TWI667706B - Substrate processing method and substrate processing apparatus - Google Patents

Substrate processing method and substrate processing apparatus Download PDF

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TWI667706B
TWI667706B TW107108202A TW107108202A TWI667706B TW I667706 B TWI667706 B TW I667706B TW 107108202 A TW107108202 A TW 107108202A TW 107108202 A TW107108202 A TW 107108202A TW I667706 B TWI667706 B TW I667706B
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molar ratio
water
mixed acid
concentration
acid
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TW201836004A (en
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山口侑二
基村雅洋
岸田拓也
杉岡真治
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日商斯庫林集團股份有限公司
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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
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    • H01L21/3105—After-treatment
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Abstract

基板處理方法包括：混合酸加熱步驟，對包含磷酸、硝酸及水的混合液的混合酸進行加熱；莫耳比調節步驟，為了使P/W莫耳比(混合酸中所含的磷酸的莫耳數/混合酸中所含的水的莫耳數)維持在莫耳比上限值與莫耳比下限值之間，藉由將水加入至混合酸而使P/W莫耳比下降；以及蝕刻步驟，藉由將加入水的混合酸供給至基板而對基板上的金屬膜進行蝕刻。 The substrate processing method includes: a mixed acid heating step of heating a mixed acid containing a mixed solution of phosphoric acid, nitric acid, and water; a molar ratio adjusting step for making a P/W molar ratio (a molar ratio of phosphoric acid contained in the mixed acid) The number of ears/the number of moles of water contained in the mixed acid is maintained between the upper limit of the molar ratio and the lower limit of the molar ratio, and the P/W molar ratio is decreased by adding water to the mixed acid. And an etching step of etching the metal film on the substrate by supplying a mixed acid to which water is added to the substrate.

Description

基板處理方法以及基板處理裝置 Substrate processing method and substrate processing apparatus

本發明是有關於一種對基板進行處理的基板處理方法及基板處理裝置。在作為處理對象的基板中，例如包含半導體晶圓、液晶顯示裝置用基板、電漿顯示器用基板、場發射顯示器(Field Emission Display，FED)用基板、光碟用基板、磁碟用基板、磁光碟用基板、光罩用基板、陶瓷基板、太陽電池用基板等。 The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate. The substrate to be processed includes, for example, a semiconductor wafer, a substrate for a liquid crystal display device, a substrate for a plasma display, a substrate for a field emission display (FED), a substrate for a disk, a substrate for a disk, and a magneto-optical disk. A substrate, a substrate for a photomask, a ceramic substrate, a substrate for a solar cell, or the like.

在半導體裝置或液晶顯示裝置等的製程中，會使用對半導體晶圓或液晶顯示裝置用玻璃基板等基板進行處理的基板處理裝置。 In a process of a semiconductor device, a liquid crystal display device, or the like, a substrate processing apparatus that processes a substrate such as a semiconductor wafer or a glass substrate for a liquid crystal display device is used.

在專利文獻1中，已揭示一種對基板一片片地進行處理的單片式的基板處理裝置。所述基板處理裝置包括：自旋夾盤(spin chuck)，一面水平地保持基板，一面使基板旋轉；以及噴嘴，朝向保持於自旋夾盤上的基板噴出包含SC1(氨水、過氧化氫水及純水的混合液)等多種成分的處理液。所述基板處理裝置進而包括：成分濃度測定器，測定處理液中所含的多種成分的濃度；以及控制裝置，當任一成分的濃度處於容許濃度範圍外時，將已調 整各成分的比率的處理液加入至正在使用的處理液中，以使所述成分的濃度恢復至容許濃度範圍內。 Patent Document 1 discloses a one-piece substrate processing apparatus that processes a substrate one by one. The substrate processing apparatus includes: a spin chuck that horizontally holds the substrate while rotating the substrate; and a nozzle that ejects SC1 (ammonia water, hydrogen peroxide water) toward the substrate held on the spin chuck A treatment liquid of various components such as a mixed liquid of pure water. The substrate processing apparatus further includes a component concentration measuring device that measures a concentration of a plurality of components contained in the processing liquid, and a control device that adjusts when the concentration of any component is outside the allowable concentration range The treatment liquid of the ratio of the respective components is added to the treatment liquid to be used to restore the concentration of the components to the allowable concentration range.

[現有技術文獻] [Prior Art Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利5448521公報 [Patent Document 1] Japanese Patent No. 54485521

處理液的濃度藉由處理液中所含的成分的蒸發或分解而發生變化。若頻繁地更換處理液，可將穩定的濃度的處理液持續供給至基板，但如此一來運轉費用(running cost)會大幅增加。因此，通常是補充處理液的成分，來使處理液的濃度穩定。並且，當開始使用處理液後經過某種程度的時間時，會將舊的處理液更換為新的處理液。 The concentration of the treatment liquid changes by evaporation or decomposition of the components contained in the treatment liquid. If the treatment liquid is frequently changed, a stable concentration of the treatment liquid can be continuously supplied to the substrate, but as a result, the running cost is greatly increased. Therefore, it is usual to supplement the components of the treatment liquid to stabilize the concentration of the treatment liquid. Further, when a certain amount of time elapses after the start of the use of the treatment liquid, the old treatment liquid is replaced with a new treatment liquid.

若處理液為水溶液，即，若水以外的成分僅為一種，則成分濃度容易穩定化，而當處理液包含水以外的兩種以上的成分時，則難以使成分濃度穩定化。其原因在於，若使某種成分的濃度發生變化，則其他成分的濃度亦會發生變化。因此，通常如專利文獻1所述，並非使所有成分的濃度穩定，而是使特定的成分的濃度穩定。 When the treatment liquid is an aqueous solution, that is, if the components other than water are only one type, the concentration of the components is easily stabilized, and when the treatment liquid contains two or more components other than water, it is difficult to stabilize the concentration of the components. This is because if the concentration of a certain component is changed, the concentration of other components also changes. Therefore, generally, as described in Patent Document 1, the concentration of all components is not stabilized, but the concentration of a specific component is stabilized.

當利用蝕刻液對在基板的表層上露出的薄膜進行蝕刻時，需要使相同的基板上的蝕刻量的最大值及最小值處於基準範圍內，並且提高蝕刻的面內均勻性。此外，亦需要使多塊基板間 的蝕刻量的不均處於基準範圍內。為了滿足後者的要求，重要的是在更換蝕刻液之前的整個期間內使蝕刻率(每單位時間的蝕刻量)穩定。 When the thin film exposed on the surface layer of the substrate is etched by the etching liquid, it is necessary to set the maximum value and the minimum value of the etching amount on the same substrate within the reference range, and to improve the in-plane uniformity of etching. In addition, it is also necessary to make multiple substrates The unevenness of the etching amount is within the reference range. In order to satisfy the latter requirements, it is important to stabilize the etching rate (the etching amount per unit time) for the entire period before the replacement of the etching liquid.

根據本發明者等人的研究，已獲知在利用包含磷酸、硝酸及水的混合酸對基板上的金屬膜進行蝕刻的蝕刻處理中，若使混合酸中的水的濃度穩定，可抑制金屬膜的蝕刻率的變動，從而可降低多塊基板間的蝕刻量的不均。此外，已獲知若不使水的濃度穩定，而使混合酸中所含的磷酸的莫耳數相對於混合酸中所含的水的莫耳數的比率穩定，則可進一步降低多塊基板間的蝕刻量的不均。 According to the study by the inventors of the present invention, it has been found that in an etching treatment for etching a metal film on a substrate by using a mixed acid containing phosphoric acid, nitric acid, and water, if the concentration of water in the mixed acid is stabilized, the metal film can be suppressed. The variation of the etching rate can reduce the unevenness of the etching amount between the plurality of substrates. Further, it has been found that if the ratio of the number of moles of phosphoric acid contained in the mixed acid to the number of moles of water contained in the mixed acid is stabilized without stabilizing the concentration of water, the number of substrates can be further reduced. The amount of etching is uneven.

因此，本發明的一個目的在於提供一種可降低多塊基板間的蝕刻量的不均的基板處理方法及基板處理裝置。 Accordingly, it is an object of the present invention to provide a substrate processing method and a substrate processing apparatus which can reduce unevenness in etching amount between a plurality of substrates.

本發明的一實施形態提供一種基板處理方法，藉由將包含磷酸、硝酸及水的混合液的混合酸供給至露出有金屬膜的基板，而對所述金屬膜進行蝕刻，所述基板處理方法包括：混合酸加熱步驟，在供給至所述基板之前對所述混合酸進行加熱；莫耳比調節步驟，包含水補充步驟，使P/W莫耳比維持在莫耳比上限值與莫耳比下限值之間，所述水補充步驟是藉由將水加入至在所述混合酸加熱步驟中經加熱的所述混合酸中，而使所述P/W莫耳比下降，所述P/W莫耳比表示所述混合酸中所含的磷酸的莫耳數相對於所述混合酸中所含的水的莫耳數的比率；以及蝕刻步驟， 藉由將在所述水補充步驟中已加入水的所述混合酸供給至所述基板，而對所述基板上的所述金屬膜進行蝕刻。 An embodiment of the present invention provides a substrate processing method for etching a metal film by supplying a mixed acid containing a mixed solution of phosphoric acid, nitric acid, and water to a substrate on which a metal film is exposed. The method includes: a mixed acid heating step of heating the mixed acid before being supplied to the substrate; and a molar ratio adjusting step including a water replenishing step to maintain the P/W molar ratio at the upper limit of the molar ratio and Mo Between the ear ratio lower limit value, the water replenishing step is to lower the P/W molar ratio by adding water to the mixed acid heated in the mixed acid heating step. The P/W molar ratio represents a ratio of the number of moles of phosphoric acid contained in the mixed acid to the number of moles of water contained in the mixed acid; and an etching step, The metal film on the substrate is etched by supplying the mixed acid to which water has been added in the water replenishing step to the substrate.

根據所述構成，對包含磷酸、硝酸及水的混合液的混合酸進行加熱。由此，混合酸中所含的硝酸及水進行蒸發，該些物質的濃度下降。混合酸中所含的磷酸亦稍有蒸發，但由於沸點高於硝酸及水，故而磷酸的蒸發量少於硝酸及水。因此，混合酸中所含的水的莫耳數減少，另一方面，混合酸中所含的磷酸的莫耳數增加。因此，在對混合酸進行加熱的期間內，P/W莫耳比(混合酸中所含的磷酸的莫耳數/混合酸中所含的水的莫耳數)持續上升。 According to the above configuration, the mixed acid containing a mixed liquid of phosphoric acid, nitric acid, and water is heated. Thereby, nitric acid and water contained in the mixed acid are evaporated, and the concentrations of these substances are lowered. The phosphoric acid contained in the mixed acid also slightly evaporates, but since the boiling point is higher than that of nitric acid and water, the amount of phosphoric acid evaporated is less than that of nitric acid and water. Therefore, the number of moles of water contained in the mixed acid is decreased, and on the other hand, the number of moles of phosphoric acid contained in the mixed acid is increased. Therefore, during the heating of the mixed acid, the P/W molar ratio (the number of moles of phosphoric acid contained in the mixed acid/the number of moles of water contained in the mixed acid) continues to rise.

當P/W莫耳比因水等的蒸發而上升時，在混合酸中加入水。由此，水的莫耳數增加。由於磷酸的莫耳數幾乎不變，另一方面，水的莫耳數增加，故而P/W莫耳比藉由水的補充而下降。由此，使P/W莫耳比維持在莫耳比上限值與莫耳比下限值之間。並且，將P/W莫耳比經管理的混合酸供給至基板，對在基板的表層上所露出的金屬膜以穩定的蝕刻率進行蝕刻。 When the P/W molar ratio rises due to evaporation of water or the like, water is added to the mixed acid. Thereby, the number of moles of water increases. Since the number of moles of phosphoric acid is almost constant, on the other hand, the number of moles of water is increased, and thus the P/W molar ratio is lowered by the replenishment of water. Thereby, the P/W molar ratio is maintained between the upper molar ratio and the lower molar ratio. Further, the P/W molar is supplied to the substrate in a controlled mixed acid, and the metal film exposed on the surface layer of the substrate is etched at a stable etching rate.

為了降低在不同的時期所處理的多塊基板間的蝕刻量的不均，重要的是在更換蝕刻液之前的整個期間內使蝕刻率穩定。根據本發明者等人的研究，已獲知若使P/W莫耳比穩定，可減小多塊基板間的蝕刻量的不均。如上所述，藉由使P/W莫耳比穩定，可減小多塊基板間的蝕刻量的不均。 In order to reduce the unevenness of the etching amount between the plurality of substrates processed at different times, it is important to stabilize the etching rate for the entire period before the replacement of the etching liquid. According to the study by the inventors of the present invention, it has been found that if the P/W molar ratio is stabilized, the unevenness of the etching amount between the plurality of substrates can be reduced. As described above, by stabilizing the P/W molar ratio, the unevenness of the etching amount between the plurality of substrates can be reduced.

在本實施形態中，亦可在所述基板處理方法中添加以下 的至少一個特徵。 In this embodiment, the following may be added to the substrate processing method. At least one feature.

所述基板處理方法進而包括：成分濃度檢測步驟，檢測所述混合酸中的磷酸的濃度及所述混合酸中的水的濃度；莫耳比計算步驟，根據在所述成分濃度檢測步驟中檢測出的檢測值，計算所述P/W莫耳比；以及莫耳比判定步驟，判定在所述莫耳比計算步驟中所計算出的所述P/W莫耳比是否超過所述莫耳比下限值，且未達所述莫耳比上限值。 The substrate processing method further includes: a component concentration detecting step of detecting a concentration of phosphoric acid in the mixed acid and a concentration of water in the mixed acid; and a molar ratio calculating step of detecting according to the component concentration detecting step a detected value, calculating the P/W molar ratio; and a molar ratio determining step of determining whether the P/W molar ratio calculated in the molar ratio calculating step exceeds the molar It is lower than the lower limit value and does not reach the upper limit of the molar ratio.

根據所述構成，檢測出混合酸中的磷酸的濃度及混合酸中的水的濃度，且根據該些濃度計算P/W莫耳比。然後，判定P/W莫耳比是否處於莫耳比上限值與莫耳比下限值之間。當P/W莫耳比為莫耳比上限值以上時，在混合酸中加入水，使P/W莫耳比下降至莫耳比上限值與莫耳比下限值之間的值為止。如上所述，由於監視P/W莫耳比自身，故而能夠以高精度管理P/W莫耳比，從而可降低蝕刻率的變動量。 According to the above configuration, the concentration of phosphoric acid in the mixed acid and the concentration of water in the mixed acid are detected, and the P/W molar ratio is calculated based on the concentrations. Then, it is determined whether the P/W molar ratio is between the upper molar ratio and the lower molar ratio. When the P/W molar ratio is above the upper limit of the molar ratio, water is added to the mixed acid to lower the P/W molar ratio to a value between the upper molar ratio and the lower molar ratio. until. As described above, since the P/W molar ratio is monitored, the P/W molar ratio can be managed with high precision, and the amount of fluctuation in the etching rate can be reduced.

所述基板處理方法進而包括檢測所述混合酸中的水的濃度的成分濃度檢測步驟，所述水補充步驟包括水濃度控制步驟，所述水濃度控制步驟是藉由將水加入至在所述混合酸加熱步驟中經加熱的所述混合酸中，而使在所述成分濃度檢測步驟中檢測的水的濃度接近於伴隨著時間的經過而增加的水濃度目標值，使所述P/W莫耳比維持在所述莫耳比上限值與所述莫耳比下限值之間。 The substrate processing method further includes a component concentration detecting step of detecting a concentration of water in the mixed acid, the water replenishing step including a water concentration controlling step of adding water to the Mixing the heated mixed acid in the acid heating step, so that the concentration of the water detected in the component concentration detecting step is close to the water concentration target value which increases with the passage of time, so that the P/W The molar ratio is maintained between the upper molar ratio and the lower molar ratio.

在將混合酸的溫度調解成固定的期間，若不進行水等成 分液的補充或混入，則混合酸中的磷酸的濃度及莫耳數通常以大致固定的比例持續上升。與之相反，若不進行成分液的補充等，則混合酸中的水的濃度及莫耳數通常以大致固定的比例持續下降。此時，即使不監視P/W莫耳比自身，只要監視磷酸及水中的至少一者的濃度，亦可間接地監視P/W莫耳比。 During the period in which the temperature of the mixed acid is adjusted to a fixed period, if water is not formed, When the liquid is added or mixed, the concentration of the phosphoric acid in the mixed acid and the number of moles generally increase in a substantially fixed ratio. On the other hand, if the component liquid is not replenished or the like, the concentration of water and the number of moles in the mixed acid are usually continuously decreased in a substantially constant ratio. At this time, even if the P/W molar ratio is not monitored, the P/W molar ratio can be indirectly monitored by monitoring the concentration of at least one of phosphoric acid and water.

根據所述構成，對混合酸中的水的濃度進行檢測。由此，可間接地監視P/W莫耳比。此外，使所檢測出的水的濃度接近於水濃度目標值。水濃度目標值是以伴隨著時間的經過而階段性地或連續性地增加的方式設定。其原因在於，在對混合酸進行加熱的期間，硝酸等水以外的成分亦會蒸發，故而即便使水的濃度維持固定，P/W莫耳比亦會持續上升。此外，水濃度目標值的增加方式是以使P/W莫耳比維持在莫耳比上限值與莫耳比下限值之間的方式設定。因此，藉由使混合酸中的水的濃度接近於水濃度目標值，可抑制蝕刻率的變動。 According to the above configuration, the concentration of water in the mixed acid is detected. Thereby, the P/W molar ratio can be monitored indirectly. Further, the detected concentration of water is made close to the water concentration target value. The water concentration target value is set in such a manner as to increase stepwise or continuously with the passage of time. This is because the components other than water such as nitric acid also evaporate during the heating of the mixed acid, so that the P/W molar ratio continues to increase even if the concentration of water is kept constant. Further, the water concentration target value is increased in such a manner that the P/W molar ratio is maintained between the upper molar ratio and the lower molar ratio. Therefore, by making the concentration of water in the mixed acid close to the water concentration target value, variation in the etching rate can be suppressed.

所述水補充步驟包括定時定量水補充步驟，所述定時定量水補充步驟是藉由在指定時間將指定量的水加入至在所述混合酸加熱步驟中經加熱的所述混合酸中，而使所述P/W莫耳比維持在所述莫耳比上限值與所述莫耳比下限值之間。 The water replenishing step includes a timed quantitative water replenishing step by adding a specified amount of water to the mixed acid heated in the mixed acid heating step by a specified time. The P/W molar ratio is maintained between the upper molar ratio and the lower molar ratio.

如上所述，在將混合酸的溫度調節成固定的期間，若不進行水等成分液的補充或混入，則混合酸中的磷酸的濃度及莫耳數通常以大致固定的比例持續上升，混合酸中的水的濃度及莫耳數通常以大致固定的比例持續下降。此時，即使不實際測定在某 個時間的磷酸及水的濃度等，亦可預測該些濃度。因此，亦可預測在某個時間的P/W莫耳比。 As described above, when the temperature of the mixed acid is adjusted to be constant, if the component liquid such as water is not replenished or mixed, the concentration of the phosphoric acid and the number of moles in the mixed acid are generally increased at a substantially constant ratio, and the mixture is mixed. The concentration of water in the acid and the number of moles generally continue to decrease in a substantially fixed ratio. At this time, even if it is not actually measured at a certain These concentrations can also be predicted for the concentration of phosphoric acid and water at a time. Therefore, the P/W molar ratio at a certain time can also be predicted.

根據所述構成，在基板處理裝置的控制裝置中預先記憶有將水加入至混合酸中的時間及所加入的水的量。水是在指定時間以指定量自動加入至混合酸中。指定量是以使在指定時間的P/W莫耳比維持在莫耳比上限值與莫耳比下限值之間的方式設定。或者，指定時間是以當將指定量的水加入至混合酸中時，P/W莫耳比維持在莫耳比上限值與莫耳比下限值之間的方式而設定。由此，不實際測定水的濃度等，便可抑制蝕刻率的變動。 According to the above configuration, the time for adding water to the mixed acid and the amount of water to be added are previously stored in the control device of the substrate processing apparatus. Water is automatically added to the mixed acid in the specified amount at the specified time. The specified amount is set such that the P/W molar ratio at the specified time is maintained between the upper molar ratio and the lower molar ratio. Alternatively, the specified time is set such that when a specified amount of water is added to the mixed acid, the P/W molar ratio is maintained between the upper molar ratio and the lower molar ratio. Thereby, the fluctuation of the etching rate can be suppressed without actually measuring the concentration of water or the like.

所述莫耳比調節步驟是如下的步驟：一面容許所述混合酸中的磷酸的濃度及所述混合酸中的水的濃度中的至少一者的變化，一面使所述P/W莫耳比維持在所述莫耳比上限值與所述莫耳比下限值之間。所述莫耳比調節步驟亦可為如下的步驟：一面除了磷酸及水中的至少一者以外，亦容許硝酸等其他成分的濃度的變化，一面使所述P/W莫耳比維持在所述莫耳比上限值與所述莫耳比下限值之間。 The molar ratio adjusting step is a step of allowing the P/W Moer while allowing a change in at least one of a concentration of phosphoric acid in the mixed acid and a concentration of water in the mixed acid. The ratio is maintained between the upper molar ratio and the lower molar ratio. The molar ratio adjusting step may be a step of maintaining the P/W molar ratio while maintaining the concentration of other components such as nitric acid in addition to at least one of phosphoric acid and water. The molar ratio upper limit value is between the lower molar ratio and the molar ratio.

根據所述構成，使P/W莫耳比維持在莫耳比上限值與莫耳比下限值之間，另一方面，容許混合酸中的磷酸的濃度及混合酸中的水的濃度中的至少一者的變化。換言之，若預先使P/W莫耳比穩定，則即使磷酸及水的濃度稍有變動，亦可抑制蝕刻率的變動。因此，不對混合酸中的磷酸及水的濃度進行嚴格管理，便可降低多塊基板間的蝕刻量的不均。 According to the above configuration, the P/W molar ratio is maintained between the molar ratio upper limit value and the molar ratio lower limit value, and on the other hand, the concentration of phosphoric acid in the mixed acid and the concentration of water in the mixed acid are allowed. Change in at least one of them. In other words, if the P/W molar ratio is stabilized in advance, the fluctuation of the etching rate can be suppressed even if the concentration of phosphoric acid and water slightly changes. Therefore, the concentration of phosphoric acid and water in the mixed acid can be strictly controlled, and the unevenness of the etching amount between the plurality of substrates can be reduced.

所述基板處理方法進而包括檢測所述混合酸中的磷酸的濃度及所述混合酸中的水的濃度中的至少一者的成分濃度檢測步驟，所述莫耳比調節步驟進而包括水補充禁止步驟，所述水補充禁止步驟是藉由一面禁止向所述混合酸中供給水，一面對所述混合酸進行加熱，而使所述P/W莫耳比自所述莫耳比下限值以下的值上升至所述莫耳比上限值與莫耳比下限值之間的值為止。 The substrate processing method further includes a component concentration detecting step of detecting at least one of a concentration of phosphoric acid in the mixed acid and a concentration of water in the mixed acid, the step of adjusting the molar ratio further including prohibiting water replenishment Step, the water replenishing prohibiting step is to prevent the P/W molar ratio from being lower than the Mohr ratio by heating the supply of water to the mixed acid while heating the mixed acid The value below the value rises to a value between the upper molar ratio and the lower molar ratio.

若因某種原因而將過量的水補充至混合酸，則混合酸中的水的濃度會過度上升，使得P/W莫耳比變為莫耳比下限值以下。在批次式的基板處理裝置中，存在將經水濡濕的基板浸漬於混合酸中，使得水混入至混合酸中的情況。此時，若附著在基板上的水的量多，則P/W莫耳比會變為莫耳比下限值以下。P/W莫耳比變為莫耳比下限值以下是根據包含混合酸中的水的濃度的判定資訊來判定。 If excessive water is added to the mixed acid for some reason, the concentration of water in the mixed acid will rise excessively, so that the P/W molar ratio becomes equal to or lower than the lower molar ratio. In the batch type substrate processing apparatus, there is a case where the water-wet substrate is immersed in a mixed acid so that water is mixed into the mixed acid. At this time, if the amount of water adhering to the substrate is large, the P/W molar ratio becomes equal to or lower than the lower molar ratio. The P/W molar ratio becomes the molar ratio lower limit or less, and is determined based on the determination information including the concentration of water in the mixed acid.

根據所述構成，若P/W莫耳比為莫耳比下限值以下，則暫時禁止將水補充及混入至混合酸中。在所述狀態下對混合酸進行加熱。由此，混合酸中所含的水等進行蒸發，水的濃度下降。伴隨於此，P/W莫耳比上升。並且，若P/W莫耳比超過莫耳比下限值，則解除水的補充及混入的禁止。以如上所述的方式，使P/W莫耳比維持在莫耳比上限值與莫耳比下限值之間。 According to the above configuration, when the P/W molar ratio is equal to or less than the lower molar ratio, the water is temporarily prevented from being mixed and mixed into the mixed acid. The mixed acid is heated in the state described. Thereby, water or the like contained in the mixed acid is evaporated, and the concentration of water is lowered. Along with this, the P/W molar ratio increases. Further, if the P/W molar ratio exceeds the lower limit of the molar ratio, the replenishment of the water and the prohibition of the mixing are released. In the manner described above, the P/W molar ratio is maintained between the upper molar ratio and the lower molar ratio.

所述混合酸進而包含醋酸。 The mixed acid further contains acetic acid.

根據所述構成，將除了磷酸、硝酸及水以外亦包含醋酸的混合酸供給至基板。藉由硝酸對金屬膜的氧化而產生的氫氣會 殘留在基板的一部分表面上，從而抑制硝酸對金屬膜的氧化。因此，當氫氣位於基板的表面時，蝕刻的均勻性會下降。醋酸會促進氫氣自基板剝離，結果促進硝酸對金屬膜的氧化。由此，可抑制或防止蝕刻的均勻性的下降。 According to the above configuration, a mixed acid containing acetic acid in addition to phosphoric acid, nitric acid, and water is supplied to the substrate. Hydrogen produced by oxidation of a metal film by nitric acid It remains on a part of the surface of the substrate, thereby suppressing oxidation of the metal film by the nitric acid. Therefore, when hydrogen gas is located on the surface of the substrate, the uniformity of etching is lowered. Acetic acid promotes the stripping of hydrogen from the substrate, and as a result, promotes oxidation of the metal film by nitric acid. Thereby, it is possible to suppress or prevent a decrease in the uniformity of etching.

所述水補充步驟包括非處理中水補充步驟，所述非處理中水補充步驟是僅在未對所述基板供給所述混合酸的期間，將水加入至所述混合酸，而使所述P/W莫耳比下降。 The water replenishing step includes a non-treatment water replenishing step of adding water to the mixed acid only during a period in which the mixed acid is not supplied to the substrate, and the P/W molar ratio decreased.

根據所述構成，僅在未將混合酸供給至基板的非供給期間，將水加入至混合酸中。若將水加入至混合酸中，則混合酸的均勻性暫時下降。因此，藉由在對基板供給混合酸的供給期間內禁止水的補充，可防止將此種混合酸供給至基板。 According to the above configuration, water is added to the mixed acid only during the non-feed period in which the mixed acid is not supplied to the substrate. If water is added to the mixed acid, the uniformity of the mixed acid temporarily decreases. Therefore, by disabling the replenishment of water during the supply of the mixed acid to the substrate, it is possible to prevent such mixed acid from being supplied to the substrate.

本發明的另一實施形態提供一種基板處理裝置，其包括：加熱器，對包含磷酸、硝酸及水的混合液的混合酸進行加熱；水噴出口，噴出要加入至所述混合酸中的水；混合酸噴出口，藉由噴出所述混合酸，而對露出有金屬膜的基板供給所述混合酸，對所述金屬膜進行蝕刻；以及控制裝置，對基板處理裝置進行控制。 Another embodiment of the present invention provides a substrate processing apparatus including: a heater that heats a mixed acid containing a mixed solution of phosphoric acid, nitric acid, and water; and a water discharge port that ejects water to be added to the mixed acid a mixed acid discharge port that supplies the mixed acid to the substrate on which the metal film is exposed by ejecting the mixed acid, and etches the metal film, and a control device that controls the substrate processing device.

所述控制裝置執行：混合酸加熱步驟，在供給至所述基板之前，使所述加熱器對所述混合酸進行加熱；莫耳比調節步驟，包含水補充步驟，使P/W莫耳比維持在莫耳比上限值與莫耳比下限值之間，所述水補充步驟是藉由使所述水噴出口將水加入至在所述混合酸加熱步驟中經加熱的所述混合酸中，而使所述P/W莫 耳比下降，所述P/W莫耳比表示所述混合酸中所含的磷酸的莫耳數相對於所述混合酸中所含的水的莫耳數的比率；以及蝕刻步驟，藉由使所述混合酸噴出口將在所述水補充步驟中已加入水的所述混合酸供給至所述基板，而對所述基板上的所述金屬膜進行蝕刻。根據所述構成，可獲得與以上所述的效果同樣的效果。 The control device performs: a mixed acid heating step of heating the mixed acid by the heater before being supplied to the substrate; and a molar ratio adjusting step including a water replenishing step to make the P/W molar ratio Maintained between a molar ratio upper limit value and a molar ratio lower limit, the water replenishing step is performed by adding water to the water jet outlet to the mixture heated in the mixed acid heating step In the acid, and the P/W The ear ratio decreases, the P/W molar ratio represents a ratio of the number of moles of phosphoric acid contained in the mixed acid to the number of moles of water contained in the mixed acid; and an etching step by The mixed acid ejection port is supplied to the substrate by the mixed acid to which water has been added in the water replenishing step, and the metal film on the substrate is etched. According to the above configuration, the same effects as those described above can be obtained.

在本實施形態中，亦可在所述基板處理裝置中加入以下的至少一個特徵。 In the present embodiment, at least one of the following features may be added to the substrate processing apparatus.

所述基板處理裝置進而包括：成分濃度計，檢測所述混合酸中的磷酸的濃度及所述混合酸中的水的濃度；莫耳比計算部，根據所述成分濃度計的檢測值，計算所述P/W莫耳比；以及莫耳比判定部，判定經所述莫耳比計算部計算出的所述P/W莫耳比是否超過所述莫耳比下限值，且未達所述莫耳比上限值。 The substrate processing apparatus further includes a component concentration meter that detects a concentration of phosphoric acid in the mixed acid and a concentration of water in the mixed acid, and a molar ratio calculating unit that calculates based on a detected value of the component concentration meter And the P/W molar ratio; and the Mohr ratio determining unit determines whether the P/W molar ratio calculated by the Mohr ratio calculating unit exceeds the Mohr ratio lower limit value and does not reach The molar ratio is the upper limit.

所述控制裝置進而執行：成分濃度檢測步驟，使所述成分濃度計檢測所述混合酸中的磷酸的濃度及所述混合酸中的水的濃度；莫耳比計算步驟，根據在所述成分濃度檢測步驟中檢測出的檢測值，使所述莫耳比計算部計算所述P/W莫耳比；以及莫耳比判定步驟，使所述莫耳比判定部判定在所述莫耳比計算步驟中所計算出的所述P/W莫耳比是否超過所述莫耳比下限值，且未達所述莫耳比上限值。根據所述構成，可獲得與以上所述的效果同樣的效果。 The control device further performs a component concentration detecting step of causing the component concentration meter to detect a concentration of phosphoric acid in the mixed acid and a concentration of water in the mixed acid; a molar ratio calculating step according to the component a detection value detected in the concentration detecting step, causing the molar ratio calculating unit to calculate the P/W molar ratio; and a molar ratio determining step, causing the molar ratio determining unit to determine the molar ratio Whether the P/W molar ratio calculated in the calculating step exceeds the molar ratio lower limit value and does not reach the upper molar ratio. According to the above configuration, the same effects as those described above can be obtained.

所述基板處理裝置進而包括檢測所述混合酸中的水的濃度的成分濃度計，所述控制裝置進而執行使所述成分濃度計檢 測所述混合酸中的水的濃度的成分濃度檢測步驟，所述水補充步驟包括水濃度控制步驟，所述水濃度控制步驟是藉由使所述水噴出口將水加入至在所述混合酸加熱步驟中經加熱的所述混合酸中，而使在所述成分濃度檢測步驟中檢測的水的濃度接近於伴隨著時間的經過而增加的水濃度目標值，使所述P/W莫耳比維持在所述莫耳比上限值與所述莫耳比下限值之間。根據所述構成，可獲得與以上所述的效果同樣的效果。 The substrate processing apparatus further includes a component concentration meter that detects a concentration of water in the mixed acid, and the control device further performs measurement of the component concentration a component concentration detecting step of measuring a concentration of water in the mixed acid, the water replenishing step including a water concentration controlling step of adding water to the mixing by causing the water spout In the mixed acid heated in the acid heating step, the concentration of the water detected in the component concentration detecting step is close to the water concentration target value which increases with the passage of time, so that the P/W is The ear ratio is maintained between the upper molar ratio and the lower molar ratio. According to the above configuration, the same effects as those described above can be obtained.

所述水補充步驟包括定時定量水補充步驟，所述定時定量水補充步驟是藉由在指定時間使所述水噴出口將指定量的水加入至在所述混合酸加熱步驟中經加熱的所述混合酸中，而使所述P/W莫耳比維持在所述莫耳比上限值與所述莫耳比下限值之間。根據所述構成，可獲得與以上所述的效果同樣的效果。 The water replenishing step includes a timed quantitative water replenishing step of adding a specified amount of water to the heated in the mixed acid heating step by causing the water spout to be heated at the specified time. In the mixed acid, the P/W molar ratio is maintained between the upper molar ratio and the lower molar ratio. According to the above configuration, the same effects as those described above can be obtained.

所述莫耳比調節步驟是如下的步驟：一面容許所述混合酸中的磷酸的濃度及所述混合酸中的水的濃度中的至少一者的變化，一面使所述P/W莫耳比維持在所述莫耳比上限值與所述莫耳比下限值之間。根據所述構成，可獲得與以上所述的效果同樣的效果。 The molar ratio adjusting step is a step of allowing the P/W Moer while allowing a change in at least one of a concentration of phosphoric acid in the mixed acid and a concentration of water in the mixed acid. The ratio is maintained between the upper molar ratio and the lower molar ratio. According to the above configuration, the same effects as those described above can be obtained.

所述基板處理裝置進而包括檢測所述混合酸中的磷酸的濃度及所述混合酸中的水的濃度中的至少一者的成分濃度計，所述莫耳比調節步驟進而包括水補充禁止步驟，所述水補充禁止步驟是藉由一面禁止對所述混合酸供給水，一面使所述加熱器對所述混合酸進行加熱，而使所述P/W莫耳比自所述莫耳比下限值 以下的值上升至所述莫耳比上限值與莫耳比下限值之間的值為止。根據所述構成，可獲得與以上所述的效果同樣的效果。 The substrate processing apparatus further includes a component concentration meter that detects at least one of a concentration of phosphoric acid in the mixed acid and a concentration of water in the mixed acid, and the molar ratio adjusting step further includes a water supplement prohibiting step The water replenishing prohibiting step is to cause the heater to heat the mixed acid while prohibiting the supply of water to the mixed acid, so that the P/W molar ratio is from the molar ratio lower limit The following values rise to a value between the upper molar ratio and the lower molar ratio. According to the above configuration, the same effects as those described above can be obtained.

所述混合酸進而包含醋酸。根據所述構成，可獲得與以上所述的效果同樣的效果。 The mixed acid further contains acetic acid. According to the above configuration, the same effects as those described above can be obtained.

所述水補充步驟包括非處理中水補充步驟，所述非處理中水補充步驟是藉由僅在未對所述基板供給所述混合酸的期間內，使所述水噴出口將水加入至所述混合酸中，而使所述P/W莫耳比下降。根據所述構成，可獲得與以上所述的效果同樣的效果。 The water replenishing step includes a non-treatment water replenishing step of causing the water spout to add water to the non-processing water replenishing step by only supplying the mixed acid to the substrate In the mixed acid, the P/W molar ratio is decreased. According to the above configuration, the same effects as those described above can be obtained.

本發明中的以上所述的目的或進而其他目的、特徵及效果是藉由以下參照隨附圖式而描述的實施形態的說明來闡明。 The above and other objects, features, and advantages of the invention will be apparent from the description of the embodiments described herein.

1‧‧‧基板處理裝置 1‧‧‧Substrate processing unit

~‧‧‧現象 ~ ‧‧‧phenomenon

2‧‧‧處理單元 2‧‧‧Processing unit

3、103‧‧‧控制裝置 3, 103‧‧‧ control device

3a‧‧‧電腦主體 3a‧‧‧ computer subject

3b‧‧‧周邊裝置 3b‧‧‧ peripheral devices

4‧‧‧第1藥液處理槽 4‧‧‧1st liquid treatment tank

5‧‧‧第1沖洗處理槽 5‧‧‧1st processing tank

6‧‧‧第2藥液處理槽 6‧‧‧2nd liquid treatment tank

7‧‧‧第2沖洗處理槽 7‧‧‧2nd rinsing tank

8‧‧‧乾燥處理槽 8‧‧‧Drying tank

9‧‧‧載體搬運裝置 9‧‧‧Carrier handling device

10‧‧‧姿勢變換機器人 10‧‧‧ pose transformation robot

11‧‧‧主搬運機器人 11‧‧‧Main handling robot

12‧‧‧副搬運機器人 12‧‧‧Auxiliary handling robot

12A‧‧‧第1副搬運機器人 12A‧‧‧1st handling robot

12B‧‧‧第2副搬運機器人 12B‧‧‧2nd handling robot

13‧‧‧升降機 13‧‧‧ Lifts

14‧‧‧固持器 14‧‧‧Retainer

15‧‧‧外槽 15‧‧‧ outer trough

16‧‧‧內槽 16‧‧‧Inner slot

21‧‧‧循環系統 21‧‧‧Circulatory system

22‧‧‧混合酸噴嘴 22‧‧‧ mixed acid nozzle

22a‧‧‧混合酸噴出口 22a‧‧‧ mixed acid spray outlet

23‧‧‧循環配管 23‧‧‧Recycling piping

23d‧‧‧下游配管 23d‧‧‧Downstream piping

23u‧‧‧上游配管 23u‧‧‧Upstream piping

24‧‧‧過濾器 24‧‧‧Filter

25‧‧‧加熱器 25‧‧‧heater

26‧‧‧循環泵 26‧‧‧Circulating pump

31‧‧‧補充系統 31‧‧‧Supplemental system

32‧‧‧水補充噴嘴 32‧‧‧Water replenishing nozzle

32a‧‧‧水噴出口 32a‧‧‧Water spout

33‧‧‧水配管 33‧‧‧Water piping

34‧‧‧開關閥 34‧‧‧ switch valve

35‧‧‧流量調整閥 35‧‧‧Flow adjustment valve

36‧‧‧流量計 36‧‧‧ Flowmeter

37‧‧‧成分濃度計 37‧‧‧Component concentration meter

41‧‧‧CPU 41‧‧‧CPU

42‧‧‧主記憶裝置 42‧‧‧Main memory device

43、143‧‧‧輔助記憶裝置 43,143‧‧‧Auxiliary memory device

44‧‧‧讀取裝置 44‧‧‧Reading device

45‧‧‧通信裝置 45‧‧‧Communication device

46‧‧‧顯示裝置 46‧‧‧ display device

47‧‧‧警報裝置 47‧‧‧Alarm device

48‧‧‧輸入裝置 48‧‧‧ Input device

51‧‧‧莫耳比調節部 51‧‧‧Morbi Adjustment Department

52‧‧‧莫耳比計算部 52‧‧‧Morby Computing Department

53‧‧‧莫耳比判定部 53‧‧Morby Judging Department

54、154‧‧‧水補充部 54, 154‧‧ Water Supplement

55、155‧‧‧水補充禁止部 55, 155‧‧ Water Restriction Prohibition Department

56‧‧‧水濃度控制部 56‧‧‧Water Concentration Control Department

57‧‧‧定時定量水補充部 57‧‧‧Timed Quantitative Water Replenishment Department

61‧‧‧自旋夾盤 61‧‧‧ Spin chuck

62‧‧‧沖洗液噴嘴 62‧‧‧ rinse liquid nozzle

63‧‧‧沖洗液配管 63‧‧‧ rinse liquid piping

64‧‧‧沖洗液閥 64‧‧‧ rinse valve

65‧‧‧供給配管 65‧‧‧Supply piping

66‧‧‧噴出閥 66‧‧‧Spray valve

67‧‧‧噴嘴移動單元 67‧‧‧Nozzle mobile unit

68‧‧‧槽罐 68‧‧‧Slots

151‧‧‧濃度比調節部 151‧‧‧ concentration ratio adjustment department

152‧‧‧濃度比計算部 152‧‧‧ concentration ratio calculation department

153‧‧‧濃度比判定部 153‧‧‧ concentration ratio determination department

A1‧‧‧旋轉軸線 A1‧‧‧Rotation axis

C‧‧‧載體 C‧‧‧ Carrier

HC‧‧‧主電腦 HC‧‧‧ main computer

LP‧‧‧裝載埠 LP‧‧‧Loader

M‧‧‧可移媒體 M‧‧‧Removable Media

P‧‧‧程式 P‧‧‧ program

S1~S5、S11~S19‧‧‧步驟 S1~S5, S11~S19‧‧‧ steps

W‧‧‧基板 W‧‧‧Substrate

T1、T2、T3‧‧‧指定時間 T 1 , T 2 , T 3 ‧‧‧Specified time

V1、V2、V3‧‧‧指定量 V 1 , V 2 , V 3 ‧ ‧ specified amount

圖1是表示本發明的第1實施形態的基板處理裝置的佈局(layout)的圖解性的俯視圖。 1 is a schematic plan view showing a layout of a substrate processing apparatus according to a first embodiment of the present invention.

圖2是表示第2藥液處理槽的鉛垂剖面、使混合酸循環的循環系統及補充混合酸的成分液的補充系統的剖面圖。 2 is a cross-sectional view showing a vertical cross section of the second chemical liquid processing tank, a circulation system for circulating the mixed acid, and a replenishing system for the component liquid supplemented with the mixed acid.

圖3是表示基板處理裝置的電性構成的方塊圖。 3 is a block diagram showing an electrical configuration of a substrate processing apparatus.

圖4是表示控制裝置的功能塊的方塊圖。 Fig. 4 is a block diagram showing functional blocks of the control device.

圖5是用以說明藉由基板處理裝置而進行的基板的處理的一例的步驟圖。 FIG. 5 is a process diagram for explaining an example of processing of a substrate by a substrate processing apparatus.

圖6是用以說明藉由混合酸來對鎢進行蝕刻的機制的基板的剖面圖。 6 is a cross-sectional view of a substrate for explaining a mechanism of etching tungsten by mixing an acid.

圖7是用以說明使P/W莫耳比穩定的控制的一例的流程圖。 FIG. 7 is a flowchart for explaining an example of control for stabilizing the P/W molar ratio.

圖8A是表示P/W莫耳比的時間性的變化的圖表。 Fig. 8A is a graph showing temporal changes in P/W molar ratio.

圖8B是表示P/W莫耳比的時間性的變化的圖表。 Fig. 8B is a graph showing temporal changes in P/W molar ratio.

圖9是表示本發明的第2實施形態的P/W莫耳比的時間性的變化及混合酸中的水的濃度的時間性的變化的圖表。 FIG. 9 is a graph showing temporal changes in the P/W molar ratio and temporal changes in the concentration of water in the mixed acid according to the second embodiment of the present invention.

圖10是表示本發明的第3實施形態的P/W莫耳比的時間性的變化、將水加入至混合酸中的時間及所加入的水的量的圖表。 Fig. 10 is a graph showing the temporal change of the P/W molar ratio in the third embodiment of the present invention, the time during which water is added to the mixed acid, and the amount of water to be added.

圖11是表示本發明的第4實施形態的基板處理裝置的概略構成的示意圖。 FIG. 11 is a schematic diagram showing a schematic configuration of a substrate processing apparatus according to a fourth embodiment of the present invention.

圖12是表示控制裝置的功能塊的方塊圖。 Fig. 12 is a block diagram showing functional blocks of the control device.

圖1是表示本發明的第1實施形態的基板處理裝置1的佈局的圖解性的俯視圖。 1 is a schematic plan view showing a layout of a substrate processing apparatus 1 according to a first embodiment of the present invention.

基板處理裝置1是統一處理多塊基板W的批次式的裝置。基板處理裝置1包括：裝載埠(load port)LP，搬運收容半導體晶圓等圓板狀的基板W的載體C；處理單元2，利用藥液或沖洗液等處理液對自裝載埠LP搬運的基板W進行處理；多個搬運機器人，在裝載埠LP與處理單元2之間搬運基板W；以及控制裝置3，對基板處理裝置1進行控制。 The substrate processing apparatus 1 is a batch type apparatus that collectively processes a plurality of substrates W. The substrate processing apparatus 1 includes a load port LP that transports a carrier C that accommodates a disk-shaped substrate W such as a semiconductor wafer, and a processing unit 2 that transports the liquid from the loading cassette by a processing liquid such as a chemical liquid or a rinse liquid. The substrate W is processed; a plurality of transfer robots transport the substrate W between the load cassette LP and the processing unit 2; and the control device 3 controls the substrate processing apparatus 1.

處理單元2包括：第1藥液處理槽4，存積浸漬多塊基板W的第1藥液；第1沖洗處理槽5，存積浸漬多塊基板W的第1沖洗液；第2藥液處理槽6，存積浸漬多塊基板W的第2藥液； 以及第2沖洗處理槽7，存積浸漬多塊基板W的第2沖洗液。處理單元2進而包括使多塊基板W乾燥的乾燥處理槽8。 The processing unit 2 includes a first chemical liquid processing tank 4 that stores a first chemical liquid in which a plurality of substrates W are impregnated, a first processing tank 5 that stores a first rinse liquid in which a plurality of substrates W are impregnated, and a second chemical liquid. Processing the tank 6 to store the second chemical liquid impregnated with the plurality of substrates W; And the second rinse processing tank 7 stores the second rinse liquid in which the plurality of substrates W are impregnated. The processing unit 2 further includes a drying treatment tank 8 that dries a plurality of substrates W.

第1藥液例如為SC1或氫氟酸(hydrofluoric acid)。第2藥液例如為磷酸、醋酸、硝酸及水的混合液的混合酸。第1沖洗液及第2沖洗液例如為純水(去離子水：Deionized water)。第1藥液亦可為SC1及氫氟酸以外的藥液。同樣地，第1沖洗液及第2沖洗液亦可為純水以外的沖洗液。第1沖洗液及第2沖洗液亦可為互不相同的種類的沖洗液。 The first chemical liquid is, for example, SC1 or hydrofluoric acid. The second chemical liquid is, for example, a mixed acid of a mixed solution of phosphoric acid, acetic acid, nitric acid, and water. The first rinse liquid and the second rinse liquid are, for example, pure water (deionized water). The first chemical solution may be a chemical solution other than SC1 or hydrofluoric acid. Similarly, the first rinse liquid and the second rinse liquid may be rinse liquids other than pure water. The first rinse liquid and the second rinse liquid may be flush liquids of different types.

多個搬運機器人包括：載體搬運裝置9，在裝載埠LP與處理單元2之間搬運載體C，收容多個載體C；以及姿勢變換機器人10，對保持於載體搬運裝置9上的載體C進行多塊基板W的搬入及搬出，在水平姿勢與鉛垂姿勢之間變更基板W的姿勢。姿勢變換機器人10進行批次組合動作及批次解除動作，所述批次組合動作是利用自所述多個載體C取出的多塊基板W形成1個批次，所述批次解除動作是將1個批次中所含的多塊基板W收容於多個載體C上。 The plurality of transport robots include a carrier transport device 9 that transports the carrier C between the loading cassette LP and the processing unit 2, and accommodates a plurality of carriers C. The posture changing robot 10 performs a plurality of carriers C held on the carrier conveying device 9. The loading and unloading of the block substrate W changes the posture of the substrate W between the horizontal posture and the vertical posture. The posture conversion robot 10 performs a batch combination operation in which one batch is formed by using a plurality of substrates W taken out from the plurality of carriers C, and a batch release operation in which the batch release operation is performed. The plurality of substrates W included in one lot are accommodated in the plurality of carriers C.

多個搬運機器人進而包括：主搬運機器人11，在姿勢變換機器人10與處理單元2之間搬運多塊基板W；以及多個副搬運機器人12，在主搬運機器人11與處理單元2之間搬運多塊基板W。多個副搬運機器人12包括：第1副搬運機器人12A，在第1藥液處理槽4與第1沖洗處理槽5之間搬運多塊基板W；以及第2副搬運機器人12B，在第2藥液處理槽6與第2沖洗處理槽7之 間搬運多塊基板W。 The plurality of transport robots further include a main transport robot 11 that transports a plurality of substrates W between the posture conversion robot 10 and the processing unit 2, and a plurality of sub transport robots 12 that transport between the main transport robot 11 and the processing unit 2 Block substrate W. The plurality of sub transport robots 12 include a first sub transport robot 12A, and a plurality of substrates W are transported between the first chemical liquid processing tank 4 and the first rinse processing tank 5, and the second sub transport robot 12B is in the second medicine. The liquid processing tank 6 and the second rinsing tank 7 A plurality of substrates W are transported therebetween.

主搬運機器人11自姿勢變換機器人10接收包含多塊(例如50塊)基板W的1個批次的基板W。主搬運機器人11將自姿勢變換機器人10接收到的1個批次的基板W遞交至第1副搬運機器人12A及第2副搬運機器人12B，且接收由第1副搬運機器人12A及第2副搬運機器人12B保持著的1個批次的基板W。主搬運機器人11進而將1個批次的基板W搬運至乾燥處理槽8。 The main transport robot 11 receives the one-piece substrate W including a plurality of (for example, 50) substrates W from the posture conversion robot 10. The main transport robot 11 delivers the one-substrate substrate W received from the posture-converting robot 10 to the first sub-transport robot 12A and the second sub-transport robot 12B, and receives the first sub-transport robot 12A and the second sub-transporter 12B. One batch of the substrate W held by the robot 12B. The main transport robot 11 further transports one batch of the substrate W to the drying processing tank 8.

第1副搬運機器人12A在第1藥液處理槽4與第1沖洗處理槽5之間搬運自主搬運機器人11接收到的1個批次的基板W，且使其浸漬於第1藥液處理槽4內的第1藥液或第1沖洗處理槽5內的第1沖洗液中。同樣地，第2副搬運機器人12B在第2藥液處理槽6與第2沖洗處理槽7之間搬運自主搬運機器人11接收到的1個批次的基板W，且使其浸漬於第2藥液處理槽6內的第2藥液或第2沖洗處理槽7內的第2沖洗液中。 The first sub-transporting robot 12A transports one batch of the substrate W received by the autonomous transport robot 11 between the first chemical liquid processing tank 4 and the first rinse processing tank 5, and immerses it in the first chemical liquid processing tank. The first chemical liquid in the fourth liquid or the first rinse liquid in the first rinse processing tank 5. In the same manner, the second sub-transporting robot 12B transfers the one-substrate substrate W received by the autonomous transport robot 11 between the second chemical liquid processing tank 6 and the second rinse processing tank 7 and immerses it in the second medicine. The second chemical liquid in the liquid processing tank 6 or the second rinse liquid in the second rinse processing tank 7.

圖2是表示第2藥液處理槽6的鉛垂剖面、使混合酸循環的循環系統21及補充混合酸的成分液的補充系統31的剖面圖。雖未圖示，但關於第1藥液處理槽4、第1沖洗處理槽5及第2沖洗處理槽7，亦具備與第2藥液處理槽6同樣的構成。 2 is a cross-sectional view showing a vertical cross section of the second chemical liquid processing tank 6, a circulation system 21 for circulating a mixed acid, and a replenishing system 31 for supplementing the component liquid of the mixed acid. Though not shown, the first chemical liquid processing tank 4, the first rinse processing tank 5, and the second rinse processing tank 7 have the same configuration as that of the second chemical liquid processing tank 6.

第2藥液處理槽6包括：內槽16，其是存積磷酸、醋酸、硝酸及水的混合液的混合酸的混合酸存積容器的一例；以及外槽15，存積自內槽16溢出的混合酸。基板處理裝置1包括：循環系 統21，一面對第2藥液處理槽6內的混合酸進行加熱，一面使所述混合酸循環；以及補充系統31，藉由補充混合酸的成分液來調整混合酸中所含的磷酸的莫耳數相對於混合酸中所含的水的莫耳數的比率。 The second chemical liquid processing tank 6 includes an inner tank 16 which is an example of a mixed acid storage container in which a mixed acid of phosphoric acid, acetic acid, nitric acid and water is stored, and an outer tank 15 which is stored from the inner tank 16 Spilled mixed acid. The substrate processing apparatus 1 includes: a circulation system The system 21 circulates the mixed acid while heating the mixed acid in the second chemical liquid processing tank 6, and the replenishing system 31 adjusts the phosphoric acid contained in the mixed acid by supplementing the component liquid of the mixed acid The molar ratio of the molar number relative to the molar number of water contained in the mixed acid.

循環系統21包括混合酸噴嘴22，所述混合酸噴嘴22藉由自配置在內槽16內的混合酸噴出口22a噴出混合酸，而將混合酸供給至內槽16內，並且在內槽16內的混合酸中形成上升流。循環系統21進而包括：循環配管23，將外槽15內的混合酸導引至混合酸噴嘴22；循環泵26，將循環配管23內的混合酸輸送至混合酸噴嘴22；加熱器25，以高於室溫(例如20℃~30℃)的溫度對在循環配管23內流動的混合酸進行加熱；以及過濾器(filter)24，自在循環配管23內流動的混合酸去除異物。 The circulation system 21 includes a mixed acid nozzle 22 that supplies a mixed acid into the inner tank 16 by discharging the mixed acid from the mixed acid discharge port 22a disposed in the inner tank 16, and the inner tank 16 An upflow is formed in the mixed acid within. The circulation system 21 further includes a circulation pipe 23 for guiding the mixed acid in the outer tank 15 to the mixed acid nozzle 22, and a circulation pump 26 for conveying the mixed acid in the circulation pipe 23 to the mixed acid nozzle 22; The mixed acid flowing in the circulation pipe 23 is heated at a temperature higher than room temperature (for example, 20 ° C to 30 ° C); and a filter 24 is removed from the mixed acid flowing in the circulation pipe 23 to remove foreign matter.

混合酸在由內槽16、外槽15、混合酸噴嘴22及循環配管23形成的循環路徑內循環。在此期間，利用加熱器25對混合酸進行加熱。由此，使內槽16內的混合酸維持在高於室溫的固定的溫度。循環泵26經常輸送循環配管23內的混合酸。循環配管23包括自外槽15延伸至下游的上游配管23u、以及自上游配管23u進行分支的多個下游配管23d。混合酸噴嘴22的混合酸噴出口22a在內槽16內噴出自循環配管23供給的混合酸。由此，內槽16內的混合酸的量增加，從而一部分混合酸自內槽16溢出。 The mixed acid circulates in a circulation path formed by the inner tank 16, the outer tank 15, the mixed acid nozzle 22, and the circulation pipe 23. During this time, the mixed acid is heated by the heater 25. Thereby, the mixed acid in the inner tank 16 is maintained at a fixed temperature higher than room temperature. The circulation pump 26 often supplies the mixed acid in the circulation piping 23. The circulation pipe 23 includes an upstream pipe 23u extending from the outer tank 15 to the downstream, and a plurality of downstream pipes 23d branched from the upstream pipe 23u. The mixed acid discharge port 22a of the mixed acid nozzle 22 discharges the mixed acid supplied from the circulation pipe 23 in the inner tank 16. Thereby, the amount of the mixed acid in the inner tank 16 is increased, so that a part of the mixed acid overflows from the inner tank 16.

副搬運機器人12包括：多個固持器14，以鉛垂的姿勢保持多塊基板W；以及升降機(lifter)13，使多個固持器14在上 位與下位(圖2所示的位置)之間鉛垂地升降，所述上位是保持於固持器14上的多塊基板W向上方遠離內槽16內的混合酸的位置，所述下位是使保持於固持器14上的多塊基板W浸漬於內槽16內的混合酸中的位置。保持於固持器14上的多塊基板W通過設置於內槽16的上端部的開口部而進入至內槽16中，且通過內槽16的開口部而排出至內槽16外。 The sub-handling robot 12 includes a plurality of holders 14 that hold a plurality of substrates W in a vertical posture, and a lifter 13 that allows the plurality of holders 14 to be placed thereon. The position is vertically raised and lowered between the lower position (the position shown in FIG. 2) which is a position at which the plurality of substrates W held on the holder 14 are moved upward away from the mixed acid in the inner groove 16, the lower position being The plurality of substrates W held on the holder 14 are immersed in a position in the mixed acid in the inner tank 16. The plurality of substrates W held by the holder 14 enter the inner groove 16 through the opening provided at the upper end portion of the inner groove 16, and are discharged to the outside of the inner groove 16 through the opening of the inner groove 16.

補充系統31包括自水噴出口32a噴出純水的水補充噴嘴32、將純水導引至水補充噴嘴32的水配管33、藉由使水配管33開關而控制對水補充噴嘴32的純水的供給的開關閥34、變更自水配管33供給至水補充噴嘴32的純水的流量的流量調整閥35、以及檢測自水配管33供給至水補充噴嘴32的純水的流量的流量計36。亦可取代流量計36，或除了流量計36以外，將送出固定量的液體的定量泵插裝在水配管33上。 The replenishing system 31 includes a water replenishing nozzle 32 that ejects pure water from the water discharge port 32a, a water pipe 33 that guides the pure water to the water replenishing nozzle 32, and controls the pure water to the water replenishing nozzle 32 by opening and closing the water pipe 33. The on-off valve 34 that is supplied, the flow rate adjustment valve 35 that changes the flow rate of the pure water supplied from the water pipe 33 to the water supply nozzle 32, and the flow rate meter 36 that detects the flow rate of the pure water supplied from the water pipe 33 to the water supply nozzle 32 . Instead of or in addition to the flow meter 36, a metering pump that sends a fixed amount of liquid may be inserted into the water pipe 33.

水補充噴嘴32在由內槽16、外槽15、混合酸噴嘴22及循環配管23形成的循環路徑的任一位置上將純水加入至混合酸中。圖2表示水補充噴嘴32的水噴出口32a位於外槽15的上方，將自水噴出口32a噴出的純水供給至外槽15內的混合酸中的示例。若為循環路徑上的位置，則最早供給自水補充噴嘴32噴出的純水的位置亦可為外槽15以外的位置。例如，亦可將水補充噴嘴32與循環配管23連接。 The water replenishing nozzle 32 adds pure water to the mixed acid at any position of the circulation path formed by the inner tank 16, the outer tank 15, the mixed acid nozzle 22, and the circulation piping 23. 2 shows an example in which the water discharge port 32a of the water supply nozzle 32 is located above the outer tank 15, and the pure water sprayed from the water discharge port 32a is supplied to the mixed acid in the outer tank 15. In the case of the position on the circulation path, the position of the pure water that is first supplied from the water replenishing nozzle 32 may be a position other than the outer tank 15. For example, the water replenishing nozzle 32 may be connected to the circulation pipe 23.

補充系統31包括檢測混合酸中所含的各成分的濃度的成分濃度計37。成分濃度計37檢測例如混合酸中所含的所有成分 的濃度。控制裝置3藉由根據成分濃度計37的檢測值設定流量調整閥35的開度，而將適當量的純水加入至混合酸中。自水補充噴嘴32供給至外槽15的純水自外槽15流入至循環配管23，且自循環配管23流入至混合酸噴嘴22。在此期間，純水混雜在正在使用的混合酸中，且均勻地分散於混合酸中。 The replenishing system 31 includes a component concentration meter 37 that detects the concentration of each component contained in the mixed acid. The component concentration meter 37 detects, for example, all the components contained in the mixed acid concentration. The control device 3 sets an opening amount of the flow rate adjusting valve 35 based on the detected value of the component concentration meter 37, and adds an appropriate amount of pure water to the mixed acid. The pure water supplied from the water supply nozzle 32 to the outer tank 15 flows into the circulation pipe 23 from the outer tank 15, and flows into the mixed acid nozzle 22 from the circulation pipe 23. During this time, pure water is mixed in the mixed acid being used and uniformly dispersed in the mixed acid.

圖3是表示基板處理裝置1的電性構成的方塊圖。圖4是表示控制裝置3的功能塊的方塊圖。 FIG. 3 is a block diagram showing an electrical configuration of the substrate processing apparatus 1. FIG. 4 is a block diagram showing functional blocks of the control device 3.

如圖3所示，控制裝置3包括電腦主體3a、以及與電腦主體3a連接的周邊裝置3b。電腦主體3a包括執行各種命令的中央處理裝置(central processing unit，CPU)41、以及記憶資訊的主記憶裝置42。周邊裝置3b包括記憶程式P等資訊的輔助記憶裝置43、自可移媒體(removable media)M讀取資訊的讀取裝置44、以及與主電腦(host computer)HC等控制裝置3以外的裝置進行通信的通信裝置45。 As shown in FIG. 3, the control device 3 includes a computer main body 3a and a peripheral device 3b connected to the computer main body 3a. The computer main body 3a includes a central processing unit (CPU) 41 that executes various commands, and a main memory device 42 that memorizes information. The peripheral device 3b includes an auxiliary memory device 43 for storing information such as the program P, a reading device 44 for reading information from the removable media M, and a device other than the control device 3 such as a host computer HC. Communication device 45 for communication.

控制裝置3與輸入裝置48及顯示裝置46連接。輸入裝置48是在使用者或維護負責人等操作者向基板處理裝置1輸入資訊時被操作。資訊顯示於顯示裝置46的畫面中。輸入裝置48既可為鍵盤、指向設備(pointing device)及觸控面板中的任一者，亦可為該些以外的裝置。亦可在基板處理裝置1上設置有兼作輸入裝置48及顯示裝置46的觸控面板顯示器(touch panel display)。 The control device 3 is connected to the input device 48 and the display device 46. The input device 48 is operated when an operator such as a user or a maintenance person inputs information to the substrate processing device 1. The information is displayed on the screen of the display device 46. The input device 48 can be any of a keyboard, a pointing device, and a touch panel, or can be other devices. A touch panel display that doubles as the input device 48 and the display device 46 may be provided on the substrate processing apparatus 1.

CPU 41執行輔助記憶裝置43中所記憶的程式P。輔助記憶裝置43內的程式P既可預先安裝至控制裝置3中，亦可通過 讀取裝置44自可移媒體M發送至輔助記憶裝置43，亦可自主電腦HC等外部裝置通過通信裝置45發送至輔助記憶裝置43。 The CPU 41 executes the program P stored in the auxiliary memory device 43. The program P in the auxiliary memory device 43 can be pre-installed in the control device 3 or through The reading device 44 is sent from the removable medium M to the auxiliary storage device 43, and the external device such as the autonomous computer HC is sent to the auxiliary storage device 43 via the communication device 45.

輔助記憶裝置43及可移媒體M是即使不供給電力亦保持記憶的非揮發性記憶體。輔助記憶裝置43例如是硬碟驅動器(hard disk drive)等磁記憶裝置。可移媒體M例如是密閉磁碟(compact disk)等光碟或記憶卡等半導體記憶體。可移媒體M是記錄有程式P的電腦可讀取的記錄媒體的一例。 The auxiliary memory device 43 and the removable medium M are non-volatile memories that are kept in memory even if power is not supplied. The auxiliary memory device 43 is, for example, a magnetic memory device such as a hard disk drive. The removable medium M is, for example, a semiconductor memory such as a compact disk or a compact disk or a memory card. The removable medium M is an example of a computer-readable recording medium on which the program P is recorded.

如圖4所示，控制裝置3包括使P/W莫耳比(混合酸中所含的磷酸的莫耳數/混合酸中所含的水的莫耳數)維持在莫耳比上限值與莫耳比下限值之間的莫耳比調節部51。莫耳比調節部51是藉由CPU 41執行安裝至控制裝置3中的程式P來實現的功能塊。莫耳比調節部51包括根據成分濃度計37的檢測值計算P/W莫耳比的莫耳比計算部52、判定經莫耳比計算部52計算出的P/W莫耳比是否超過莫耳比下限值且未達莫耳比上限值的莫耳比判定部53。 As shown in FIG. 4, the control device 3 includes maintaining the P/W molar ratio (the number of moles of phosphoric acid contained in the mixed acid/the number of moles of water contained in the mixed acid) at the upper limit of the molar ratio. The molar ratio adjusting portion 51 between the lower limit value and the molar ratio. The moiré adjustment section 51 is a functional block realized by the CPU 41 executing the program P installed in the control device 3. The molar ratio adjusting unit 51 includes a molar ratio calculating unit 52 that calculates a P/W molar ratio based on the detected value of the component concentration meter 37, and determines whether or not the P/W molar ratio calculated by the molar ratio calculating unit 52 exceeds the Mo ratio. The molar ratio determining unit 53 whose ear ratio is lower than the lower limit and does not reach the upper limit of the molar ratio.

莫耳比調節部51進而包括：水補充部54，當莫耳比判定部53判定為P/W莫耳比為莫耳比上限值以上時，使補充系統31將水加入至混合酸中；以及水補充禁止部55，當莫耳比判定部53判定為P/W莫耳比為莫耳比下限值以下時，使補充系統31及副搬運機器人12暫時禁止將水供給至混合酸中。水補充部54是例如當未將混合酸供給至基板W時，即，當未將基板W浸漬於混合酸中時，使補充系統31將水加入至混合酸中的非處理中水補充 部。 The moiré adjusting unit 51 further includes a water replenishing unit 54 that causes the replenishing system 31 to add water to the mixed acid when the Mohr ratio determining unit 53 determines that the P/W molar ratio is equal to or greater than the molar ratio upper limit value. And the water replenishing prohibiting unit 55 causes the replenishing system 31 and the sub transport robot 12 to temporarily prohibit the supply of water to the mixed acid when the Mo ratio detecting unit 53 determines that the P/W molar ratio is equal to or lower than the Mohr ratio lower limit value. in. The water replenishing portion 54 is a non-treated water replenishment that causes the replenishing system 31 to add water to the mixed acid, for example, when the mixed acid is not supplied to the substrate W, that is, when the substrate W is not immersed in the mixed acid. unit.

控制裝置3對基板處理裝置1進行控制，以按照主電腦HC所指定的配方(recipe)對基板W進行處理。輔助記憶裝置43記憶有多個配方。配方是規定基板W的處理內容、處理條件及處理順序的資訊。多個配方在基板W的處理內容、處理條件及處理順序中的至少一者上互不相同。以下的各步驟是藉由控制裝置3對基板處理裝置1進行控制來執行。換言之，控制裝置3是以執行以下的各步驟的方式而編程。 The control device 3 controls the substrate processing apparatus 1 to process the substrate W in accordance with a recipe designated by the host computer HC. The auxiliary memory device 43 memorizes a plurality of recipes. The recipe is information that specifies the processing contents, processing conditions, and processing order of the substrate W. The plurality of recipes are different from each other in at least one of processing contents, processing conditions, and processing orders of the substrate W. The following steps are performed by controlling the substrate processing apparatus 1 by the control device 3. In other words, the control device 3 is programmed in such a manner as to perform the following steps.

圖5是用以說明藉由基板處理裝置1而進行的基板W的處理的一例的步驟圖。以下，參照圖1、圖2及圖5。又，以下，對蝕刻處理進行說明，所述蝕刻處理是對表層上露出有作為金屬膜的一例的鎢的薄膜(參照圖6)的基板W，供給磷酸、醋酸、硝酸及水的混合液的混合酸，而對鎢的薄膜進行蝕刻。 FIG. 5 is a process diagram for explaining an example of processing of the substrate W by the substrate processing apparatus 1. Hereinafter, reference is made to Figs. 1, 2, and 5. In the following, an etching process is described in which a mixture of phosphoric acid, acetic acid, nitric acid, and water is supplied to a substrate W on which a tungsten thin film (see FIG. 6) as an example of a metal film is exposed on the surface layer. The acid is mixed and the tungsten film is etched.

主搬運機器人11自姿勢變換機器人10接收包含多塊基板W的1個批次的基板W。主搬運機器人11將自姿勢變換機器人10接收到的1個批次的基板W搬運至第1副搬運機器人12A，且遞交至第1副搬運機器人12A。第1副搬運機器人12A使自主搬運機器人11接收到的1個批次的基板W浸漬於第1藥液處理槽4內的第1藥液中(圖5的步驟S1)，然後，浸漬於第1沖洗處理槽5內的第1沖洗液中(圖5的步驟S2)。然後，第1副搬運機器人12A將1個批次的基板W遞交至主搬運機器人11。 The main transport robot 11 receives the one-piece substrate W including the plurality of substrates W from the posture conversion robot 10 . The main transport robot 11 transports the one-substrate substrate W received from the posture-converting robot 10 to the first sub-transport robot 12A, and delivers it to the first sub-transport robot 12A. The first sub-transporting robot 12A immerses the one-substrate substrate W received by the autonomous transport robot 11 in the first chemical liquid in the first chemical liquid processing tank 4 (step S1 in FIG. 5), and then immerses it in the first 1 rinses the first rinse liquid in the treatment tank 5 (step S2 of Fig. 5). Then, the first sub-transport robot 12A delivers one batch of the substrate W to the main transport robot 11 .

主搬運機器人11將自第1副搬運機器人12A接收到的 1個批次的基板W遞交至第2副搬運機器人12B。第2副搬運機器人12B使自主搬運機器人11接收到的1個批次的基板W浸漬於第2藥液處理槽6內的第2藥液、即混合酸中(圖5的步驟S3)，然後，浸漬於第2沖洗處理槽7內的第2沖洗液中(圖5的步驟S4)。然後，第2副搬運機器人12B將1個批次的基板W遞交至主搬運機器人11。主搬運機器人11將自第2副搬運機器人12B接收到的1個批次的基板W搬運至乾燥處理槽8。 The main transport robot 11 receives the first sub transport robot 12A. The one-substrate substrate W is delivered to the second sub-transport robot 12B. The second sub-transport robot 12B immerses the one-substrate substrate W received by the autonomous transport robot 11 in the second chemical liquid in the second chemical liquid processing tank 6, that is, the mixed acid (step S3 in FIG. 5), and then It is immersed in the second rinse liquid in the second rinse processing tank 7 (step S4 in Fig. 5). Then, the second sub-transport robot 12B delivers the one-substrate substrate W to the main transport robot 11 . The main transport robot 11 transports the one-piece substrate W received from the second sub-transport robot 12B to the drying processing tank 8.

乾燥處理槽8利用減壓乾燥等乾燥方法使藉由主搬運機器人11而搬運的1個批次的基板W乾燥(圖5的步驟S5)。然後，主搬運機器人11將1個批次的基板W遞交至姿勢變換機器人10。姿勢變換機器人10將自主搬運機器人11接收到的1個批次的基板W的姿勢自鉛垂姿勢變更為水平姿勢，然後，將1個批次的基板W收容於保持在載體搬運裝置9上的多個載體C上。藉由重複進行所述一系列的動作，而對搬運至基板處理裝置1的多塊基板W進行處理。 The drying treatment tank 8 dries one batch of the substrate W conveyed by the main conveyance robot 11 by a drying method such as vacuum drying (step S5 of FIG. 5). Then, the main transport robot 11 delivers one batch of the substrate W to the posture conversion robot 10. The posture changing robot 10 changes the posture of the one-substrate substrate W received by the autonomous transport robot 11 from the vertical posture to the horizontal posture, and then accommodates one batch of the substrate W in the carrier transport device 9 Multiple carriers C. The plurality of substrates W transported to the substrate processing apparatus 1 are processed by repeating the series of operations.

圖6是用以說明藉由混合酸來對鎢進行蝕刻的機制的基板W的剖面圖。圖6中由圓圈包圍的數字對應於以下說明的現象的編號。例如，圖6中的由圓圈包圍的1對應於以下說明的現象1。 Fig. 6 is a cross-sectional view showing a substrate W for explaining a mechanism of etching tungsten by mixing an acid. The numbers surrounded by circles in Fig. 6 correspond to the numbers of the phenomena explained below. For example, 1 surrounded by a circle in FIG. 6 corresponds to the phenomenon 1 explained below.

如圖6所示，在混合酸中，含有磷酸(H3PO4)、醋酸(CH3COOH)、硝酸(HNO3)、水(H2O)。硝酸使鎢(W)氧化(現象1)。由此，生成鎢化合物(W(NO3)x)及氫氣(H2)(現象2)。 As shown in Fig. 6, the mixed acid contains phosphoric acid (H 3 PO 4 ), acetic acid (CH 3 COOH), nitric acid (HNO 3 ), and water (H 2 O). Nitric acid oxidizes tungsten (W) (phenomenon 1). Thereby, a tungsten compound (W(NO 3 ) x ) and hydrogen (H 2 ) (phenomenon 2) were produced.

藉由硝酸對鎢的氧化而產生的鎢化合物(W(NO3)x)是藉由磷酸水溶液(磷酸+水)而蝕刻，且溶解於磷酸水溶液中(現象3)。所述蝕刻是藉由混合酸的加熱來促進(現象4)。因此，混合酸的加熱間接有助於鎢的蝕刻。 The tungsten compound (W(NO 3 ) x ) produced by oxidation of tungsten by nitric acid is etched by an aqueous phosphoric acid solution (phosphoric acid + water) and dissolved in an aqueous phosphoric acid solution (phenomenon 3). The etching is promoted by heating of the mixed acid (Phenomenon 4). Therefore, the heating of the mixed acid indirectly contributes to the etching of tungsten.

另一方面，藉由硝酸對鎢的氧化而產生的氫氣殘留在基板W的一部分表面，從而抑制硝酸對鎢的氧化(現象5)。因此，若氫氣位於基板W的表面，則蝕刻的均勻性下降。醋酸會促進氫氣自基板W剝離，結果促進硝酸對鎢的氧化(現象6)。基板W上的混合酸的流動亦會促進氫氣自基板W剝離(現象7)。由此，可抑制或防止蝕刻的均勻性的下降。 On the other hand, hydrogen generated by oxidation of tungsten by nitric acid remains on a part of the surface of the substrate W, thereby suppressing oxidation of tungsten by nitric acid (phenomenon 5). Therefore, if hydrogen gas is located on the surface of the substrate W, the uniformity of etching is lowered. Acetic acid promotes the stripping of hydrogen from the substrate W, and as a result, promotes the oxidation of tungsten by tungsten (phenomenon 6). The flow of the mixed acid on the substrate W also promotes the separation of hydrogen from the substrate W (Phenomenon 7). Thereby, it is possible to suppress or prevent a decrease in the uniformity of etching.

若一面對含有磷酸、醋酸、硝酸及水的混合酸進行加熱，一面使所述混合酸循環，則藉由各成分的蒸發等，鎢的蝕刻率會伴隨著時間的經過而下降。本發明者等人已進行用以使蝕刻率的下降量減少的研究。其結果獲知，混合酸中的硝酸及醋酸的濃度的變動對蝕刻率的變動的影響小。因此可知，磷酸及水中的兩者或一者對蝕刻率的變動造成大的影響。 When the mixed acid containing phosphoric acid, acetic acid, nitric acid, and water is heated, and the mixed acid is circulated, the etching rate of tungsten is lowered by the passage of time by evaporation of each component. The inventors of the present invention have conducted research to reduce the amount of decrease in the etching rate. As a result, it was found that the fluctuation in the concentration of nitric acid and acetic acid in the mixed acid had little effect on the fluctuation of the etching rate. Therefore, it is understood that either or both of phosphoric acid and water have a large influence on the variation of the etching rate.

根據本發明者等人的研究，已獲知若使混合酸中的水的濃度穩定，則可抑制鎢的蝕刻率的減少。此外，已獲知若不使混合酸中的水的濃度穩定，而使P/W莫耳比(磷酸的莫耳濃度/水的莫耳濃度)穩定，則可進一步抑制鎢的蝕刻率的減少。P/W莫耳比的容許變動量，即，莫耳比上限與莫耳比下限值的差例如為0.01~0.05，較佳為0.01~0.03。 According to the study by the inventors of the present invention, it has been found that when the concentration of water in the mixed acid is stabilized, the reduction in the etching rate of tungsten can be suppressed. Further, it has been found that the P/W molar ratio (the molar concentration of phosphoric acid/the molar concentration of water) is stabilized without stabilizing the concentration of water in the mixed acid, and the reduction in the etching rate of tungsten can be further suppressed. The allowable variation amount of the P/W molar ratio, that is, the difference between the upper molar ratio and the lower molar ratio is, for example, 0.01 to 0.05, preferably 0.01 to 0.03.

表1是表示混合酸中所含的各成分(磷酸、醋酸、硝酸及水)的濃度及以水的莫耳數為基準的各成分的莫耳數的表。 Table 1 is a table showing the concentration of each component (phosphoric acid, acetic acid, nitric acid, and water) contained in the mixed acid and the number of moles of each component based on the number of moles of water.

表1中的編號(number，NO.)2~NO.4均表示一面調整混合酸的溫度，一面使混合酸循環直至混合酸的更換時期為止時的計算值。表1中的NO.3不同於NO.2的方面在於使混合酸中的水的濃度穩定。表1中的NO.4不同於NO.3的方面在於使P/W莫耳比穩定。 The numbers (number, NO.) 2 to NO. 4 in Table 1 indicate the calculated values when the mixed acid was circulated until the mixed acid exchange period was adjusted while adjusting the temperature of the mixed acid. The aspect of NO. 3 in Table 1 different from that of NO. 2 is to stabilize the concentration of water in the mixed acid. The aspect of NO. 4 in Table 1 different from that of NO. 3 is that the P/W molar ratio is stabilized.

如表1所示，NO.4的磷酸的濃度與NO.1的新的磷酸的濃度不同。同樣地，NO.3的磷酸的濃度與NO.1的新的磷酸的濃度不同。關於相對於新的磷酸的濃度的變化量，NO.4大於NO.3。儘管如此，仍獲得NO.4的鎢的蝕刻率的變動量更小的結果。 As shown in Table 1, the concentration of phosphoric acid of NO. 4 is different from the concentration of new phosphoric acid of NO. Similarly, the concentration of phosphoric acid of NO. 3 is different from the concentration of new phosphoric acid of NO. Regarding the amount of change with respect to the concentration of the new phosphoric acid, NO. 4 is larger than NO. In spite of this, the amount of change in the etching rate of tungsten of No. 4 was obtained to be smaller.

如表1所示，雖然NO.4的磷酸的莫耳比與NO.2的磷酸的莫耳比不同，即，與水的濃度的穩定化及P/W莫耳比的穩定化均未進行時的磷酸的莫耳比不同，但NO.4的磷酸的濃度與NO.2的磷酸的濃度相等。NO.2及NO.4儘管磷酸的濃度彼此相等，但仍獲得NO.4的蝕刻率的變動量更小的結果。 As shown in Table 1, although the molar ratio of the phosphoric acid of NO. 4 is different from the molar ratio of the phosphoric acid of NO. 2, that is, the stabilization of the concentration of water and the stabilization of the P/W molar ratio are not performed. The molar ratio of phosphoric acid at the time is different, but the concentration of phosphoric acid of NO. 4 is equal to the concentration of phosphoric acid of NO. 2. Although NO. 2 and NO. 4 have the same concentration of phosphoric acid, the amount of change in the etching rate of NO. 4 was smaller.

由以上所述可知，即使混合酸中所含的各成分(磷酸、醋酸、硝酸及水)的濃度稍有變動，只要使P/W莫耳比穩定，亦可與使水的濃度穩定的情況相比減少鎢的蝕刻率的變動量。因此，只要對基板W供給混合酸的時間為固定，便可在更換混合酸之前的整個期間，降低多塊基板W之間的鎢的蝕刻量的不均。 As described above, even if the concentration of each component (phosphoric acid, acetic acid, nitric acid, and water) contained in the mixed acid slightly changes, the P/W molar ratio can be stabilized, and the concentration of water can be stabilized. The amount of variation in the etching rate of tungsten is reduced. Therefore, if the time for supplying the mixed acid to the substrate W is fixed, the unevenness of the etching amount of tungsten between the plurality of substrates W can be reduced throughout the period before the replacement of the mixed acid.

以下，對使P/W莫耳比穩定的控制的一例進行說明。 Hereinafter, an example of control for stabilizing the P/W molar ratio will be described.

圖7是用以說明使P/W莫耳比穩定的控制的一例的流程圖。圖8A及圖8B是表示P/W莫耳比的時間性的變化的圖表。以下的各步驟是藉由控制裝置3對基板處理裝置1進行控制來執行。 FIG. 7 is a flowchart for explaining an example of control for stabilizing the P/W molar ratio. 8A and 8B are graphs showing temporal changes in P/W molar ratio. The following steps are performed by controlling the substrate processing apparatus 1 by the control device 3.

控制裝置3監視P/W莫耳比是否位於莫耳比上限值與莫耳比下限值之間。具體而言，控制裝置3判定P/W莫耳比是否未達莫耳比上限值(圖7的步驟S11)。若P/W莫耳比未達莫耳比上限值(圖7的步驟S11中為是(Yes))，則控制裝置3判定P/W莫耳比是否超過莫耳比下限值(圖7的步驟S12)。若P/W莫耳比超 過莫耳比下限值(圖7的步驟S12中為是(Yes))，則控制裝置3在規定時間經過之後，再次判定P/W莫耳比是否未達莫耳比上限值(返回至圖7的步驟S11)。 The control device 3 monitors whether the P/W molar ratio is between the upper molar ratio and the lower molar ratio. Specifically, the control device 3 determines whether the P/W molar ratio has not reached the upper limit of the molar ratio (step S11 of Fig. 7). If the P/W molar ratio does not reach the upper limit of the molar ratio (Yes in step S11 of FIG. 7), the control device 3 determines whether the P/W molar ratio exceeds the lower limit of the molar ratio (Fig. Step S12). If P/W Mobibi is super When the molar ratio lower limit value is exceeded (Yes in step S12 of FIG. 7), the control device 3 determines again whether the P/W molar ratio does not reach the upper limit of the molar ratio after the lapse of the predetermined time (return) Go to step S11) of FIG.

磷酸、醋酸、硝酸及水的沸點分別為213℃、118℃、82.6℃、100℃。若一面調節混合酸的溫度，一面使混合酸循環，則混合酸中所含的醋酸、硝酸及水會蒸發。混合酸中所含的磷酸雖亦稍有蒸發，但蒸發量少於其他成分，故而混合酸中所含的磷酸的量幾乎不變。因此，水的莫耳數伴隨著時間的經過而不斷下降，另一方面，磷酸的莫耳數則伴隨著時間的經過而不斷上升。因此，若不將水等其他成分液追加至混合酸中，則P/W莫耳比會隨著時間的經過而不斷上升。 The boiling points of phosphoric acid, acetic acid, nitric acid and water are 213 ° C, 118 ° C, 82.6 ° C, and 100 ° C, respectively. When the mixed acid is circulated while adjusting the temperature of the mixed acid, acetic acid, nitric acid, and water contained in the mixed acid evaporate. Although the phosphoric acid contained in the mixed acid is slightly evaporated, the amount of evaporation is less than that of the other components, so the amount of phosphoric acid contained in the mixed acid hardly changes. Therefore, the number of moles of water is continuously decreased with the passage of time. On the other hand, the number of moles of phosphoric acid increases with time. Therefore, if no other component liquid such as water is added to the mixed acid, the P/W molar ratio will increase as time passes.

當P/W莫耳比為莫耳比上限值以上時(圖7的步驟S11中為否(No))，控制裝置3判定在第2藥液處理槽6內的混合酸中是否浸漬有基板W(圖7的步驟S13)。當浸漬有基板W時(圖7的步驟S13中為是(Yes))，控制裝置3在規定時間經過後，再次判定在第2藥液處理槽6內的混合酸中是否浸漬有基板W(圖7的步驟S13)。當未浸漬基板W時(圖7的步驟S13中為否(No))，即，當第2藥液處理槽6中無基板W時，控制裝置3打開開關閥34(參照圖2)，使水補充噴嘴32噴出水，而使P/W莫耳比下降至莫耳比上限值與莫耳比下限值之間的值為止(圖7的步驟S14)。然後，控制裝置3再次判定P/W莫耳比是否未達莫耳比上限值(返回至圖7的步驟S11)。 When the P/W molar ratio is equal to or greater than the upper limit of the molar ratio (No in step S11 of FIG. 7), the control device 3 determines whether or not the mixed acid in the second chemical liquid processing tank 6 is immersed. Substrate W (step S13 of Fig. 7). When the substrate W is immersed (Yes in the step S13 of FIG. 7), the control device 3 determines again whether or not the substrate W is immersed in the mixed acid in the second chemical liquid processing tank 6 after a predetermined period of time has passed ( Step S13) of Fig. 7 . When the substrate W is not immersed (NO in step S13 of FIG. 7), that is, when the substrate W is not present in the second chemical liquid processing tank 6, the control device 3 opens the switching valve 34 (refer to FIG. 2) so that The water replenishing nozzle 32 ejects water to lower the P/W molar ratio to a value between the upper molar ratio and the lower molar ratio (step S14 of Fig. 7). Then, the control device 3 determines again whether the P/W molar ratio has not reached the upper limit of the molar ratio (return to step S11 of Fig. 7).

如圖8A所示，若P/W莫耳比達到莫耳比上限值，則將水加入至混合酸中，P/W莫耳比下降。若水的追加量適當，則P/W莫耳比減少至莫耳比上限值與莫耳比下限值之間的值為止。藉由水的追加而對P/W莫耳比進行調節之後，藉由醋酸、硝酸及水的蒸發，P/W莫耳比再次上升至莫耳比上限值為止。P/W莫耳比通常重複進行如上所述的變動。 As shown in Fig. 8A, if the P/W molar ratio reaches the upper limit of the molar ratio, water is added to the mixed acid, and the P/W molar ratio is lowered. When the amount of water added is appropriate, the P/W molar ratio is reduced to a value between the upper molar ratio and the lower molar ratio. After the P/W molar ratio was adjusted by the addition of water, the P/W molar ratio was again raised to the upper limit of the molar ratio by evaporation of acetic acid, nitric acid, and water. The P/W molar ratio is usually repeated as described above.

圖8B表示P/W莫耳比下降至莫耳比下限值以下為止時的示例。在所述基板W的處理的一例中，基板W是自第1沖洗處理槽5搬運至第2藥液處理槽6。因此，使附著有純水的基板W浸漬於第2藥液處理槽6內的混合酸中，從而第1沖洗處理槽5內的純水混入至第2藥液處理槽6中。在圖8B中，表示純水多次混入至混合酸中的示例。若混入至混合酸中的純水多，則存在P/W莫耳比下降至莫耳比下限值以下為止的情況。 FIG. 8B shows an example when the P/W molar ratio falls below the molar ratio lower limit value. In an example of the processing of the substrate W, the substrate W is transported from the first rinse processing tank 5 to the second chemical liquid processing tank 6. Therefore, the substrate W to which the pure water is adhered is immersed in the mixed acid in the second chemical liquid processing tank 6, and the pure water in the first rinse processing tank 5 is mixed into the second chemical liquid processing tank 6. In Fig. 8B, an example in which pure water is mixed into a mixed acid a plurality of times is shown. When the amount of pure water mixed in the mixed acid is large, there is a case where the P/W molar ratio falls below the lower limit of the molar ratio.

當P/W莫耳比為莫耳比下限值以下時(圖7的步驟S12中為否(No))，控制裝置3執行使基板W浸漬於第2藥液處理槽6內的混合酸中的新投入的禁止(圖7的步驟S15)，且令警報裝置47(參照圖4)產生通知第2藥液處理槽6中產生有異常的警報(圖7的步驟S16)。若新投入被禁止，則不會產生自第1沖洗處理槽5向第2藥液處理槽6的純水的混入，故而P/W莫耳比藉由混合酸的各成分的蒸發而不斷上升。 When the P/W molar ratio is equal to or less than the lower molar ratio (No in step S12 of FIG. 7), the control device 3 performs a mixed acid in which the substrate W is immersed in the second chemical liquid processing tank 6. The prohibition of the new input (step S15 of FIG. 7) causes the alarm device 47 (see FIG. 4) to generate an alarm notifying that an abnormality has occurred in the second chemical liquid processing tank 6 (step S16 of FIG. 7). When the new injection is prohibited, the pure water from the first rinse tank 5 to the second chemical treatment tank 6 is not mixed, so that the P/W molar ratio is continuously increased by evaporation of the components of the mixed acid. .

控制裝置3在禁止新投入後經過規定時間之後，判定P/W莫耳比是否超過莫耳比下限值(圖7的步驟S17)。若P/W莫 耳比為莫耳比下限值以下(圖7的步驟S17中為否(No))，則控制裝置3在規定時間經過之後，再次判定P/W莫耳比是否超過莫耳比下限值(圖7的步驟S17)。 The control device 3 determines whether the P/W molar ratio exceeds the molar ratio lower limit value after a predetermined time has elapsed after the new input is prohibited (step S17 of Fig. 7). If P/W Mo When the ear ratio is equal to or less than the lower molar ratio (NO in step S17 of FIG. 7), the control device 3 determines again whether the P/W molar ratio exceeds the lower limit of the molar ratio after the lapse of the predetermined time. (Step S17 of Fig. 7).

若P/W莫耳比超過莫耳比下限值(圖7的步驟S17中為是(Yes))，則控制裝置3解除新投入的禁止(圖7的步驟S18)，且令警報裝置47停止警報的產生(圖7的步驟S19)。然後，控制裝置3再次判定P/W莫耳比是否未達莫耳比上限值(返回至圖7的步驟S11)。 When the P/W molar ratio exceeds the lower molar ratio (Yes in step S17 of Fig. 7), the control device 3 releases the prohibition of the new input (step S18 of Fig. 7), and causes the alarm device 47. The generation of the alarm is stopped (step S19 of Fig. 7). Then, the control device 3 determines again whether the P/W molar ratio has not reached the upper limit of the molar ratio (return to step S11 of Fig. 7).

如以上所述在本實施形態中，若P/W莫耳比藉由水等的蒸發而上升，則在混合酸中加入水。由此，水的莫耳數增加。磷酸的莫耳數幾乎不變，另一方面，水的莫耳數增加，故而P/W莫耳比藉由水的補充而下降。由此，P/W莫耳比維持在莫耳比上限值與莫耳比下限值之間。並且，將P/W莫耳比經管理的混合酸供給至基板W，對作為金屬膜的一例的鎢的薄膜以穩定的蝕刻率進行蝕刻。 As described above, in the present embodiment, when the P/W molar ratio rises by evaporation of water or the like, water is added to the mixed acid. Thereby, the number of moles of water increases. The number of moles of phosphoric acid is almost constant. On the other hand, the number of moles of water increases, and thus the P/W molar ratio decreases by the replenishment of water. Thus, the P/W molar ratio is maintained between the upper molar ratio and the lower molar ratio. Further, the P/W molar is supplied to the substrate W in a controlled mixed acid, and the tungsten thin film which is an example of the metal film is etched at a stable etching rate.

為了降低在不同的時期所處理的多塊基板W之間的蝕刻量的不均，重要的是在更換蝕刻液之前的整個期間使蝕刻率穩定。根據本發明者等人的研究，已獲知若使P/W莫耳比穩定，可減小多塊基板W之間的蝕刻量的不均。如上所述，藉由使P/W莫耳比穩定，可減小多塊基板W之間的蝕刻量的不均。 In order to reduce the unevenness of the etching amount between the plurality of substrates W processed at different times, it is important to stabilize the etching rate for the entire period before the replacement of the etching liquid. According to the study by the inventors of the present invention, it has been found that if the P/W molar ratio is stabilized, the unevenness of the etching amount between the plurality of substrates W can be reduced. As described above, by stabilizing the P/W molar ratio, the unevenness of the etching amount between the plurality of substrates W can be reduced.

在本實施形態中，檢測混合酸中的磷酸的濃度及混合酸中的水的濃度，且根據該些濃度計算P/W莫耳比。例如，利用成 分濃度計37來檢測磷酸與水的質量比(例如，磷酸的質量濃度：水的質量濃度=75%：15%)。並且，利用莫耳比計算部52將磷酸與水的質量比除以各成分的分子量，計算P/W莫耳比(例如，(75%/98)：(15%/18)=(0.92：1))。 In the present embodiment, the concentration of phosphoric acid in the mixed acid and the concentration of water in the mixed acid are detected, and the P/W molar ratio is calculated based on the concentrations. For example, using The concentration meter 37 measures the mass ratio of phosphoric acid to water (for example, the mass concentration of phosphoric acid: mass concentration of water = 75%: 15%). Then, the mass ratio of phosphoric acid to water is divided by the molecular weight of each component by the molar ratio calculating unit 52, and the P/W molar ratio is calculated (for example, (75%/98): (15%/18) = (0.92: 1)).

然後，判定P/W莫耳比是否位於莫耳比上限值與莫耳比下限值之間。當P/W莫耳比為莫耳比上限值以上時，將水加入至混合酸中，P/W莫耳比下降至莫耳比上限值與莫耳比下限值之間的值為止。如上所述，由於監視P/W莫耳比自身，故而可以高精度管理P/W莫耳比，從而可降低蝕刻率的變動量。 Then, it is determined whether the P/W molar ratio is between the upper molar ratio and the lower molar ratio. When the P/W molar ratio is above the upper limit of the molar ratio, water is added to the mixed acid, and the P/W molar ratio is decreased to a value between the upper molar ratio and the lower molar ratio. until. As described above, since the P/W molar ratio is monitored, the P/W molar ratio can be managed with high precision, and the amount of fluctuation in the etching rate can be reduced.

在本實施形態中，使P/W莫耳比維持在莫耳比上限值與莫耳比下限值之間，另一方面，容許混合酸中的磷酸的濃度與混合酸中的水的濃度中的至少一者的變化。換言之，若預先使P/W莫耳比穩定，則即使磷酸及水的濃度稍有變動，亦可抑制蝕刻率的變動。因此，不對混合酸中的磷酸及水的濃度進行嚴格管理，便可降低多塊基板W之間的蝕刻量的不均。 In the present embodiment, the P/W molar ratio is maintained between the molar ratio upper limit value and the molar ratio lower limit value, and on the other hand, the concentration of phosphoric acid in the mixed acid and the water in the mixed acid are allowed. A change in at least one of the concentrations. In other words, if the P/W molar ratio is stabilized in advance, the fluctuation of the etching rate can be suppressed even if the concentration of phosphoric acid and water slightly changes. Therefore, the concentration of phosphoric acid and water in the mixed acid can be strictly controlled, and the unevenness of the etching amount between the plurality of substrates W can be reduced.

當因某種原因而將過量的水補充至混合酸中時，混合酸中的水的濃度會過度上升，P/W莫耳比會變為莫耳比下限值以下。在批次式的基板處理裝置1中，存在將經水濡濕的基板W浸漬於混合酸中，使得水混入至混合酸中的情況。此時，若附著於基板W上的水的量多，則P/W莫耳比會變為莫耳比下限值以下。P/W莫耳比變為莫耳比下限值以下是根據包含混合酸中的水的濃度在內的判定資訊來判定。 When an excessive amount of water is added to the mixed acid for some reason, the concentration of water in the mixed acid excessively rises, and the P/W molar ratio becomes equal to or lower than the lower molar ratio. In the batch type substrate processing apparatus 1, there is a case where the water-wet substrate W is immersed in a mixed acid so that water is mixed into the mixed acid. At this time, if the amount of water adhering to the substrate W is large, the P/W molar ratio becomes equal to or lower than the lower molar ratio. The P/W molar ratio becomes the molar ratio lower limit or less, and is determined based on the determination information including the concentration of water in the mixed acid.

在本實施形態中，若P/W莫耳比為莫耳比下限值以下，則暫時禁止將水補充及混入至混合酸中。在所述狀態下對混合酸進行加熱。由此，混合酸中所含的水等進行蒸發，水的濃度下降。伴隨於此，P/W莫耳比上升。並且，當P/W莫耳比超過莫耳比下限值時，解除水的補充及混入的禁止。以如上所述的方式，使P/W莫耳比維持在莫耳比上限值與莫耳比下限值之間。 In the present embodiment, when the P/W molar ratio is equal to or less than the lower molar ratio, it is temporarily prohibited to replenish and mix water into the mixed acid. The mixed acid is heated in the state described. Thereby, water or the like contained in the mixed acid is evaporated, and the concentration of water is lowered. Along with this, the P/W molar ratio increases. Further, when the P/W molar ratio exceeds the lower limit of the molar ratio, the replenishment of the water and the prohibition of the mixing are released. In the manner described above, the P/W molar ratio is maintained between the upper molar ratio and the lower molar ratio.

在本實施形態中，將除了磷酸、硝酸及水以外亦包含醋酸的混合酸供給至基板W。藉由硝酸對金屬膜的氧化而產生的氫氣會殘留在基板W的一部分表面上，從而抑制硝酸對金屬膜的氧化。因此，若氫氣位於基板W的表面，則蝕刻的均勻性下降。醋酸會促進氫氣自基板W剝離，結果促進硝酸對金屬膜的氧化。由此，可抑制或防止蝕刻的均勻性的下降。 In the present embodiment, a mixed acid containing acetic acid in addition to phosphoric acid, nitric acid, and water is supplied to the substrate W. Hydrogen generated by oxidation of the metal film by nitric acid remains on a part of the surface of the substrate W, thereby suppressing oxidation of the metal film by the nitric acid. Therefore, if hydrogen gas is located on the surface of the substrate W, the uniformity of etching is lowered. Acetic acid promotes the stripping of hydrogen from the substrate W, and as a result, promotes oxidation of the metal film by nitric acid. Thereby, it is possible to suppress or prevent a decrease in the uniformity of etching.

在本實施形態中，僅在未將混合酸供給至基板W的非供給期間，將水加入至混合酸中。若將水加入至混合酸中，則混合酸的均勻性會暫時下降。因此，藉由在對基板W供給混合酸的供給期間禁止水的補充，可防止將此種混合酸供給至基板W。 In the present embodiment, water is added to the mixed acid only during the non-supply period in which the mixed acid is not supplied to the substrate W. If water is added to the mixed acid, the uniformity of the mixed acid will temporarily decrease. Therefore, by disabling the replenishment of water during the supply of the mixed acid to the substrate W, it is possible to prevent such mixed acid from being supplied to the substrate W.

第2實施形態 Second embodiment

圖9是表示本發明的第2實施形態的P/W莫耳比的時間性的變化及混合酸中的水的濃度的時間性的變化的圖表。以下，參照圖4及圖9。 FIG. 9 is a graph showing temporal changes in the P/W molar ratio and temporal changes in the concentration of water in the mixed acid according to the second embodiment of the present invention. Hereinafter, reference is made to FIGS. 4 and 9.

如圖4所示，第2實施形態是在莫耳比調節部51中，取代莫耳比計算部52及莫耳比判定部53，或除了莫耳比計算部 52及莫耳比判定部53以外，包括對混合酸中的水的濃度進行控制的水濃度控制部56。 As shown in FIG. 4, in the second embodiment, in place of the molar ratio calculating unit 52 and the molar ratio determining unit 53, or in addition to the molar ratio calculating unit, in the molar ratio adjusting unit 51. The 52 and the molar ratio determining unit 53 include a water concentration control unit 56 that controls the concentration of water in the mixed acid.

水濃度控制部56進行反饋(feedback)控制，即，根據成分濃度計37的檢測值，變更自水補充噴嘴32(參照圖2)噴出的水的量。由此，如圖10所示，使混合酸中的水的濃度接近於伴隨著時間的經過而連續地增加的水濃度目標值。水濃度目標值記憶於輔助記憶裝置43中。 The water concentration control unit 56 performs feedback control, that is, changes the amount of water ejected from the water replenishing nozzle 32 (see FIG. 2) based on the detected value of the component concentration meter 37. Thereby, as shown in FIG. 10, the concentration of water in the mixed acid is made close to the water concentration target value which continuously increases with the passage of time. The water concentration target value is stored in the auxiliary memory device 43.

在將混合酸的溫度調節為固定的期間，若不進行水等成分液的補充或混入，則混合酸中的磷酸的濃度及莫耳數通常以大致固定的比例持續上升。與此相反，若不進行成分液的補充等，則混合酸中的水的濃度及莫耳數通常以大致固定的比例持續下降。此時，即使不監視P/W莫耳比自身，只要監視磷酸及水中的至少一者的濃度，亦可間接地監視P/W莫耳比。 When the temperature of the mixed acid is adjusted to be constant, if the component liquid such as water is not replenished or mixed, the concentration of the phosphoric acid and the number of moles in the mixed acid are generally increased in a substantially constant ratio. On the other hand, if the component liquid is not replenished or the like, the concentration of water and the number of moles in the mixed acid are generally continuously decreased in a substantially constant ratio. At this time, even if the P/W molar ratio is not monitored, the P/W molar ratio can be indirectly monitored by monitoring the concentration of at least one of phosphoric acid and water.

在本實施形態中，對混合酸中的水的濃度進行檢測。由此，可間接地監視P/W莫耳比。此外，所檢測出的水的濃度接近於水濃度目標值。水濃度目標值是以伴隨著時間的經過而增加的方式設定。其原因在於，在對混合酸進行加熱的期間，硝酸等水以外的成分亦會蒸發，故而即便使水的濃度維持固定，P/W莫耳比亦會持續上升。此外，水濃度目標值的增加方式是以使P/W莫耳比維持在莫耳比上限值與莫耳比下限值之間的方式設定。因此，藉由使混合酸中的水的濃度接近於水濃度目標值，可抑制蝕刻率的變動。 In the present embodiment, the concentration of water in the mixed acid is detected. Thereby, the P/W molar ratio can be monitored indirectly. Further, the detected concentration of water is close to the water concentration target value. The water concentration target value is set in such a manner as to increase with the passage of time. This is because the components other than water such as nitric acid also evaporate during the heating of the mixed acid, so that the P/W molar ratio continues to increase even if the concentration of water is kept constant. Further, the water concentration target value is increased in such a manner that the P/W molar ratio is maintained between the upper molar ratio and the lower molar ratio. Therefore, by making the concentration of water in the mixed acid close to the water concentration target value, variation in the etching rate can be suppressed.

第3實施形態 Third embodiment

圖10是表示本發明的第3實施形態的P/W莫耳比的時間性的變化、將水加入至混合酸中的時間以及所加入的水的量的圖表。以下，參照圖4及圖10。 Fig. 10 is a graph showing the temporal change of the P/W molar ratio in the third embodiment of the present invention, the time during which water is added to the mixed acid, and the amount of water to be added. Hereinafter, reference is made to FIGS. 4 and 10.

如圖4所示，第3實施形態是在莫耳比調節部51中，取代莫耳比計算部52及莫耳比判定部53，或除了莫耳比計算部52及莫耳比判定部53以外，包含在指定時間將指定量的水加入至混合酸中的定時定量水補充部57。在第3實施形態中，亦可省略成分濃度計37(參照圖2)。 As shown in FIG. 4, in the third embodiment, the Mohr ratio adjusting unit 51 is substituted for the Mohr ratio calculating unit 52 and the Mohr ratio determining unit 53, or the Mohr ratio calculating unit 52 and the Mohr ratio determining unit 53. In addition, a predetermined amount of water replenishing portion 57 that adds a specified amount of water to the mixed acid at a specified time is included. In the third embodiment, the component concentration meter 37 (see Fig. 2) may be omitted.

指定時間及指定量記憶於輔助記憶裝置43中。指定時間及指定量既可包含於配方中，亦可藉由主電腦HC或操作者而輸入至控制裝置3。圖10表示在多個指定時間(即指定時間T1、T2、T3)將水加入至混合酸中的示例。此時，指定量(即指定量V1、V2、V3)，即，加入至混合酸中的水的量既可伴隨著時間的經過而連續地或階段性地增加，亦可為固定。 The specified time and the specified amount are memorized in the auxiliary memory device 43. The specified time and the specified amount may be included in the recipe or may be input to the control device 3 by the host computer HC or the operator. 10 shows a plurality of specified time (i.e., the specified time T 1, T 2, T 3 ) adding water to the mixed acid of example. At this time, the specified amount (ie, the specified amount V 1 , V 2 , V 3 ), that is, the amount of water added to the mixed acid may be continuously or stepwisely increased with time, or may be fixed. .

在將混合酸的溫度調節為固定的期間，若不進行水等成分液的補充或混入，則混合酸中的磷酸的濃度及莫耳數通常以大致固定的比例持續上升，混合酸中的水的濃度及莫耳數通常以大致固定的比例持續下降。此時，即使不實際測定在某個時間的磷酸及水的濃度等，亦可預測該些濃度。因此，亦可預測在某個時間的P/W莫耳比。 When the temperature of the mixed acid is adjusted to be constant, if the component liquid such as water is not replenished or mixed, the concentration of the phosphoric acid and the number of moles in the mixed acid are generally increased in a substantially constant ratio, and the water in the acid is mixed. The concentration and molar number generally decrease continuously in a substantially fixed ratio. At this time, even if the concentration of phosphoric acid and water at a certain time or the like is not actually measured, the concentrations can be predicted. Therefore, the P/W molar ratio at a certain time can also be predicted.

在本實施形態中，是將純水在指定時間以指定量自動加 入至混合酸中。指定量是以使在指定時間的P/W莫耳比維持在莫耳比上限值與莫耳比下限值之間的方式設定。或者，指定時間是以當將指定量的水加入至混合酸中時，使P/W莫耳比維持在莫耳比上限值與莫耳比下限值之間的方式設定。由此，不實際測定水的濃度等，便可抑制蝕刻率的變動。 In this embodiment, pure water is automatically added at a specified time by a specified amount. Into the mixed acid. The specified amount is set such that the P/W molar ratio at the specified time is maintained between the upper molar ratio and the lower molar ratio. Alternatively, the specified time is set such that the P/W molar ratio is maintained between the upper molar ratio and the lower molar ratio when a specified amount of water is added to the mixed acid. Thereby, the fluctuation of the etching rate can be suppressed without actually measuring the concentration of water or the like.

第4實施形態 Fourth embodiment

圖11是表示本發明的第4實施形態的基板處理裝置1的概略構成的示意圖。對與所述圖1~圖10所示的構成相同的構成，標註與圖1等相同的參照符號並省略其說明。 FIG. 11 is a schematic diagram showing a schematic configuration of a substrate processing apparatus 1 according to a fourth embodiment of the present invention. The same components as those in the above-described configurations shown in FIG. 1 to FIG. 10 are denoted by the same reference numerals as those in FIG. 1 and the description thereof will be omitted.

第4實施形態的基板處理裝置1是對基板W一片片地進行處理的單片式的裝置。基板處理裝置1的處理單元2包括：自旋夾盤61，一面水平地保持基板W，一面使所述基板W圍繞著穿過基板W的中央部的鉛垂的旋轉軸線A1而旋轉；沖洗液噴嘴62，朝向保持於自旋夾盤61上的基板W噴出沖洗液；以及混合酸噴嘴22，朝向保持於自旋夾盤61上的基板W自混合酸噴出口22a噴出混合酸。 The substrate processing apparatus 1 of the fourth embodiment is a one-piece apparatus that processes the substrate W piece by piece. The processing unit 2 of the substrate processing apparatus 1 includes a spin chuck 61 that horizontally holds the substrate W while rotating the substrate W around a vertical rotation axis A1 passing through a central portion of the substrate W; The nozzle 62 ejects the rinse liquid toward the substrate W held on the spin chuck 61, and the mixed acid nozzle 22 ejects the mixed acid from the mixed acid discharge port 22a toward the substrate W held on the spin chuck 61.

沖洗液噴嘴62與插裝有沖洗液閥64的沖洗液配管63連接。處理單元2亦可包括噴嘴移動單元，所述噴嘴移動單元使沖洗液噴嘴62在處理位置與退避位置之間水平移動，所述處理位置是將自沖洗液噴嘴62噴出的沖洗液供給至基板W的位置，所述退避位置是沖洗液噴嘴62在俯視時遠離基板W的位置。 The rinse liquid nozzle 62 is connected to the rinse liquid pipe 63 into which the rinse liquid valve 64 is inserted. The processing unit 2 may further include a nozzle moving unit that horizontally moves the rinse liquid nozzle 62 between the processing position and the retracted position, the processing position is to supply the flushing liquid sprayed from the rinse liquid nozzle 62 to the substrate W The position of the retracted position is a position at which the rinsing liquid nozzle 62 is away from the substrate W in plan view.

若打開沖洗液閥64，則將沖洗液自沖洗液配管63供給 至沖洗液噴嘴62，且自沖洗液噴嘴62噴出。沖洗液例如為純水。沖洗液並不限於純水，亦可為碳酸水、電解離子水、氫水、臭氧水及稀釋濃度(例如，10ppm~100ppm程度)的鹽酸水中的任一者。 When the rinse liquid valve 64 is opened, the rinse liquid is supplied from the rinse liquid pipe 63. The rinse liquid nozzle 62 is sprayed from the rinse liquid nozzle 62. The rinsing liquid is, for example, pure water. The rinsing liquid is not limited to pure water, and may be any of carbonated water, electrolytic ionized water, hydrogen water, ozone water, and hydrochloric acid water having a diluted concentration (for example, about 10 ppm to 100 ppm).

混合酸噴嘴22與插裝有噴出閥66的供給配管65連接。對混合酸噴嘴22的藥液的供給及供給停止是藉由噴出閥66來切換。處理單元2包括噴嘴移動單元67，所述噴嘴移動單元67使混合酸噴嘴22在處理位置與退避位置之間水平移動，所述處理位置是將自混合酸噴嘴22噴出的藥液供給至基板W的上表面的位置，所述退避位置是混合酸噴嘴22在俯視時遠離基板W的位置。 The mixed acid nozzle 22 is connected to a supply pipe 65 into which the discharge valve 66 is inserted. The supply and supply stop of the chemical solution to the mixed acid nozzle 22 are switched by the discharge valve 66. The processing unit 2 includes a nozzle moving unit 67 that horizontally moves the mixed acid nozzle 22 between the processing position and the retracted position, which is to supply the liquid medicine ejected from the mixed acid nozzle 22 to the substrate W. The position of the upper surface, which is the position where the mixed acid nozzle 22 is away from the substrate W in plan view.

循環系統21包括作為混合酸存積容器的另一例的槽罐(tank)68，來取代第2藥液處理槽6(參照圖2)。槽罐68內的混合酸在由循環配管23及槽罐68形成的循環路徑中循環。將混合酸導引至混合酸噴嘴22的供給配管65與循環配管23連接。自水補充噴嘴32的水噴出口32a噴出的純水例如被供給至槽罐68的內部。由此，可使P/W莫耳比維持在莫耳比上限值與莫耳比下限值之間，從而可降低多塊基板W之間的蝕刻量的不均。 The circulation system 21 includes a tank 68 as another example of a mixed acid storage container instead of the second chemical liquid processing tank 6 (see FIG. 2). The mixed acid in the tank 68 circulates in a circulation path formed by the circulation pipe 23 and the tank 68. The supply pipe 65 that guides the mixed acid to the mixed acid nozzle 22 is connected to the circulation pipe 23. The pure water sprayed from the water discharge port 32a of the water supply nozzle 32 is supplied to the inside of the tank 68, for example. Thereby, the P/W molar ratio can be maintained between the upper limit of the molar ratio and the lower limit of the molar ratio, so that the unevenness of the etching amount between the plurality of substrates W can be reduced.

其他實施形態 Other embodiments

本發明並不限定於所述實施形態的內容，而可進行各種變更。 The present invention is not limited to the contents of the above embodiments, and various modifications can be made.

例如，藉由混合酸而蝕刻的金屬膜並不限於鎢的薄膜，亦可為鋁等其他金屬的薄膜。 For example, a metal film etched by mixing an acid is not limited to a film of tungsten, and may be a film of another metal such as aluminum.

混合酸中所含的醋酸主要僅是提高蝕刻的面內均勻 性，故只要容許面內均勻性的下降，則亦可使混合酸中不含醋酸。 The acetic acid contained in the mixed acid is mainly only to improve the in-plane uniformity of the etching. Since the solubility in the in-plane uniformity is allowed to be lowered, acetic acid may not be contained in the mixed acid.

亦可除了水以外，或取代水，將硝酸等其他成分液加入至混合酸中。此時，不僅使P/W莫耳比穩定，亦可使混合酸中所含的各成分的濃度穩定。 Other components such as nitric acid may be added to the mixed acid in addition to or in place of water. At this time, not only the P/W molar ratio is stabilized, but also the concentration of each component contained in the mixed acid can be stabilized.

對混合酸的水的補充，既可僅在將混合酸供給至基板W的供給期間進行，亦可在供給期間及非供給期間兩者內進行。 The replenishment of the mixed acid water may be performed only during the supply period in which the mixed acid is supplied to the substrate W, or may be performed in both the supply period and the non-supply period.

若使P/W質量比，即，使混合酸中的磷酸的質量濃度相對於混合酸中的水的質量濃度的比率穩定，則會使P/W莫耳比穩定，故而亦可使P/W質量比維持在質量比上限值(與後述濃度比上限值為同義)與質量比下限值(與後述濃度比下限值為同義)之間。 When the P/W mass ratio is stabilized, that is, the ratio of the mass concentration of phosphoric acid in the mixed acid to the mass concentration of water in the mixed acid is stabilized, the P/W molar ratio is stabilized, so that P/ can also be made. The W mass ratio is maintained between the upper limit of the mass ratio (synonymous with the upper limit of the concentration ratio described later) and the lower limit of the mass ratio (synonymous with the lower limit of the concentration ratio described later).

所述控制例如可藉由圖12所示的控制裝置103來實現。圖12是表示控制裝置103的功能方塊圖的方塊圖。濃度比調節部151、濃度比計算部152、濃度比判定部153、水補充部154及水補充禁止部155是藉由具備圖3所示的電腦主體3a及周邊裝置3b等硬體構成的控制裝置103來實現。 The control can be implemented, for example, by the control device 103 shown in FIG. FIG. 12 is a block diagram showing a functional block diagram of the control device 103. The concentration ratio adjusting unit 151, the concentration ratio calculating unit 152, the concentration ratio determining unit 153, the water replenishing unit 154, and the water replenishing prohibiting unit 155 are controlled by a hardware such as the computer main body 3a and the peripheral device 3b shown in Fig. 3 . Device 103 is implemented.

在控制裝置103中，利用濃度比計算部152，來計算P/W質量濃度比(自成分濃度計37輸出的磷酸的質量濃度與水的質量濃度的比率)作為P/W質量比。輔助記憶裝置143記憶有濃度比上限值(將以上利用圖4而描述的莫耳比上限值換算成質量濃度值的值)。同樣地，輔助記憶裝置143記憶有濃度比下限值(將以上利用圖4而描述的莫耳比下限值換算成質量濃度值的值)。 In the control device 103, the P/W mass concentration ratio (ratio of the mass concentration of phosphoric acid output from the component concentration meter 37 to the mass concentration of water) is calculated by the concentration ratio calculating unit 152 as the P/W mass ratio. The auxiliary memory device 143 stores a concentration ratio upper limit value (a value obtained by converting the above-described molar ratio upper limit value described using FIG. 4 into a mass concentration value). Similarly, the auxiliary memory device 143 stores a concentration ratio lower limit value (a value obtained by converting the molar ratio lower limit value described above with reference to FIG. 4 into a mass concentration value).

濃度比判定部153按照與以上利用圖8而描述的處理流程同樣的處理流程，判定濃度比計算部152所計算出的P/W質量濃度比是否位於濃度比上限值與濃度比下限值之間。當P/W質量濃度比不在濃度比上限值與濃度比下限值之間時，按照與以上利用圖7而描述的處理流程同樣的處理流程，執行水補充部154的水補充(圖7中的步驟S14)或水補充禁止部155的警告(alarm)產生(圖7中的步驟S16)等的控制。 The concentration ratio determination unit 153 determines whether the P/W mass concentration ratio calculated by the concentration ratio calculation unit 152 is located at the concentration ratio upper limit value and the concentration ratio lower limit value in the same processing flow as that described above with reference to Fig. 8 . between. When the P/W mass concentration ratio is not between the concentration ratio upper limit value and the concentration ratio lower limit value, the water replenishment portion 154 is replenished according to the same processing flow as that described above with reference to Fig. 7 (Fig. 7). The control of the step S14) or the water replenishing prohibition unit 155 is generated (alarm in step S16 in Fig. 7).

在第1實施形態中，亦可省略第1藥液處理槽4及第1沖洗處理槽5。 In the first embodiment, the first chemical liquid processing tank 4 and the first rinse processing tank 5 may be omitted.

在第4實施形態中，亦可使混合酸不循環而供給至基板。 In the fourth embodiment, the mixed acid may be supplied to the substrate without circulating.

亦可將所述全部構成中的兩個以上加以組合。亦可將所述全部步驟中的兩個以上加以組合。 Two or more of the above configurations may be combined. It is also possible to combine two or more of all the above steps.

本申請案對應於2017年3月27日向日本專利局提交的特願2017-061394號，所述申請案的所有揭示藉由引用而編入於此文。 The present application corresponds to Japanese Patent Application No. 2017-061394, filed on Jan. 27,,,,,,,,,,,,,

已對本發明的實施形態進行詳細說明，但該些實施形態僅為用以闡明本發明的技術內容的具體例，本發明不應限定於該些具體例來解釋，本發明的精神及範圍僅藉由隨附的申請專利範圍來限定。 The embodiments of the present invention have been described in detail, but the embodiments are merely specific examples for illustrating the technical contents of the present invention. The present invention is not limited to the specific examples, and the spirit and scope of the present invention are only It is defined by the scope of the attached patent application.

Claims (16)

一種基板處理方法，藉由將包含磷酸、硝酸及水的混合液的混合酸供給至露出有金屬膜的基板，而對所述金屬膜進行蝕刻，所述基板處理方法包括： 混合酸加熱步驟，在供給至所述基板之前對所述混合酸進行加熱； 莫耳比調節步驟，包括水補充步驟，使P/W莫耳比維持在莫耳比上限值與莫耳比下限值之間，所述水補充步驟是藉由將水加入至在所述混合酸加熱步驟中經加熱的所述混合酸中，而使所述P/W莫耳比下降，所述P/W莫耳比表示所述混合酸中所含的磷酸的莫耳數相對於所述混合酸中所含的水的莫耳數的比率；以及 蝕刻步驟，藉由將在所述水補充步驟中已加入水的所述混合酸供給至所述基板，而對所述基板上的所述金屬膜進行蝕刻。A substrate processing method for etching a metal film by supplying a mixed acid containing a mixed solution of phosphoric acid, nitric acid, and water to a substrate on which a metal film is exposed, the substrate processing method comprising: a mixed acid heating step, Heating the mixed acid before being supplied to the substrate; a molar ratio adjusting step including a water replenishing step to maintain the P/W molar ratio between the upper molar ratio and the lower molar ratio The water replenishing step of lowering the P/W molar ratio by adding water to the mixed acid heated in the mixed acid heating step, the P/W molar ratio a ratio indicating a molar number of phosphoric acid contained in the mixed acid to a molar number of water contained in the mixed acid; and an etching step by which water has been added in the water replenishing step The mixed acid is supplied to the substrate, and the metal film on the substrate is etched. 如申請專利範圍第1項所述的基板處理方法，其中進而包括： 成分濃度檢測步驟，檢測所述混合酸中的磷酸的濃度及所述混合酸中的水的濃度； 莫耳比計算步驟，根據在所述成分濃度檢測步驟中檢測出的檢測值，計算所述P/W莫耳比；以及 莫耳比判定步驟，判定在所述莫耳比計算步驟中所計算出的所述P/W莫耳比是否超過所述莫耳比下限值，且未達所述莫耳比上限值。The substrate processing method according to claim 1, further comprising: a component concentration detecting step of detecting a concentration of phosphoric acid in the mixed acid and a concentration of water in the mixed acid; a molar ratio calculating step, Calculating the P/W molar ratio according to the detected value detected in the component concentration detecting step; and a molar ratio determining step of determining the P/ calculated in the molar ratio calculating step Whether the W molar ratio exceeds the lower molar ratio and does not reach the upper molar ratio. 如申請專利範圍第1項所述的基板處理方法，其中 所述基板處理方法進而包括檢測所述混合酸中的水的濃度的成分濃度檢測步驟， 所述水補充步驟包括水濃度控制步驟，所述水濃度控制步驟是藉由將水加入至在所述混合酸加熱步驟中經加熱的所述混合酸中，而使在所述成分濃度檢測步驟中檢測的水的濃度接近於伴隨著時間的經過而增加的水濃度目標值，使所述P/W莫耳比維持在所述莫耳比上限值與所述莫耳比下限值之間。The substrate processing method according to claim 1, wherein the substrate processing method further comprises a component concentration detecting step of detecting a concentration of water in the mixed acid, wherein the water replenishing step includes a water concentration controlling step, The water concentration control step is such that the concentration of water detected in the component concentration detecting step is close to the accompanying time by adding water to the mixed acid heated in the mixed acid heating step. The increased water concentration target value is passed such that the P/W molar ratio is maintained between the upper molar ratio and the lower molar ratio. 如申請專利範圍第1項所述的基板處理方法，其中所述水補充步驟包括定時定量水補充步驟，所述定時定量水補充步驟是藉由在指定時間將指定量的水加入至在所述混合酸加熱步驟中經加熱的所述混合酸中，而使所述P/W莫耳比維持在所述莫耳比上限值與所述莫耳比下限值之間。The substrate processing method of claim 1, wherein the water replenishing step comprises a timed quantitative water replenishing step of adding a specified amount of water to the The mixed acid in the heated acid heating step is mixed to maintain the P/W molar ratio between the upper molar ratio and the lower molar ratio. 如申請專利範圍第1項至第4項中任一項所述的基板處理方法，其中所述莫耳比調節步驟是如下步驟：一面容許所述混合酸中的磷酸的濃度與所述混合酸中的水的濃度中的至少一者的變化，一面使所述P/W莫耳比維持在所述莫耳比上限值與所述莫耳比下限值之間。The substrate processing method according to any one of claims 1 to 4, wherein the molar ratio adjusting step is a step of allowing a concentration of phosphoric acid in the mixed acid to be mixed with the mixed acid The P/W molar ratio is maintained between the molar ratio upper limit value and the molar ratio lower limit value while at least one of the concentration of water in the medium is changed. 如申請專利範圍第1項至第4項中任一項所述的基板處理方法，其中 所述基板處理方法進而包括檢測所述混合酸中的磷酸的濃度及所述混合酸中的水的濃度中的至少一者的成分濃度檢測步驟， 所述莫耳比調節步驟進而包括水補充禁止步驟，所述水補充禁止步驟是藉由一面禁止向所述混合酸中供給水，一面對所述混合酸進行加熱，而使所述P/W莫耳比自所述莫耳比下限值以下的值上升至所述莫耳比上限值與莫耳比下限值之間的值為止。The substrate processing method according to any one of claims 1 to 4, wherein the substrate processing method further comprises detecting a concentration of phosphoric acid in the mixed acid and a concentration of water in the mixed acid. a component concentration detecting step of at least one of the steps, the mol ratio adjusting step further comprising a water replenishing prohibiting step of inhibiting supply of water to the mixed acid while facing the The mixed acid is heated, and the P/W molar ratio is increased from a value equal to or lower than the lower molar ratio to a value between the molar ratio upper limit value and the molar ratio lower limit value. 如申請專利範圍第1項至第4項中任一項所述的基板處理方法，其中所述混合酸進而包含醋酸。The substrate processing method according to any one of claims 1 to 4, wherein the mixed acid further comprises acetic acid. 如申請專利範圍第1項至第4項中任一項所述的基板處理方法，其中所述水補充步驟包括非處理中水補充步驟，所述非處理中水補充步驟是藉由僅在未對所述基板供給所述混合酸的期間，將水加入至所述混合酸中，而使所述P/W莫耳比下降。The substrate processing method according to any one of claims 1 to 4, wherein the water replenishing step includes a non-treatment water replenishing step, and the non-processing water replenishing step is by only While the mixed acid is supplied to the substrate, water is added to the mixed acid to lower the P/W molar ratio. 一種基板處理裝置，包括： 加熱器，對包含磷酸、硝酸及水的混合液的混合酸進行加熱； 水噴出口，噴出要加入至所述混合酸中的水； 混合酸噴出口，藉由噴出所述混合酸，而對露出有金屬膜的基板供給所述混合酸，而對所述金屬膜進行蝕刻；以及 控制裝置，對基板處理裝置進行控制；並且 所述控制裝置執行： 混合酸加熱步驟，在供給至所述基板之前，使所述加熱器對所述混合酸進行加熱； 莫耳比調節步驟，包括水補充步驟，使P/W莫耳比維持在莫耳比上限值與莫耳比下限值之間，所述水補充步驟是藉由使所述水噴出口將水加入至在所述混合酸加熱步驟中經加熱的所述混合酸中，而使所述P/W莫耳比下降，所述P/W莫耳比表示所述混合酸中所含的磷酸的莫耳數相對於所述混合酸中所含的水的莫耳數的比率；以及 蝕刻步驟，藉由使所述混合酸噴出口將在所述水補充步驟中已加入水的所述混合酸供給至所述基板，而對所述基板上的所述金屬膜進行蝕刻。A substrate processing apparatus comprising: a heater for heating a mixed acid containing a mixed solution of phosphoric acid, nitric acid and water; a water discharge port for discharging water to be added to the mixed acid; and a mixed acid discharge port for ejecting Mixing the acid, supplying the mixed acid to the substrate on which the metal film is exposed, and etching the metal film; and controlling the device to control the substrate processing device; and the control device performs: a mixed acid heating step The heater is heated to the mixed acid before being supplied to the substrate; the molar ratio adjusting step includes a water replenishing step to maintain the P/W molar ratio at the upper limit of the molar ratio and Mo Between the ear ratio and the lower limit, the water replenishing step is performed by adding water to the mixed acid heated in the mixed acid heating step by causing the water discharge port to make the P/W The molar ratio is decreased, and the P/W molar ratio represents a ratio of the number of moles of phosphoric acid contained in the mixed acid to the number of moles of water contained in the mixed acid; and an etching step By making the mixed acid squirt The water in the water has been added supplementary step of supplying the mixed acid to the substrate, and the metal film on the substrate is etched. 如申請專利範圍第9項所述的基板處理裝置，其中 所述基板處理裝置進而包括： 成分濃度計，檢測所述混合酸中的磷酸的濃度及所述混合酸中的水的濃度； 莫耳比計算部，根據所述成分濃度計的檢測值，計算所述P/W莫耳比；以及 莫耳比判定部，判定經所述莫耳比計算部計算出的所述P/W莫耳比是否超過所述莫耳比下限值，且未達所述莫耳比上限值；並且 所述控制裝置進而執行： 成分濃度檢測步驟，使所述成分濃度計檢測所述混合酸中的磷酸的濃度及所述混合酸中的水的濃度； 莫耳比計算步驟，根據在所述成分濃度檢測步驟中檢測出的檢測值，使所述莫耳比計算部計算所述P/W莫耳比；以及 莫耳比判定步驟，使所述莫耳比判定部判定在所述莫耳比計算步驟中所計算出的所述P/W莫耳比是否超過所述莫耳比下限值，且未達所述莫耳比上限值。The substrate processing apparatus according to claim 9, wherein the substrate processing apparatus further comprises: a component concentration meter that detects a concentration of phosphoric acid in the mixed acid and a concentration of water in the mixed acid; a ratio calculating unit that calculates the P/W molar ratio based on the detected value of the component concentration meter; and a molar ratio determining unit that determines the P/W molar calculated by the molar ratio calculating unit Whether the ratio exceeds the lower molar ratio and does not reach the upper limit of the molar ratio; and the control device further performs: a component concentration detecting step of causing the component concentration meter to detect the mixed acid a concentration of phosphoric acid and a concentration of water in the mixed acid; a molar ratio calculating step of causing the molar ratio calculating unit to calculate the P/W according to the detected value detected in the component concentration detecting step An ear ratio; and a molar ratio determining step, wherein the molar ratio determining unit determines whether the P/W molar ratio calculated in the molar ratio calculating step exceeds the Mohr ratio lower limit value And the molar ratio upper limit is not reached. 如申請專利範圍第9項所述的基板處理裝置，其中 所述基板處理裝置進而包括檢測所述混合酸中的水的濃度的成分濃度計， 所述控制裝置進而執行使所述成分濃度計檢測所述混合酸中的水的濃度的成分濃度檢測步驟， 所述水補充步驟包括水濃度控制步驟，所述水濃度控制步驟是藉由使所述水噴出口將水加入至在所述混合酸加熱步驟中經加熱的所述混合酸中，而使在所述成分濃度檢測步驟中檢測的水的濃度接近於伴隨著時間的經過而增加的水濃度目標值，使所述P/W莫耳比維持在所述莫耳比上限值與所述莫耳比下限值之間。The substrate processing apparatus according to claim 9, wherein the substrate processing apparatus further includes a component concentration meter that detects a concentration of water in the mixed acid, and the control device further performs detection of the component concentration meter a component concentration detecting step of the concentration of water in the mixed acid, the water replenishing step comprising a water concentration controlling step of adding water to the mixed acid by causing the water spout And heating the mixed acid in the heating step, so that the concentration of the water detected in the component concentration detecting step is close to a water concentration target value which increases with the passage of time, so that the P/W molar is made. The ratio is maintained between the upper molar ratio and the lower molar ratio. 如申請專利範圍第9項所述的基板處理裝置，其中所述水補充步驟包括定時定量水補充步驟，所述定時定量水補充步驟是藉由在指定時間使所述水噴出口將指定量的水加入至在所述混合酸加熱步驟中經加熱的所述混合酸中，而使所述P/W莫耳比維持在所述莫耳比上限值與所述莫耳比下限值之間。The substrate processing apparatus of claim 9, wherein the water replenishing step comprises a timed quantitative water replenishing step of causing the water spout to have a specified amount by a specified time Water is added to the mixed acid heated in the mixed acid heating step, and the P/W molar ratio is maintained at the upper molar ratio and the lower molar ratio between. 如申請專利範圍第9項至第12項中任一項所述的基板處理裝置，其中所述莫耳比調節步驟是如下的步驟：一面容許所述混合酸中的磷酸的濃度及所述混合酸中的水的濃度中的至少一者的變化，一面使所述P/W莫耳比維持在所述莫耳比上限值與所述莫耳比下限值之間。The substrate processing apparatus according to any one of claims 9 to 12, wherein the molar ratio adjusting step is a step of allowing a concentration of the phosphoric acid in the mixed acid and the mixing The change in at least one of the concentrations of water in the acid maintains the P/W molar ratio between the upper molar ratio and the lower molar ratio. 如申請專利範圍第9項至第12項中任一項所述的基板處理裝置，其中 所述基板處理裝置進而包括檢測所述混合酸中的磷酸的濃度及所述混合酸中的水的濃度中的至少一者的成分濃度計， 所述莫耳比調節步驟進而包括水補充禁止步驟，所述水補充禁止步驟是藉由一面禁止對所述混合酸供給水，一面使所述加熱器對所述混合酸進行加熱，而使所述P/W莫耳比自所述莫耳比下限值以下的值上升至所述莫耳比上限值與莫耳比下限值之間的值為止。The substrate processing apparatus according to any one of claims 9 to 12, wherein the substrate processing apparatus further comprises detecting a concentration of phosphoric acid in the mixed acid and a concentration of water in the mixed acid. In the component concentration meter of at least one of the components, the molar ratio adjusting step further includes a water replenishing prohibiting step of disabling the supply of water to the mixed acid while allowing the heater pair Heating the mixed acid to increase the P/W molar ratio from a value below the lower molar ratio to a value between the upper molar ratio and the lower molar ratio until. 如申請專利範圍第9項至第12項中任一項所述的基板處理裝置，其中所述混合酸進而包含醋酸。The substrate processing apparatus according to any one of claims 9 to 12, wherein the mixed acid further contains acetic acid. 如申請專利範圍第9項至第12項中任一項所述的基板處理裝置，其中所述水補充步驟包括非處理中水補充步驟，所述非處理中水補充步驟是藉由僅在未對所述基板供給所述混合酸的期間內，使所述水噴出口將水加入至所述混合酸中，而使所述P/W莫耳比下降。The substrate processing apparatus according to any one of claims 9 to 12, wherein the water replenishing step includes a non-treatment water replenishing step, and the non-processing water replenishing step is by only During the supply of the mixed acid to the substrate, the water discharge port is caused to add water to the mixed acid to lower the P/W molar ratio.
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