200830391 九、發明說明 【發明所屬之技術領域】 本發明，係有關於在將被處理基板浸漬於洗淨液中的 同時，在洗淨液中使超音波產生，而將附著在被處理基板 上之粒子（髒污等）除去的基板洗淨方法以及基板洗淨裝 置，特別是，係有關於能夠在大幅抑制配線圖案之損傷的 同時，而以高除去效率來將粒子從被處理基板上除去的基 板洗淨方法以及基板洗淨裝置。 又，本發明，係有關於在將被處理基板浸漬於洗淨液 中的同時，在洗淨液中使超音波產生，而將附著在被處理 基板上之粒子（髒污等）除去的基板洗淨方法，特別是， 係有關於用以實行能夠在大幅抑制配線圖案之損傷的同時 ，而以局除去效率來將粒子從被處理基板上除去的基板洗 淨方法之程式，以及記憶有該程式之程式記錄媒體。 【先前技術】 在將被處理基板以保持在保持構件上之狀態下而浸漬 在洗淨液中的同時，於洗淨液中使超音波產生，而對被處 理基板作洗淨的方法，亦即是所謂的超音波洗淨（亦稱爲 mega sonic處理），例如係從日本特開昭64-4285號公報 而爲既知。 在超音波洗淨中，主要，係藉由在洗淨液中使空泡現 象（Cavitation )產生，而將粒子從被處理基板上除去。 但，另一方面，若是產生有強烈的空泡現象，則由於伴隨 200830391 著空泡現象所產生的衝擊波，而會產生有對被形成於被處 理基板之表面上的配線圖案造成損傷的問題。而，在曰本 特開昭64-428 5號公報中，係提案有：藉由在洗淨液中使 氣泡產生，而一面抑制配線圖案之損傷，一面將被處理基 板作洗淨的方法。 然而，在本案發明者所累積之硏究成果下，發現了： 若是在洗淨液中使氣泡產生，則粒子之除去效率係會下降 。又，在近年，由於配線圖案係有更加細微化之傾向，因 此，細微化後之配線圖案，會容易因爲衝擊波而受到損傷 。故而，係要求有更加有效的配線圖案之損傷防止策略。 【發明內容】 本發明，係考慮有此些事態而進行者，其目的，係在 於提供一種：在將被處理基板浸漬於洗淨液中的同時，在 洗淨液中使超音波產生，而將附著在被處理基板上之粒子 (髒污等）除去的基板洗淨方法以及基板洗淨裝置，特別 是，係在於提供一種：能夠在大幅抑制配線圖案之損傷的 同時，而以高除去效率來將粒子從被處理基板上除去的基 板洗淨方法以及基板洗淨裝置。 又，本發明之目的，係在於提供一種：在將被處理基 板浸漬於洗淨液中的同時，在洗淨液中使超音波產生，而 將附著在被處理基板上之粒子（髒污等）除去的基板洗淨 方法，特別是，係在於提供一種用以實行能夠在大幅抑制 配線圖案之損傷的同時，而以高除去效率來將粒子從被處 -5- 200830391 理基板上除去的基板洗淨方法之程式，以及記憶有該程式 之程式記錄媒體。 在本案發明者進行了各種實驗後，得到了以下之實驗 結果：（η大量之氣泡的產生，係會對粒子除去效率之 提昇造成阻礙；（2 )溶存於洗淨液中之氣體，對於配線 圖案之損傷防止係爲有效。本發明，係根據此種實驗結果 而進行者。 本發明所致之基板洗淨裝置，其特徵爲，具備有：儲 存洗淨液之洗淨槽；和產生超音波之超音波產生裝置；和 供給溶解有難以溶解於洗淨液中之氣體的洗淨液之第1供 給管；和溶解有易於溶解於洗淨液中之氣體的洗淨液之第 2供給管。 在本發明所致之基板洗淨裝置中，亦可設爲：前述第 1供給管，係被連接於前述洗淨槽，並將溶解有難以溶解 於洗淨液中之氣體的洗淨液供給至前述洗淨槽內，前述第 2供給管，係被連接於前述洗淨槽，並將溶解有易於溶解 於洗淨液中之氣體的洗淨液供給至前述洗淨槽內。或者是 ，本發明所致之基板洗淨裝置，係亦可設爲：更具備有混 合供給管，其係在被連接於前述第1供給管以及前述第2 供給管的同時，亦被連接於前述洗淨槽，而能夠將從前述 第1供給管所供給之洗淨液與從前述第2供給管所供給之 洗淨液混合並供給至前述洗淨槽內。或者是，在本發明所 致之基板洗淨裝置中，亦可設爲將前述第1供給管以及前 述第2供給管作串聯連接。 -6- 200830391 又’本發明所致之基板洗淨裝置，係亦可設爲更進而 具備有：第3供給管，其係被連接於前述第1供給管以及 前述第2供給管，並將被脫氣後之洗淨液供給至前述第1 供給管以及前述第2供給管；和第1溶解裝置，其係被安 裝於前述第1供給管，並使前述難以溶解之氣體溶解於前 述第1供給管內所流動之洗淨液中；和第2溶解裝置，其 係被安裝於前述第2供給管，並使前述易於溶解之氣體溶 解於前述第2供給管內所流動之洗淨液中在此種本發明所 致之基板洗淨裝置中，亦可設爲：從前述第3供給管而供 給至前述第1供給管以及前述第2供給管中的脫氣後之洗 淨液，其溶存氣體濃度，若是將小數點以下作四捨五A， 則係爲0 %。 進而，在本發明所致之基板洗淨裝置中，係亦可設爲 :前述難以溶解之氣體，係爲氮、氫、氧中之任一的氣體 ，以及此些的組合中之任一者。 進而，在本發明所致之基板洗淨裝置中，亦可設爲： 前述難以溶解之氣體係爲氮，從前述第1供給管所供給之 洗淨液中的前述氮之溶存氣體濃度，若是將小數點以下作 四捨五入，則係爲14%。 進而，在本發明所致之基板洗淨裝置中，係亦可設爲 :前述易於溶解之氣體，係爲二氧化碳。 進而，在本發明所致之基板洗淨裝置中，係亦可設爲 ••在洗淨中之前述洗淨槽內的洗淨液之溫度，係被保持在 2 8 °C以下。 200830391 本發明所致之基板洗淨方法’其特徵爲’具備有：在 洗淨槽內將被處理基板浸漬於洗淨液中之工程；和使超音 波產生於前述洗淨槽內的洗淨液中之工程’在前述使超首 波產生之工程中，易於溶解於洗淨液中之氣體’與難以溶 解於洗淨液中之氣體，係溶解於前述洗淨槽內之前述洗淨 液中。 本發明所致之基板洗淨方法，亦可設爲在前述使超音 波產生之工程中’係僅有前述易於溶解於洗淨液中之氣體 和前述難以溶解於洗淨液中之氣體被溶解於前述洗淨槽內 之洗淨液中。 又，在本發明所致之基板洗淨方法中，係亦可設爲： 前述難以溶解之氣體’係爲氮、氫、氧中之任一的氣體’ 以及此些的組合中之任一者。 進而，在本發明所致之基板洗淨方法中，亦可設爲： 前述難以溶解之氣體係爲氮，前述洗淨液中的前述氮之溶 存氣體濃度，若是將小數點以下作四捨五入，則係爲14% 〇 進而，在本發明所致之基板洗淨方法中，係亦可設爲 ••前述易於溶解之氣體，係爲二氧化碳。 進而，在本發明所致之基板洗淨方法中，係亦可設爲 :在前述使超音波產生之工程中，前述洗淨槽內的洗淨液 之溫度，係爲28°c以下。 本發明所致之程式，係爲經由對基板洗淨裝置作控制 之電腦而被實行的程式，其特徵爲，經由在前述電腦中實 -8- 200830391 行該程式，而在基板洗淨裝置中實施被處理基板之洗淨方 法，該洗淨方法，係具備有··在洗淨槽內將被處理基板浸 漬於洗淨液中之工程；和使超音波產生於前述洗淨槽內的 洗淨液中之工程，在前述使超音波產生之工程中，易於溶 > 解於洗淨液中之氣體，與難以溶解於洗淨液中之氣體，係 溶解於前述洗淨槽內之前述洗淨液中。 本發明所致之程式記錄媒體，係爲被記錄有經由對基 Φ 板洗淨裝置作控制之電腦而被實行的程式之電腦可讀取的 記錄媒體，其特徵爲，經由以前述電腦來實行前述程式， 而在基板洗淨裝置中實施被處理基板之洗淨方法，該洗淨 方法，係具備有：在洗淨槽內將被處理基板浸漬於洗淨液 中之工程；和使超音波產生於前述洗淨槽內的洗淨液中之 工程，在前述使超音波產生之工程中，易於溶解於洗淨液 中之氣體，與難以溶解於洗淨液中之氣體，係溶解於前述 洗淨槽內之前述洗淨液中。 • 若藉由本發明，則藉由溶存於洗淨液中之難以溶解的 氣體，能夠使空泡現象活躍的產生。另一方面，藉由溶存 於洗淨液中之易於溶解的氣體，能夠將起因於空泡現象而 在洗淨液中傳播的衝擊波作吸收。藉由此，能在大幅抑制 被形成於被處理基板上的配線圖案之損傷的同時，而以高 除去效率來將例子從被處理基板上除去之基板洗淨方法。 【實施方式】 以下，參考圖面，並針對本發明之其中一種實施形態 -9 - 200830391 作說明。另外，在以下之實施形態中，係對將本 之基板洗淨裝置適用於半導體晶圓之洗淨裝置中 說明。但是，本發明之基板洗淨裝置，係並不限 導體晶圚洗淨裝置之適用，而可廣泛適用於基板 〇 圖1乃至圖4，係爲用以說明本發明所致之 方法、基板洗淨裝置、程式、以及記錄媒體的其 施形態之圖。 其中，圖1係爲將基板洗淨裝置之構成作槪 圖，圖2係爲展示基板洗淨裝置之處理槽的上面 以及圖4係爲f彳在洗淨液中之超音波的傳播作用 圖。 如圖1所示，在本實施形態中之基板洗淨奏 係具備有：洗淨槽（DIP槽）12、和將洗淨液供 槽12內之洗淨液供給設備40、和將被處理晶圓 基板）W作保持之保持構件（亦稱爲晶圓埠）20 淨槽12內之洗淨液中使超音波產生之超音波產兰 、和被連接於洗淨液供給設備40之控制裝置18 板洗淨裝置1 〇，係在將被處理基板浸漬在儲存 1 2內之洗淨液中的狀態下，在洗淨液中使超音 並藉由此來將被處理晶圓W作超音波洗淨的裝置 首先，針對洗淨液供給設備49作詳述。如6 ，洗淨液供給設備40,係具備有：被連接於洗詞 並將第1洗淨液供給至洗淨槽內之第1供給管 發明所致 的例子作 定於對半 之洗淨中 基板洗淨 中一種實 略展示之 圖，圖3 作說明之 !置 10， 給至洗淨 (被處理 、和在洗 裝置30 。此種基 於洗淨槽 波產生， 〇 圓1所示 β 槽 12， 5 0，和被 -10- 200830391 連接於洗淨槽1 2，並將第2洗淨液供給至洗淨槽內之第2 供給管60，和在被連接於第1供給管5 0以及第2供給管 60的同時，將被脫氣後之洗淨液（第3洗淨液）供給至 第1供給管50以及第2供給管60中的第3供給管70， 和對第3供給管7〇供給洗淨液之洗淨液源72。另外，在 本實施形態中，係成爲從洗淨液源72而將純水（DIW ) 作爲洗淨液而供給至第3供給管70中。 於此，所謂第1洗淨液，係指將難以溶解於身爲洗淨 液之純水中的氣體，以特定之溶存濃度而溶解於第3洗淨 液中所成者。其中’所謂「難以溶解之氣體」，係指在被 溶解於純水中之狀態下難以安定的氣體。故而，當此些之 氣體溶存於純水中的情況時，若是對純水照射超音波，則 起因於此些之氣體的空泡現象係活躍地產生。又，若是產 生空泡現象，則溶存於純水中之此些的氣體係成爲容易氣 泡化。作爲此種「難以溶解之氣體」，例如，係可使用氮 、氫、氧之任一的氣體，以及此些之組合中的任一者。 另一方面，於此，所謂第2洗淨液，係指將易於溶解 (溶存）於身爲洗淨液之純水中的氣體’以特定之溶存濃 度而溶解於第2洗淨液中所成者。其中，所謂「易於溶解 之氣體」，係指在被溶解於純水中之狀態下易於安定的氣 體。故而，當此些之氣體溶存在純水中的情況時’就算是 對純水照射超音波，起因於此些之氣體的空泡現象亦不易 產生。又，由於難以產生空泡現象，因此溶存在純水中之 此些的氣體係難以氣泡化。作爲此種「易於溶解之氣體」 -11 - 200830391 ，例如係可使用二氧化碳。 如圖1所示，於洗淨液源72，係被連接有第3供給 管70之上流側的端部。另一方面，在第3供給管之下流 側的端部，係經由分歧管43，而被連接有第1供給管50 之上流側的端部以及第2供給管60之上流側的端部。又 ，在第3供給管70，係被設置有將流動於第3供給管70 內之洗淨液脫氣的脫氣裝置75。藉由此種構成，從洗淨 液源72而送入至第3供給管70之洗淨液（純水）係經由 脫氣裝置75而被脫氣，並產生脫氣後之洗淨液（第3洗 淨液）。所產生之第3洗淨液，係經由分歧管43，而被 供給至第1供給管50以及第2供給管60。 於此，作爲脫氣裝置75，係可採用利用有膜脫氣或 是真空脫氣等之原理的各種之周知的脫氣裝置。而後，將 脫氣裝置75之輸出與在各個輸出下能從洗淨液所脫氣之 氣體的量（亦即是，在各輸出下之溶存濃度的降低量）間 之關係預先作把握，並根據該所把握的關係，來因應於目 標之脫氣量而決定脫氣裝置7 5之輸出，並以該輸出來使 脫氣裝置75動作，藉由此，能夠得到被脫氣之洗淨液（ 第3洗淨液）。此脫氣裝置75係被連接於控制裝置1 8， 並成爲經由控制裝置1 8來對其動作作控制。 另外，在本實施形態中，第3洗淨液之溶存氣體濃度 係被設定爲Oppm。在此種情況中，藉由將脫氣裝置之輸 出，設定爲較根據前述所把握之關係所決定的輸出爲些許 更高之輸出，而能夠較爲容易且較爲安定的將第3洗淨液 -12- 200830391 之溶存氣體濃度設定爲預定之溶存氣體濃度（0ppm)。 然而’在本案中所使用之溶存氣體濃度，係設定爲以 「ppm」作爲單位’而將小數點以下作四捨五入後的値來 判斷者。例如，所謂在本案中所使用之「〇ppm」，係指 若是將小數點以下第1位作四捨五入，則會成爲0ppm之 溶存氣體濃度。亦即是，係爲包含有不滿〇.5ppm之溶存 氣體濃度者。 接下來，針對洗淨液供給設備4 0之分歧管4 3之後的 構成作詳細敘述。 如圖1所示，在第1供給管50以及第2供給管60處 ，係被設置有：將各供給管50、60作開閉之開閉閥54、 64，和能夠對流動於各供給管50、60中之洗淨液的流量 作調節之流量計52、62。各流量計52、62，係被連接於 控制裝置1 8。而，流動於第1供給管5 0內之洗淨液的流 量，以及流動於第2供給管6 0內之洗淨液的流量，係經 由各流量計5 2、62，而可藉由控制裝置1 8來作控制。 又，在第1供給管50中，係被安裝有用以使難以溶 解之氣體溶解於流動在第1供給管5 0內之洗、淨液的第1 溶解裝置55。在第1溶解裝置55中，係被連接有供給難 以溶解之氣體的第1氣體源55a。在本實施形態中’作爲 難以溶解之氣體的氮’係成爲從第1氣體源55&而被供給 至第1溶解裝置55中。藉由此種構成’使用第1溶解裝 置5 5，來使氮溶解於從第3供給管7 G而迭:入至弟1供給 管5 0內的第3洗淨液中’並從脫氣後之洗淨液（第3洗 -13- 200830391 淨液）而產生第1洗淨液。 同樣的，在第2供給管60中，係被安裝有用以使易 於溶解之氣體溶解於流動在第2供給管60內之洗淨液的 第2溶解裝置65。在第2溶解裝置65中，係被連接有供 /給易於溶解之氣體的第2氣體源65a。在本實施形態中， 作爲易於溶解之氣體的二氧化碳，係成爲從第2氣體源 65a而被供給至第2溶解裝置65中。藉由此種構成，使 φ 用第2溶解裝置65，來使二氧化碳溶解於從第3供給管 70而送入至第2供給管60內的第3洗淨液中，並從脫氣 後之洗淨液（第3洗淨液）而產生第2洗淨液。 於此，作爲第1以及第2溶解裝置55、65，係與上 述之脫氣裝置75同樣的，可使用各種之周知的溶解裝置 。而後，將溶解裝置55、65之輸出與在各個輸出下能溶 解於洗淨液中之氣體的量（亦即是，在各輸出下之溶存濃 度的上升量）間之關係預先作把握，並根據該所把握的關 # 係，而決定溶解裝置55、65之輸出，並以該輸出來使溶 解裝置55、65動作，藉由此，能夠得到以所期望之溶存 •氣體濃度而溶解有氣體之第1以及第2洗淨液。另外，第 _ 1溶解裝置5 5以及第2溶解裝置65，係分別被連接於控 制裝置1 8，並成爲經由控制裝置1 8，而分別對其之動作 作控制。 又，如圖1所示，於第1供給管50以及第2供給管 60，係被設置有調溫機構58、68。經由此調溫機構58、 68，能夠將流動於第1供給管50內之第1洗淨液的溫度 -14 - 200830391 以及流動於第2供給管60內之第2洗淨液的溫度分別在 所期望之溫度範圍內作調節。另外，由後述之理由可以得 知，爲了抑制在洗淨槽1 2內之氣泡的產生，洗淨液之溫 度係以較低者爲有利’故’根據後述之實施例的實績，係 以設定在2 8 °C以下爲理想。 進而，如圖1及圖2所示一般，在第丨供給管5〇之 洗淨槽1 2側的下流側之端部，係沿著洗淨槽1 2之相對向 的壁面，而設置有2個的第1洗淨用噴嘴5 6。同樣的， 在第2供給管60之洗淨槽1 2側的下流側之端部，係沿著 洗淨槽12之相對向的壁面，而設置有2個的第5洗淨用 噴嘴66。另外，在圖2中所係僅圖示有第1洗淨液用噴 嘴56，但是第1洗淨液用噴嘴66係亦成爲與圖示之第1 洗淨液用噴嘴5 6相同的構成。 第1洗淨用噴嘴5 6以及第2洗淨用噴嘴66，係由沿 著洗淨槽12之壁面而延伸爲細長狀的筒狀之構件所成， 而，於此筒狀構件，係沿著其長度方向，而設置有以空出 有一定之間隔的方式而配置的多數之噴嘴孔56a、66a。 噴嘴孔56a、66a之配置位置，係如後述一般，根據經由 保持構件20而被保持之被處理晶圓W的配置位置而被決 定。如圖1所示，在本實施形態中，第1洗淨用噴嘴5 6 係被配置於第2洗淨用噴嘴66之上方。但是，並不限定 於此，第2洗淨用噴嘴66係亦可配置於第1洗淨用噴嘴 5 6之上方，或者是，如同於後作爲變形例而說明一般， 亦可在將第1洗淨液與第2洗淨液混合之後，再經由相同 -15-200830391 IX. OBJECT OF THE INVENTION [Technical Field] The present invention relates to immersing a substrate to be processed in a cleaning liquid, and generating ultrasonic waves in the cleaning liquid to adhere to the substrate to be processed. In the substrate cleaning method and the substrate cleaning device, the particles are removed from the substrate to be processed with high removal efficiency while greatly reducing the damage of the wiring pattern. The substrate cleaning method and the substrate cleaning device. Further, the present invention relates to a substrate in which ultrasonic waves are generated in a cleaning liquid while immersing the substrate to be processed in a cleaning liquid, and particles (dirt or the like) adhering to the substrate to be processed are removed. In particular, the cleaning method is a program for performing a substrate cleaning method for removing particles from the substrate to be processed while reducing the damage of the wiring pattern while substantially reducing the damage of the wiring pattern, and Program program recording media. [Prior Art] A method in which a substrate to be processed is immersed in a cleaning liquid while being held on a holding member, and ultrasonic waves are generated in the cleaning liquid, and the substrate to be processed is washed. That is, the so-called ultrasonic cleaning (also referred to as mega sonic processing) is known from Japanese Laid-Open Patent Publication No. 64-4285. In ultrasonic cleaning, mainly, particles are removed from the substrate to be processed by causing a cavitation phenomenon in the cleaning liquid. On the other hand, if a strong bubble phenomenon occurs, a shock wave generated by the bubble phenomenon in 200830391 may cause damage to the wiring pattern formed on the surface of the substrate to be processed. In JP-A-64-428-5, there is proposed a method of cleaning a substrate to be treated while suppressing damage of a wiring pattern by causing bubbles to be generated in the cleaning liquid. However, in the results of the research conducted by the inventors of the present invention, it was found that if bubbles are generated in the cleaning liquid, the efficiency of particle removal is lowered. In addition, in recent years, the wiring pattern has a tendency to be more fine. Therefore, the wiring pattern after the miniaturization is easily damaged by the shock wave. Therefore, it is required to have a more effective damage prevention strategy for the wiring pattern. SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and an object thereof is to provide an ultrasonic wave in a cleaning liquid while immersing a substrate to be processed in a cleaning liquid. The substrate cleaning method and the substrate cleaning apparatus for removing particles (dirt or the like) adhering to the substrate to be processed are, in particular, provided that the damage of the wiring pattern can be greatly suppressed and the removal efficiency is high. A substrate cleaning method for removing particles from a substrate to be processed, and a substrate cleaning device. Further, an object of the present invention is to provide a method of immersing a substrate to be treated in a cleaning liquid, and generating ultrasonic waves in the cleaning liquid to adhere the particles to the substrate to be processed (dirty, etc.) The method of cleaning the substrate to be removed, in particular, is to provide a substrate for performing the removal of particles from the substrate to be removed -5-200830391 with high removal efficiency while greatly suppressing damage of the wiring pattern. The program of the cleaning method, and the program recording medium in which the program is memorized. After the various experiments were conducted by the inventors of the present invention, the following experimental results were obtained: (the generation of a large number of bubbles causes an increase in the efficiency of particle removal; (2) the gas dissolved in the cleaning liquid, for wiring The damage prevention of the pattern is effective. The present invention is based on the results of such an experiment. The substrate cleaning apparatus according to the present invention is characterized in that it comprises: a cleaning tank for storing the cleaning liquid; a sonic ultrasonic generating device; and a first supply pipe for supplying a cleaning liquid in which a gas which is hardly dissolved in the cleaning liquid is supplied; and a second supply of a cleaning liquid in which a gas which is easily dissolved in the cleaning liquid is dissolved In the substrate cleaning apparatus according to the present invention, the first supply pipe may be connected to the cleaning tank and be cleaned by dissolving a gas which is hardly dissolved in the cleaning liquid. The liquid is supplied into the cleaning tank, and the second supply pipe is connected to the cleaning tank, and a cleaning liquid in which a gas which is easily dissolved in the cleaning liquid is dissolved is supplied to the cleaning tank. Yes, the invention The substrate cleaning apparatus may further include a mixed supply pipe that is connected to the first supply pipe and the second supply pipe, and is also connected to the cleaning tank. The cleaning liquid supplied from the first supply pipe may be mixed with the cleaning liquid supplied from the second supply pipe and supplied to the cleaning tank. Alternatively, the substrate cleaning device of the present invention may be used. In addition, the first supply pipe and the second supply pipe may be connected in series. -6- 200830391 Further, the substrate cleaning device according to the present invention may be further provided with: a supply pipe that is connected to the first supply pipe and the second supply pipe, and supplies the degassed cleaning liquid to the first supply pipe and the second supply pipe; and the first dissolution device. The first supply pipe is attached to the first supply pipe, and the gas that is difficult to dissolve is dissolved in the cleaning liquid flowing through the first supply pipe, and the second dissolution device is attached to the second supply pipe. And dissolving the aforementioned easily soluble gas in the foregoing In the substrate cleaning device according to the present invention, the cleaning device that flows in the second supply pipe may be supplied from the third supply pipe to the first supply pipe and the second supply. The concentration of the dissolved gas in the degassing liquid in the tube is 0% if it is equal to or less than the decimal point. Further, in the substrate cleaning apparatus according to the present invention, it is also possible to set The gas which is difficult to dissolve is any one of nitrogen, hydrogen, and oxygen, and any combination thereof. Further, in the substrate cleaning apparatus of the present invention, it may be The gas system which is hard to dissolve is nitrogen, and the concentration of the dissolved gas of the nitrogen in the cleaning liquid supplied from the first supply pipe is 14% if the decimal point or less is rounded off. In the substrate cleaning apparatus according to the invention, the gas which is easily dissolved may be carbon dioxide. Further, in the substrate cleaning apparatus according to the present invention, the temperature of the cleaning liquid in the cleaning tank during the cleaning may be maintained at 28 ° C or lower. 200830391 The method for cleaning a substrate according to the present invention is characterized in that it includes a process of immersing a substrate to be processed in a cleaning liquid in a cleaning tank, and cleaning the ultrasonic wave in the cleaning tank. In the liquid, the gas which is easily dissolved in the cleaning liquid and the gas which is hard to be dissolved in the cleaning liquid in the above-described process of generating the super first wave are the above-mentioned cleaning liquid dissolved in the cleaning tank. in. The substrate cleaning method according to the present invention may be such that in the above-described process for generating ultrasonic waves, only the gas which is easily dissolved in the cleaning liquid and the gas which is hardly dissolved in the cleaning liquid are dissolved. In the washing liquid in the aforementioned washing tank. Further, in the substrate cleaning method according to the present invention, the gas which is difficult to dissolve may be a gas of any one of nitrogen, hydrogen, and oxygen, and any combination thereof. . Further, in the substrate cleaning method according to the present invention, the gas system which is difficult to dissolve may be nitrogen, and if the concentration of the dissolved gas of the nitrogen in the cleaning liquid is rounded off or less, Further, in the substrate cleaning method according to the present invention, it is also possible to use the above-mentioned gas which is easily dissolved and is carbon dioxide. Further, in the substrate cleaning method according to the present invention, the temperature of the cleaning liquid in the cleaning tank may be 28 ° C or less in the above-described process for generating ultrasonic waves. The program according to the present invention is a program that is executed by a computer that controls the substrate cleaning device, and is characterized in that the program is executed in the computer in the above-mentioned computer, and in the substrate cleaning device. A method of cleaning a substrate to be processed, wherein the cleaning method includes immersing the substrate to be processed in the cleaning liquid in the cleaning tank, and washing the ultrasonic wave in the cleaning tank. In the above-mentioned process of purifying the ultrasonic wave, the gas which is easily dissolved in the cleaning liquid and the gas which is hardly dissolved in the cleaning liquid are dissolved in the aforementioned washing tank. In the cleaning solution. The program recording medium according to the present invention is a computer-readable recording medium on which a program executed by a computer for controlling the base Φ board cleaning device is recorded, and is characterized in that it is implemented by the aforementioned computer. In the above-described procedure, a cleaning method of the substrate to be processed is performed in the substrate cleaning apparatus, and the cleaning method includes a process of immersing the substrate to be processed in the cleaning liquid in the cleaning tank; and supersonicizing In the process of generating the ultrasonic wave in the cleaning liquid, the gas which is easily dissolved in the cleaning liquid and the gas which is hardly dissolved in the cleaning liquid are dissolved in the above-mentioned Wash the above-mentioned cleaning solution in the tank. • According to the present invention, the cavitation phenomenon can be actively generated by the gas which is dissolved in the cleaning liquid and which is difficult to dissolve. On the other hand, the shock wave propagating in the cleaning liquid due to the cavitation phenomenon can be absorbed by the gas which is easily dissolved in the cleaning liquid. As a result, the substrate cleaning method in which the example is removed from the substrate to be processed with high removal efficiency while greatly suppressing the damage of the wiring pattern formed on the substrate to be processed can be suppressed. [Embodiment] Hereinafter, one embodiment of the present invention, -9 - 200830391, will be described with reference to the drawings. Further, in the following embodiments, the substrate cleaning apparatus of the present invention is applied to a semiconductor wafer cleaning apparatus. However, the substrate cleaning device of the present invention is not limited to the application of the conductor wafer cleaning device, and can be widely applied to the substrate, FIG. 1 to FIG. 4, for explaining the method and substrate washing method of the present invention. A diagram of the net device, program, and recording medium. 1 is a schematic diagram of the structure of the substrate cleaning device, FIG. 2 is a view showing the upper surface of the processing tank of the substrate cleaning device, and FIG. 4 is a propagation diagram of the ultrasonic wave in the cleaning liquid. . As shown in Fig. 1, the substrate cleaning system according to the present embodiment includes a cleaning tank (DIP tank) 12, and a cleaning liquid supply device 40 for supplying the cleaning liquid into the tank 12, and will be processed. Wafer substrate) W is a holding member (also referred to as wafer crucible) 20. The ultrasonic wave generated by the ultrasonic wave in the cleaning liquid in the cleaning tank 12 and the control connected to the cleaning liquid supply device 40 In the state in which the substrate to be processed is immersed in the cleaning liquid in the storage 12, the ultrasonic wave is superimposed on the cleaning liquid, thereby using the wafer W to be processed. The apparatus for ultrasonic cleaning is first described in detail with respect to the cleaning liquid supply device 49. For example, the cleaning liquid supply device 40 is provided with an example in which the first supply pipe that is connected to the washing word and supplies the first cleaning liquid to the washing tank is in the form of a half-cleaning. A schematic diagram of the middle substrate cleaning, which is illustrated in Fig. 3! Set to 10, to be washed (treated, and in the washing device 30. This is based on the cleaning of the groove wave, shown by the circle 1) The tanks 12, 50 and -10-200830391 are connected to the washing tank 12, and the second washing liquid is supplied to the second supply pipe 60 in the washing tank, and is connected to the first supply pipe 5 In addition to the second supply pipe 60, the degassed cleaning liquid (third cleaning liquid) is supplied to the third supply pipe 50 in the first supply pipe 50 and the second supply pipe 60, and (3) The supply pipe 7 is supplied with the cleaning liquid source 72. In the present embodiment, pure water (DIW) is supplied as a cleaning liquid from the cleaning liquid source 72 to the third supply pipe. Here, the first cleaning liquid refers to a gas which is hardly dissolved in pure water which is a cleaning liquid, and is dissolved in the third cleaning liquid at a specific dissolved concentration. In the case of "the gas that is difficult to dissolve", it means a gas that is difficult to stabilize in a state of being dissolved in pure water. Therefore, when such a gas is dissolved in pure water, if it is pure water When the ultrasonic wave is irradiated, the cavitation phenomenon of the gas is actively generated. Further, if the cavitation phenomenon occurs, the gas system dissolved in the pure water is easily bubbled. The dissolved gas may be, for example, any one of nitrogen, hydrogen, and oxygen, and any combination thereof. On the other hand, the second cleaning liquid means that it is easy to be used. The gas which is dissolved (dissolved) in the pure water which is a cleaning liquid is dissolved in the second cleaning liquid at a specific dissolved concentration. The term "a gas which is easy to dissolve" means that it is dissolved. A gas that is easy to stabilize in the state of pure water. Therefore, when such a gas is dissolved in pure water, even if the ultrasonic wave is irradiated to the pure water, the bubble phenomenon of the gas caused by the gas is not easily generated. Again, because it is difficult to create an empty space The bubble phenomenon is such that it is difficult to bubble the gas system dissolved in pure water. As such a "easy-dissolving gas" -11 - 200830391, for example, carbon dioxide can be used. As shown in Fig. 1, the source of the cleaning liquid 72 is connected to the end portion on the upstream side of the third supply pipe 70. On the other hand, the end portion on the downstream side of the third supply pipe is connected to the first supply pipe 50 via the branch pipe 43. An end portion on the upstream side and an end portion on the upstream side of the second supply pipe 60. Further, the third supply pipe 70 is provided with a deaeration device that deaerates the cleaning liquid flowing in the third supply pipe 70. 75. With such a configuration, the cleaning liquid (pure water) sent from the cleaning liquid source 72 to the third supply pipe 70 is deaerated via the deaerator 75, and is degassed and then washed. Liquid (third cleaning solution). The third cleaning liquid generated is supplied to the first supply pipe 50 and the second supply pipe 60 via the branch pipe 43. Here, as the deaerator 75, various well-known deaerators using the principles of membrane degassing or vacuum degassing can be employed. Then, the relationship between the output of the deaeration device 75 and the amount of gas that can be degassed from the cleaning liquid at each output (that is, the amount of decrease in the concentration of the solution at each output) is grasped in advance, and According to the grasped relationship, the output of the deaerator 75 is determined in accordance with the amount of degassing of the target, and the deaerator 75 is operated by the output, whereby the degassed cleaning liquid can be obtained ( The third cleaning solution). The deaerator 75 is connected to the control unit 18 and is controlled by the control unit 18. Further, in the present embodiment, the dissolved gas concentration of the third cleaning liquid is set to 0 ppm. In this case, by setting the output of the degasser to a slightly higher output than the output determined based on the above-described relationship, the third cleaning can be performed relatively easily and stably. The dissolved gas concentration of Liquid-12-200830391 was set to a predetermined dissolved gas concentration (0 ppm). However, the concentration of the dissolved gas used in the present case is set to "ppm" as a unit, and the decimal point is rounded off to determine the enthalpy. For example, "〇ppm" as used in this case means that if the first digit below the decimal point is rounded off, it will become a dissolved gas concentration of 0 ppm. That is, it is a solution containing a dissolved gas concentration of less than .5 ppm. Next, the configuration after the branch pipe 4 3 of the cleaning liquid supply device 40 will be described in detail. As shown in FIG. 1, the first supply pipe 50 and the second supply pipe 60 are provided with on-off valves 54 and 64 that open and close the supply pipes 50 and 60, and flowable to the respective supply pipes 50. The flow rate of the cleaning liquid in 60 is adjusted by the flow meters 52 and 62. The flow meters 52, 62 are connected to the control unit 18. The flow rate of the cleaning liquid flowing through the first supply pipe 50 and the flow rate of the cleaning liquid flowing through the second supply pipe 60 are controlled by the respective flow meters 5 2, 62. Device 18 is used for control. Further, in the first supply pipe 50, a first dissolving device 55 for dissolving a gas which is difficult to dissolve in the washing and purifying liquid flowing in the first supply pipe 50 is attached. In the first dissolution apparatus 55, a first gas source 55a for supplying a gas which is difficult to dissolve is connected. In the present embodiment, 'nitrogen as a gas which is difficult to dissolve' is supplied from the first gas source 55 & to the first dissolution apparatus 55. By using the first dissolution device 5, the nitrogen is dissolved in the third cleaning liquid from the third supply pipe 7 G into the third cleaning liquid in the supply pipe 50, and degassed. The first cleaning solution is produced by the subsequent cleaning solution (third wash-13-200830391 clean solution). Similarly, in the second supply pipe 60, a second dissolution device 65 for dissolving the gas which is easily dissolved in the cleaning liquid flowing in the second supply pipe 60 is attached. In the second dissolution apparatus 65, a second gas source 65a for supplying/supplying a gas which is easy to dissolve is connected. In the present embodiment, carbon dioxide, which is a gas that is easily dissolved, is supplied to the second dissolution device 65 from the second gas source 65a. With this configuration, φ is dissolved in the third cleaning liquid supplied from the third supply pipe 70 to the second supply pipe 60 by the second dissolution device 65, and is degassed. The cleaning liquid (third cleaning liquid) generates a second cleaning liquid. Here, as the first and second dissolution apparatuses 55 and 65, various well-known dissolution apparatuses can be used similarly to the above-described deaerator 75. Then, the relationship between the output of the dissolving devices 55 and 65 and the amount of gas which can be dissolved in the washing liquid at each output (that is, the amount of increase in the dissolved concentration at each output) is grasped in advance, and The output of the dissolving devices 55 and 65 is determined based on the grasped system, and the dissolving devices 55 and 65 are operated by the output, whereby the gas dissolved in the desired dissolved gas concentration can be obtained. The first and second cleaning liquids. Further, the first _1 dissolving device 505 and the second dissolving device 65 are connected to the control device 18, respectively, and are controlled by the control device 18, respectively. Further, as shown in Fig. 1, temperature control mechanisms 58 and 68 are provided in the first supply pipe 50 and the second supply pipe 60. By the temperature adjustment mechanisms 58 and 68, the temperature of the first cleaning liquid flowing in the first supply pipe 50 - 1430391 and the temperature of the second cleaning liquid flowing in the second supply pipe 60 can be respectively Adjustments are made within the desired temperature range. In addition, it is understood from the reason described later that in order to suppress the generation of bubbles in the cleaning tank 12, the temperature of the cleaning liquid is lower, which is advantageous according to the performance of the examples described later. Ideal below 2 8 °C. Further, as shown in FIG. 1 and FIG. 2, the end portion on the downstream side of the cleaning tank 1 2 side of the second supply pipe 5 is provided along the opposing wall surface of the cleaning tank 12 Two first cleaning nozzles 5 6 . In the end portion on the downstream side of the cleaning tank 12 side of the second supply pipe 60, two fifth cleaning nozzles 66 are provided along the opposing wall surfaces of the cleaning tank 12. In addition, only the first cleaning liquid nozzle 56 is shown in Fig. 2, but the first cleaning liquid nozzle 66 also has the same configuration as the first cleaning liquid nozzle 56 shown. The first cleaning nozzle 56 and the second cleaning nozzle 66 are formed of a tubular member that extends along the wall surface of the cleaning tank 12 to be elongated, and the cylindrical member is tied along the tubular member. In the longitudinal direction thereof, a plurality of nozzle holes 56a and 66a which are disposed so as to be spaced apart from each other are provided. The arrangement positions of the nozzle holes 56a and 66a are determined in accordance with the arrangement position of the wafer W to be processed held by the holding member 20 as will be described later. As shown in Fig. 1, in the present embodiment, the first cleaning nozzles 56 are disposed above the second cleaning nozzles 66. However, the second cleaning nozzle 66 may be disposed above the first cleaning nozzle 56 or may be described as a modification as in the following. After the cleaning solution is mixed with the second cleaning solution, the same -15-
200830391 之噴嘴來供給至洗淨槽1 2內。 接下來，針對從洗淨液供給設備40而接受第1 液以及第2洗淨液之洗淨槽1 2作說明。洗淨槽1 2， 圖10及圖2所示一般，具有略直方體之輪廓。在沒 12中，係如後述一般，被形成有用以將晶圓 之上方開口。又，在洗淨槽12之底面，係被設置有 將所儲存之洗淨液排出的排出管1 3。 又，如圖1所示，以包圍洗淨槽12之上方開C 式，而被設置有外槽1 5。此外槽1 5，係成爲將從沒 1 2之上方開口所溢出的洗淨液作回收。與洗淨槽12 的，於外槽1 5，係亦被設置有用以將所回收之洗拝 出的排出管1 6。 此種洗淨槽1 2以及外槽1 5，例如，係使用富窄 性之石英等而形成。又，從洗淨槽1 2以及外槽1 5之 管1 3、1 6所排出的洗淨液，係可直接廢棄，亦可竹 再利用。 接下來，針對保持晶圓W之保持構件2 0作說曰J 圖1以及圖2所示，保持構件2 0，係具備有延伸东 平方向之4根的棒狀構件2 2，和將4根的棒狀構件 單側來作單處支持的基部24。棒狀保持構件22,信 將被進行過一次洗淨處理之複數的晶圓W，例如5 0 晶圓w，從下方來作支持。因此，在各棒狀構件22 係沿著其長度方向而被形成有空出有一定間隔而被画 溝（未圖示）。晶圓W，係嵌合於此溝，並成爲使名 洗淨 係如 淨槽 搬出 用以 的方 淨槽 同樣 液排 耐藥 排出 循環 。如 略水 22從 :成爲 枚之 處， :列之 晶圓 -16- 200830391 w之板面與棒狀構件之延伸方向成爲略垂直交會的方式， 亦即是使各晶圓W之板面成爲沿著垂直方向的方式，而 經由保持構件20來作保持（參考圖1 )。 然而，如同由圖2而可以理解一般，上述之第1洗淨 液用噴嘴56以及第2洗淨液用噴嘴66之噴嘴孔56&、 6 6 a的配置間距，係成爲與被保持在保持構件2 0之晶圓 W的配置間距略爲相同。又，上述之第1洗淨液用噴嘴 56以及第2洗淨液用噴嘴66之多數的噴嘴孔56a、66a， 係以能夠在被保持於保持構件20之晶圓W之間吐出洗淨 液的方式而被配列。 另一方面，保持構件20之基部24，係被連結於未圖 示之升降機構。藉由以此升降機構來使保持晶圓W之保 持構件20降下，而能夠將晶圓W浸漬在被儲存於洗淨槽 1 2內的洗淨液中。另外，升降機構係被連接於控制裝置 1 8，而成爲經由控制裝置1 8來控制晶圓W之對洗淨液的 浸漬。 接下來，針對超音波裝置3 0作說明。如圖1所示， 超音波產生裝置30,係具備有：被安裝於洗淨槽12之底 部外面的振動子38，和用以驅動振動子38之高頻驅動電 源32，和被連接於高頻驅動電源32之超音波震盪器34。 在本實施形態中，係被設置有複數之振動子3 8，各振動 子3 8，係以佔據洗淨槽1 2之底部外面的一部份之方式而 被配列。又，如圖1所不，超首波產生裝置3 0 ’係更進 而具備有連接於超音波震盪器34以及各振動子3 8之驅動 -17- 200830391 切換機構36。經由此驅動切換機構36，成爲可對複數之 振動子3 8作全體驅動，以及可對1個又或是2以上之振 動子作各別驅動。 若是振動子3 8被驅動並振動，則經由洗淨槽1 2之底 部，超音波係在儲存於洗淨槽1 2內之洗淨液中傳播，藉 由此，使超音波在洗淨槽1 2內之洗淨液中產生。另外， 超音波產生裝置3 0係被連接於控制裝置1 8，而成爲經由 控制裝置1 8來控制對洗淨液之超音波的賦予。 接下來，針對控制裝置1 8作說明。如上述一般，控 制裝置1 8，係被連接於基板洗淨裝置1 0之各構成要素， 而成爲對各構成要素之動作作控制。在本實施形態中，控 制裝置1 8係包含有電腦，經由以此電腦來實行被預先記 憶在記錄媒體1 9中之程式，而成爲實行使用有基板洗淨 裝置10之被處理晶圓W的洗淨。 接下來，針對使用有由此種構成所成之基板洗淨裝置 1 0的晶圓W之洗淨方法的其中一例作說明。 首先，從洗淨液源72，將純水作爲洗淨液而供給至 第3供給管70。流動在第3供給管70中之洗淨液，係經 由脫氣裝置75而被脫氣，而產生若是將小數點以下作四 捨五入則其溶存氣體濃度係爲Oppm之第3洗淨液。而後 ，溶存氣體濃度爲Oppm之第3洗淨液，係經由分歧管43 ，而一部份流至第1供給管50中，剩餘部分則流至第2 供給管60中。 流入第1供給管50之第3洗淨液，係經由第1溶解 -18- 200830391 裝置55，而被溶解有作爲難以溶解之氣體的氮。如此地 ，從第3洗淨液，係可得到以特定之濃度而溶解有氮的第 1洗淨液。在本實施形態中，係以使洗淨槽1 2內之洗淨 液的溶存氮濃度成爲14PPm的方式，來考慮從第1供給 管50而流向洗淨槽12之第1洗淨液的流量，以及從第2 供給管60而流向洗淨槽12之第2洗淨液的流量，而決定 對第1洗淨液之氮的溶解量。第1洗淨液之供給量，係藉 由根據控制裝置1 8所預先設定之程式來對流量計52的開 度作調節，而決定之。又，控制裝置1 8，係根據預先所 設定之程式，而對溫調裝置5 8作控制。其結果，在洗淨 槽12中，係成爲將具備有特定之溫度的第1洗淨液，以 特定之濃度（p p m )以及供給量（1 / m i η )來供給。 同樣的，流入第2供給管60之第3洗淨液，係經由 第2溶解裝置65，而被溶解有作爲易於溶解之氣體的二 氧化碳。如此地，從第3洗淨液，係可得到以特定之濃度 而溶解有二氧化碳的第2洗淨液。在本實施形態中，係以 使洗淨槽1 2內之洗淨液的溶存二氧化碳濃度成爲3 3 0 p p m 的方式，來考慮從第1供給管5 0而流向洗淨槽12之第1 洗淨液的流量，以及從第2供給管60而流向洗浄槽1 2之 第2洗淨液的流量，而決定對第2洗淨液之二氧化碳的溶 解量。第2洗淨液之供給量，係藉由根據控制裝置1 8所 預先設定之程式來對流量計62的開度作調節，而決定之 。又’控制裝置1 8，係根據預先所設定之程式，而對溫 調裝置6 8作控制。其結果，在洗淨槽1 2中，係成爲將具 -19- 200830391 備有特定之溫度的第2洗淨液，以特定之濃度（ppm )以 及供給量（1 / m i η )來供給。 如上述一般，在洗淨槽12內，係被儲存有將氮與二 氧化碳分別以特定之溶存氣體濃度而溶存之洗淨液。 接下來，將保持有特定枚（例如5 0枚）之被處理晶 圓W的保持構件20降下，並將被處理晶圓W浸漬在洗淨 槽1 2內之洗淨液中。 而後，控制裝置1 8，係使超音波產生裝置3 0動作， 而使超音波在洗淨槽1 2內之洗淨液中產生。藉由此，被 浸漬在洗淨槽12內之晶圓W，係成爲被超音波洗淨（ me gas onic處理）。其結果，附著在晶圓W之表面的粒子 (髒污等）係被除去。 在本實施形態中，於此工程中，第1洗淨液係持續從 第1供給管5 0而被供給至洗淨槽12內，第2洗淨液係持 續從第2供給管60而被供給至洗淨槽12內。如圖1及圖 2所示一般，第1洗淨液，係朝向被保持在保持構件20 之2枚的晶圓W之間，而吐出於斜上方。同樣的，第2 洗淨液，亦係朝向被保持在保持構件20之2枚的晶圓W 之間，而吐出於斜上方。故而，藉由此種第1洗淨液以及 第2洗淨液之吐出，而促進使從晶圓W而被除去之粒子 浮上至洗淨槽12內之洗淨液的液面的效果，進而，亦促 進使洗淨液從洗淨槽12而溢出至外槽15的效果。藉由此 ，能夠防止一度被從晶圓W而除去的粒子再度附著於晶 圓W之其他部分。但是，在此工程中，對洗淨槽12內持 -20- 200830391 續供給洗淨液一事係並非爲必須，而亦可對洗淨液之供給 時間作限制，又，亦可設爲完全不供給洗淨液。 若藉由此種本實施形態，則如同由後述之實施例而可 f 清楚得知一般，在能夠以高除去效率來將粒子除去的同時 、，亦能大幅抑制對配線圖案所造成之損傷。對於產生此種 現象之機制，雖尙不明瞭，但是，於此主要使用圖3以及 圖4，對可視爲此現象之其中一重要原因的機制作說明。 φ 但是，本發明係並非被限定爲以下之機制者。 在本案發明者累積了各種硏究結果後，發現了 ：如同 後述之實驗結果一般（參考實施例），（1 )大量之氣泡 的產生，係會對粒子之除去造成阻礙；（2 )溶存於洗淨 液中之氣體，係能夠有效的抑制對於配線圖案之損傷。而 ，在本實施形態中，在超音波洗淨工程中，於洗淨液內， 難以溶解於洗淨液中之氣體（氮），和易於溶解於洗淨液 中之氣體（二氧化碳），係溶解於洗淨槽1 2內之洗淨液 # 中。 若是對洗淨液照射超音波而使洗淨液中之壓力變動， 則難以溶解於洗淨液中之氣體（在洗淨液中缺乏安定性之. 氣體）之分子係產生急遽的狀態變化，而引起空泡現象。 而，可以將此空泡現象，考慮爲將附著在晶圓W上之粒 子從晶圓上剝去（除去）的主要原因之一。故而，難以溶 解於洗淨液中之氣體，係對粒子之除去效率的提昇有所貢 獻。 另外，若是產生空泡現象，則伴隨著急遽的壓力變化 -21 - 200830391 ，溶存於洗淨液中之氣體係成爲容易氣泡化。如上述所示 ’大量之氣泡的產生，係會對粒子之除去造成阻礙。此係 可推測爲··如圖3所示，所產生之氣泡，會對洗淨液中之 超音波的傳播造成阻礙，而使超音波無法涵蓋晶圓W之 板面而作移動之故。亦即是，若是難以溶解之氣體過度溶 解於洗淨液中’則在使晶圓中之粒子被除去的區域片面集 中的同時，亦有使除去效率降低之虞。 另一方面，就算是超音波照射於洗淨液，而使洗淨液 中之壓力變動，洗淨液中之易於溶解的氣體（於洗淨液中 具有安定性之氣體）的分子係不會產生狀態變化。亦即是 ，易於溶解之氣體，係不會引起空泡現象，伴隨此，氣泡 化之可能性亦變少。故而，溶存於洗淨液中之易於溶解的 氣體，係不會成爲超音波之減衰的原因，而如圖4所示一 般，超音波係在洗淨槽1 2內廣泛的移動。然而，如上述 一般，溶存於洗淨液中之氣體，係會有效地抑制對配線圖 案所造成之損傷。此係可以推測爲：溶存在洗淨液中之氣 體，係會吸收經由空泡現象而產生的衝擊波，其結果，能 夠防止起因於衝擊波之配線圖案的損傷之故。亦即是，易 於溶解之氣體，係不會氣泡化而對超音波之傳播造成阻礙 ，而能夠有效的抑制對配線圖案所造成之損傷。 藉由此種難以溶解於洗淨液中之氣體的作用以及易於 溶解於洗淨液中之氣體的作用，在本實施形態中，係能夠 在大幅抑制對被形成於晶圓W上之配線圖案所造成之損 傷的同時，以高除去效率來將粒子從晶圓W上除去。 -22- 200830391 如上述一般之使超苜波在洗淨槽1 2內之洗淨液中產 生的超音波洗淨工程，例如係繼續5分鐘左右。而後，停 止超音波產生裝置3 0所致之超音波的照射，而結束超音 波洗淨工程。 若是結束了對晶圓W之超音波洗淨，則保持構件20 係上升，而將晶圓從洗淨槽12中搬出。如上述一般，而 結束對於被處理晶圓W之一連串的洗淨工程。 如上述一般，若藉由本實施形態，則當在洗淨槽1 2 之洗淨液內使超音波產生時，易於溶解於洗淨液中之氣體 和難以溶解於洗淨液中之氣體，係溶解於洗淨槽1 2內之 洗淨液中。溶存於洗淨液中之難以溶解的氣體，係使空泡 現象活躍的產生。藉由此空泡現象，能夠以高除去效率來 將粒子從晶圓W上除去。另一方面，溶存於洗淨液中之 易於溶解的氣體，係使空泡現象變得難以產生，並難以伴 隨空泡現象而氣泡化。而，易於溶解之氣體，係維持在溶 存於洗淨液中之狀態，而吸收起因於空泡現象而傳播的衝 擊波。故而，能夠防止對被形成於晶圓W上之圖案所造 成的損傷。藉由此，能在大幅抑制晶圓W的配線圖案之 損傷的同時，而以高除去效率來將粒子從晶圓W上除去 〇 關於上述之實施形態，在本發明之要旨的範圍內，可 作各種之變更。以下，針對變形例之其中一例作說明。 在上述之實施形態中，雖係展示：作爲洗淨液，係使 用純水，而對被處理晶圓W進行超音波洗淨之例，但是 -23- 200830391 ，係並不限定於此。作爲洗淨液，亦可使用藥液，例如使 用 SCI (過氨水；NH4OH/ H202/ H20 )，並對被處理晶 圓W進行超音波洗淨。又，當使用藥液來進行洗淨時， 在藥液所致之洗淨處理後，係成爲有必要進行使用有純水 之洗滌洗淨。作爲使用有此純水之洗滌洗淨處理，亦可採 用上述之使用有純水之基板洗淨方法。 又，在上述之實施形態中，雖係展示將第1洗淨液與 第2洗淨液經由個別之供給管50、60來供給至洗淨槽1 2 內的例子，但是，並不限定於此。例如，亦可如圖5所示 一般，進而設置將第1供給管5 0與第2供給管60相連接 之混合供給管8 0，而成爲將第1洗淨液與第2洗淨液混 合而供給至洗淨槽12中。在圖5所示之例中，第1供給 管50以及第2供給管60，係係經由混合閥82，而被連接 於混合供給管8 0。又，在圖示之例中，於混合供給管8 0 ’係被設置有調溫機構8 8，而在第1供給管5 0以及第2 供給管60中，係並未被設置有調溫機構。經由此調溫機 構8 8，從混合供給管8 0而供給至洗淨槽1 2內之洗淨液 的溫度係被調節。 另外，於圖5所示之變形例，係除了更進而設置有混 合供給管8 0和混合閥8 2，以及調溫機構之配置位置係爲 相異之外，其他構成係和圖1乃至圖4所示之實施形態略 爲相同。於圖5中，係將與圖1乃至圖4所示之實施形態 相同的部分，附加上同樣的符號，同時，將重複之詳細說 明作省略。 -24 - 200830391 或者是，如在圖1中以2點鍊線所示一般，亦可將第 1供給管5 0與第2供給管6 0作串聯連接。換言之，可使 第1洗淨液從第1供給管50而流入至第2供給管60，並 使易於溶解之氣體溶解於此洗淨液中，而後，將溶解有易 於溶解之氣體與難以溶解之氣體之兩者的洗淨液供給至洗 淨槽12內；或者是，可使第2洗淨液從第2供給管60而 流入至第1供給管50，並使難以溶解之氣體溶解於此洗 淨液中，而後，將溶解有易於溶解之氣體與難以溶解之氣 體之兩者的洗淨液供給至洗淨槽1 2內。 進而’在上述之實施形態中，各洗淨液之溶存氣體濃 度係僅爲例示，而可作各種之變更。 然而’如上述所示，基板洗淨裝置10，係具備包含 有電腦之控制裝置1 8。藉由此控制裝置1 8，而使基板洗 淨裝置1 〇之各構成要素動作，並成爲實行對被處理晶圓 W之洗淨。而’爲了實施使用有基板洗淨裝置10的晶圓 W之洗淨而經由控制裝置18之電腦所實行的程式，亦爲 本申請案之對象。又，記錄有該程式之電腦可讀取的記錄 媒體1 9，亦爲本申請案之對象。於此，所謂記錄媒體i 9 ，係亦包含有軟碟（可撓性碟片）或是硬碟裝置等之可作 爲單體而辨識者。 另外，在以上之說明中，雖係展示將本發明所致之基 板洗淨方法、基板洗淨裝置、程式、以及記錄媒體適用在 晶圓W之洗淨處理中的例子，但是，係並不限定於此， 而亦可適用於LCD基板或是CD基板等之洗淨處理中。 -25- 200830391 〔實施例〕 爲了藉由實施例而對本發明作更詳細之說明，而進行 了以下所說明之2個的實驗。 〔實驗1〕 將以相異之溶存濃度而溶解有氮的洗淨液儲存於洗淨 槽中，並將試驗用晶圓浸漬於洗淨液中，而使超音波產生 。在本實驗中所使用之洗淨液，係被脫氣至溶存氣體濃度 成爲0PPm爲止，而後，以相異之溶存氣體濃度，來將氮 溶解於該洗淨液中。亦即是，在洗淨槽內之洗淨液中，作 爲氣體，係僅溶存有氮。實驗中，係將氮之溶存濃度設定 爲 8ppm、lOppm、12ppm、14ppm 以及 16ppm 的 5 個而進 行。 溶存氣體以外的條件，係設爲被使用於晶圓之超音波 洗淨中的一般之條件。例如，使超音波產生的時間，係設 爲10分鐘。在被使用於實驗中之晶圓上，係預先均勻地 被附著有4000個的粒子，又，如圖1以及圖2所示一般 ，在本實驗中，係使用有可收容複數之晶圓，且在下方側 部設置有用以供給洗淨液之洗淨用噴嘴之洗淨槽。 於表1、圖6以及圖7中，展示實驗結果。表1以及 圖6，係展示溶存氣體濃度與在各溶存氣體濃度下之粒子 除去效率（=(1 一（在超音波洗淨後殘留於試驗用晶圓 上之粒子的數）/4000) xlOO%)之間的關係。又，對超 -26- 200830391 音波洗淨後之試驗用晶圓作觀察，而調查了試驗用晶圓中 之粒子被以高除去效率而除去之區域。於圖7中，係展示 有在溶存氣體濃度爲14ppm之情況以及16ppm之情況下 的晶圓之觀察結果。於圖7中，斜線部分，係爲視認出粒 子係以高除去效率而被除去之區域。又，在圖7之斜線部 中的斜線之密度，係略比例於在被視認之該當部分中的除 去效率。另外，在圖7之紙面中的試驗用晶圓之配置，係 對應於在洗淨槽內之試驗用晶圓的配置。亦即是，在圖7 之紙面中的試驗用晶圓之下側部分，係成爲在超音波洗淨 中被配置於洗淨槽內的下側（超音波產生裝置之振動子側 )之部分。 〔表1〕 表1 :實驗1之實驗結果 氣體溶存濃度（ppm) 8 10 12 14 16 粒子除去效率（％) 38.2 53.5 64.4 7 8.9 6 0.5 如同由表1以及圖6而能夠理解一般，當溶存氣體濃 度爲14ppm時，係能夠以最高的除去效率來將粒子除去 。又，隨著溶存氣體濃度從8ppm而上升至14ppm，粒子 除去效率亦提昇（上升）。 又，在對洗淨槽內之氣泡的產生作觀察後，發現了， 隨著溶存氣體濃度之上升，在洗淨槽內之氣泡的產生量亦 上升。特別是，當溶存氣體濃度爲14PPm以及16ppm的 情況時，氣泡之產生係爲活躍。如圖7所示，當溶存氣體 -27- 200830391 濃度爲14ppm以及16ppm的情況時，在試驗用晶圓之上 側的粒子之除去效率係降低。相較於溶存氣體濃度爲 14ppm之情況，在16ppm的情況時，粒子之除去效率降 低的區域（圖7中之白色區域）係爲更廣。另一方面，若 是將視認出係以高除去效率而將粒子除去的區域彼此作比 較，則相較於溶存氣體濃度爲14ppm之情況，在16PPm 的情況時，係以更高的除去效率而將粒子除去。 由此些之結果，可以推測出：氣泡係吸收在洗淨液中 之超音波的傳播，其結果，大量之氣泡之產生係會阻礙粒 子除去效率之提昇。 〔實驗2〕 將氮的溶存濃度爲14ppm，而二氧化碳之溶存濃度係 成爲相異之値的洗淨液儲存於洗淨槽中，並將試驗用晶圓 浸漬於洗淨槽內之洗淨液中，而於洗淨液中使超音波產生 。在本實驗中所使用之洗淨液，係被脫氣至溶存氣體濃度 成爲Oppm爲止，而後，在將氮之溶存氣體濃度調整至 1 4ppm的同時，對二氧化碳之溶存氣體濃度作調整。亦即 是，在洗淨槽內之洗淨液中，作爲氣體，係僅溶存有氮與 一^氧化碳。實驗，係將一氧化之溶存濃度設定爲〇ppm (比較例）、33〇ppm (實施例）而進行。超音波洗淨， 係進行4分鐘。作爲洗淨液，係使用純水。超音波之輸出 ，係設爲96W。又，試驗用晶圓，係與實驗〗同樣的，使 用：預先均勻地附著有4000個的粒子，且進而形成有大 -28- 200830391 略1 000億個的損傷評價用之突部者。 將實驗結果展示於表2。表2，係展示二氧化碳之溶 存氣體濃度與在各溶存氣體濃度下之粒子除去效率（=( 1 -（在超音波洗淨後殘留於試驗用晶圓上之粒子的數） / 4000 ) xl 00% )之間的關係。又，表2，係展示二氧化 碳之溶存氣體濃度與在各溶存氣體濃度下之配線圖案之損 傷數量（二（在超音波洗淨後倒下之試驗用晶圓突部的數 量））之間的關係。 〔表2〕 表2:實驗2之實驗結果 比較例 實施例 C〇2溶存氣體濃度（ppm) 0 330 粒子除去效率（％ ) 36.5 3 6.6 損傷數量（pee) 1473 195 當二氧化碳係溶解於洗淨液中的情況時，配線圖案之 損傷數量係急遽降低。 又，粒子之除去效率，在二氧化碳之溶存氣體濃度爲 Oppm的情況時和3 3 0ppm的情況時，係略爲相同。亦即 是，當將二氧化碳以溶存氣體濃度33 Oppm來溶解的情況 時，相較於未溶解有二氧化碳的情況，在具有同等之粒子 除去作用的同時，相較於未溶解有二氧化碳的情況，能夠 大幅度的降低損傷數量。 在對洗淨槽中之氣泡的產生作觀察後，發現了，在二 -29- 200830391 氧化碳之溶存氣體濃度爲0PPm的情況和33〇PPm的情況 中，係略爲相同。 另外，表2之結果，係爲將洗淨槽內之洗淨液的溫度 ‘ 設爲28 °c時之結果。當將洗淨槽內之溫度設爲4〇°C時， ¥ 氣泡之產生係爲顯著，又，粒子之除去效率亦降低。 【圖式簡單說明】 φ 〔圖1〕圖1，係爲將本發明之基板洗淨裝置的其中 一種實施型態之構成作槪略展示的圖。 〔圖2〕圖2，係爲展示基板洗淨裝置之處理槽的上 面圖。 〔圖3〕圖3，係爲用以說明當在洗淨槽內產生有大 量氣泡的情況時，於洗淨液中的超音波之傳播作用的圖。 〔圖4〕圖4，係爲用以說明當在洗淨槽內產生有少 量氣泡的情況時，於洗淨液中的超音波之傳播作用的圖。 φ 〔圖5〕圖5，係爲對應於圖1之圖，而爲將圖1所 示之基板洗淨裝置的變形例之構成作槪略展示的圖。 〔圖6〕圖6，係爲用以說明溶存氣體濃度與粒子除 去效率間之關係的圖。 〔圖7〕圖7，係爲用以說明溶存氣體濃度與晶圓中 之粒子除去效率變高的區域間之關係的圖。 【主要元件符號說明】 1 〇 :基板洗淨裝置 -30- 200830391 12 :洗淨槽 13 :排出管 1 5 :外槽 1 6 :排出管 ~ 1 8 :控制裝置 1 9 :記錄媒體 20 :保持構件 _ 22 :棒狀構件 24 :基部 3 〇 :超音波產生裝置 3 2 :筒頻驅動電源 34:超音波震盪器 3 6 :驅動切換機構 3 8 :振動子 40 :洗淨液供給設備 φ 43 :分歧管 5 0 :第1供給管 5 2 :流量計 54 :開閉閥 55 :第1溶解裝置 5 5 a :第1氣體源 5 6 :第1洗淨用噴嘴 56a :噴嘴孔 5 8 :調溫機構 -31 - 200830391 60 :第2供給管 62 :流量計 64 :開閉閥 65 :第2溶解裝置 65a :第2氣體源 66 :第2洗淨用噴嘴 66a ：噴嘴孔 68 :調溫機構 70 :第3供給管 72 :洗淨液源 75 :脫氣裝置 W :被處理晶圓The nozzle of 200830391 is supplied to the washing tank 1 2 . Next, the cleaning tank 1 2 that receives the first liquid and the second cleaning liquid from the cleaning liquid supply device 40 will be described. The cleaning tank 1 2, as shown in Figs. 10 and 2, has a substantially rectangular parallelepiped profile. In the absence of 12, it is formed to open the upper side of the wafer as will be described later. Further, on the bottom surface of the washing tank 12, a discharge pipe 13 for discharging the stored washing liquid is provided. Further, as shown in Fig. 1, an outer groove 15 is provided to open the C-shape above the cleaning tank 12. Further, the tank 15 is used to recover the washing liquid overflowing from the opening above the upper side. And the outer tank 15 of the washing tank 12 is also provided with a discharge pipe 16 for washing the recovered washing. The cleaning tank 1 2 and the outer tank 15 are formed, for example, by using a narrow quartz or the like. Further, the washing liquid discharged from the washing tank 1 2 and the tubes 1 3 and 16 of the outer tank 15 can be directly discarded or can be reused. Next, with respect to the holding member 20 for holding the wafer W, as shown in FIG. 1 and FIG. 2, the holding member 20 is provided with four rod-shaped members 2 2 extending in the east-plane direction, and four. The rod member is unilaterally provided as a single supported base 24. The rod-shaped holding member 22 is a plurality of wafers W, for example, 50 wafers w, which have been subjected to a single cleaning process, and is supported from below. Therefore, each of the rod-shaped members 22 is formed with a groove (not shown) at a predetermined interval along the longitudinal direction thereof. The wafer W is fitted into the groove, and is used as a clean groove for carrying out the cleaning of the name, such as a clean tank, and the same liquid discharge resistance discharge cycle. For example, if the water is 22, it becomes a place, and the surface of the wafer 16-200830391 w and the extending direction of the rod member become a slightly perpendicular intersection, that is, the surface of each wafer W becomes It is held in the vertical direction via the holding member 20 (refer to FIG. 1). However, as can be understood from Fig. 2, the arrangement pitches of the nozzle holes 56 & 6 6 a of the first cleaning liquid nozzle 56 and the second cleaning liquid nozzle 66 are maintained and maintained. The arrangement pitch of the wafers W of the members 20 is slightly the same. Further, the plurality of nozzle holes 56a and 66a of the first cleaning liquid nozzle 56 and the second cleaning liquid nozzle 66 are capable of discharging the cleaning liquid between the wafers W held by the holding member 20. The way it is arranged. On the other hand, the base portion 24 of the holding member 20 is coupled to a lifting mechanism (not shown). By lowering the holding member 20 for holding the wafer W by the elevating mechanism, the wafer W can be immersed in the cleaning liquid stored in the cleaning tank 12. Further, the elevating mechanism is connected to the control device 18, and the immersion of the cleaning liquid by the wafer W is controlled via the control device 18. Next, the description will be given for the ultrasonic device 30. As shown in Fig. 1, the ultrasonic generating device 30 is provided with a vibrator 38 attached to the outside of the bottom of the washing tank 12, and a high-frequency driving power source 32 for driving the vibrator 38, and is connected to the high. The ultrasonic oscillator 34 of the frequency drive power source 32. In the present embodiment, a plurality of vibrators 3 8 are provided, and the vibrators 3 8 are arranged so as to occupy a part of the outer surface of the bottom of the washing tank 1 2 . Further, as shown in Fig. 1, the super-first wave generating means 30' is further provided with a drive mechanism -17-200830391 switching mechanism 36 connected to the ultrasonic oscillator 34 and the respective vibrators 38. By driving the switching mechanism 36, the plurality of vibrators 38 can be driven as a whole, and one or two or more vibrators can be individually driven. When the vibrator 38 is driven and vibrates, the ultrasonic wave propagates through the bottom of the washing tank 1 2 in the washing liquid stored in the washing tank 12, whereby the ultrasonic wave is in the washing tank. Produced in the cleaning solution in 1 2 . Further, the ultrasonic generating device 30 is connected to the control device 18, and the ultrasonic wave of the cleaning liquid is controlled via the control device 18. Next, the control device 18 will be described. As described above, the control device 18 is connected to each component of the substrate cleaning device 10, and controls the operation of each component. In the present embodiment, the control device 18 includes a computer, and executes a program stored in the recording medium 19 in advance by the computer, thereby executing the processed wafer W using the substrate cleaning device 10. Wash. Next, an example of a cleaning method using the wafer W having the substrate cleaning apparatus 10 formed by such a configuration will be described. First, pure water is supplied from the cleaning liquid source 72 to the third supply pipe 70 as a cleaning liquid. The cleaning liquid flowing through the third supply pipe 70 is degassed by the deaerator 75, and the third cleaning liquid having a dissolved gas concentration of 0 ppm is obtained by rounding off the decimal point. Then, the third cleaning liquid having a dissolved gas concentration of 0 ppm flows through the branch pipe 43 to a portion of the first supply pipe 50, and the remainder flows to the second supply pipe 60. The third cleaning liquid that has flowed into the first supply pipe 50 is dissolved in nitrogen as a gas that is difficult to dissolve, via the first dissolution -18-200830391 device 55. In this manner, the first cleaning liquid in which nitrogen is dissolved at a specific concentration can be obtained from the third cleaning liquid. In the present embodiment, the flow rate of the first cleaning liquid flowing from the first supply pipe 50 to the cleaning tank 12 is considered so that the dissolved nitrogen concentration of the cleaning liquid in the cleaning tank 1 is 14 ppm. And the flow rate of the second cleaning liquid flowing from the second supply pipe 60 to the cleaning tank 12 determines the amount of nitrogen dissolved in the first cleaning liquid. The supply amount of the first cleaning liquid is determined by adjusting the opening degree of the flow meter 52 in accordance with a program preset by the control unit 18. Further, the control unit 18 controls the temperature adjustment unit 58 based on a program set in advance. As a result, in the cleaning tank 12, the first cleaning liquid having a specific temperature is supplied at a specific concentration (p p m ) and a supply amount (1 / m i η ). Similarly, the third cleaning liquid that has flowed into the second supply pipe 60 is dissolved in carbon dioxide which is a gas which is easily dissolved, via the second dissolution device 65. In this way, from the third cleaning liquid, a second cleaning liquid in which carbon dioxide is dissolved at a specific concentration can be obtained. In the present embodiment, the first washing of the washing tank 12 from the first supply pipe 50 is considered so that the dissolved carbon dioxide concentration of the washing liquid in the washing tank 1 2 is 3 3 0 ppm. The flow rate of the clean liquid and the flow rate of the second cleaning liquid flowing from the second supply pipe 60 to the cleaning tank 12 determine the amount of carbon dioxide dissolved in the second cleaning liquid. The supply amount of the second cleaning liquid is determined by adjusting the opening degree of the flow meter 62 in accordance with a program set in advance by the control unit 18. Further, the control unit 18 controls the temperature adjustment unit 68 based on a program set in advance. As a result, in the cleaning tank 12, the second cleaning liquid having a specific temperature of -19-200830391 is supplied at a specific concentration (ppm) and a supply amount (1 / m i η ). As described above, in the cleaning tank 12, a cleaning liquid in which nitrogen and carbon dioxide are respectively dissolved in a specific dissolved gas concentration is stored. Next, the holding member 20 holding the processed wafer W of a specific number (for example, 50 pieces) is lowered, and the wafer W to be processed is immersed in the cleaning liquid in the cleaning tank 12. Then, the control device 18 operates the ultrasonic generating device 30 to cause the ultrasonic waves to be generated in the washing liquid in the washing tank 12. Thereby, the wafer W immersed in the cleaning tank 12 is subjected to ultrasonic cleaning (me gas onic treatment). As a result, particles (dirt, etc.) adhering to the surface of the wafer W are removed. In the present embodiment, in the above-described process, the first cleaning liquid is continuously supplied from the first supply pipe 50 to the cleaning tank 12, and the second cleaning liquid is continuously supplied from the second supply pipe 60. It is supplied to the washing tank 12. As shown in Fig. 1 and Fig. 2, in general, the first cleaning liquid is placed between the wafers W held by the holding member 20, and is spit obliquely upward. Similarly, the second cleaning liquid is also placed between the wafers W held by the holding member 20, and is spit obliquely upward. Therefore, the discharge of the first cleaning liquid and the second cleaning liquid promotes the effect of floating the particles removed from the wafer W to the liquid level of the cleaning liquid in the cleaning tank 12, and further It also promotes the effect of overflowing the cleaning liquid from the washing tank 12 to the outer tank 15. Thereby, it is possible to prevent the particles once removed from the wafer W from adhering to the other portions of the wafer W again. However, in this project, it is not necessary to continue to supply the cleaning liquid to the cleaning tank 12 for -20-200830391, and it is also possible to limit the supply time of the cleaning liquid, or it may be set to be completely absent. Supply the cleaning solution. According to the present embodiment, as is apparent from the examples described later, it is possible to remove the particles with high removal efficiency and to suppress the damage to the wiring pattern. Although the mechanism for generating such a phenomenon is not clear, the use of Fig. 3 and Fig. 4 mainly for the description of the machine which can be regarded as one of the important reasons for this phenomenon. φ However, the present invention is not limited to the following mechanisms. After the inventors of the present invention accumulated various investigation results, it was found that, like the experimental results described later (refer to the examples), (1) the generation of a large number of bubbles hindered the removal of particles; (2) dissolved in The gas in the cleaning liquid can effectively suppress damage to the wiring pattern. In the present embodiment, in the ultrasonic cleaning process, the gas (nitrogen) which is hardly dissolved in the cleaning liquid in the cleaning liquid, and the gas (carbon dioxide) which is easily dissolved in the cleaning liquid are used. Dissolved in the washing liquid # in the washing tank 1 2 . When the pressure of the cleaning liquid is changed by irradiating the ultrasonic wave with the ultrasonic wave, the molecular system which is hard to be dissolved in the cleaning liquid (the gas lacking stability in the cleaning liquid) is in an imminent state change. And caused by vacuoles. However, this bubble phenomenon can be considered as one of the main causes of peeling (removing) particles adhering to the wafer W from the wafer. Therefore, it is difficult to dissolve the gas in the cleaning liquid, which contributes to the improvement of the removal efficiency of the particles. In addition, if a cavitation phenomenon occurs, the gas system dissolved in the cleaning liquid becomes easily bubbled with a sudden pressure change -21 - 200830391. As described above, the generation of a large number of bubbles hinders the removal of particles. This system can be presumed to be as shown in Fig. 3. The generated air bubbles hinder the propagation of ultrasonic waves in the cleaning liquid, and the ultrasonic waves cannot cover the surface of the wafer W and move. In other words, if the gas which is difficult to dissolve is excessively dissolved in the cleaning liquid, the area in which the particles in the wafer are removed is concentrated on one side, and the removal efficiency is lowered. On the other hand, even if the ultrasonic wave is irradiated to the cleaning liquid, the pressure in the cleaning liquid is changed, and the molecular system which is easy to dissolve in the cleaning liquid (a gas having stability in the cleaning liquid) does not Produce a state change. That is to say, the gas which is easily dissolved does not cause cavitation, and the possibility of bubble formation is also reduced. Therefore, the gas which is easily dissolved in the cleaning liquid does not cause the deterioration of the ultrasonic wave, and as shown in Fig. 4, the ultrasonic wave is widely moved in the cleaning tank 12. However, as described above, the gas dissolved in the cleaning liquid effectively suppresses damage to the wiring pattern. In this case, it is presumed that the gas dissolved in the cleaning liquid absorbs the shock wave generated by the cavitation phenomenon, and as a result, the damage of the wiring pattern caused by the shock wave can be prevented. In other words, the gas which is easily dissolved does not cause bubble formation and hinders the propagation of ultrasonic waves, and can effectively suppress damage to the wiring pattern. In the present embodiment, the wiring pattern formed on the wafer W can be greatly suppressed by the action of the gas which is hardly dissolved in the cleaning liquid and the action of the gas which is easily dissolved in the cleaning liquid. The damage is caused, and the particles are removed from the wafer W with high removal efficiency. -22- 200830391 As described above, the ultrasonic cleaning process for causing super-chopper in the washing liquid in the washing tank 1 2 is continued for about 5 minutes, for example. Then, the ultrasonic wave irradiation by the ultrasonic generating device 30 is stopped, and the ultrasonic cleaning process is ended. When the ultrasonic cleaning of the wafer W is completed, the holding member 20 is lifted, and the wafer is carried out from the cleaning tank 12. As described above, the cleaning process for one of the processed wafers W is completed. As described above, in the present embodiment, when ultrasonic waves are generated in the cleaning liquid of the cleaning tank 1 2, the gas which is easily dissolved in the cleaning liquid and the gas which is hardly dissolved in the cleaning liquid are It is dissolved in the washing liquid in the washing tank 1 2 . The gas which is dissolved in the cleaning liquid and which is difficult to dissolve is caused by the active bubble phenomenon. By this cavitation phenomenon, particles can be removed from the wafer W with high removal efficiency. On the other hand, the gas which is easily dissolved in the cleaning liquid makes it difficult to generate a cavitation phenomenon, and it is difficult to bubble with the cavitation phenomenon. On the other hand, the gas which is easily dissolved is maintained in a state of being dissolved in the cleaning liquid, and absorbs the shock wave which is caused by the bubble phenomenon. Therefore, damage to the pattern formed on the wafer W can be prevented. Thereby, the particles can be removed from the wafer W with high removal efficiency while greatly reducing the damage of the wiring pattern of the wafer W. The above embodiments are within the scope of the present invention. Make various changes. Hereinafter, an example of a modification will be described. In the above-described embodiment, the cleaning liquid is subjected to ultrasonic cleaning using the pure water as the cleaning liquid, but -23-200830391 is not limited thereto. As the cleaning liquid, a chemical liquid such as SCI (permine ammonia; NH4OH/H202/H20) may be used, and the treated crystal W may be ultrasonically washed. Further, when the chemical liquid is used for washing, it is necessary to wash and wash with pure water after the washing treatment by the chemical liquid. As the washing and washing treatment using the pure water, the above-described substrate washing method using pure water may be employed. Further, in the above-described embodiment, the first cleaning liquid and the second cleaning liquid are supplied to the cleaning tank 1 2 via the individual supply pipes 50 and 60, but the invention is not limited thereto. this. For example, as shown in FIG. 5, a mixed supply pipe 80 that connects the first supply pipe 50 and the second supply pipe 60 may be provided, and the first cleaning liquid and the second cleaning liquid may be mixed. It is supplied to the washing tank 12. In the example shown in Fig. 5, the first supply pipe 50 and the second supply pipe 60 are connected to the mixing supply pipe 80 via the mixing valve 82. Further, in the illustrated example, the temperature adjustment mechanism 8 is provided in the mixing supply pipe 80', and the temperature adjustment is not provided in the first supply pipe 50 and the second supply pipe 60. mechanism. The temperature of the washing liquid supplied from the mixing supply pipe 80 to the washing tank 1 2 is adjusted by the temperature adjusting mechanism 8 8 . In addition, in the modification shown in FIG. 5, the mixing supply pipe 80 and the mixing valve 8 2 are further provided, and the arrangement positions of the temperature control mechanisms are different, and other components and FIG. 1 to FIG. The embodiment shown in Fig. 4 is slightly the same. In the same manner as in the embodiment shown in Fig. 1 and Fig. 4, the same reference numerals will be given to the same components, and the detailed description will be omitted. -24 - 200830391 Alternatively, as shown in Fig. 1, the first supply pipe 50 and the second supply pipe 60 may be connected in series as shown by a two-dot chain line. In other words, the first cleaning liquid can be caused to flow from the first supply pipe 50 to the second supply pipe 60, and the gas which is easily dissolved can be dissolved in the cleaning liquid, and then the gas which is easily dissolved can be dissolved and dissolved. The cleaning liquid of both of the gases is supplied to the cleaning tank 12; or the second cleaning liquid can flow from the second supply pipe 60 to the first supply pipe 50, and the gas which is difficult to dissolve is dissolved in the gas. In the cleaning liquid, a cleaning liquid in which both a gas which is easily dissolved and a gas which is difficult to dissolve are dissolved is supplied into the cleaning tank 1 2 . Further, in the above-described embodiments, the concentration of the dissolved gas in each of the cleaning liquids is merely an example, and various changes can be made. However, as described above, the substrate cleaning apparatus 10 is provided with a control unit 18 including a computer. By the control device 18, the components of the substrate cleaning apparatus 1 are operated, and the cleaning of the wafer W to be processed is performed. Further, the program executed by the computer of the control device 18 for performing the cleaning using the wafer W having the substrate cleaning apparatus 10 is also the object of the present application. Further, the computer readable recording medium 169 in which the program is recorded is also the object of the present application. Here, the recording medium i 9 also includes a floppy disk (a flexible disk) or a hard disk device or the like which can be recognized as a single body. In addition, in the above description, the substrate cleaning method, the substrate cleaning apparatus, the program, and the recording medium according to the present invention are applied to the cleaning process of the wafer W, but the example is not The present invention is limited to this, and can be applied to a cleaning process such as an LCD substrate or a CD substrate. -25-200830391 [Examples] In order to explain the present invention in more detail by way of examples, two experiments described below were carried out. [Experiment 1] A washing solution in which nitrogen was dissolved in a different dissolved concentration was stored in a washing tank, and the test wafer was immersed in the washing liquid to generate ultrasonic waves. The cleaning liquid used in this experiment was deaerated until the concentration of the dissolved gas became 0 ppm, and then nitrogen was dissolved in the cleaning liquid at a concentration of the dissolved gas. That is, in the cleaning liquid in the washing tank, as a gas, only nitrogen is dissolved. In the experiment, the concentration of nitrogen dissolved was set to 5 at 8 ppm, 10 ppm, 12 ppm, 14 ppm, and 16 ppm. The conditions other than the dissolved gas are generally used in the ultrasonic cleaning of the wafer. For example, the time at which the ultrasonic wave is generated is set to 10 minutes. On the wafer used in the experiment, 4000 particles were uniformly attached in advance, and as shown in FIG. 1 and FIG. 2, in this experiment, a wafer capable of accommodating a plurality of wafers was used. Further, a washing tank for supplying a cleaning nozzle for supplying the cleaning liquid is provided on the lower side portion. The results of the experiment are shown in Table 1, Figure 6, and Figure 7. Table 1 and Figure 6 show the dissolved gas concentration and the particle removal efficiency at each dissolved gas concentration (= (1 (the number of particles remaining on the test wafer after ultrasonic cleaning) / 4000) xlOO %)The relationship between. Further, the test wafers after the ultrasonic cleaning of Super-26-200830391 were observed, and the regions in which the particles in the test wafer were removed with high removal efficiency were examined. In Fig. 7, the observation results of the wafer in the case where the dissolved gas concentration is 14 ppm and 16 ppm are shown. In Fig. 7, the hatched portion is a region in which the particle system is recognized as being removed with high removal efficiency. Further, the density of the oblique lines in the oblique line portion of Fig. 7 is slightly proportional to the removal efficiency in the portion to be recognized. Further, the arrangement of the test wafer in the paper surface of Fig. 7 corresponds to the arrangement of the test wafer in the cleaning tank. In other words, the lower portion of the test wafer in the paper surface of Fig. 7 is placed on the lower side (the vibrator side of the ultrasonic generating device) disposed in the cleaning tank during ultrasonic cleaning. . [Table 1] Table 1: Experimental results of experiment 1 Gas storage concentration (ppm) 8 10 12 14 16 Particle removal efficiency (%) 38.2 53.5 64.4 7 8.9 6 0.5 As can be understood from Table 1 and Figure 6, when dissolved When the gas concentration is 14 ppm, the particles can be removed with the highest removal efficiency. Further, as the concentration of the dissolved gas increases from 8 ppm to 14 ppm, the particle removal efficiency also increases (rises). Further, after observing the generation of the bubbles in the washing tank, it was found that as the concentration of the dissolved gas increased, the amount of generation of bubbles in the washing tank also increased. In particular, when the dissolved gas concentration is 14 ppm and 16 ppm, the generation of bubbles is active. As shown in Fig. 7, when the concentration of the dissolved gas -27-200830391 was 14 ppm and 16 ppm, the removal efficiency of the particles on the upper side of the test wafer was lowered. When the concentration of the dissolved gas is 14 ppm, in the case of 16 ppm, the region where the particle removal efficiency is lowered (the white region in Fig. 7) is wider. On the other hand, in the case where the regions in which the particles are removed with high removal efficiency are compared with each other, the concentration of the dissolved gas is 14 ppm, and in the case of 16 ppm, the removal efficiency is higher. Particles are removed. As a result of this, it is presumed that the bubble absorbs the propagation of the ultrasonic wave in the cleaning liquid, and as a result, the generation of a large number of bubbles hinders the improvement of the particle removal efficiency. [Experiment 2] A cleaning solution in which the dissolved concentration of nitrogen is 14 ppm, and the dissolved concentration of carbon dioxide is stored in a washing tank, and the test wafer is immersed in a washing tank. In the middle, the ultrasonic waves are generated in the washing liquid. The cleaning liquid used in this experiment was degassed until the concentration of the dissolved gas became 0 ppm, and then the concentration of the dissolved gas of nitrogen was adjusted to 14 ppm, and the concentration of the dissolved gas of carbon dioxide was adjusted. That is, in the cleaning liquid in the washing tank, as the gas, only nitrogen and carbon monoxide are dissolved. The experiment was carried out by setting the dissolved concentration of monooxidation to 〇ppm (comparative example) and 33 〇ppm (Example). Ultrasonic cleaning, for 4 minutes. As the washing liquid, pure water is used. The output of the ultrasonic wave is set to 96W. Further, the test wafer was used in the same manner as in the experiment, and 4,000 particles were uniformly adhered in advance, and a projection for damage evaluation of a large amount of 280-200830391 was formed. The experimental results are shown in Table 2. Table 2 shows the dissolved gas concentration of carbon dioxide and the particle removal efficiency at each dissolved gas concentration (= (1 - (number of particles remaining on the test wafer after ultrasonic cleaning) / 4000) xl 00 % )The relationship between. Further, Table 2 shows the concentration of the dissolved gas of carbon dioxide and the number of damages of the wiring pattern at each dissolved gas concentration (two (the number of test wafer protrusions fallen after ultrasonic cleaning)) relationship. [Table 2] Table 2: Experimental results of Experiment 2 Comparative Example Example C〇2 Dissolved gas concentration (ppm) 0 330 Particle removal efficiency (%) 36.5 3 6.6 Damage amount (pee) 1473 195 When carbon dioxide is dissolved in the wash In the case of liquid, the number of damages in the wiring pattern is drastically reduced. Further, the particle removal efficiency is slightly the same when the dissolved gas concentration of carbon dioxide is Oppm and when it is 30,000 ppm. That is, when carbon dioxide is dissolved at a dissolved gas concentration of 33 Oppm, it is possible to have an equivalent particle removal effect and a case where carbon dioxide is not dissolved, compared to the case where carbon dioxide is not dissolved. Significantly reduce the number of damage. After observing the generation of the bubbles in the washing tank, it was found that in the case where the dissolved gas concentration of the carbon oxide was 0 ppm and the case of 33 〇 PPm in the second -29-200830391, the system was slightly the same. Further, the results of Table 2 are the results of setting the temperature of the washing liquid in the washing tank to 28 °C. When the temperature in the washing tank is set to 4 ° C, the generation of bubbles is remarkable, and the removal efficiency of the particles is also lowered. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a configuration of one embodiment of a substrate cleaning apparatus of the present invention. Fig. 2 is a top plan view showing a processing tank of the substrate cleaning apparatus. Fig. 3 is a view for explaining the propagation effect of ultrasonic waves in the cleaning liquid when a large number of bubbles are generated in the cleaning tank. Fig. 4 is a view for explaining the propagation effect of ultrasonic waves in the cleaning liquid when a small amount of air bubbles are generated in the cleaning tank. Fig. 5 is a view corresponding to Fig. 1 and is a schematic view showing a configuration of a modification of the substrate cleaning apparatus shown in Fig. 1. Fig. 6 is a view for explaining the relationship between the concentration of dissolved gas and the efficiency of particle removal. Fig. 7 is a view for explaining the relationship between the concentration of the dissolved gas and the region where the particle removal efficiency in the wafer is high. [Main component symbol description] 1 〇: Substrate cleaning device -30- 200830391 12 : Cleaning tank 13 : Discharge pipe 1 5 : Outer groove 1 6 : Discharge pipe ~ 1 8 : Control device 1 9 : Recording medium 20 : Hold Member _ 22 : Rod member 24 : Base portion 3 超: Ultrasonic wave generating device 3 2 : Tube frequency driving power source 34: Ultrasonic oscillator 3 6 : Drive switching mechanism 3 8 : Vibrator 40 : Cleaning liquid supply device φ 43 : manifold 5 0 : first supply pipe 5 2 : flow meter 54 : opening and closing valve 55 : first dissolution device 5 5 a : first gas source 5 6 : first cleaning nozzle 56a : nozzle hole 5 8 : Temperature mechanism - 31 - 200830391 60 : Second supply pipe 62 : Flow meter 64 : Opening and closing valve 65 : Second dissolution device 65 a : Second gas source 66 : Second cleaning nozzle 66 a : Nozzle hole 68 : Temperature adjustment mechanism 70 : 3rd supply pipe 72: cleaning liquid source 75: degasser W: processed wafer
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