JP6903446B2 - Substrate processing equipment and substrate processing method - Google Patents

Substrate processing equipment and substrate processing method Download PDF

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JP6903446B2
JP6903446B2 JP2017027341A JP2017027341A JP6903446B2 JP 6903446 B2 JP6903446 B2 JP 6903446B2 JP 2017027341 A JP2017027341 A JP 2017027341A JP 2017027341 A JP2017027341 A JP 2017027341A JP 6903446 B2 JP6903446 B2 JP 6903446B2
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JP2017163134A (en
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裕樹 齊藤
裕樹 齊藤
林　航之介
航之介 林
崇 大田垣
崇 大田垣
裕次 長嶋
裕次 長嶋
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Shibaura Mechatronics Corp
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Priority to US15/450,542 priority patent/US9972513B2/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30604—Chemical etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67017—Apparatus for fluid treatment
    • H01L21/67063—Apparatus for fluid treatment for etching
    • H01L21/67075—Apparatus for fluid treatment for etching for wet etching
    • H01L21/67086—Apparatus for fluid treatment for etching for wet etching with the semiconductor substrates being dipped in baths or vessels
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67017—Apparatus for fluid treatment
    • H01L21/67063—Apparatus for fluid treatment for etching
    • H01L21/67075—Apparatus for fluid treatment for etching for wet etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/6715—Apparatus for applying a liquid, a resin, an ink or the like
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/677—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for conveying, e.g. between different workstations
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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Description

本発明は、半導体ウェーハ等の基板に処理液を供給して当該基板を処理する基板処理装置及び基板処理方法に関する。 The present invention relates to a substrate processing apparatus and a substrate processing method for processing a substrate by supplying a processing liquid to a substrate such as a semiconductor wafer.

半導体装置や液晶表示装置等の電子部品のウェットエッチング工程で用いられる基板処理装置が知られている（例えば、特許文献１参照。）。基板処理装置は、半導体ウェーハ等の基板の製造工程において、基板表面にある歪み層や基板表面に存在する重金属等の不純物を除去する方法として、基板表面を薬液でエッチングする方法が知られている。 A substrate processing device used in a wet etching step of an electronic component such as a semiconductor device or a liquid crystal display device is known (see, for example, Patent Document 1). As a substrate processing apparatus, a method of etching the substrate surface with a chemical solution is known as a method of removing impurities such as a strain layer on the substrate surface and heavy metals existing on the substrate surface in a substrate manufacturing process such as a semiconductor wafer. ..

エッチング方法としては、例えば、フッ酸（ＨＦ）、硝酸（ＨＮＯ３）及び純水を所定の配合比で混合したエッチング液を半導体ウェーハに供給して行う方法が用いられている。エッチング液でエッチングに寄与するのは、亜硝酸（ＨＮＯ２）であることは知られている。このため、フッ酸と硝酸が含まれた溶液に、Ｓｉ基板（半導体ウェーハ等）を溶解させることで亜硝酸を生成し、エッチング液を生成している。 As an etching method, for example, a method is used in which an etching solution obtained by mixing hydrofluoric acid (HF), nitric acid (HNO 3 ) and pure water in a predetermined blending ratio is supplied to a semiconductor wafer. It is known that nitrite (HNO 2 ) contributes to etching in the etching solution. Therefore, nitrite is generated by dissolving a Si substrate (semiconductor wafer or the like) in a solution containing hydrofluoric acid and nitric acid to generate an etching solution.

特開平１１−２６４２５号公報Japanese Unexamined Patent Publication No. 11-26425

上述した基板処理装置では、エッチング液中の亜硝酸濃度が低いと、半導体ウェーハのエッチング処理時間が長くなる。このため、十分な量のＳｉ基板の溶解が必要となるが、Ｓｉ基板の溶解には時間がかかり、生産性が低下するという問題があった。 In the substrate processing apparatus described above, if the nitrite concentration in the etching solution is low, the etching processing time of the semiconductor wafer becomes long. Therefore, it is necessary to dissolve a sufficient amount of the Si substrate, but there is a problem that it takes time to dissolve the Si substrate and the productivity is lowered.

そこで本発明は、エッチングに適した亜硝酸濃度を有するエッチング液を効率よく生成し、エッチングの効率を高めることができる基板処理装置及び基板処理方法を提供することを目的とする。 Therefore, an object of the present invention is to provide a substrate processing apparatus and a substrate processing method capable of efficiently generating an etching solution having a nitrite concentration suitable for etching and increasing the etching efficiency.

前記課題を解決し目的を達成するために、本発明の基板処理装置及び基板処理方法は次のように構成されている。 In order to solve the above problems and achieve the object, the substrate processing apparatus and the substrate processing method of the present invention are configured as follows.

フッ酸及び硝酸を含む処理液を用いて基板を処理する基板処理装置において、前記処理液を貯留する貯留タンクと、前記処理液にアルコールを供給するアルコール供給部と、前記アルコールが供給された処理液を前記基板に供給する供給部と、を備え、前記供給部に供給される前記処理液中の亜硝酸濃度を検出する濃度センサをさらに備え、前記濃度センサにより検出された亜硝酸濃度が所定値以下である場合、前記アルコール供給部は前記処理液にアルコールを供給することを特徴とする。 In a substrate processing apparatus that processes a substrate using a treatment liquid containing nitrous acid and nitric acid, a storage tank for storing the treatment liquid, an alcohol supply unit for supplying alcohol to the treatment liquid, and a treatment to which the alcohol is supplied. A supply unit for supplying the liquid to the substrate is provided , and a concentration sensor for detecting the nitrite concentration in the processing liquid supplied to the supply unit is further provided, and the nitrite concentration detected by the concentration sensor is predetermined. When it is equal to or less than the value, the alcohol supply unit is characterized by supplying alcohol to the treatment liquid .

フッ酸及び硝酸を含む処理液を用いて基板を処理する基板処理方法において、前記処理液を貯留タンクに貯留し、前記処理液にアルコールを供給し、前記アルコールが供給された処理液を前記基板に供給し、前記貯留タンクから前記基板に供給される前記処理液の亜硝酸濃度を検出し、検出された前記処理液の亜硝酸濃度が所定値以下である場合、前記処理液に前記アルコールを供給することを特徴とする。
In a substrate treatment method for treating a substrate using a treatment liquid containing hydrofluoric acid and nitric acid, the treatment liquid is stored in a storage tank, alcohol is supplied to the treatment liquid, and the treatment liquid to which the alcohol is supplied is used as the substrate. The nitrite concentration of the treatment liquid supplied from the storage tank to the substrate is detected, and when the detected nitrite concentration of the treatment liquid is equal to or less than a predetermined value, the alcohol is added to the treatment liquid. It is characterized by supplying .

この発明によれば、エッチングに適した亜硝酸濃度を有するエッチング液を効率よく生成し、エッチングの効率を高めることが可能となる。 According to the present invention, it is possible to efficiently generate an etching solution having a nitrite concentration suitable for etching and increase the etching efficiency.

本発明の一実施の形態に係る基板処理装置を模式的に示す説明図。The explanatory view which shows typically the substrate processing apparatus which concerns on one Embodiment of this invention. 同基板処理装置における亜硝酸生成量を示す説明図。Explanatory drawing which shows the amount of nitrite production in the substrate processing apparatus. 同基板処理装置における動作フローを示す説明図。The explanatory view which shows the operation flow in the substrate processing apparatus. 同基板処理装置の変形例を示す説明図。Explanatory drawing which shows the modification of the substrate processing apparatus. 同基板処理装置の別の変形例を示す説明図。Explanatory drawing which shows another modification of the substrate processing apparatus.

図１は本発明の一実施の形態に係る基板処理装置１０を模式的に示す説明図、図２は基板処理装置１０における亜硝酸生成量を示す説明図、図３は基板処理装置１０における動作フローを示す説明図である。なお、図１中Ｗは半導体ウェーハ（基板）を示している。 FIG. 1 is an explanatory diagram schematically showing a substrate processing apparatus 10 according to an embodiment of the present invention, FIG. 2 is an explanatory diagram showing an amount of nitrite produced in the substrate processing apparatus 10, and FIG. 3 is an operation in the substrate processing apparatus 10. It is explanatory drawing which shows the flow. In addition, W in FIG. 1 shows a semiconductor wafer (board).

基板処理装置１０は、基板処理ユニット１００と、この基板処理ユニット１００にエッチング液Ｌを供給するエッチング液供給ユニット２００と、基板処理ユニット１００及びエッチング液供給ユニット２００を制御する制御部３００とを備えている。 The substrate processing apparatus 10 includes a substrate processing unit 100, an etching solution supply unit 200 that supplies the etching solution L to the substrate processing unit 100, and a control unit 300 that controls the substrate processing unit 100 and the etching solution supply unit 200. ing.

基板処理ユニット１００は、カップ体１０１内で半導体ウェーハＷを支持するウェーハチャック１０２がモータ１０３によって回転する構造となっている。そして、後述するようにエッチング液供給ユニット２００から供給されるエッチング処理液が、半導体ウェーハＷの上方に配置されたノズル（供給部）１０４から当該半導体ウェーハＷに供給される。このエッチング処理液によってウェーハチャック１０２の回転に伴って回転する半導体ウェーハＷの表面のエッチング処理がなされる。 The substrate processing unit 100 has a structure in which a wafer chuck 102 that supports a semiconductor wafer W in a cup body 101 is rotated by a motor 103. Then, as will be described later, the etching treatment liquid supplied from the etching liquid supply unit 200 is supplied to the semiconductor wafer W from the nozzle (supply unit) 104 arranged above the semiconductor wafer W. The etching treatment liquid etches the surface of the semiconductor wafer W that rotates with the rotation of the wafer chuck 102.

エッチング液供給ユニット２００は、エッチング液を収容する貯留タンク２１０と、使用済のエッチング液を収容する回収タンク２２０、フッ酸、硝酸、酢酸（CH3COOH）、純水が、予め設定された所定比率で混合された新液を収容する新液供給タンク２３０、アルコールの一例であるＩＰＡ（イソプロピルアルコール）を収容するアルコール供給タンク２４０を備えている。貯留タンク２１０と基板処理ユニット１００との間にはエッチング液供給ライン２５０と、回収ライン２６０とが、それぞれ設けられている。回収ライン２６０の途中には、回収タンク２２０が介在される。新液供給タンク２３０と貯留タンク２１０との間には、新液供給ライン２７０が設けられている。アルコール供給タンク２４０と貯留タンク２１０との間にはアルコール供給ライン２８０が設けられている。 The etching solution supply unit 200 contains a storage tank 210 for accommodating the etching solution, a recovery tank 220 for accommodating the used etching solution, carboxylic acid, nitric acid, acetic acid (CH 3 COOH), and pure water. It is provided with a new liquid supply tank 230 for accommodating a new liquid mixed in a ratio, and an alcohol supply tank 240 for accommodating IPA (isopropyl alcohol) which is an example of alcohol. An etching solution supply line 250 and a recovery line 260 are provided between the storage tank 210 and the substrate processing unit 100, respectively. A recovery tank 220 is interposed in the middle of the recovery line 260. A new liquid supply line 270 is provided between the new liquid supply tank 230 and the storage tank 210. An alcohol supply line 280 is provided between the alcohol supply tank 240 and the storage tank 210.

貯留タンク２１０は、密閉構造のタンク本体２１１と、このタンク本体２１１の上部に設けられた開放弁２１２とを備えている。 The storage tank 210 includes a tank main body 211 having a closed structure and an open valve 212 provided on the upper portion of the tank main body 211.

回収タンク２２０は、密閉構造のタンク本体２２１を備えている。新液供給タンク２３０は、密閉構造のタンク本体２３１を備えている。アルコール供給タンク２４０は、密閉構造のタンク本体２４１を備えている。 The recovery tank 220 includes a tank body 221 having a closed structure. The new liquid supply tank 230 includes a tank body 231 having a closed structure. The alcohol supply tank 240 includes a tank body 241 having a closed structure.

新液供給タンク２３０には、フッ酸の供給管２３２、硝酸の供給管２３３、酢酸の供給管２３４、純水の供給管２３５が接続され、それぞれ開閉弁２３２ａ，２３３ａ，２３４ａ，２３５ａが設けられている。各供給管２３２〜２３５から上述したように所定比率で混合されるように所定の量が供給される。 The hydrofluoric acid supply pipe 232, the nitric acid supply pipe 233, the acetic acid supply pipe 234, and the pure water supply pipe 235 are connected to the new liquid supply tank 230, and on-off valves 232a, 233a, 234a, and 235a are provided, respectively. ing. A predetermined amount is supplied from each supply pipe 223 to 235 so as to be mixed in a predetermined ratio as described above.

エッチング液供給ライン２５０は、入口端がタンク本体２１１の底部に設けられ、出口端が基板処理ユニット１００のノズル１０４に接続されたメインライン２５１と、このメインライン２５１の途中に設けられたポンプ２５２及び開閉弁２５３と、ポンプ２５２とノズル１０４との間に設けられた分岐部２５４と、この分岐部２５４からタンク本体２１１内に戻る戻りライン２５５とを備えている。戻りライン２５５の中途部には亜硝酸の濃度を測定する濃度センサ２５６及び開閉弁２５７が設けられている。なお、濃度センサ２５６はメインライン２５１の中途部に設けてもよい。 The etching solution supply line 250 has a main line 251 having an inlet end provided at the bottom of the tank body 211 and an outlet end connected to a nozzle 104 of the substrate processing unit 100, and a pump 252 provided in the middle of the main line 251. It also includes an on-off valve 253, a branch portion 254 provided between the pump 252 and the nozzle 104, and a return line 255 that returns from the branch portion 254 to the inside of the tank body 211. A concentration sensor 256 and an on-off valve 257 for measuring the concentration of nitrite are provided in the middle of the return line 255. The density sensor 256 may be provided in the middle of the main line 251.

回収ライン２６０は、入口端が基板処理ユニット１００の底部に設けられ、出口端がタンク本体２１１内に設けられたメインライン２６１を備えている。メインライン２６１には、タンク本体２２１と、ポンプ２６２とが設けられている。 The recovery line 260 includes a main line 261 having an inlet end provided at the bottom of the substrate processing unit 100 and an outlet end provided inside the tank body 211. The main line 261 is provided with a tank body 221 and a pump 262.

新液供給ライン２７０は、入口端がタンク本体２３１の底部に設けられ、出口端がタンク本体２１１の天井部に設けられたメインライン２７１と、このメインライン２７１の途中に設けられた開閉弁２７２と、ポンプ２７３とを備えている。 The new liquid supply line 270 has a main line 271 having an inlet end provided at the bottom of the tank body 231 and an outlet end provided at the ceiling of the tank body 211, and an on-off valve 272 provided in the middle of the main line 271. And a pump 273.

アルコール供給ライン２８０は、入口端がタンク本体２４１の底部に設けられ、出口端がタンク本体２１１に接続されたメインライン２８１と、このメインライン２８１の途中に設けられたポンプ２８２と、ポンプ２８２とタンク本体２１１との間に設けられた、開閉弁２８４、逆止弁２８５とを備えている。 The alcohol supply line 280 includes a main line 281 having an inlet end provided at the bottom of the tank body 241 and an outlet end connected to the tank body 211, a pump 282 provided in the middle of the main line 281, and a pump 282. It is provided with an on-off valve 284 and a check valve 285 provided between the tank body 211.

メインライン２８１の出口端がタンク本体２１１に接続される位置は、タンク本体２１１に供給されるエッチング液Ｌの液面より下方の側壁に設けられている。すなわち、図１に示すように、タンク本体２１１内にエッチング液Ｌがある程度溜まっている状態で、エッチング液Ｌ中に直接的にＩＰＡが供給される構成とする。なお、エッチング液Ｌの液面が変動することや、ＩＰＡがエッチング液Ｌの比重よりも軽いことを考慮すれば、ＩＰＡがエッチング液Ｌの液面に近い所だけで反応しないようにするためにも、メインライン２８１の出口端は、タンク本体２１１の下方の側壁であってもより底壁に近い側、あるいは底壁に設けられていることが好ましい。 The position where the outlet end of the main line 281 is connected to the tank main body 211 is provided on the side wall below the liquid level of the etching liquid L supplied to the tank main body 211. That is, as shown in FIG. 1, the IPA is directly supplied into the etching solution L in a state where the etching solution L is accumulated to some extent in the tank body 211. Considering that the liquid level of the etching solution L fluctuates and that the IPA is lighter than the specific gravity of the etching solution L, in order to prevent the IPA from reacting only near the liquid level of the etching solution L. Further, it is preferable that the outlet end of the main line 281 is provided on the side closer to the bottom wall or on the bottom wall even if it is the lower side wall of the tank main body 211.

なお、本実施の形態では、アルコール供給タンク２４０、アルコール供給ライン２８０、メインライン２８１、ポンプ２８２、開閉弁２８４、逆止弁２８５は、アルコール供給部３１０を構成する。 In the present embodiment, the alcohol supply tank 240, the alcohol supply line 280, the main line 281, the pump 282, the on-off valve 284, and the check valve 285 constitute the alcohol supply unit 310.

なお、上記した各開閉弁、各ポンプは、制御部３００により制御される。予め設定された亜硝酸濃度（亜硝酸濃度の所定値）は、例えば、制御部３００に設定されている。制御部３００は、以下に述べるように基板処理装置１０を制御する。 The on-off valve and each pump described above are controlled by the control unit 300. The preset nitrite concentration (predetermined value of the nitrite concentration) is set in, for example, the control unit 300. The control unit 300 controls the substrate processing device 10 as described below.

なお、本実施の形態では、基板として半導体ウエーハを用い、半導体ウエーハの表面に形成された酸化膜をエッチング除去する例で説明する。 In this embodiment, an example will be described in which a semiconductor wafer is used as a substrate and an oxide film formed on the surface of the semiconductor wafer is etched and removed.

最初に処理開始前の準備について説明する。処理開始前においては、全ての弁が閉じている。次に、タンク本体２３１に接続されたフッ酸の供給管２３２、硝酸の供給管２３３、酢酸の供給管２３４、純水の供給管２３５のそれぞれ開閉弁２３２ａ，２３３ａ，２３４ａ，２３５ａを開閉し、各供給管２３２〜２３５からフッ酸、硝酸、酢酸、純水を予め設定された所定比率で混合されるように所定の量を供給し、新しいエッチング液Ｌを生成する。次に、開放弁２１２と開閉弁２７２とを開き、ポンプ２７３を作動させ、新しいエッチング液Ｌを貯留タンク２１０のタンク本体２１１内に供給する。タンク本体２１１内に所定量の新しいエッチング液Ｌが溜まったら、開閉弁２７２を閉じて、供給を停止する。次に、開放弁２１２を閉じ、開閉弁２５７を開き、ポンプ２５２を駆動して、エッチング液Ｌの循環を行う。ここで、エッチング液Ｌが濃度センサ２５６を通過することで、エッチング液Ｌ内の亜硝酸濃度が検出される。硝酸はそのままでも分解することで亜硝酸を生成するが、エッチング液Ｌ内の亜硝酸濃度は当初は低い値となる。 First, the preparation before the start of processing will be described. Before the start of processing, all valves are closed. Next, the on-off valves 232a, 233a, 234a, and 235a of the hydrofluoric acid supply pipe 232, the nitric acid supply pipe 233, the acetic acid supply pipe 234, and the pure water supply pipe 235 connected to the tank body 231 are opened and closed, respectively. A predetermined amount of hydrofluoric acid, nitric acid, acetic acid, and pure water is supplied from each supply pipe 223 to 235 so as to be mixed at a preset predetermined ratio to generate a new etching solution L. Next, the open valve 212 and the on-off valve 272 are opened, the pump 273 is operated, and the new etching solution L is supplied into the tank body 211 of the storage tank 210. When a predetermined amount of new etching solution L is accumulated in the tank body 211, the on-off valve 272 is closed to stop the supply. Next, the opening valve 212 is closed, the on-off valve 257 is opened, and the pump 252 is driven to circulate the etching solution L. Here, when the etching solution L passes through the concentration sensor 256, the nitrite concentration in the etching solution L is detected. Nitrite is produced by decomposing nitric acid as it is, but the concentration of nitrite in the etching solution L is initially low.

次に、開放弁２１２及びアルコール供給ライン２８０のメインライン２８１の開閉弁２８４を開き、ポンプ２８２を駆動してタンク本体２１１にＩＰＡを供給する。ここで、タンク本体２１１内では、エッチング液Ｌ中の硝酸が分解されて亜硝酸と硝酸ガスが発生する。これにより、エッチング液Ｌ内の亜硝酸濃度が高まり、濃度センサ２５６で検出される亜硝酸濃度が所定値になるまで、アルコール供給部３１０は、タンク本体２１１に対するＩＰＡの供給を継続する。その亜硝酸濃度が所定値になった時点で、開放弁２１２及び開閉弁２８４を閉じる。そして、ポンプ２８２を停止してＩＰＡ供給を停止する。なお、濃度センサ２５６によってＩＰＡの供給量を決める他、所定の処理時間、半導体ウエーハの所定の処理枚数等の条件に基づいてＩＰＡの必要な供給量を算出してもよい。 Next, the open valve 212 and the on-off valve 284 of the main line 281 of the alcohol supply line 280 are opened, and the pump 282 is driven to supply IPA to the tank body 211. Here, in the tank body 211, nitric acid in the etching solution L is decomposed to generate nitrite and nitric acid gas. As a result, the alcohol supply unit 310 continues to supply IPA to the tank body 211 until the nitrite concentration in the etching solution L increases and the nitrite concentration detected by the concentration sensor 256 reaches a predetermined value. When the nitrite concentration reaches a predetermined value, the open valve 212 and the on-off valve 284 are closed. Then, the pump 282 is stopped to stop the IPA supply. In addition to determining the supply amount of IPA by the concentration sensor 256, the required supply amount of IPA may be calculated based on conditions such as a predetermined processing time and a predetermined number of processed semiconductor wafers.

図２は、フッ酸、硝酸、酢酸、純水の混合液１００ｃｃ（硝酸濃度２３．８％）に対して、ＩＰＡを添加しない場合と、５μＬのＩＰＡを添加した場合とでの亜硝酸濃度を比較した説明図である。放置した場合は２２４ｐｐｍであるのに対し、ＩＰＡを添加した場合は１３７７ｐｐｍであり、６倍の濃度を実現できる。 FIG. 2 shows the nitrite concentration in 100 cc (nitric acid concentration 23.8%) of a mixed solution of hydrofluoric acid, nitric acid, acetic acid, and pure water when IPA is not added and when 5 μL of IPA is added. It is explanatory drawing which compared. When left unattended, the concentration is 224 ppm, whereas when IPA is added, the concentration is 1377 ppm, which is 6 times higher.

図１に戻り、タンク本体２１１内のエッチング液Ｌの量と、その亜硝酸濃度が所定の値になった時点で、ポンプ２５２を停止して、エッチング液Ｌの循環を停止する。 Returning to FIG. 1, when the amount of the etching solution L in the tank body 211 and the nitrite concentration thereof reach a predetermined value, the pump 252 is stopped to stop the circulation of the etching solution L.

次に、エッチング処理について図３に基づいて説明する。エッチング処理を開始すると（ＳＴ１）、開放弁２１２及び開閉弁２５３を開き、開閉弁２５７を閉じ、ポンプ２５２を駆動する。これにより、タンク本体２１１内のエッチング液Ｌがメインライン２５１を通って基板処理ユニット１００のノズル１０４に供給される。そして、ノズル１０４から、モータ１０３の駆動によって回転される半導体ウェーハＷの表面にエッチング液Ｌが供給される。エッチング液Ｌはカップ体１０１を介して回収され、回収タンク２２０のタンク本体２２１に貯留される。貯留されたエッチング液Ｌは、ポンプ２６２を駆動して適時、タンク本体２１１内に戻される。所定の枚数の半導体ウェーハＷのエッチング処理が終わったらエッチング処理を終了する（ＳＴ２）。 Next, the etching process will be described with reference to FIG. When the etching process is started (ST1), the open valve 212 and the on-off valve 253 are opened, the on-off valve 257 is closed, and the pump 252 is driven. As a result, the etching solution L in the tank body 211 is supplied to the nozzle 104 of the substrate processing unit 100 through the main line 251. Then, the etching solution L is supplied from the nozzle 104 to the surface of the semiconductor wafer W that is rotated by driving the motor 103. The etching solution L is collected via the cup body 101 and stored in the tank body 221 of the collection tank 220. The stored etching solution L drives the pump 262 and is returned to the tank body 211 in a timely manner. When the etching process for a predetermined number of semiconductor wafers W is completed, the etching process is completed (ST2).

次に、開放弁２１２及び開閉弁２５３を閉じ、開閉弁２５７を開き、ポンプ２５２を駆動して、エッチング液Ｌの循環を行う。この時、濃度センサ２５６によりエッチング液Ｌ内の亜硝酸濃度が検出される。亜硝酸濃度が所定値以上か否かであるかが判断され（ＳＴ３）、亜硝酸濃度が所定値未満の場合は、アルコール供給ライン２８０の開閉弁２８４を開き、ポンプ２８２を駆動してタンク本体２１１にＩＰＡを供給し（ＳＴ４）、亜硝酸を生成する。これにより、エッチング液Ｌ内の亜硝酸濃度が高まる。濃度センサ２５６で検出される亜硝酸濃度が所定値以上になるまで、アルコール供給部３１０は、タンク本体２１１へのＩＰＡの供給を継続する。制御部３００は、濃度センサ２５６の出力値から、亜硝酸濃度が所定値に達した時点を検知すると、開放弁２１２と開閉弁２５７、開閉弁２８４を閉じる。そして、次のエッチング処理を開始する（ＳＴ５）。 Next, the opening valve 212 and the on-off valve 253 are closed, the on-off valve 257 is opened, and the pump 252 is driven to circulate the etching solution L. At this time, the concentration sensor 256 detects the nitrite concentration in the etching solution L. Whether or not the nitrite concentration is equal to or higher than the predetermined value is determined (ST3), and if the nitrite concentration is less than the predetermined value, the on-off valve 284 of the alcohol supply line 280 is opened and the pump 282 is driven to drive the tank body. IPA is supplied to 211 (ST4) to produce nitrite. As a result, the nitrite concentration in the etching solution L increases. The alcohol supply unit 310 continues to supply IPA to the tank body 211 until the nitrite concentration detected by the concentration sensor 256 becomes equal to or higher than a predetermined value. When the control unit 300 detects the time when the nitrite concentration reaches a predetermined value from the output value of the concentration sensor 256, the control unit 300 closes the open valve 212, the on-off valve 257, and the on-off valve 284. Then, the next etching process is started (ST5).

なお、ノズル１０４から半導体ウェーハＷの表面に向けてエッチング液Ｌを供給しているエッチング処理中に、開閉弁２５７を開いた状態にして、ポンプ２５２によって供給されるエッチング液Ｌを分岐部２５４で基板処理ユニット１００とタンク本体２１１とに分流できるようにしても良い。この場合、分岐部２５４から戻りライン２５５を介して、タンク本体２１１に供給されるエッチング液は、濃度センサ２５６にてエッチング液Ｌ中の亜硝酸濃度が検出される。つまり、ノズル１０４からエッチング液Ｌを半導体ウエーハＷに供給してエッチング処理を行ないつつ、ノズル１０４から供給されるエッチング液Ｌの亜硝酸濃度を検出することになる。このとき、検出された亜硝酸濃度が所定値以下であった場合、その時点で開閉弁２５３を閉じても良いが、エッチング処理中の半導体ウェーハＷの処理が終了した時点をもって、開閉弁２５３を閉じ、ノズル１０４へのエッチング液Ｌの供給を停止するようにすると好ましい。エッチング処理を途中で停止させることによる不良品発生が、防止できるからである。その後、前述したように、タンク本体２１１へＩＰＡが供給され、エッチング液Ｌ中の亜硝酸濃度を調整する。 During the etching process in which the etching solution L is supplied from the nozzle 104 to the surface of the semiconductor wafer W, the on-off valve 257 is opened, and the etching solution L supplied by the pump 252 is supplied by the branch portion 254. It may be possible to divide the flow into the substrate processing unit 100 and the tank body 211. In this case, the concentration sensor 256 detects the nitrite concentration in the etching solution L in the etching solution supplied from the branch portion 254 to the tank body 211 via the return line 255. That is, the nitrite concentration of the etching solution L supplied from the nozzle 104 is detected while the etching solution L is supplied from the nozzle 104 to the semiconductor wafer W to perform the etching process. At this time, if the detected nitrite concentration is equal to or less than a predetermined value, the on-off valve 253 may be closed at that time, but the on-off valve 253 is closed at the time when the processing of the semiconductor wafer W during the etching process is completed. It is preferable to close the nozzle and stop the supply of the etching solution L to the nozzle 104. This is because the occurrence of defective products due to stopping the etching process in the middle can be prevented. Then, as described above, IPA is supplied to the tank body 211 to adjust the nitrite concentration in the etching solution L.

このように本実施の形態に係る基板処理装置１０によれば、エッチング液Ｌの亜硝酸濃度が所定値を下回ったら、ＩＰＡを加えることで亜硝酸を生成し、エッチング処理の効率を高める。したがって、半導体ウェーハＷの生産効率が向上する。 As described above, according to the substrate processing apparatus 10 according to the present embodiment, when the nitrite concentration of the etching solution L falls below a predetermined value, nitrite is generated by adding IPA to improve the efficiency of the etching process. Therefore, the production efficiency of the semiconductor wafer W is improved.

図４は、基板処理装置１０の変形例に係る基板処理装置１０Ａの要部を示す説明図である。図４において、図１と同一機能部分には同一符号を付し、その詳細な説明は省略する。 FIG. 4 is an explanatory diagram showing a main part of the substrate processing apparatus 10A according to a modified example of the substrate processing apparatus 10. In FIG. 4, the same functional parts as those in FIG. 1 are designated by the same reference numerals, and detailed description thereof will be omitted.

基板処理装置１０Ａにおいては、アルコール供給部３１０を構成するメインライン２８１の、タンク本体２１１内に位置する出口端に、ＩＰＡを霧状に噴射する、例えば一流体ノズル等のノズル２９０を設けた。ノズル２９０の位置は、エッチング液Ｌの液面より下方となる位置である。ＩＰＡがノズル２９０から供給される構造であるため、エッチング液Ｌがメインライン２８１側に逆流することがなく、また、霧状に噴射することで、エッチング液Ｌとの接触面積が大きくなり、液状にＩＰＡを供給した場合よりも反応を促進させやすい。エッチング処理の手順、及び、効果は上述した基板処理装置１０と同様である。 In the substrate processing apparatus 10A, a nozzle 290 for injecting IPA in a mist form, for example, a one-fluid nozzle, is provided at the outlet end of the main line 281 constituting the alcohol supply unit 310, which is located in the tank body 211. The position of the nozzle 290 is a position below the liquid level of the etching liquid L. Since the IPA is supplied from the nozzle 290, the etching solution L does not flow back to the main line 281 side, and by injecting it in a mist form, the contact area with the etching solution L becomes large and liquid. It is easier to accelerate the reaction than when IPA is supplied to the The procedure and effect of the etching process are the same as those of the substrate processing apparatus 10 described above.

図５は基板処理装置１０は別の変形例に係る基板処理装置１０Ｂの要部を示す説明図である。図５において、図１と同一機能部分には同一符号を付し、その詳細な説明は省略する。 FIG. 5 is an explanatory view showing a main part of the substrate processing apparatus 10B according to another modification of the substrate processing apparatus 10. In FIG. 5, the same functional parts as those in FIG. 1 are designated by the same reference numerals, and detailed description thereof will be omitted.

基板処理装置１０Ｂにおいては、アルコール供給部３１０を構成するメインライン２８１の出口端をエッチング液供給ライン２５０のメインライン２５１に接続した構成を有している。 The substrate processing apparatus 10B has a configuration in which the outlet end of the main line 281 constituting the alcohol supply unit 310 is connected to the main line 251 of the etching solution supply line 250.

このように構成された基板処理装置１０Ｂでは、次のようにして基板Ｗのエッチング処理を行う。処理開始前において、基板処理装置１０と同様にして貯留タンク２１０のタンク本体２１１内に所定量の新しいエッチング液Ｌを溜める。次に、開放弁２１２を閉じ、開閉弁２５７を開き、ポンプ２５２を駆動して、エッチング液Ｌの循環を行う。エッチング液Ｌが濃度センサ２５６を通過することで、エッチング液Ｌ内の亜硝酸濃度が検出される。 In the substrate processing apparatus 10B configured in this way, the etching process of the substrate W is performed as follows. Before the start of the treatment, a predetermined amount of the new etching solution L is stored in the tank body 211 of the storage tank 210 in the same manner as in the substrate processing apparatus 10. Next, the opening valve 212 is closed, the on-off valve 257 is opened, and the pump 252 is driven to circulate the etching solution L. When the etching solution L passes through the concentration sensor 256, the nitrite concentration in the etching solution L is detected.

また、開放弁２１２及びメインライン２８１の開閉弁２８４を開き、ポンプ２８２を駆動してメインライン２５１にＩＰＡを供給する。 Further, the open valve 212 and the on-off valve 284 of the main line 281 are opened, and the pump 282 is driven to supply the IPA to the main line 251.

一方、タンク本体２１１内では、エッチング液Ｌ中の硝酸が分解されて亜硝酸と硝酸ガスが発生する。これにより、エッチング液Ｌ内の亜硝酸濃度が高まり、濃度センサ２５６で検出される亜硝酸濃度が所定値になるまで、アルコール供給部３１０は、メインライン２５１へのＩＰＡの供給を継続する。その亜硝酸濃度が所定値になった時点で、開放弁２１２及び開閉弁２８４を閉じる。そして、ポンプ２８２を停止してＩＰＡの供給を停止する。 On the other hand, in the tank body 211, nitric acid in the etching solution L is decomposed to generate nitrite and nitric acid gas. As a result, the alcohol supply unit 310 continues to supply IPA to the main line 251 until the nitrite concentration in the etching solution L increases and the nitrite concentration detected by the concentration sensor 256 reaches a predetermined value. When the nitrite concentration reaches a predetermined value, the open valve 212 and the on-off valve 284 are closed. Then, the pump 282 is stopped to stop the supply of IPA.

このように構成されていると、エッチング液Ｌの循環路にＩＰＡを添加するため、エッチング液ＬとＩＰＡとの混合を促進できる。エッチング処理の手順、及び、効果は上述した基板処理装置１０と同様である。 With such a configuration, since IPA is added to the circulation path of the etching solution L, mixing of the etching solution L and the IPA can be promoted. The procedure and effect of the etching process are the same as those of the substrate processing apparatus 10 described above.

なお、メインライン２８１の出口端をエッチング液供給ライン２５０のメインライン２５１に接続したが、分岐部２５４とノズル１０４との間に接続しても良い。 Although the outlet end of the main line 281 is connected to the main line 251 of the etching solution supply line 250, it may be connected between the branch portion 254 and the nozzle 104.

上述した例では、アルコールとしてＩＰＡを例示したが、エチルアルコールを用いても同様の効果が得られる。気体のアルコール、固体のアルコールを用いてもよい。また、亜硝酸濃度は、エッチング液Ｌの循環時の他、エッチング処理時に計測してもよい。 In the above-mentioned example, IPA was exemplified as the alcohol, but the same effect can be obtained by using ethyl alcohol. Gaseous alcohol or solid alcohol may be used. Further, the nitrite concentration may be measured not only during the circulation of the etching solution L but also during the etching process.

また、エッチング液Ｌを半導体ウェーハＷに供給する方法として、基板を回転させて処理する基板処理ユニットを例示したが、処理槽内にエッチング液Ｌを貯留し、その中に複数枚の半導体ウェーハＷを浸漬して処理するバッチ式を用いてもよい。 Further, as a method of supplying the etching solution L to the semiconductor wafer W, a substrate processing unit for processing by rotating the substrate has been illustrated, but the etching solution L is stored in the processing tank and a plurality of semiconductor wafers W are stored therein. A batch type in which the wafer is immersed and processed may be used.

バッチ式を採用する場合、基板処理ユニット１００の代わりにバッチ式の処理槽を用いても良い。また、エッチング液供給ユニット２００の貯留タンク２１０をバッチ式の処理槽に置き換えても良い。この場合、バッチ式の処理槽に直接アルコール供給ラインを接続して、ＩＰＡを添加するようにしても良い。 When the batch type is adopted, a batch type processing tank may be used instead of the substrate processing unit 100. Further, the storage tank 210 of the etching solution supply unit 200 may be replaced with a batch type processing tank. In this case, the alcohol supply line may be directly connected to the batch type processing tank to add IPA.

なお、基板は半導体ウェーハに限定されず、液晶基板、フォトマスク基板などのガラス基板でも良い。また、処理は、エッチング処理に限定されない。 The substrate is not limited to the semiconductor wafer, and may be a glass substrate such as a liquid crystal substrate or a photomask substrate. Further, the treatment is not limited to the etching treatment.

以上、本発明のいくつかの実施形態を説明したが、これらの実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これら新規な実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。これら実施形態やその変形は、発明の範囲や要旨に含まれるとともに、特許請求の範囲に記載された発明とその均等の範囲に含まれる。 Although some embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other embodiments, and various omissions, replacements, and changes can be made without departing from the gist of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are also included in the scope of the invention described in the claims and the equivalent scope thereof.

１０，１０Ａ，１０Ｂ…基板処理装置、１００…基板処理ユニット、２００…エッチング液供給ユニット、２１０…貯留タンク、２１１…タンク本体、２１２…開放弁、２２０…回収タンク、２３０…新液供給タンク、２４０…アルコール供給タンク、２５０…エッチング液供給ライン、２５１…メインライン、２５２…ポンプ、２５３…開閉弁、２５６…濃度センサ、２６０…回収ライン、２６１…メインライン、２６２…ポンプ、２７０…新液供給ライン、２７１…メインライン、２７２…開閉弁、２８０…アルコール供給ライン、２８１…メインライン、２８２…ポンプ、２８４…開閉弁、２８５…逆止弁、２９０…ノズル、３００…制御部、３１０…アルコール供給部。 10, 10A, 10B ... Substrate processing device, 100 ... Substrate processing unit, 200 ... Etching liquid supply unit, 210 ... Storage tank, 211 ... Tank body, 212 ... Open valve, 220 ... Recovery tank, 230 ... New liquid supply tank, 240 ... alcohol supply tank, 250 ... etching solution supply line, 251 ... main line, 252 ... pump, 253 ... on-off valve, 256 ... concentration sensor, 260 ... recovery line, 261 ... main line, 262 ... pump, 270 ... new liquid Supply line, 271 ... main line, 272 ... on-off valve, 280 ... alcohol supply line, 281 ... main line, 282 ... pump, 284 ... on-off valve, 285 ... check valve, 290 ... nozzle, 300 ... control unit, 310 ... Alcohol supply unit.

Claims (9)

フッ酸及び硝酸を含む処理液を用いて基板を処理する基板処理装置において、
前記処理液を貯留する貯留タンクと、
前記処理液にアルコールを供給するアルコール供給部と、
前記アルコールが供給された処理液を前記基板に供給する供給部と、を備え、
前記供給部に供給される前記処理液中の亜硝酸濃度を検出する濃度センサをさらに備え、
前記濃度センサにより検出された亜硝酸濃度が所定値以下である場合、前記アルコール供給部は前記処理液にアルコールを供給することを特徴とする基板処理装置。 In a substrate processing apparatus that processes a substrate using a treatment liquid containing hydrofluoric acid and nitric acid.
A storage tank for storing the treatment liquid and
An alcohol supply unit that supplies alcohol to the treatment liquid and
A supply unit for supplying the treatment liquid to which the alcohol is supplied to the substrate is provided .
Further provided with a concentration sensor for detecting the nitrite concentration in the processing liquid supplied to the supply unit,
When the nitrite concentration detected by the concentration sensor is not more than a predetermined value, the alcohol supply unit supplies alcohol to the treatment liquid . 前記アルコール供給部は、前記貯留タンクに貯留する前記処理液の液面より下方の位置に前記アルコールを供給することを特徴とする請求項１に記載の基板処理装置。 The substrate processing apparatus according to claim 1, wherein the alcohol supply unit supplies the alcohol to a position below the liquid level of the treatment liquid stored in the storage tank. 前記供給部と前記貯留タンクとを接続するメインラインと、
このメインラインの途中に設けられた分岐部と、
この分岐部から前記貯留タンクに接続する戻りラインとを備えていることを特徴とする請求項１に記載の基板処理装置。 A main line connecting the supply unit and the storage tank,
The branch part provided in the middle of this main line and
The substrate processing apparatus according to claim 1, further comprising a return line connecting the branch portion to the storage tank. 前記濃度センサにより検出された前記処理液中の亜硝酸濃度が所定値よりも低下した場合、前記処理液が前記供給部に供給されるのを停止させる制御部を有し、
前記制御部は、前記基板の処理中に、前記処理液中の亜硝酸濃度が所定値よりも低下したことを前記濃度センサによって検出された場合、前記基板の処理が完了した後、前記供給部に前記処理液を供給させるのを停止させることを特徴とする請求項１に記載の基板処理装置。 It has a control unit that stops the supply of the treatment liquid to the supply unit when the nitrite concentration in the treatment liquid detected by the concentration sensor drops below a predetermined value.
When the concentration sensor detects that the nitrite concentration in the processing liquid is lower than a predetermined value during the processing of the substrate, the control unit performs the processing of the substrate and then the supply unit. the substrate processing apparatus according to claim 1, characterized in that stopping the cause supply the processing liquid to. 前記アルコール供給部は、前記メインラインにおける前記貯留タンクと前記分岐部との間に前記アルコールを供給することを特徴とする請求項３に記載の基板処理装置。 The substrate processing apparatus according to claim 3, wherein the alcohol supply unit supplies the alcohol between the storage tank and the branch portion in the main line. フッ酸及び硝酸を含む処理液を用いて基板を処理する基板処理方法において、
前記処理液を貯留タンクに貯留し、
前記処理液にアルコールを供給し、
前記アルコールが供給された処理液を前記基板に供給し、
前記貯留タンクから前記基板に供給される前記処理液の亜硝酸濃度を検出し、検出された前記処理液の亜硝酸濃度が所定値以下である場合、前記処理液に前記アルコールを供給することを特徴とする基板処理方法。 In a substrate processing method for processing a substrate using a treatment liquid containing hydrofluoric acid and nitric acid,
The treatment liquid is stored in a storage tank and
Alcohol is supplied to the treatment liquid,
The treatment liquid to which the alcohol was supplied was supplied to the substrate, and the treatment liquid was supplied .
The nitrite concentration of the treatment liquid supplied from the storage tank to the substrate is detected, and when the detected nitrite concentration of the treatment liquid is equal to or less than a predetermined value, the alcohol is supplied to the treatment liquid. A characteristic substrate processing method. 前記貯留タンク内へ前記アルコールを供給する際に、前記貯留タンクに貯留する前記処理液の液面より下方の位置で供給することを特徴とする請求項６に記載の基板処理方法。 The substrate processing method according to claim 6 , wherein when the alcohol is supplied into the storage tank, the alcohol is supplied at a position below the liquid level of the treatment liquid stored in the storage tank. 前記貯留タンクから前記基板に供給する前記処理液の亜硝酸濃度を検出しつつ、その一部を前記貯留タンクに戻すことを特徴とする請求項６に記載の基板処理方法。 The substrate processing method according to claim 6 , wherein a part of the nitrite concentration of the treatment liquid supplied from the storage tank to the substrate is returned to the storage tank. 前記基板の処理中に、前記処理液中の前記亜硝酸濃度が所定値よりも低下したら、前記基板の処理が完了した後に前記処理液の供給を止めることを特徴とする請求項８に記載の基板処理方法。 The eighth aspect of the present invention, wherein when the nitrite concentration in the treatment liquid drops below a predetermined value during the treatment of the substrate, the supply of the treatment liquid is stopped after the treatment of the substrate is completed. Substrate processing method.
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