＨＦ濃度が連続して４回設定濃度範囲から外れた場合、エラー通報を行い、作業を一時中止にする。
【００４４】
以上のように、定期的にＨＦ濃度を測定し、設定範囲を外れた場合にこれを是正する成分を追加補充することで、洗浄液によるエッチング処理を均一／安定化（すなわち、酸化膜に対するエッチング量を一定に維持する。）が図れ、従来のように洗浄液の液交換を頻繁に行う必要がなくなる。これにより、洗浄液の長寿命化が図れることになり、液交換頻度の低減により洗浄液の消費量の低減（省資源）と、洗浄液の排水処理に必要とされる排水処理剤の低減（省資源）にも貢献できる。さらには、これら薬品の使用量の低減から、排水処理時に発生する汚泥や排水の排出量を低減（廃棄物発生量の低減）することにも貢献できることになる。
【００４５】
以上のことより、本発明は単に基板処理の均一／安定化を図るばかりではなく、省資源、廃棄物発生量の低減等の面で地球環境保全にも貢献するものである。
【００４６】
【発明の効果】
以上に述べたように、本発明の方法、装置を用いることにより、弗化アンモニウムを含む水溶液により基板の洗浄を行う際に、処理の均一安定化が図れるとともに、洗浄液の液交換頻度の低減が可能となるため、薬品（洗浄液、排水処理剤）の省資源化やこれに伴い発生する汚泥や排水の排出量の大幅な低減が可能となる。
【図面の簡単な説明】
【図１】洗浄液における経過時間とエッチングレートの関係を示す特性図である。
【図２】経過時間と洗浄液中のＨＦ濃度の関係を示す特性図である。
【図３】本発明を適用した洗浄システムにおける処理フローを示すフローチャートである。
【図４】洗浄液の廃液処理工程を説明するための図である。
【図５】洗浄液の廃液処理に必要な資源を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a substrate cleaning method and a substrate cleaning apparatus using an aqueous solution containing ammonium fluoride as a cleaning liquid, and is a novel substrate cleaning developed for the purpose of uniform cleaning treatment and reduction of the amount of cleaning liquid used. The present invention relates to a method and a substrate cleaning apparatus.
[0002]
[Prior art]
Ammonium fluoride aqueous solution (including any liquid mixture of hydrofluoric acid and ammonia, and those containing surfactants) is mixed with hydrofluoric acid, etc., to produce a semiconductor (mainly silicon oxide film). Widely used in semiconductor and LCD manufacturing processes for the purpose of cleaning and etching of substrates and glass substrates.
[0003]
In these fields, a fine processing technique with a higher degree of integration is required for the purpose of reducing the weight, size and power consumption of products. For this reason, higher precision processing is desired also in cleaning of a substrate with an ammonium fluoride aqueous solution or a mixed solution of the aqueous solution and hydrofluoric acid.
[0004]
[Problems to be solved by the invention]
By the way, in the above cleaning and etching, chemical components (NH 4 F, HF) and moisture in the cleaning liquid change (evaporate) over time, and this changes (increases) the etching rate for the silicon oxide film and the glass substrate. Have the problem of
[0005]
This is due to the fact that the concentration of the hydrofluoric acid component in the cleaning solution gradually increases over time during use, but at present, the concentration of various components in the cleaning solution is increased by frequently changing the cleaning solution. I was taking action against the change.
[0006]
However, in this measure, a very large amount of the cleaning solution is used. [Especially, the ammonium fluoride-containing cleaning solution is used in a high concentration state of several tens% (for example, about 40% by weight). Compared to other cleaning liquids used at a concentration of 1, the amount of chemicals consumed per liquid change is larger. As a result, the amount of ammonium fluoride or hydrofluoric acid used (chemical cost) increases.
[0007]
In addition, when the cleaning liquid has been used, wastewater treatment as shown in FIG. 4 is required. In this case, a large amount of resources (wastewater treatment agent) is consumed, and a large amount of waste (wastewater Sludge) is generated (see FIG. 5).
[0008]
FIG. 4 illustrates the waste liquid treatment process of the cleaning liquid. The waste liquid generated from the cleaning tank 81 is conveyed to the
[0009]
In the treatment step, as shown in FIG. 5, 20 kg of calcium hydroxide 2.0 kg, 8% aluminum sulfate 0.3 kg, and polymer flocculant 1.6 kg are required for 1 kg of 40% ammonium fluoride aqueous solution. A solid content of 70% sludge of 2.6 kg and a sewage wastewater of 2.3 kg are produced.
[0010]
In recent years, global environmental issues have become a global concern, and the environmental impact of manufacturing substrates such as semiconductors and LCDs has become a problem in recent years. In addition, environmental conservation measures such as resource saving, waste reduction, and environmental purification are strongly demanded.
[0011]
The present invention has been proposed in view of such a conventional situation, and a substrate cleaning method and a substrate cleaning apparatus that can perform uniform and stable substrate cleaning, save resources, reduce waste, and the like. The purpose is to provide.
[0012]
[Means for Solving the Problems]
In order to achieve the above object, the substrate cleaning method of the present invention measures the concentration of HF in the cleaning solution when cleaning the substrate using an aqueous solution containing ammonium fluoride as the cleaning solution, and the measurement result is 0. When it falls below the range of 05-0.1% by weight, the HF component is replenished. When the measurement result exceeds 0.05-0.1% by weight, the ammonia component is replenished. The concentration is maintained in the above 0.05 to 0.1 wt% range .
[0013]
The substrate cleaning apparatus of the present invention is a substrate cleaning apparatus for cleaning a substrate using an aqueous solution containing ammonium fluoride as a cleaning liquid, and measures a concentration of HF in the substrate cleaning processing tank for storing the cleaning liquid and the cleaning liquid. When the measurement result in the concentration measuring means and the concentration measuring means falls below the range of 0.05 to 0.1% by weight, the HF component is replenished, and the measurement result is in the range of 0.05 to 0.1% by weight. In the case where the concentration exceeds the above range, the ammonia component is replenished, and a replenishing means for maintaining the HF concentration in the range of 0.05 to 0.1% by weight is provided.
[0014]
When cleaning or etching a substrate using an aqueous ammonium fluoride solution or a mixed solution of an aqueous ammonium fluoride solution and hydrofluoric acid as a cleaning solution, the concentration of various chemical components in the cleaning solution changes with the passage of time of use of the cleaning solution. .
[0015]
In the present invention, the concentration of a predetermined component in the cleaning liquid is measured, and when the measurement result is out of the set range, the necessary component is replenished in the cleaning liquid to correct the component concentration. As a result, the substrate cleaning process is uniformly stabilized (the etching amount is made uniform).
[0016]
At the same time, the liquid replacement frequency of the cleaning liquid is reduced, the amount of cleaning liquid used is reduced, the amount of chemicals required for wastewater treatment of the cleaning liquid is reduced, and the wastewater and sludge discharged by the wastewater treatment It is possible to reduce the amount of generation.
[0017]
That is, according to the present invention, uniform stabilization of the substrate cleaning process is achieved, and the amount of cleaning liquid used and the amount of discharge are reduced.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, a substrate cleaning method and a substrate cleaning apparatus to which the present invention is applied will be described in detail with reference to the drawings.
[0019]
In the substrate cleaning (or etching) using an aqueous solution of ammonium fluoride or a mixed solution of an aqueous solution of ammonium fluoride and hydrofluoric acid as a cleaning liquid, water is added to the cleaning liquid according to changes in the concentration of various components in the cleaning liquid. , Replenish necessary components such as ammonia, aqueous ammonia, ammonium fluoride aqueous solution, etc., correct this, replace the cleaning liquid according to the cumulative usage time of the cleaning liquid, and always wash with a constant concentration of cleaning liquid It is.
[0020]
FIG. 1 shows the relationship between the passage of time and the etching rate for the thermal oxide film with respect to a mixed solution of ammonium fluoride and hydrogen fluoride. The composition of the cleaning liquid is NH 4 F (40%) / HF (50%) = 400/1, the temperature of the cleaning liquid is 25 ° C., and the thermal oxide film is SiO 2 .
[0021]
As can be seen from FIG. 1, the etching rate with respect to the thermal oxide film greatly increases with time.
[0022]
As described above, in the substrate cleaning using the above-described cleaning liquid, the etching rate changes every moment, but there is a very high correlation (proportional relationship) between the etching rate and the elapsed time. is there. This is because the water and chemicals (NH 4 F, HF) components in the cleaning solution have changed (evaporated) over time, specifically, the water and ammonia components in the cleaning solution have evaporated at a certain rate. This means that the concentration of the HF component (a direct component resulting from etching of the thermal oxide film) in the cleaning liquid increases at a constant rate.
[0023]
FIG. 2 shows the change of the HF concentration in the cleaning liquid with the passage of time. It can be seen that the concentration of HF increases at a constant rate with the passage of time.
[0024]
From the above, the substrate cleaning (etching) treatment with an aqueous ammonium fluoride solution or a hydrofluoric acid mixed solution needs to maintain the HF concentration in the cleaning solution uniformly and stably.
[0025]
Therefore, in the present invention, the HF concentration in the cleaning liquid is maintained within the set range by the cleaning system as shown in FIG.
[0026]
In this cleaning system, the concentration of the cleaning liquid is periodically measured, and subsequent operations are performed based on the measurement result.
[0027]
Here, a description will be given by taking as an example a cleaning system whose measurement target is HF concentration.
[0028]
As described above, since the HF concentration gradually changes with the passage of time, in the present cleaning system, the HF concentration is measured periodically (for example, every 6 × n hours: n is an integer less than 8) with a concentration meter.
[0029]
Here, as a method of measuring the concentration of the constituent component (for example, HF) in the cleaning liquid, measurement of absorbance at a predetermined wavelength, infrared / ultraviolet absorption spectrum, refractive index, specific gravity, transmittance, conductivity, etc. is used. Alternatively, a measuring device such as a Karl Fischer's water concentration meter or liquid (ion) chromatography may be used.
[0030]
In this concentration measurement, when the HF concentration is within a set range, for example, the HF concentration is within a range of 0.05 to 0.1% by weight, a cleaning process is performed.
[0031]
Then, after a predetermined period of use, when the time for liquid replacement comes, all the cleaning liquid in the cleaning tank is replaced. In this case, the liquid replacement time was 48 hours later.
[0032]
When the liquid is exchanged, the concentration measurement is performed after a predetermined time, for example, 10 minutes.
[0033]
In addition, cleaning is continuously performed until the time for liquid replacement comes, but the time after concentration measurement is counted, and a predetermined time (for example, every 6 × n hours: n is an integer less than 8) has elapsed. Later, the concentration is measured again to confirm the HF concentration.
[0034]
In the above flow, either confirmation of the liquid exchange time or confirmation of the elapsed time after the concentration measurement may be performed first.
[0035]
On the other hand, in the concentration measurement, when the HF concentration is out of the set range, for example, when the HF concentration is out of the range of 0.05 to 0.1% by weight, components for correcting this are contained in the cleaning liquid. To replenish.
[0036]
For example, when the measured HF concentration exceeds the set range, an ammonia component is replenished in the cleaning liquid to lower the HF concentration.
[0037]
At this time, if ammonia corresponding to the number of moles of the difference between the set concentration of HF and the measured concentration is supplied, the HF concentration can be returned to the set range.
[0038]
In particular,
[HF concentration at the time of measurement (% by weight) −set concentration of HF (% by weight)] × (molecular weight of ammonia / molecular weight of HF) × ammonia gas containing an ammonia component in an amount represented by the total weight of the cleaning liquid, Alternatively, ammonia water is supplied to the cleaning liquid.
[0039]
When the ammonia component is replenished, HF is neutralized to ammonium fluoride, and as a result, the HF concentration in the cleaning liquid is suppressed. In the case of aqueous ammonia, both the effect of dilution and the effect of neutralization can be expected.
[0040]
Conversely, when the measured HF concentration falls below the set range, the HF component is replenished in the cleaning solution to increase the HF concentration.
[0041]
At this time, if the HF component of the difference between the set concentration of HF and the measured concentration is supplied, the HF concentration can be returned to the set range.
[0042]
In particular,
[HF concentration (wt%) at the time of measurement−set concentration (wt%) of HF] × the amount of HF component, for example, HF gas or hydrofluoric acid, which is expressed by the total weight of the cleaning liquid, is supplied to the cleaning liquid.
[0043]
In this cleaning system, if the HF concentration does not fall within the set concentration range no matter how many times the concentration measurement is performed, an error is reported and the operation is temporarily stopped. For example, if the HF concentration is out of the set concentration range four times in succession, an error notification is made and the operation is temporarily stopped.
[0044]
As described above, by periodically measuring the HF concentration and supplementing the component that corrects the HF concentration when it is outside the set range, the etching process with the cleaning liquid is made uniform / stabilized (that is, the etching amount with respect to the oxide film) Can be maintained at a constant level), and there is no need to frequently replace the cleaning liquid as in the prior art. As a result, the service life of the cleaning liquid can be extended, the consumption of cleaning liquid can be reduced by reducing the liquid replacement frequency (resource saving), and the amount of wastewater treatment agent required for wastewater treatment of the cleaning liquid (resource saving). Can also contribute. Furthermore, reduction of the amount of these chemicals used can contribute to reduction of sludge and wastewater generated during wastewater treatment (reduction of waste generation).
[0045]
From the above, the present invention not only aims at uniform / stabilization of substrate processing, but also contributes to global environment conservation in terms of resource saving and reduction of waste generation.
[0046]
【The invention's effect】
As described above, by using the method and apparatus of the present invention, when cleaning a substrate with an aqueous solution containing ammonium fluoride, it is possible to achieve uniform treatment and reduce the frequency of cleaning liquid replacement. Therefore, it becomes possible to save resources of chemicals (cleaning liquid and waste water treatment agent) and to greatly reduce the amount of sludge and waste water generated by this.
[Brief description of the drawings]
FIG. 1 is a characteristic diagram showing a relationship between an elapsed time and an etching rate in a cleaning liquid.
FIG. 2 is a characteristic diagram showing the relationship between elapsed time and HF concentration in a cleaning solution.
FIG. 3 is a flowchart showing a processing flow in a cleaning system to which the present invention is applied.
FIG. 4 is a diagram for explaining a cleaning liquid waste liquid treatment step;
FIG. 5 is a diagram showing resources necessary for waste liquid treatment of a cleaning liquid.
Claims (8)
上記洗浄液中のＨＦの濃度を測定し、測定結果が０．０５〜０．１重量％の範囲を下回った場合にはＨＦ成分を補充し、測定結果が０．０５〜０．１重量％の範囲を上回った場合にはアンモニア成分を補充し、上記ＨＦの濃度を０．０５〜０．１重量％の範囲に維持する基板洗浄方法。When cleaning a substrate using an aqueous solution containing ammonium fluoride as a cleaning liquid,
The concentration of HF in the cleaning solution is measured. If the measurement result falls below the range of 0.05 to 0.1% by weight, the HF component is replenished, and the measurement result is 0.05 to 0.1% by weight. A substrate cleaning method in which an ammonia component is replenished when exceeding the range, and the HF concentration is maintained in the range of 0.05 to 0.1% by weight.
上記洗浄液は、４８時間経過後に交換する請求項２記載の基板洗浄方法。The concentration of HF is measured every 6 × n hours (n is an integer less than 8).
The substrate cleaning method according to claim 2, wherein the cleaning liquid is replaced after 48 hours.
上記洗浄液を収容する基板洗浄処理槽と、
上記洗浄液中のＨＦの濃度を測定する濃度測定手段と、
上記濃度測定手段における測定結果が０．０５〜０．１重量％の範囲を下回った場合にはＨＦ成分を補充し、測定結果が０．０５〜０．１重量％の範囲を上回った場合にはアンモニア成分を補充し、上記ＨＦの濃度を０．０５〜０．１重量％の範囲に維持する補充手段とを備える基板洗浄装置。In a substrate cleaning apparatus for cleaning a substrate using an aqueous solution containing ammonium fluoride as a cleaning liquid,
A substrate cleaning tank for storing the cleaning liquid;
A concentration measuring means for measuring the concentration of HF in the cleaning liquid;
When the measurement result in the concentration measuring means falls below the range of 0.05 to 0.1% by weight, the HF component is replenished, and when the measurement result exceeds the range of 0.05 to 0.1% by weight. Includes a replenishing means for replenishing the ammonia component and maintaining the concentration of HF in the range of 0.05 to 0.1% by weight.
上記液交換手段は、４８時間経過後に上記洗浄液を交換する請求項６記載の基板洗浄装置。In the concentration measuring means, the concentration of the HF is measured every 6 × n hours (n is an integer less than 8),
The substrate cleaning apparatus according to claim 6, wherein the liquid replacement means replaces the cleaning liquid after 48 hours.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000341094A JP4419315B2 (en) | 2000-11-08 | 2000-11-08 | Substrate cleaning method and substrate cleaning apparatus |
| US09/985,396 US6799589B2 (en) | 2000-11-08 | 2001-11-02 | Method and apparatus for wet-cleaning substrate |
| KR1020010069158A KR20020035779A (en) | 2000-11-08 | 2001-11-07 | Method and apparatus for wet-cleaning substrate |
| EP01402866A EP1205539A3 (en) | 2000-11-08 | 2001-11-08 | Method and apparatus for wet-cleaning a substrate |
| TW090127758A TW517300B (en) | 2000-11-08 | 2001-11-08 | Method and apparatus for wet-cleaning substrate |
| US10/898,366 US6938626B2 (en) | 2000-11-08 | 2004-07-26 | Method and apparatus for wet-cleaning substrate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000341094A JP4419315B2 (en) | 2000-11-08 | 2000-11-08 | Substrate cleaning method and substrate cleaning apparatus |
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| JP2002151457A JP2002151457A (en) | 2002-05-24 |
| JP4419315B2 true JP4419315B2 (en) | 2010-02-24 |
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| CN100385629C (en) * | 2006-09-18 | 2008-04-30 | 无锡华润华晶微电子有限公司 | Method and device for cleaning semiconductor crystal wafer |
| JP6383254B2 (en) * | 2014-11-04 | 2018-08-29 | 株式会社東芝 | Processing apparatus and processing method |
| JP6393238B2 (en) * | 2015-06-10 | 2018-09-19 | 東京エレクトロン株式会社 | Substrate liquid processing apparatus, substrate liquid processing method, and storage medium |
| CN110104866A (en) * | 2019-06-14 | 2019-08-09 | 安徽浩悦环境科技有限责任公司 | A kind of processing unit and its treatment process of high-concentration acidic wastewater fluorination waste liquor of ammonium |
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