200837513 九、發明說明 【發明所屬之技術領域】 本發明關於顯像液的濃度調節方法及調製裝置以及顯 像液，更詳細而言是關於，使用於液晶基板、印刷基板等 的製程之光阻劑的顯像處理之鹼性的調節顯像液的鹼濃度 方法，調節成理想的濃度，使得可維持一定的顯像速度， 達到更高品質的顯像處理之顯像液的濃度調節方法、可理 想地進行該濃度調節方法的實施之顯像液的調製裝置、以 及藉由這些濃度調節方法及調製裝置所能獲得之顯像液。 【先前技術】 爲了進行液晶基板、印刷基板等的製程之光阻劑的顯 像處理，將以氫氧化四甲銨（TMAH )等爲主成分之鹼水 溶液作爲顯像液來使用。該鹼性的顯像液，至今，隨著基 板尺寸的大型化或處理之進歩，逐漸成爲多量使用，由成 本降低等的觀點來看，將使用過者回收後，再生供給至顯 像裝置。但，隨著反復使用，處理程序停止中等，因與光 阻劑中的酸之反應、空氣中的碳酸氣體或氧之反應，造成 鹼濃度降低，因此，在顯像處理，光阻劑圖案的尺寸精度 及未曝光部之膜厚精度降低，故，將鹼濃度管理成一定爲 重要課題。 針對顯像液的濃度管理，例如，揭示有一種管理裝置 ’是用來管理使用於光阻劑的顯像之鹼系顯像液的裝置， 對顯像裝置，循環供給顯像液，並且，同時管理所循環之 -5- 200837513 顯像液的鹼濃度及顯像液中的溶解樹脂濃度雙方’用以防 止顯像性能之劣化的「顯像液管理裝置」。在該顯像液管 理裝置，藉由吸光光度計檢測顯像液中的溶解樹脂濃度， 藉由導電率計檢測顯像液的鹼濃度，然後排出裝置內的顯 像液且補給顯像液的原液與純水或補給新調製的顯像液， 使得鹼濃度、溶解樹脂濃度及裝置內的顯像液的液面水平 成爲一定。 〔專利文獻1〕日本特許第2561578號公報 【發明內容】 〔發明所欲解決之課題〕 在基板的製造，不受將顯像液的鹼濃度或顯像液中的 溶解樹脂濃度管理成一定的影響，而進行了顯像處理及蝕 刻處理之情況，可見到形成於光罩或基板之電路等的圖案 的線寬變動之現象。實際上，當循環使用顯像液時，會有 因藉由顯像處理，造成形成於基板之電路等的光阻劑圖案 的線寬（CD値）由基準値（設計値）逐漸地偏離之傾向 。即，在顯像處理，於反復進行處理中，顯像速度、換言 之，對光阻劑之溶解速度變動，所獲得之光阻劑圖案的尺 寸精度逐漸降低。其結果，會對藉由蝕刻而形成於基板之 圖案的線寬產生影響。因此，在顯像液的供給管理，期望 不會對顯像速度帶來變動之改善的管理方法。 本發明是有鑑於上述實情而開發完成之發明，其目的 在於提供一種顯像液的濃度調節方法，其是用來調節使用 -6 - 200837513 於液晶基板、印刷基板等的製程之光阻劑的顯像處理之驗 性的顯像液的濃度調節方法，其能夠維持一定的顯像速度 ，且可進行更高品質的顯像處理之顯像液的濃度調節方法 。又，本發明的其他目的在於提供一種顯像液的調製裝置 ，其使用由光阻劑的顯像程序所回收之鹼性的使用過的顯 像液，可調製進行更高品質的顯像處理之顯像液之顯像液 的調製裝置。又，本發明的其他目的是在於，使用上述濃 度調節方法及調製裝置且有效利用使用過的顯像液所獲得 之鹼性的顯像液，其爲可進行高品質的顯像處理之顯像液 〔用以解決課題之手段〕 爲了解決上述的課題，本發明者等進行各種檢討，確 認了在顯像液，不受鹼濃度被維持於基準濃且溶解樹脂濃 度被管理所影響，主要吸收空氣中的碳酸氣體，而生成於 顯像液中之碳酸鹽會抵銷顯像液的溶解能，使顯像液的溶 解速度降低。且，關於碳酸鹽對顯像液的溶解能之影響， 著眼於CD.値與顯像液中的碳酸鹽濃度之關係進行檢討之 結果得知，不容易受到溶解樹脂濃度之變化所影響，而會 因碳酸鹽濃度的上昇，顯像液的溶解能以一定的傾向降低 。又，發現，伴隨著顯像液中的碳酸鹽濃度的上昇，根據 特定的關係提高鹼濃度地進行濃度調節的話，可使顯像液 對光阻劑之溶解能維持於一定，而完成了本發明。 即，本發明的第1型態，是用來調節使用於光阻劑的 200837513 顯像處理之鹼性的顯像液的鹼性濃度之濃度調節方法，其 特徵爲：測定顯像液的鹼濃度及顯像液中的碳酸鹽濃度， 根據預先所製作的能夠發揮進行顯像處理所獲得之CD値 成爲一定的値之溶解能的鹼濃度與碳酸鹽濃度之關係，來 調節鹼濃度。 又，本發明的第2型態，是一種調製裝置，用來調製 使用於光阻劑的顯像處理之鹼性的顯像液的調製裝置，其 特徵爲：具備有：用來調製所定濃度的顯像液之調製槽； 將所調製的顯像液供給至顯像程序之供給管；將使用過的 顯像液承接至前述調製槽之回收管；將鹼濃度較基準濃度 更高濃度的新的顯像液原液供給至前述調製槽之原液供給 管；用來檢測前述調製槽內的顯像液的鹼濃度及顯像液中 的碳酸鹽濃度之濃度計；及根據該濃度計之檢測濃度，控 制來自於前述原液供給管之顯像液原液的供給之控制裝置 ，該控制裝置是根據藉由前述濃度計所測定到的顯像液的 鹼濃度及顯像液中的碳酸鹽濃度、與能夠發揮進行顯像處 理所獲得之CD値成爲一定的値之溶解能的鹼濃度與碳酸 鹽濃度之預先所製作的關係，控制顯像液原液的供給，具 有調節鹼濃度功能。 且，在本發明，爲了更高精度調節鹼濃度，亦可考量 顯像液中的碳酸鹽濃度及溶解樹脂濃度，來調節鹼濃度。 即，本發明的第3型態，是一種顯像液的濃度調節方法， 用來調節使用於光阻劑的顯像處理之鹼性的顯像液的_濃 度之濃度調節方法，其特徵爲：測定顯像液的鹼濃度、顯 -8- 200837513 像液中的碳酸鹽濃度及溶解樹脂濃度，根據能夠發揮進行 顯像處理所獲得之CD値成爲一定的値之溶解能的鹼濃度 與碳酸鹽濃度與溶解樹脂濃度之預先所製作的關係’調節 鹼濃度。 又，本發明的第4型態是一種顯像液的調製裝置，是 用來調製使用於光阻劑的顯像處理之鹼性的顯像液之調製 裝置，其特徵爲··用來調製所定濃度的顯像液之調製槽； 將所調製的顯像液供給至顯像程序之供給管；將使用過的 顯像液承接至前述調製槽之回收管；將鹼濃度較基準濃度 更高濃度的新的顯像液原液供給至前述調製槽之原液供給 管；用來檢測前述調製槽內的顯像液的鹼濃度、顯像液中 的碳酸鹽濃度及溶解樹脂濃度之濃度計；及根據該濃度計 之檢測濃度，控制來自於前述原液供給管之顯像液原液的 供給之控制裝置，該控制裝置是根據藉由前述濃度計所測 定到的顯像液的鹼濃度、顯像液中的碳酸鹽濃度及溶解樹 脂濃度、與能夠發揮進行顯像處理所獲得之C D値成爲一 定的値之溶解能的鹼濃度與碳酸鹽濃度與溶解樹脂濃度之 預先所製作的關係，控制顯像液原液的供給，具有調節鹼 濃度功能。 〔發明的效果〕 右根據本發明的話，伴隨顯像液中的碳酸鹽濃度的上 升’根據特定的關係，調節顯像液的鹼濃度，將對光阻劑 之顯像液的丨谷解能維持於一定，故，在光阻劑的顯像處理 - 9 - 200837513 ’能夠維持一定的顯像速度，可進行更高品質的顯像處理 。又’因應顯像液中的碳酸鹽濃度及溶解樹脂濃度，根據 特定的關係，調節顯像液的鹼濃度，能夠進行更高品質的 顯像處理。 【貫施方式】 參照圖面，說明關於本發明之顯像液的濃度調節方法 及顯像液的調製裝置的一實施形態。 本發明之顯像液的濃度調節方法（以下簡稱爲「濃度 調節方法」。）是在包含旋轉顯影裝置、塗佈顯影裝置等 的顯像裝置之顯像處理程序，調節使用於光阻劑的顯像處 理之鹼性的顯像液（以下簡稱爲「顯像液」。）的鹼濃度 濃度調節方法’又，本發明之顯像液的調製裝置（以下簡 稱爲「調製裝置」。）爲用來調製前述的顯像液之調製裝 置’本發明特別可理想地適用於，以顯像裝置，對由液晶 基板、印刷基板等的製程之光阻劑的顯像程序所回收之使 用過的顯像液予以再利用之情況。 在本發明，作爲顯像液的鹼成分，可舉出例如由氫氧 化鉀、氫氧化鈉、磷酸鈉、矽酸鈉等的無機鹼單獨或混合 物所構成之無機鹼水溶液、或氫氧化四甲銨（TMAH )、 膽鹼等的有機鹼水溶液等。在作爲顯像液，使用TMAH之 情況，TMAH濃度（鹼濃度）被設定成例如2.3 80wt%。又 ，在顯像液，亦可含有非離子性界面活性劑或氟系界面活 性劑等的習知之添加物。 -10- 200837513 再者，在本發明，「C D値」是指，藉由顯像處理， 在基板上所獲得之光阻劑圖案的線寬。又，後述的鹼的「 基準濃度」是指，所能獲得之以下的CD値之鹼的濃度（ 初期的鹼濃度）。上述的CD値爲進行預先所設定之一定 時間的顯像處理時之CD値，且成爲該値產生變化前之評 価的基準之當初的CD値。又，成爲該基準之鹼，亦可爲 單獨鹼，亦可爲含有上述這樣的添加物者，關於使用含有 添加物之實液的情況時之鹼的基準濃度，增加因添加物所 引起之溶解度的差爲佳。 首先，說明關於可理想地適用於本發明的濃度調節方 法之實施的調製裝置。本發明的調製裝置是如圖4所示， 爲用來調製使用於顯像處理之顯像液的調製裝置，使用由 顯像程序所回收之使用過的顯像液，調製前述的顯像液。 該調製裝置具備有：用來調製所定濃度的顯像液之調製槽 (1 );將所調製之顯像液供給至顯像裝置（9 )等的顯像 程序（以下，稱爲「顯像裝置」。）之供給管（2 );將 使用過的顯像液承接至調製槽（1 )之回收管（3 );將鹼 濃度較基準濃度更高濃度的新的顯像液原液供給至調製槽 (1 )之原液供給管（6 ):檢測調製槽（1 )內的顯像液 的鹼濃度及顯像液中的碳酸鹽濃度之濃度計（5 ):及根 據該濃度計之檢測濃度，控制來自於原液供給管（6 )的 顯像液原液之供給的控制裝置（未圖示）。 調製槽（1 )是將顯像液的濃度調節成一定的目標値 ，並且，因應需要，將進行了濃度調節之顯像液供給至顯 -11 - 200837513 像裝置（9 )的供給槽，藉由例如，內容積100 〃 升左右的耐腐蝕性之容器所構成。在調製槽（1 將所收容之顯像液維持於均等的濃度，設有作爲 攪拌手段之介裝有泵浦（41)的循環流路（4) 述這種循環之攪拌手段，比起在槽內設置有螺桿 裝置，所產生之顆粒少，能夠降低顯像液受到污 又，所回收之使用過的顯像液，在顯像裝· 調節成一定溫度，調製槽（1 )內的顯像液也維 定溫度。但，爲了藉由後述的濃度計（5 )更正 顯像液的濃度，理想爲將調製槽（1 )內的顯像 正確地保持於一定溫度（例如25 °C )。因此，在 態，在調製槽（1 )或循環流路（4 )，設置包含 或冷却器之溫度調節手段（未圖示）。 供給管（2 )是由從調製槽（1 )至顯像裝價 流路及介裝於該流路之泵浦（2 1 )所構成，將標 )內的所調製之顯像液供給至顯像裝置（9 )。 管（3 )是以顯像裝置（9 )的使用過的顯像液的 室的排水口）至調製槽（1 )之流路所構成，使 在該流路或顯像裝置（9 )側之泵浦（未圖示） 過的顯像液回收至調製槽（1 )。再者’雖未圖 收管（3 )，亦可設置暫時儲存使用過的顯像液 ，且，將使用過的顯像液的溫度調節成與調製我 的顯像液同等的溫度，因此，亦可設置恆溫槽等 節手段。 “ 2000 公 )，爲了 顯像液的 。藉由上 等的攪拌 杂。 ί ( 9 )被 持大致一 確地測定 液的溫度 理想的形 有加熱器 ί ( 9 )之 1製槽（1 又，回收 排出口（ 用於設置 ，將使用 式，在回 之緩衝槽 ί ( 1 )內 的溫度調 -12- 200837513 原液供給管（6 )是由從原液供給機構（A )(未圖示 )至調製槽（1 )之流路及介裝於該流路之流量調整閥（ 6 1 )所構成，當調製槽（1 )內的顯像液的濃度降低時， 藉由後述的控制裝置之流量調整閥（6 1 )的控制，將較基 準濃度更高濃度的顯像液原液例如在TMAH之情況爲20 〜25wt%的濃度的顯像液原液供給至調製槽（1 )。原液供 給機構（A )主要是藉由預先收容高濃度的顯像液原液用 之內容積5 00〜3000公升左右的原液貯槽、由原液貯槽對 到調製槽（1 )之上述的流路輸送顯像液原液之泵浦所構 成。 又，在本發明的調製裝置，在調製槽（1 )內的顯像 液的鹼濃度變得較目標濃度更高的情況時，會降低顯像液 的濃度，故，通常，具備有對調製槽（1 )供給稀釋水之 稀釋水供給管（7 )。稀釋水供給管（7 )是由從稀釋水供 給機構（B )(未圖示）至調製槽（1 )之流路及介裝於該 流路之流量調整閥（7 1 )所構成，藉由後述的控制裝置之 對流量調整閥（71 )的控制，對調製槽（1 )供給超純水 。作爲稀釋水供給機構（B )，通常使用含有儲存槽及送 液泵浦之純水製造裝置。 且，在本發明的調製裝置，爲了在調製槽（1 )內的 顯像液的量減少至一定量以下之情況時，會補充顯像液， 故，具備有將基準濃度的新的顯像液供給至調製槽（1 ) 之新液供給管（8 )。新液供給管（8 )是由從新液供給機 構（C )(未圖示）至調製槽（1 )之流路及介裝於該流路 -13- 200837513 之流量調整閥（8 1 )所構成，藉由後述的控制裝置對流量 調整閥（8 1 )的控制，對調製槽（1 )供給基準濃度的顯 像液（例如濃度2.38wt%的TMAH )。新液供給機構（C )主要是藉由預先收容新的顯像液用之內容積500〜3000 公升左右的新液貯槽、由新液貯槽對到調製槽（1 )之上 述的流路輸送顯像液之泵浦所構成。 在本發明的調製裝置，濃度計（5 )，爲了更正確地 測定調製槽（1 )內的顯像液的鹼濃度及顯像液中的碳酸 鹽濃度，通常介裝於前述的循環流路（4 )。作爲濃度計 (5 )，爲了不受顯像液中的溶解樹脂濃度的變動所影響 且可高精度地進行濃度測定，而使用特定的濃度計。具體 而言，作爲上述的濃度計（5 )，使用下數濃度計，即， 測量顯像液的溫度、超音波傳播速度及電磁導電率，依據 預先所製作的預定的溫度、鹼濃度及碳酸鹽濃度之超音波 傳播速度與電磁導電率之關係（矩陣），可檢測到顯像液 的鹼濃度及顯像液中的碳酸鹽濃度之多成分濃度計。 上述的多成分濃度計爲藉由測定一定溫度的溶液中的 超音波傳播速度及電磁導電率，可同時即時地測定鹼與碳 酸鹽之2種成分的濃度之濃度計。即，多成分濃度計爲依 據若溶液的溫度一定的話，因應各成分的濃度’首要地特 定液中的超音波之傳播速度及電磁導電率之原理者’在例 如測定2成分之情況，主要是由超音波變換器、超音波發 信器、電磁導電率變換器、電磁導電率發信器及進行預定 的運算之微處理器所構成。 •14- 200837513 在多成分濃度計’適用於上述這樣的顯像液的濃度測 定之情況時，藉由以針對每個鹼濃度及碳酸鹽濃度的各種 組合，在一定溫度條件下預先所測量之超音波傳播速度與 電磁導電率之關係作爲矩陣而預先準備，即，藉由寫入至 微處理器，根據前述的矩陣，能夠由測定値正確地推定運 算鹼濃度與碳酸鹽濃度。再者，作爲上述這樣的多成分濃 度計，可舉出例如例如富士工業社製之液體用多成分濃度 計。再者，除了上述的多成分濃度計以外，作爲測定鹼濃 度之濃度計，能夠使用利用測量流體之曲折率之利用屈折 法的濃度計、或使用利用測量接近紅外領域之波長的接近 紅外法之濃度計，又，作爲測定碳酸鹽濃度之濃度計，能 夠使用例如利用中和滴定之濃度計等。 在本發明的調製裝置，具備有：除了裝置全體的運轉 控制外，控制根據上述這種的濃度計（5 )的測定之顯像 液原液的輸送、稀釋水的輸送、新的顯像液的輸送用之控 制裝置（未圖示）。該控制裝置包含有：將各測量機器的 訊號進行數位變換之輸入裝置、程式控制器或電腦等的運 算處理裝置、及將來自於運算處理裝置之控制訊號予以類 比變換之輸出裝置。 上述的控制裝置，是根據濃度計（5 )之檢測濃度， 控制來自於原液供給管（6 )之顯像液原液的供給。即， 控制裝置是根據藉由濃度計（5 )所測定到的顯像液的鹼 濃度及顯像液中的碳酸鹽濃度、與預先所製作的碳酸鹽濃 度與鹼濃度對基準濃度之不足量之關係，換言之，能夠發 -15- 200837513 揮進行顯像處理所獲得之CD値成爲一定的値之溶解能的 鹼濃度與碳酸鹽濃度之預先所製作的關係，控制顯像液原 液的供給，具有調節鹼濃度功能。藉此，在本發明的調製 裝置，由顯像裝置（9 )回收使用過的顯像液，在調製槽 (1 )，能夠調製適當的鹼濃度的顯像液。 又，上述的控制裝置之結構爲，可控制顯像液原液的 供給，並且控制來自於稀釋水供給管（7 )之稀釋水的供 給、以及來自於新液供給管（8 )之新的顯像液的供給。 藉此，在本發明的調製裝置，能夠將調製槽（1 )內的顯 像液的液量管理成一定。 再者，在本發明的調製裝置，爲了防止顯像液或顯像 液原液與空氣之接觸，藉由氮氣等的鈍氣，密封系統內。 又，在本發明的調製裝置，爲了將系統內的液量保持於一 定，而在適當的部位設置有：當供給顯像液原液時，將剩 餘之使用過的顯像液排出至系統外的機構。雖未圖式，在 例如’調製槽（1 )，附設有包含控制閥之排洩用的流路 或溢流裝置。 其次說明，上述的調製裝置的功能及本發明的濃度調 節方法。在本發明的濃度調節方法，在使用上述這樣的調 製裝置調製顯像液時，首先，藉由回收管（3 )將由顯像 裝置（9 )所排出的使用過的顯像液回收至調製槽（1 )， 並且’ 一邊使調製槽（1 )的顯像液（包含使用過的顯像 液之顯像液）循環於循環流路（4 )並攪拌混合，一邊藉 由溫度調節手段，將顯像液保持於一定溫度，再以測量顯 -16 - 200837513 像液的鹼濃度及顯像液中的碳酸鹽濃度。作爲讀 )，使用前述的多成分濃度計。 在測定調製槽（η內的顯像液的鹼濃度及 的碳酸鹽濃度後，藉由上述的控制裝置，控制原 (6 )的流量調整閥（6 1 )，將調製槽（1 )內的 鹼濃度調節成適當的濃度。在該情況，在本發明 先所製作的碳酸鹽濃度與鹼濃度對基準濃度之不 係，即，能夠發揮CD値成爲一定的値之溶解能 與碳酸鹽濃度之預先所製作的關係，因應碳酸鹽 定値，將鹼濃度調節成基準濃度以上的値。藉此 像液對光阻劑的溶解能維持成一定。以下，更具 本發明的上述的思想。 在對顯像裝置，循環供給顯像液之情況，吸 的碳酸氣體，於顯像液中產生碳酸鹽，該碳酸鹽 對光阻劑的溶解能抵銷，造成進行顯像處理所獲 劑圖案的尺寸精度降低。其結果，形成於基板之 的線寬會與設計寬度不同。又，在將顯像液的鹼 像處理之顯像時間設定成一定之情況，CD値會 用之顯像液中的碳酸鹽濃度與高度所影響。 顯像液中的碳酸鹽濃度對CD値的影響是如 。圖2是針對碳酸鹽濃度不同之7種類的顯像滅 )，分別將鹼濃度（TMAH濃度）調節成2.20 ^ 的範圍之3〜5種類的濃度，確認在各濃度進行 顯像處理之情況時的CD値與前述的顯像液中的 I度計（5 顯像液中 液供給管 顯像液的 ，根據預 足量之關 的鹼濃度 濃度的測 ，能夠顯 體地說明 收空氣中 與顯像液 得的光阻 電路圖案 濃度及顯 受到所使 圖2所示 ：(TMAH ^ 3.27wt% 一定時間 碳酸鹽濃 -17- 200837513 度之關係者。如圖2所示，再使用碳酸鹽濃度〇ppm之新 調製之顯像液（鹼濃度不同的5種）之情況時，CD値成 爲2 · 7 7〜5 . 1 6 μηι ’相對於此，例如，在使用碳酸鹽濃度 5 2 5ppm的顯像液（鹼濃度不同的4種）之情況，CD値成 爲3_70〜5.05μιη，在使用碳酸鹽濃度1 000ρριη的顯像液 (鹼濃度不同的4種）之情況，c D値成爲3 . 5 9〜4 · 3 0 μιη 。即，圖2所示的關係是顯示著，伴隨顯像液中的碳酸鹽 濃度的上昇，顯像液對光阻劑的溶解能以一定的傾向降低 ，CD値以一定的關係增加。 因此，在顯像處理，欲將CD値維持成一定之情況， 需要因應碳酸鹽濃度，提高鹼濃度。例如，欲將CD値設 定成4.00μιη時，再使用碳酸鹽濃度Oppm的新調製之顯像 液的情況，鹼濃度（TMAH濃度）被調節成2.38wt% (基 準濃度），但，再使用碳酸鹽濃度500PPm的顯像液之情 況，必須將鹼濃度（TMAH濃度）調節成2.50wt%，又， 在使用碳酸鹽濃度1 000PPm的顯像液之情況，必須將鹼濃 度（TMAH濃度）調節成2.71 wt%。 由上述的關係，在顯像液做成所必須之鹼濃度’作爲 將CD値維持成一定之情況的碳酸鹽濃度與鹼濃度的必要 補正量之關係（鹼濃度對基準濃度之不足量之關係）’可 如圖1所表示。碳酸鹽濃度與鹼濃度對基準濃度之不足量 之關係是指，如上述’由進行規定的顯像處理（獲得一定 的C D値之處理）的情況的鹼濃度與碳酸鹽濃度的關係預 先導出之關係，指碳酸鹽濃度與對基準的鹼濃度（使用不 -18- 200837513 含碳酸鹽之新調製之顯像液的情況的該顯像液的濃度）的 不足量之關係、在圖1的圖表中’縱軸的TMAH濃度（鹼 濃度）的括弧內的數値是顯示對基準濃度（2.38wt%)之 濃度的不足量。 本發明是如上述般，著眼於將c D値維持成一定的情 況時的顯像液之鹼濃度與碳酸鹽濃度之關係，因應碳酸鹽 濃度，對成爲基準之鹼濃度進行補正者。又，在使用 TMAH之情況，圖1所示的上述的補正量（碳酸鹽濃度與 鹼濃度對基準濃度之不足量）是以下的數學式所表示。 〔數學式1〕 y = 8xl〇-8x2 + 2xlO'4x …⑴ 其中，X爲碳酸鹽濃度（ppm) 、丫爲TMAH濃度（ wt% ) 再者，爲了確認圖2之關係，找出上述的數學式及圖 1的關係，是準備不含碳酸鹽之新調製的鹼濃度不同的複 數種顯像液（例如實際所使用之TMAH水溶液）、與含有 碳酸鹽且鹼濃度不同之做爲樣品的複數種顯像液，針對每 顯像液，進行將溫度及顯像時間做成一定之規定的顯像處 理，測定各自所獲得的光阻劑圖案的C D値。此時，關於 包含碳酸鹽之各鹼濃度的顯像液，藉由一邊確認碳酸鹽濃 度’一邊添加計算量的乾冰，以碳酸鹽濃度成爲例如 lOOppm 、 3 2 5 p p m、 5 0 0 p p m 、 lOOOppm 、 1 5 0 0 p p m 、 2 OOOppm的方式調製複數種。又，由所獲得之結果，依據 統計處理來推定關係式。 -19- 200837513 在本發明，根據上述的數學式（I) 圖表之關係），即，根據能夠發揮CD値 溶解能的鹼濃度與碳酸鹽濃度之預先所製 顯像液中的碳酸鹽濃度，調節鹼濃度。換 鹽濃度的測定値，將鹼濃度調節成基準濃度 此’能夠將顯像液的溶解能維持成一定，能 Η案的尺寸精度，且能夠將cd値控制成一 顯像液中的碳酸鹽濃度爲〇ρριη的情況，驗 基準濃度。 又’在調製裝置等實施本發明之際，在 調節’爲了獲得一定的CD値，需要因應碳 定實際的鹼濃度。在該情況，根據預先所製 度與能夠發揮預定的溶解能的鹼濃度之關係 揮CD値成爲一定的値之溶解能的鹼濃度與 預先所製作的關係（碳酸鹽濃度與加上前述 濃度之關係），調節鹼濃度。上述的關係是 中，作爲横軸的碳酸鹽濃度與縱軸的TM A Η 以顯示。因此，在使用ΤΜAH之情況，上述 鹽濃度與能夠發揮預定的溶解能的鹼濃度之 以以下的數學式加以表示。 〔數學式2〕 y = 8xlO_8x2 + 2xl〇-4x + 2.38 …（II) 其中，X爲碳酸鹽濃度（ppm) 、丫爲 wt% ) 圖1所顯示的 ^爲一定的値之 ’的關係，因應 之，因應碳酸 以上的値。藉 夠提高光阻劑 定。再者，在 濃度被設定成 顯像液的濃度 酸鹽濃度，決 作的碳酸鹽濃 ，即，能夠發 碳酸鹽濃度之 的不足量之鹼 在圖1的圖表 濃度之關係加 的關係（碳酸 關係）是能夠 TMAH濃度（ -20- 200837513 在本發明的調製裝置，對控制裝置寫入濃度測定及控 制運算的運算法’在調製槽（1 )之濃度調節，根據以濃 度計（5 )所測定到的顯像液的鹼濃度及顯像液中的碳酸 鹽濃度，依據上述的數學式（II )控制原液供給管（6 )的 流量調整閥（6 1 )，添加符合鹼濃度的不足量之顯像液原 液，將鹼濃度調節成預定的目標値。又，在依照上述的關 係（數學式（II )的關係），鹼濃度變得過高之情況時， 透過稀釋水供給管（7 )，對調製槽（1 )供給稀釋用的純 水。 再者’在排出回收的使用過的顯像液的一部份等，使 得調製槽（1 )內的顯像液的量降低之情況，透過原液供 給管（6 )及稀釋水供給管（7 )，將顯像液原液及純水供 給至調製槽（1 )，並且以上述的操作進行鹼濃度的調節 ，藉此將調製槽（1 )的液量調節於一定範圍內。或，透 過新液供給管（8 )，將新的顯像液供給至調製槽（1 )來 調節液量。 顯像液原液的供給控制、稀釋水的供給控制及新的顯 像液的供給控制，分別藉由對來自於原液供給機構（A ) 之顯像液原液的供給量、來自於稀釋水供給機構（B )) 之純水的供給量及來自於新液供給管（8 )之顯像液的供 給量進行串聯控制來進行的。又在這些的控制，能夠利用 例如，日本特許第3 74 1 8 1 1號公報所記載之「鹼顯像原液 的稀釋方法及稀釋裝置」所揭示的所謂漸近法。 具體而言，在利用上述的漸近法的調製槽（1 )之例 -21 - 200837513 如鹼濃度的調節，爲了對鹼濃度降低（或驗濃度變 製槽（1 )內的顯像液添加高濃度的顯像液原液（ 水）調節成所定濃度時，執行下述製程’即’藉由 (5 )測定顯像液的濃度之濃度測定製程；及根據 測定製程所測定到的濃度與目標濃度（上述的數學 )所獲得之濃度）的差，算出顯像液原液的不足量 釋水的添加量），供給相當於所算出之不足量（或 )的8 5〜9 9 %理想爲9 2〜9 8 %之量的調製製程。又 測定到的濃度成爲預先所設定的目標濃度的區域値 爲止，由前述的濃度測定製程反復進行調製製程。 能夠更高精度地管理調製槽（1 )之顯像液中的鹼濃 如上述般，在本發明，根據預先所製作的碳酸 與鹼濃度對基準濃度之不足量之關係，因應碳酸鹽 測定値，將鹼濃度調節成基準濃度以上的値。即， 夠發揮CD値成爲一定的値之溶解能的鹼濃度與碳 度之預先所製作的關係，調節鹼濃度。藉此，能夠 液對光阻劑的溶解能維持成一定。因此，若根據本 話，在顯像裝置，能夠維持對於光阻劑之一定的顯 ，且可更進一步提高在顯像處理所製作的光阻劑圖 寸精度及膜厚精度，藉此，能夠進行更高品質的顯 〇 又，在本發明’爲了更高精度調節鹼濃度，亦 像液中的碳酸鹽濃度，一同因應溶解樹脂濃度，來 濃度。如前述般，在循環供給顯像液之情況，會有 高）調 或稀釋 濃度計 在濃度 式（Π (或稀 添加量 ，在所 內的値 藉此， 度。 鹽濃度 濃度的 根據能 酸鹽濃 將顯像 發明的 像速度 案的尺 像處理 可與顯 調節驗 下述傾 •22- 200837513 向，即，在顯像液中會產生碳酸鹽’並且’因顯像處理， 光阻劑會溶解於顯像液中，雖只有稍許，但該溶解樹脂會 使顯像液的溶解能降低。因此’爲了如前述般調節驗濃度 ，因應顯像液中的溶解樹脂濃度進行補正爲佳。 顯像液中的溶解樹脂濃度對CD値的影響是如圖3所 示。圖3是顯示在溶解樹脂（構成光阻劑之樹脂成分）的 濃度不同的6種類的顯像液（實際使用的爲濃度2.3 8 wt °/〇 的TMAH )，進行一定時間之顯像處理的情況時之溶解樹 脂濃度與CD値的變化之關係，如圖3所示’對使用溶解 樹脂濃度〇abs的顯像液（樹脂未溶解之顯像液）的情況 時之基準的C D値，使用例如，溶解樹脂濃度〇 · 2 ab s的顯 像液之情況時，CD値增加〇·〇4 μιη ’在使用溶解樹脂濃度 0.8abs的顯像液之情況時，CD値增加0·2 8 8 μιη。即，圖3 所示的關係是顯示，伴隨顯像液中的溶解樹脂濃度的上昇 ，顯像液對光阻劑的溶解能以一定的傾向降低，CD値以 一定的關係增加。 因此，能夠由實驗找出，將CD値維持成一定之情況 時的顯像液之鹼濃度與碳酸鹽濃度與溶解樹脂濃度的關係 。爲了找出上述的關係，準備不含碳酸鹽及樹脂成分（構 成光阻劑之樹脂成分）的新調製的鹼濃度不同的複數種顯 像液（例如實際所使用的TMAH水溶液）、及包含碳酸鹽 及上述的樹脂成分且鹼濃度不同的樣品之複數種顯像液， 針對各個顯像液，進行與導出前述的數學式（I )及（Π ) 之情況相同的規定的顯像處理，測定各自所獲得之光阻劑 -23- 200837513 圖案的C D値。關於鹼濃度不同的各顯像液的碳酸鹽濃度 ，與前述情況同樣地，藉由添加乾冰，能夠調節成例如 100〜20 0 〇ppm的適當値，又，關於各顯像液的溶解樹脂 濃度，藉由一邊測定溶解樹脂濃度一邊使光阻劑溶解計算 量，將鹼濃度與溶解樹脂濃度調節成例如l〇〇PPm/Oabs， 2 5 0ppm/0 · 3 abs，5 0 0ppm/0.6 ab s 5 1 00 Oppm/0 · 9 abs ° 然後，由所獲得之結果，藉由統計處理，將例如CD 値的變動量作爲從屬變數且鹼濃度與前述的碳酸鹽濃度與 溶解樹脂濃度作爲各獨立變數，進行多因子解析，藉此能 夠推定關係式。藉此，在使用例如TMAH作爲顯像液之情 況，顯像液之鹼濃度的必要補正量（與前述相同的鹼濃度 對基準濃度之不足量）即，能夠發揮CD値成爲一定的値 之溶解能用的鹼濃度的補正量是能夠以以下的數學式加以 表示。以下的數學式中，TMAH濃度（y )的數値顯示對 基準濃度之不足量。 〔數學式3〕 y= ( 2.33x1 0'6x2 + 6.36x1 0'4x + 0.36c ) /8.79 …（III) 其中，X爲碳酸鹽濃度（ppm ) ，C爲溶解樹脂濃度（ abs ) ，y 爲 TMAH 濃度（wt% )。 再者’溶解樹脂濃度的卓位abs ( absorbance)是如 昔知，藉由顯示物質對特定的波長之光的吸收強度的尺度 即吸光度來表示液中的物質的濃度之無次元量的單位，顯 像液中的溶解樹脂濃度是能以該溶解樹脂特有的吸收波長 (例如5 60nm )之吸光度來表示。 -24- 200837513 在本發明’測定顯像液的鹼濃度、顯像液中的碳酸鹽 濃度及溶解樹脂濃度，上述的數學式（III )，因應顯像液 中的碳酸鹽濃度及溶解樹脂濃度，調節鹼濃度。換言之， 因應碳酸鹽濃度的測定値，將鹼濃度調節成基準濃度以上 的値。藉此’能夠將顯像液的溶解能維持成一定，可進一 步提高光阻劑圖案的尺寸精度，又，能更進一步將CD値 控制成一定。 又，爲了在前述的調製裝置等實施本發明之際，在顯 像液的濃度調節，需要以能夠獲得一定的CD値的方式， 因應碳酸鹽濃度及溶解樹脂濃度來決定實際的鹼濃度。在 該情況，根據能夠發揮C D値成爲一定的値之溶解能的鹼 濃度與碳酸鹽濃度與溶解樹脂濃度之預先所製作的關係， 調節鹼濃度。上述的關係，在使用TMAH之情況，能利用 以下的數學式加以表示。 〔數學式4〕 y = (2.33xl(T6x2 + 6.36xl(T4x + 0.36c)/8.79 + 2.3 8 ".(IV) 其中，X爲碳酸鹽濃度（ppm ) ，C爲溶解樹脂濃度（ abs ) ，y 爲 TMAH 濃度（wt% )。 本發明的理想形態之調製裝置是與前述的形態的裝置 同樣地，藉由調製槽（1 )、供給管（2 )、回收管（3 ) 、原液供給管（6 )、濃度計（5 )及控制裝置所構成。在 該情況，作爲濃度計（5 )，使用可檢測調製槽內的顯像 液的鹼濃度、顯像液中的碳酸鹽濃度及溶解樹脂濃度之多 成分濃度計。又，上述的控制裝置是根據藉由濃度計（5 -25- 200837513 )所測定到的顯像液的鹼濃度、顯像液中的碳酸鹽濃度及 溶解樹脂濃度、與能夠發揮CD値成爲一定的値之溶解能 的鹼濃度與碳酸鹽濃度與溶解樹脂濃度之預先所製作的關 係，控制顯像液原液的供給，具有調節鹼濃度功能。 作爲濃度計（5 )，能夠使用附加有溶解樹脂濃度的 測定功能之與前述相同的多成分濃度計。該多成分濃度計 爲依據若溶液的溫度呈一定的話，因應鹼、碳酸鹽及溶解 樹脂的各成分的濃度，首要地特定液中的超音波的傳播速 度、電磁導電率及吸光度之原理者。上述的多成分濃度計 是測量顯像液的溫度、超音波傳播速度、電磁導電率及吸 光度，根據預先所製作的預定的溫度、鹼濃度、碳酸鹽濃 度及溶解樹脂濃度之超音波傳播速度與電磁導電率與吸光 度之關係（規定針對每一個預先準備之鹼濃度、碳酸鹽濃 度及溶解樹脂濃度的各種組合，在一定溫度條件下預先測 量到的超音波傳播速度、電磁導電率及吸光度之關係的矩 陣），來檢測顯像液的鹼濃度、顯像液中的碳酸鹽濃度及 溶解樹脂濃度。 在本發明的調製裝置，根據以濃度計（5 )所測定到 的顯像液的鹼濃度、顯像液中的碳酸鹽濃度及溶解樹脂濃 度，與前述的形態之裝置同樣地，依據上述的數學式（IV )，控制原液供給管（6 )的流量調整閥（6 1 )，添加符 合鹼濃度的不足量之顯像液原液，將鹼濃度調節成預定的 目標値。 再者，在依照上述的關係（數學式（IV )的關係）’ -26- 200837513 驗濃度變得過高之情況時，與前述的裝置同樣地，透過稀 釋水供給管（7 )，對調製槽（1 )供給稀釋用的純水。另 外’在調製槽（1 )內的顯像液的量降低之情況，透過原 液供給管（6 )及稀釋水供給管（7 )，將顯像液原液及純 水供給至調製槽（1 )，或透過新液供給管（8 )，將新的 顯像液供給至調製槽（1 )，藉由上述的操作來進行鹼濃 度的調節。 在本發明，如上述般，測定顯像液的鹼濃度、顯像液 中的碳酸鹽濃度及溶解樹脂濃度，根據能夠發揮CD値成 爲一定的値之溶解能的鹼濃度與碳酸鹽濃度與溶解樹脂濃 度之預先所製作的關係，調節鹼濃度。藉此，可進一步將 顯像液對光阻劑的溶解能，即，顯像速度維持成一定。因 此，若根據本發明的話，顯能夠更進一步提高在像處理所 製作之光阻劑圖案的尺寸精度及膜厚精度。 如上述般，若根據本發明的話，由於能夠在顯像處理 更進一步提高光阻劑圖案的尺寸精度及膜厚精度，故，能 夠進行更高品質的顯像處理。其結果，能夠在鈾刻處理， 於基板上，更高精度地形成圖案。且，由於因應顯像液中 的碳酸鹽濃度的上昇，設定成逐漸地使鹼濃度變高，故， 能夠提高顯像液的循環率，又，可使顯像程序更穩定。又 ，若根據本發明的調製裝置的話，使用由顯像程序所回收 的使用過的顯像液，能夠調製可進行更高品質的顯像處理 之顯像液。又，藉由本發明的濃度調節方法及調製裝置所 獲得之顯像液，由於維持對光阻劑之一定的顯像速度，故 -27- 200837513 能夠進行高品質的顯像處理。 順便一提，使用不含碳酸鹽之新調製之顯像液（實際 所使用之濃度2.38wt%的TMAH)進行規定的顯像處理， 確認所獲得之光阻劑圖案時，CD値爲4.00 μπι。相對於此 ，準備碳酸鹽濃度100〜2000ppm的數種類的使用過的顯 像液，根據前述的數學式（II)的關係調節TMAH濃度， 然後使用各顯像液，進行與上述相同的顯像處理的結果， 使用任一種的顯像液之情況，CD値均爲4.00 μπι。藉此， 確認到，藉由根據數學式（I )及（Π )的關係（圖1所示 的關係）調節鹼濃度，能夠維持一定的溶解能。 且，準備碳酸鹽濃度100〜2000ppm、溶解樹脂濃度〇 〜2. Oabs之數種類的使用過的顯像液，根據前述的數學式 (IV )的關係調節TMAH濃度。然後，使用各顯像液’進 行與上述相同的顯像處理的結果，使用任一種的顯像液之 情況，CD値均爲4·00μιη。藉此，關於溶解有樹脂之顯像 液，也確認到，藉由根據數學式（ΙΠ )及（IV )的關係調 節鹼濃度，可更進一步將溶解能維持於一定。 【圖式簡單說明】 圖1是碳酸鹽濃度與鹼濃度對基準濃度之不足量之關 係、及碳酸鹽濃度與可發揮預定的溶解能的鹼濃度之關係 的圖表。 圖2是顯示顯像液中的碳酸鹽濃度對進行顯像處理所 獲得的光阻劑圖案的線寬（CD値）的影響之圖表。 -28- 200837513 圖3是顯示顯像液中的溶解樹脂濃度對進行顯像處理 所獲得的光阻劑圖案的線寬（CD値）的影響之圖表。 圖4是顯示本發明之顯像液的調製裝置的主要結構元 件之流程圖。 【主要元件符號說明】 1 :調製槽 2 :供給管 21 :泵浦 3 :回收管 4 :循環流路 41 :泵浦 5 :濃度計 6 :原液供給管 6 1 :流量調整閥 7 :稀釋水供給管 7 1 :流量調整閥 8 =新液供給管 8 1 :流量調整閥 9 :顯像裝置 A :原液供給機構 B :稀釋水供給機構 C =新液供給機構 -29-200837513 IX. Description of the Invention [Technical Field] The present invention relates to a method for adjusting the concentration of a developing liquid, a modulating device, and a developing liquid, and more particularly to a photoresist for use in a process such as a liquid crystal substrate or a printed substrate. The alkali-concentrating method for adjusting the imaging solution of the agent is adjusted to a desired concentration, so that a certain imaging speed can be maintained, and a concentration adjustment method of the developing solution for achieving higher quality development processing, A developing device for developing a developing solution which is preferably subjected to the concentration adjusting method, and a developing liquid which can be obtained by the concentration adjusting method and the modulating device. [Prior Art] In order to perform image processing of a photoresist of a process such as a liquid crystal substrate or a printed circuit board, an alkaline water solution containing tetramethylammonium hydroxide (TMAH) or the like as a main component is used as a developing liquid. The alkaline developing solution has been used in a large amount as the size of the substrate is increased or the processing progresses, and is recovered from the use of the substrate, and then regenerated and supplied to the developing device. However, with repeated use, the processing procedure is stopped moderately, and the alkali concentration is lowered due to the reaction with the acid in the photoresist, the reaction of carbonic acid gas or oxygen in the air, and therefore, in the development process, the photoresist pattern is Since the dimensional accuracy and the film thickness accuracy of the unexposed portion are lowered, it is an important subject to manage the alkali concentration. For the concentration management of the developing liquid, for example, a management device is disclosed which is a device for managing an alkali-based developing liquid used for development of a photoresist, and a developing device is circulated and supplied with a developing liquid, and At the same time, it manages both the alkali concentration of the circulating liquid of the 5'-200837513 and the dissolved resin concentration in the developing liquid, and the "developing liquid management device" for preventing deterioration of the developing performance. In the developing solution management device, the concentration of the dissolved resin in the developing liquid is detected by an absorption photometer, the alkali concentration of the developing liquid is detected by a conductivity meter, and then the developing liquid in the apparatus is discharged and the developing liquid is replenished. The original solution and pure water or the newly prepared developing solution are fixed so that the alkali concentration, the dissolved resin concentration, and the liquid level of the developing liquid in the apparatus become constant. [Patent Document 1] Japanese Patent No. 2556178 [Disclosure] [Problems to be Solved by the Invention] In the production of a substrate, it is not necessary to manage the alkali concentration of the developing liquid or the dissolved resin concentration in the developing liquid to a constant level. When the development process and the etching process were performed, the line width of the pattern formed in the circuit of the mask or the substrate was changed. In fact, when the developing solution is recycled, the line width (CD値) of the photoresist pattern formed on the substrate or the like by the developing process is gradually deviated from the reference 値 (design 値). tendency. That is, in the development processing, in the repeated processing, the developing speed, in other words, the dissolution rate of the photoresist varies, and the dimensional accuracy of the obtained photoresist pattern gradually decreases. As a result, the line width of the pattern formed on the substrate by etching is affected. Therefore, in the supply management of the developing liquid, it is desirable to have a management method that does not bring about an improvement in the development speed. The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for adjusting a concentration of a developing liquid, which is used for adjusting a photoresist of a process for using a liquid crystal substrate, a printed substrate, or the like using -6 - 200837513. A method for adjusting the concentration of an imaging liquid that is capable of maintaining a constant imaging speed and capable of performing a higher quality development process of a developing solution. Further, another object of the present invention is to provide a developing device for a developing liquid which can be modulated to perform higher-quality developing processing using an alkaline used developing solution recovered by a developing procedure of a photoresist. A modulation device for the developing solution of the developing liquid. Further, another object of the present invention is to provide an alkaline developing solution obtained by using the used developing solution using the above-described concentration adjusting method and the modulating device, which is a high-quality developing image. Liquid [Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention conducted various reviews and confirmed that the development liquid is not affected by the alkali concentration being maintained at the reference concentration and the dissolved resin concentration being managed, and the main absorption is The carbonic acid gas in the air, and the carbonate formed in the developing solution offsets the dissolution energy of the developing solution, and lowers the dissolution rate of the developing solution. Moreover, regarding the effect of carbonate on the dissolution energy of the imaging solution, attention is paid to CD. As a result of reviewing the relationship between the cesium and the carbonate concentration in the developing solution, it is found that it is not easily affected by the change in the concentration of the dissolved resin, but the solubility of the developing solution is lowered by a certain tendency due to an increase in the concentration of the carbonate. . In addition, it has been found that when the concentration of the alkali solution is increased according to a specific relationship, the concentration of the developer can be maintained at a constant level, and the dissolution of the developer can be maintained at a constant level. invention. That is, the first aspect of the present invention is a method for adjusting the concentration of the alkaline concentration of the alkaline developing solution used for the development of the photoresist of 200837513, which is characterized in that the alkali of the developing solution is measured. The concentration of the carbonate in the developing solution and the concentration of the carbonate in the developing solution are adjusted according to the relationship between the alkali concentration and the carbonate concentration in which the CD 値 obtained by the development process can be a certain amount of enthalpy. Further, a second aspect of the present invention is a modulation apparatus for modulating an alkaline developing solution for use in a developing process of a photoresist, characterized in that: a method for modulating a predetermined concentration a developing solution of the developing liquid; supplying the prepared developing liquid to the supply tube of the developing program; receiving the used developing liquid to the recovery tube of the brewing tank; and having a higher concentration of the alkali than the reference concentration a new developing solution stock solution is supplied to the raw material supply pipe of the preparation tank; a concentration meter for detecting the alkali concentration of the developing liquid in the preparation tank and the carbonate concentration in the developing liquid; and detection according to the concentration meter a control device for controlling supply of a developing solution of the developing liquid from the raw liquid supply pipe, wherein the control device is based on an alkali concentration of the developing liquid measured by the concentration meter and a carbonate concentration in the developing liquid, The relationship between the alkali concentration and the carbonate concentration of the dissolution energy of the CD which is obtained by the development process is controlled, and the supply of the developing solution is controlled to have the function of adjusting the alkali concentration. . Further, in the present invention, in order to adjust the alkali concentration with higher precision, the alkali concentration can be adjusted by considering the carbonate concentration and the dissolved resin concentration in the developing solution. That is, the third aspect of the present invention is a method for adjusting the concentration of a developing solution, and a method for adjusting a concentration of a concentration of an alkaline developing solution for use in a developing process of a photoresist, characterized in that : Determination of the alkali concentration of the developing solution, the concentration of the carbonate in the image liquid, and the concentration of the dissolved resin in the image liquid, and the alkali concentration and carbonic acid of the dissolution energy of the CD which is obtained by the development process. The previously prepared relationship between the salt concentration and the dissolved resin concentration 'adjusts the alkali concentration. Further, a fourth aspect of the present invention is a modulating device for a developing liquid, which is a modulating device for modulating an alkaline developing liquid used for developing a photoresist, and is characterized in that it is used for modulating a preparation tank of the developing solution of a predetermined concentration; supplying the prepared developing liquid to the supply tube of the developing program; and taking the used developing liquid to the recovery tube of the preparation tank; the alkali concentration is higher than the reference concentration a concentration of the new developing solution stock solution is supplied to the raw material supply pipe of the preparation tank; and a concentration meter for detecting the alkali concentration of the developing liquid in the preparation tank, the carbonate concentration in the developing liquid, and the dissolved resin concentration; Control device for controlling the supply of the developing liquid solution from the raw liquid supply pipe according to the detected concentration of the concentration meter, wherein the control device is based on the alkali concentration of the developing liquid and the developing liquid measured by the concentration meter The carbonate concentration and the dissolved resin concentration in the medium, and the alkali concentration and the carbonate concentration and the dissolved resin concentration which are capable of exhibiting the solubility of the CD which is obtained by the development process are constant. Controlling the supply of liquid developer liquid, having a function of adjusting the alkali concentration. [Effects of the Invention] According to the present invention, the increase in the concentration of the carbonate in the developing solution is adjusted. According to a specific relationship, the alkali concentration of the developing solution is adjusted, and the solution of the photoresist to the developing solution of the photoresist is applied. It is maintained at a certain level, so the development process of the photoresist can be maintained at a certain development speed in the development process of the photoresist - 9 - 200837513. Further, in response to the carbonate concentration and the dissolved resin concentration in the developing solution, the alkali concentration of the developing liquid can be adjusted according to a specific relationship, and a higher quality developing process can be performed. [Coating Mode] An embodiment of a method for adjusting the concentration of a developing liquid of the present invention and a developing device for a developing liquid will be described with reference to the drawings. The method for adjusting the concentration of the developing liquid of the present invention (hereinafter simply referred to as "concentration adjusting method") is a development processing program for a developing device including a rotary developing device, a coating and developing device, and the like, and is adjusted for use in a photoresist. The method of adjusting the concentration of the alkali concentration of the image developing solution (hereinafter referred to as "visual liquid") is also a method of modulating the developing liquid of the present invention (hereinafter simply referred to as "modulating device"). The present invention is particularly preferably applicable to a developing device which is used for a developing device for recovering a photoresist of a process such as a liquid crystal substrate or a printed substrate. The case where the developing solution is reused. In the present invention, the alkali component of the developing solution may, for example, be an inorganic alkali aqueous solution or a tetrahydric hydroxide composed of an inorganic base such as potassium hydroxide, sodium hydroxide, sodium phosphate or sodium citrate alone or in a mixture. An aqueous solution of an organic alkali such as ammonium (TMAH) or choline. In the case of using TMAH as a developing liquid, the TMAH concentration (alkali concentration) is set to, for example, 2. 3 80wt%. Further, the developing solution may contain a conventional additive such as a nonionic surfactant or a fluorine-based surfactant. -10- 200837513 Furthermore, in the present invention, "C D値" means the line width of the photoresist pattern obtained on the substrate by the development process. Further, the "reference concentration" of the base to be described later means the concentration of the base of the CD oxime (initial alkali concentration) which can be obtained. The above CD 値 is the CD 时 at the time of performing the development processing for a predetermined period of time set in advance, and becomes the original CD 基准 which is the basis of the evaluation before the change occurs. Further, the base to be used may be a single base, or may be an additive containing the above-mentioned additives, and the solubility of the additive may be increased by the reference concentration of the base when the solid liquid containing the additive is used. The difference is better. First, a modulation apparatus which is ideally applicable to the implementation of the concentration adjustment method of the present invention will be described. The modulating device of the present invention is a modulating device for modulating a developing liquid used for development processing, and uses the used developing liquid recovered by a developing program to modulate the developing liquid as shown in FIG. . The modulation device includes a modulation groove (1) for modulating a predetermined concentration of the developing liquid, and a developing program for supplying the prepared developing liquid to the developing device (9) (hereinafter referred to as "development" Supply tube (2); the used developing liquid is taken to the recovery tube (3) of the brewing tank (1); and a new developing liquid stock solution having a higher alkali concentration than the reference concentration is supplied to The raw material supply pipe (6) of the preparation tank (1): a concentration meter (5) for detecting the alkali concentration of the developing liquid in the modulation tank (1) and the carbonate concentration in the developing liquid: and detection based on the concentration meter The concentration is a control device (not shown) for controlling the supply of the developing liquid solution from the raw liquid supply pipe (6). The brewing tank (1) adjusts the concentration of the developing liquid to a certain target enthalpy, and if necessary, supplies the developing solution whose concentration has been adjusted to the supply tank of the image device (9). For example, it is composed of a container having a corrosion resistance of about 100 liters in internal volume. In the modulating tank (1), the accommodating liquid is maintained at an equal concentration, and a circulation flow path (4) containing a pump (41) as a stirring means is provided, and the stirring means of the circulation is described. A screw device is arranged in the tank, and the generated particles are small, the staining liquid can be reduced, and the used developing liquid recovered can be adjusted to a certain temperature in the developing device, and the display tank (1) is displayed. The temperature is also constant in the image liquid. However, in order to correct the concentration of the developing liquid by the concentration meter (5) described later, it is preferable to accurately maintain the development in the preparation tank (1) at a constant temperature (for example, 25 ° C). Therefore, in the state, in the modulation tank (1) or the circulation flow path (4), a temperature adjustment means (not shown) including a cooler is provided. The supply pipe (2) is from the modulation groove (1) to the display The charge liquid flow path and the pump (2 1 ) interposed in the flow path are configured to supply the modulated developing liquid in the target to the developing device (9). The tube (3) is constituted by a flow path of the chamber of the developing liquid used for the developing device (9) to the flow path of the modulation tank (1) so as to be on the side of the flow path or the developing device (9) The pumping liquid (not shown) is recovered into the brewing tank (1). Furthermore, although the tube (3) is not shown, it is also possible to temporarily store the used developing solution, and adjust the temperature of the used developing solution to the same temperature as that of the developing liquid. Therefore, It is also possible to set a thermostatic bath and other means. "2000 liters", for the imaging liquid. With the finest stirring. ί (9) The temperature of the liquid is roughly determined to be the ideal shape of the heater ί (9) 1 (1 , recycling outlet (for setting, will use the type, in the buffer tank ί ( 1 ) temperature adjustment -12 - 200837513 raw liquid supply pipe (6) is from the raw liquid supply mechanism (A) (not shown) a flow path to the brewing tank (1) and a flow rate adjusting valve (61) interposed in the flow path. When the concentration of the developing liquid in the brewing tank (1) is lowered, the control device described later is used. The control of the flow rate adjusting valve (6 1 ) supplies a developing solution liquid having a higher concentration than the reference concentration, for example, a developing liquid solution having a concentration of 20 to 25 wt% in the case of TMAH, to the brewing tank (1). (A) mainly by preserving a stock solution of about 00 to 3,000 liters in an internal volume for a high-concentration liquid imaging solution, and transporting the developing liquid solution to the above-mentioned flow path of the preparation tank (1) from the raw material storage tank. The pump is constructed. In addition, in the modulation device of the present invention, the display in the modulation tank (1) When the alkali concentration of the liquid becomes higher than the target concentration, the concentration of the developing liquid is lowered. Therefore, the dilution water supply pipe (7) for supplying the dilution water to the preparation tank (1) is usually provided. The tube (7) is composed of a flow path from the dilution water supply mechanism (B) (not shown) to the modulation tank (1) and a flow rate adjustment valve (7 1) interposed in the flow path, which will be described later. The control unit controls the flow rate adjusting valve (71) to supply ultrapure water to the brewing tank (1). As the dilution water supply unit (B), a pure water producing apparatus including a storage tank and a liquid feeding pump is generally used. In the modulating device of the present invention, when the amount of the developing liquid in the modulating tank (1) is reduced to a certain amount or less, the developing liquid is replenished, so that a new developing liquid having a reference concentration is provided. a new liquid supply pipe (8) supplied to the brewing tank (1). The new liquid supply pipe (8) is a flow path from the fresh liquid supply mechanism (C) (not shown) to the brewing tank (1) and is interposed in The flow regulating valve (8 1 ) of the flow path-13-200837513 is configured to flow to the flow by a control device to be described later The entire control valve (81), and to the preparation tank (1) was supplied as the reference concentration solution (e.g. 2 concentration. 38wt% TMAH). The new liquid supply mechanism (C) mainly conveys the above-mentioned flow path of the modulation tank (1) by the new liquid storage tank by the new liquid storage tank of 500 to 3000 liters of the internal volume for the new imaging liquid. It is composed of a liquid pump. In the modulating device of the present invention, the concentration meter (5) is usually interposed in the above-described circulation flow path in order to more accurately measure the alkali concentration of the developing liquid in the modulating tank (1) and the carbonate concentration in the developing liquid. (4). As the concentration meter (5), a specific concentration meter is used in order to prevent the concentration of the dissolved resin in the developing solution from being affected and to perform concentration measurement with high precision. Specifically, as the concentration meter (5) described above, the lower concentration meter, that is, the temperature of the developing liquid, the ultrasonic wave propagation speed, and the electromagnetic conductivity are measured, and the predetermined temperature, alkali concentration, and carbonic acid are prepared in advance. The relationship between the ultrasonic propagation rate of the salt concentration and the electromagnetic conductivity (matrix), and the multi-component concentration meter for detecting the alkali concentration of the developing liquid and the carbonate concentration in the developing liquid. The multicomponent concentration meter described above is a concentration meter capable of simultaneously measuring the concentrations of two components of a base and a carbonate by measuring the ultrasonic wave propagation velocity and the electromagnetic conductivity in a solution at a constant temperature. In other words, the multi-component concentration meter is based on the principle that when the temperature of the solution is constant, the concentration of each component is used to determine the propagation velocity and electromagnetic conductivity of the ultrasonic wave in the liquid. It is composed of an ultrasonic transducer, an ultrasonic transmitter, an electromagnetic conductivity converter, an electromagnetic conductivity transmitter, and a microprocessor that performs predetermined calculations. • 14- 200837513 When the multi-component concentration meter is applied to the measurement of the concentration of such a developing solution as described above, it is measured in advance at a certain temperature condition by various combinations for each alkali concentration and carbonate concentration. The relationship between the ultrasonic wave propagation speed and the electromagnetic conductivity is prepared in advance as a matrix, that is, by writing to the microprocessor, the calculated alkali concentration and the carbonate concentration can be accurately estimated from the measurement 根据 based on the above-described matrix. In addition, as the multi-component concentration meter as described above, for example, a liquid multi-component concentration meter manufactured by Fuji Industrial Co., Ltd. can be mentioned. Further, in addition to the above-described multi-component concentration meter, as a concentration meter for measuring the alkali concentration, a concentration meter using a bending method using a tortuosity of a measuring fluid or a near-infrared method using a wavelength close to the infrared field can be used. Further, as the concentration meter for measuring the carbonate concentration, for example, a concentration meter using a neutralization titration or the like can be used. In the modulation apparatus of the present invention, in addition to the operation control of the entire apparatus, the conveyance of the developing liquid solution, the delivery of the dilution water, and the new developing liquid are controlled by the concentration meter (5). Control device for transport (not shown). The control device includes an input device for digitally converting the signals of the measuring devices, an arithmetic processing device such as a program controller or a computer, and an output device for analogizing the control signals from the arithmetic processing device. The above control device controls the supply of the developing liquid solution from the raw liquid supply pipe (6) based on the detected concentration of the concentration meter (5). That is, the control device is based on the alkali concentration of the developing liquid measured by the concentration meter (5) and the carbonate concentration in the developing liquid, and the insufficient amount of the carbonate concentration and the alkali concentration prepared in advance to the reference concentration. In the relationship, in other words, the CD 値 - - - - - - - -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 -15 It has the function of adjusting the alkali concentration. Thereby, in the modulating device of the present invention, the used developing liquid is recovered by the developing device (9), and a developing liquid having an appropriate alkali concentration can be prepared in the modulating tank (1). Further, the above-described control device is configured to control the supply of the developing solution liquid, and to control the supply of the dilution water from the dilution water supply pipe (7) and the new display from the new liquid supply pipe (8). Like the supply of liquid. Thereby, in the modulating device of the present invention, the liquid amount of the developing liquid in the modulating tank (1) can be managed to be constant. Further, in the modulating device of the present invention, in order to prevent the developer liquid or the developing solution liquid from coming into contact with the air, the inside of the system is sealed by an inert gas such as nitrogen. Further, in the modulating device of the present invention, in order to keep the amount of liquid in the system constant, it is provided at an appropriate portion to discharge the remaining used developing liquid to the outside of the system when the developing liquid solution is supplied. mechanism. Although not shown, for example, the 'modulation tank (1) is provided with a flow path or an overflow device for discharging the control valve. Next, the function of the above-described modulation device and the density adjustment method of the present invention will be described. In the concentration adjustment method of the present invention, when the developing liquid is modulated by using the above-described modulation device, first, the used developing liquid discharged from the developing device (9) is recovered to the brewing tank by the collecting pipe (3). (1), and 'when the developing solution (including the used developing liquid of the developing liquid) of the brewing tank (1) is circulated to the circulation flow path (4), and stirred and mixed, the temperature adjusting means is used. The developing solution is kept at a certain temperature, and then the alkali concentration of the image liquid is measured and the carbonate concentration in the developing liquid is measured. As a read), the aforementioned multi-component concentration meter was used. After measuring the alkali concentration and the carbonate concentration of the developing solution in the modulating tank (n), the flow rate adjusting valve (6 1 ) of the original (6) is controlled by the above-described control device, and the inside of the modulating tank (1) is adjusted. The alkali concentration is adjusted to an appropriate concentration. In this case, the carbonate concentration and the alkali concentration produced in the present invention are not related to the reference concentration, that is, the dissolution energy and the carbonate concentration of the enthalpy of which the CD 値 becomes constant can be exhibited. In the relationship prepared in advance, the alkali concentration is adjusted to a level higher than the reference concentration in accordance with the carbonation of the carbonate. The dissolution of the photoresist by the image liquid is maintained constant. Hereinafter, the above-described idea of the present invention is further enhanced. The developing device circulates the supply of the developing liquid, absorbs the carbonic acid gas, and generates carbonate in the developing liquid, and the dissolution of the carbonate to the photoresist can be offset, resulting in the size of the pattern of the agent obtained by the developing process. As a result, the line width formed on the substrate is different from the design width. Further, in the case where the development time of the alkali image processing of the developing liquid is set to be constant, the CD 値 will be used in the developing liquid. Carbonate concentration and The influence of height is high. The effect of carbonate concentration in the imaging solution on CD値 is as shown in Fig. 2. For the 7 kinds of development of carbonates with different carbonate concentrations, the alkali concentration (TMAH concentration) is adjusted to 2. For the concentration of 3 to 5 types in the range of 20 ^, it is confirmed that the CD 値 at the time of performing the development processing at each concentration and the I metric meter in the above-described developing solution (5 developing solution of the liquid supply tube in the developing solution) According to the measurement of the alkali concentration concentration of the pre-sufficient amount, it can be clearly explained that the concentration of the photoresist circuit pattern obtained in the air and the imaging liquid is significantly increased as shown in Fig. 2: (TMAH ^ 3. 27wt% for a certain period of time. Carbonate concentration -17- 200837513 degrees. As shown in Fig. 2, when a newly prepared developing solution (five kinds of alkali concentrations) having a carbonate concentration of 〇 ppm is used, the CD 値 is 2·7 7 to 5. 1 6 μηι ο relative to this, for example, in the case of using a developing solution having a carbonate concentration of 5 2 5 ppm (four kinds having different alkali concentrations), the CD 値 becomes 3_70 to 5. 05 μιη, in the case of using a developing solution having a carbonate concentration of 1 000 ρρηη (four kinds having different alkali concentrations), c D 値 becomes 3. 5 9~4 · 3 0 μιη. That is, the relationship shown in Fig. 2 indicates that the dissolution of the developer with respect to the photoresist tends to decrease with a certain increase in the concentration of the carbonate in the developing solution, and CD 增加 increases in a certain relationship. Therefore, in the case of development processing, in order to maintain the CD 一定 in a certain state, it is necessary to increase the alkali concentration in response to the carbonate concentration. For example, to set CD値 to 4. At 00 μιη, in the case of a newly prepared developing solution having a carbonate concentration of Oppm, the alkali concentration (TMAH concentration) was adjusted to 2. 38 wt% (reference concentration), however, in the case of using a developer solution having a carbonate concentration of 500 ppm, the alkali concentration (TMAH concentration) must be adjusted to 2. 50% by weight, in addition, in the case of using a developing solution having a carbonate concentration of 1 000 ppm, the alkali concentration (TMAH concentration) must be adjusted to 2. 71 wt%. In the above relationship, the relationship between the concentration of alkali and the amount of alkali concentration required to maintain the CD ' as a necessary amount of the alkali concentration to maintain the CD 一定 (the relationship between the alkali concentration and the base concentration) ) ' can be as shown in Figure 1. The relationship between the carbonate concentration and the alkali concentration to the shortage of the reference concentration means that the relationship between the alkali concentration and the carbonate concentration in the case of performing the predetermined development process (the process of obtaining a certain CD enthalpy) is previously derived. The relationship refers to the relationship between the carbonate concentration and the insufficient amount of the reference alkali concentration (the concentration of the developing solution in the case of using a freshly prepared developing solution containing no carbonate -18-200837513), in the graph of Fig. 1 The number in the brackets of the TMAH concentration (alkali concentration) in the 'vertical axis' is shown to the reference concentration (2. The insufficient amount of the concentration of 38 wt%). As described above, the present invention focuses on the relationship between the alkali concentration of the developing liquid and the carbonate concentration when the c D 値 is maintained at a constant level, and corrects the alkali concentration serving as the standard in accordance with the carbonate concentration. Further, in the case of using TMAH, the above-described correction amount (the shortage of the carbonate concentration and the alkali concentration to the reference concentration) shown in Fig. 1 is represented by the following mathematical expression. [Math 1] y = 8xl 〇 -8x2 + 2xlO'4x (1) where X is the carbonate concentration (ppm) and 丫 is the TMAH concentration (wt%). Further, in order to confirm the relationship of Fig. 2, the above is found. The relationship between the mathematical formula and FIG. 1 is to prepare a plurality of kinds of developing liquids (for example, an aqueous TMAH solution actually used) having a different alkali concentration which is not prepared by a new one, and a sample having a different alkali concentration than a carbonate. A plurality of developing liquids were subjected to development processing for setting a predetermined temperature and development time for each of the developing liquids, and the CD 値 of each of the obtained photoresist patterns was measured. In this case, a calculated amount of dry ice is added to the developing solution containing the alkali concentration of the carbonate, and the carbonate concentration is, for example, 100 ppm, 3 2 5 ppm, 500 ppm, and 1000 ppm. , 1 500 ppm, 2 OOOppm modulation of a plurality of species. Further, based on the obtained results, the relationship is estimated based on the statistical processing. -19-200837513 In the present invention, according to the relationship of the above formula (I), that is, according to the carbonate concentration in the previously produced developing solution capable of exhibiting the alkali concentration of the CD値 and the carbonate concentration, Adjust the alkali concentration. The change of the salt concentration 値, the alkali concentration is adjusted to the reference concentration. This can maintain the solubility of the developing solution to a certain level, can correct the dimensional accuracy of the case, and can control cd 成 to the carbonate concentration in a developing solution. For the case of 〇ρριη, check the baseline concentration. Further, when the present invention is implemented by a modulating device or the like, it is necessary to adjust the amount of alkali to be determined in accordance with the carbon in order to obtain a certain CD enthalpy. In this case, the relationship between the alkali concentration of the dissolved energy of the enthalpy of the CD and the relationship between the carbonate concentration and the concentration is based on the relationship between the predetermined system and the concentration of the alkali which can exhibit the predetermined solubility. ), adjust the alkali concentration. The above relationship is shown as the concentration of carbonate on the horizontal axis and TM A Η on the vertical axis. Therefore, in the case of using ΤΜAH, the above salt concentration and the alkali concentration capable of exhibiting a predetermined dissolution energy are expressed by the following mathematical expressions. [Math 2] y = 8xlO_8x2 + 2xl〇-4x + 2. 38 (II) where X is the carbonate concentration (ppm) and 丫 is wt%. The relationship of ^ shown in Fig. 1 is a certain 値, which corresponds to the enthalpy of carbonic acid or higher. By increasing the photoresist. In addition, the concentration is set to the concentration of the acid salt of the developing solution, and the carbonate concentration is determined, that is, the relationship between the concentration of the insufficient amount of the carbonate capable of causing the carbonate concentration in the graph concentration of FIG. 1 (carbonic acid) The relationship is the concentration of the TMAH concentration ( -20-200837513 in the modulation device of the present invention, the calculation method for writing the concentration measurement and the control calculation for the control device) in the modulation tank (1), according to the concentration meter (5) The alkali concentration of the liquid developer and the carbonate concentration in the developing solution are controlled, and the flow rate adjusting valve (6 1 ) of the raw material supply pipe (6) is controlled according to the above formula (II), and an insufficient amount in accordance with the alkali concentration is added. In the case of the above-mentioned relationship (the relationship of the formula (II)), when the alkali concentration becomes too high, the dilution water supply pipe (7) is passed through the dilution water supply pipe (7). The pure water for dilution is supplied to the brewing tank (1). Further, the amount of the developing liquid in the brewing tank (1) is lowered by discharging a portion of the used developing liquid that has been recovered. Through the raw liquid supply pipe (6) The dilution water supply pipe (7) supplies the developing solution stock solution and the pure water to the brewing tank (1), and adjusts the alkali concentration by the above operation, thereby adjusting the liquid amount of the brewing tank (1) to a certain range. Or, the new liquid supply tube (8) is supplied to the brewing tank (1) to adjust the amount of liquid. The supply control of the developing solution liquid, the supply control of the dilution water, and the new developing liquid The supply control is performed by the supply amount of the developing liquid solution from the raw liquid supply means (A), the supply amount of the pure water from the dilution water supply means (B), and the new liquid supply pipe (8). The supply amount of the developing solution is controlled in series. In addition, the so-called asymptotic method disclosed in the "dilution method and dilution device of the alkali imaging stock solution" described in Japanese Patent No. 3 74 1 8 1 1 can be used. Specifically, in the case of the modulation tank (1) using the above-described asymptotic method, the example 21 - 200837513 is adjusted such that the alkali concentration is lowered (or the concentration of the developing solution in the concentration changing tank (1) is increased. When the concentration of the developing solution liquid (water) is adjusted to a predetermined concentration, the following process is performed, that is, the concentration measuring process for measuring the concentration of the developing liquid by (5); and the concentration and target concentration measured according to the measuring process (the difference in the concentration obtained by the above-mentioned mathematics), the amount of the insufficient amount of water released from the liquid of the developing solution is calculated, and the supply of the amount of the calculated insufficient amount (or) is preferably 85 to 9 9 %. ~9 8 % of the modulation process. Further, the concentration measurement becomes a region 预先 of the target concentration set in advance, and the modulation process is repeated by the concentration measurement process described above. The alkali concentration in the developing solution of the preparation tank (1) can be managed with higher precision. As described above, in the present invention, the carbonate is measured in accordance with the relationship between the difference between the carbonic acid and the alkali concentration prepared in advance and the reference concentration. The alkali concentration is adjusted to be higher than the reference concentration. In other words, the relationship between the alkali concentration of the dissolution energy of the enthalpy of the CD and the carbonity can be adjusted in advance, and the alkali concentration can be adjusted. Thereby, the solubility of the liquid to the photoresist can be maintained constant. Therefore, according to the present invention, it is possible to maintain a constant display of the photoresist in the developing device, and it is possible to further improve the precision of the photoresist composition and the film thickness precision produced by the development process. In order to achieve higher quality, in the present invention, in order to adjust the alkali concentration with higher precision, and also like the carbonate concentration in the liquid, the concentration is dissolved in response to the concentration of the resin. As mentioned above, in the case of circulating supply of the developing solution, there will be a high or dilute concentration meter in the concentration formula (or (or a small amount added, in which the concentration of the salt is based on the degree of acid concentration). The salt concentration will be imaged in the image speed case of the invention and can be adjusted according to the following instructions. 22-200837513, that is, carbonate will be produced in the imaging solution 'and' due to imaging treatment, photoresist It dissolves in the developing solution, and although it is only slightly, the dissolved resin lowers the solubility of the developing solution. Therefore, in order to adjust the concentration as described above, it is preferable to correct the concentration of the dissolved resin in the developing solution. The effect of the dissolved resin concentration in the developing solution on CD値 is as shown in Fig. 3. Fig. 3 shows six types of developing liquids having different concentrations of dissolved resin (resin component constituting the photoresist) (actually used) For concentration 2. 3 8 wt ° / TM TMAH ), the relationship between the dissolved resin concentration and the change in CD 进行 in the case of developing for a certain period of time, as shown in FIG. 3 'for a developing solution using a dissolved resin concentration 〇abs ( In the case of a CD for the case where the resin is not dissolved, for example, when the developer liquid having a resin concentration of 〇· 2 ab s is dissolved, the CD 値 increases 〇·〇4 μιη 'in the dissolved resin concentration. 0. In the case of the 8abs imaging solution, the CD値 is increased by 0·2 8 8 μιη. That is, the relationship shown in Fig. 3 is a display, and as the concentration of the dissolved resin in the developing liquid increases, the dissolution energy of the developing solution to the photoresist decreases with a certain tendency, and CD 增加 increases in a certain relationship. Therefore, it is possible to find out by the experiment the relationship between the alkali concentration of the developing liquid and the concentration of the carbonate and the dissolved resin concentration when the CD 値 is maintained to be constant. In order to find out the above relationship, a plurality of kinds of developing liquids (for example, an aqueous TMAH solution actually used) having different alkali concentrations different from carbonate and resin components (resin components constituting the photoresist) are prepared, and carbonic acid is contained. A plurality of kinds of developing liquids of the salt and the above-mentioned resin component and the samples having different alkali concentrations are subjected to the same development processing as in the case of deriving the above-described mathematical expressions (I) and (Π) for each of the developing liquids, and the measurement is performed. The CD 图案 of the pattern of each of the obtained photoresist -23- 200837513. The carbonate concentration of each of the developing liquids having different alkali concentrations can be adjusted to an appropriate enthalpy of, for example, 100 to 20,000 ppm by adding dry ice, and the dissolved resin concentration of each developing solution can be adjusted as in the case described above. By measuring the dissolved resin concentration while dissolving the photoresist, the alkali concentration and the dissolved resin concentration are adjusted to, for example, l〇〇PPm/Oabs, 2500 ppm/0·3 abs, 5000 ppm/0. 6 ab s 5 1 00 Oppm/0 · 9 abs ° Then, from the results obtained, by statistical processing, for example, the variation of CD 作为 is taken as the dependent variable and the alkali concentration and the aforementioned carbonate concentration and dissolved resin concentration are taken as Each independent variable is subjected to multi-factor analysis, whereby the relationship can be estimated. In this case, when TMAH is used as the developing solution, the necessary correction amount of the alkali concentration of the developing liquid (the same alkali concentration as the above-mentioned alkali concentration is less than the reference concentration), that is, the CD 値 can be dissolved. The amount of correction of the usable alkali concentration can be expressed by the following mathematical formula. In the following mathematical formula, the number TM of the TMAH concentration (y) shows the deficiency to the reference concentration. [Math 3] y= ( 2. 33x1 0'6x2 + 6. 36x1 0'4x + 0. 36c) /8. 79 (III) wherein X is a carbonate concentration (ppm), C is a dissolved resin concentration (abs), and y is a TMAH concentration (wt%). Furthermore, the absorbance of the dissolved resin concentration is a unit of the dimensionless amount indicating the concentration of the substance in the liquid by the absorbance indicating the absorption intensity of light of a specific wavelength, as is known. The concentration of the dissolved resin in the developing solution can be expressed by the absorbance at the absorption wavelength (for example, 5 60 nm) peculiar to the dissolved resin. -24- 200837513 In the invention, the determination of the alkali concentration of the developing solution, the carbonate concentration in the developing solution, and the dissolved resin concentration, the above formula (III), in response to the carbonate concentration and the dissolved resin concentration in the developing solution , adjust the alkali concentration. In other words, the alkali concentration is adjusted to be higher than the reference concentration in accordance with the measurement of the carbonate concentration. Thereby, the dissolution energy of the developing solution can be maintained constant, the dimensional accuracy of the photoresist pattern can be further improved, and the CD 値 can be further controlled to be constant. Further, in order to adjust the concentration of the developing liquid in the above-described preparation device or the like, it is necessary to determine the actual alkali concentration in accordance with the carbonate concentration and the dissolved resin concentration so that a certain CD 能够 can be obtained. In this case, the alkali concentration is adjusted in accordance with the relationship between the alkali concentration at which the solubility of C 値 becomes a constant enthalpy and the carbonate concentration and the dissolved resin concentration. The above relationship can be expressed by the following mathematical expression in the case of using TMAH. [Math 4] y = (2. 33xl (T6x2 + 6. 36xl (T4x + 0. 36c)/8. 79 + 2. 3 8 ". (IV) wherein X is a carbonate concentration (ppm), C is a dissolved resin concentration (abs), and y is a TMAH concentration (wt%). The preparation device of the preferred embodiment of the present invention is a modulation tank (1), a supply pipe (2), a recovery pipe (3), a raw liquid supply pipe (6), and a concentration meter (5) in the same manner as the device of the above-described configuration. And a control device. In this case, as the concentration meter (5), a multicomponent concentration meter which can detect the alkali concentration of the developing liquid in the preparation tank, the carbonate concentration in the developing liquid, and the dissolved resin concentration is used. Further, the above-mentioned control device is based on the alkali concentration of the developing liquid measured by the concentration meter (5 - 25 - 200837513), the carbonate concentration in the developing liquid, and the dissolved resin concentration, and is capable of exhibiting CD 値. The relationship between the alkali concentration of the dissolution energy and the previously prepared relationship between the carbonate concentration and the dissolved resin concentration controls the supply of the developer liquid stock and has a function of adjusting the alkali concentration. As the concentration meter (5), the same multi-component concentration meter as described above to which the measurement function of the dissolved resin concentration is added can be used. The multi-component concentration meter is based on the principle that the concentration of each component of the alkali, carbonate, and dissolved resin depends on the concentration of the supersonic wave, the electromagnetic conductivity, and the absorbance in the liquid, depending on the temperature of the solution. The multi-component concentration meter described above measures the temperature of the developing solution, the ultrasonic wave propagation speed, the electromagnetic conductivity, and the absorbance, and the ultrasonic wave propagation speed according to the predetermined temperature, alkali concentration, carbonate concentration, and dissolved resin concentration prepared in advance. Relationship between Electromagnetic Conductivity and Absorbance (Provides the relationship between ultrasonic propagation rate, electromagnetic conductivity, and absorbance measured in advance under a certain temperature condition for each combination of previously prepared alkali concentration, carbonate concentration, and dissolved resin concentration. The matrix) is used to detect the alkali concentration of the developing solution, the carbonate concentration in the developing solution, and the dissolved resin concentration. In the modulating device of the present invention, the alkali concentration of the developing liquid measured by the concentration meter (5), the carbonate concentration in the developing liquid, and the dissolved resin concentration are the same as those of the above-described apparatus. In the mathematical formula (IV), the flow rate adjustment valve (6 1 ) of the raw liquid supply pipe (6) is controlled, and a stock solution liquid solution in which the alkali concentration is insufficient is added to adjust the alkali concentration to a predetermined target enthalpy. In the case where the concentration is too high according to the above relationship (the relationship of the mathematical formula (IV)) -26-200837513, the dilution water supply pipe (7) is passed through the dilution water supply pipe (7) in the same manner as the above-described device. The tank (1) is supplied with pure water for dilution. In addition, when the amount of the developing liquid in the brewing tank (1) is lowered, the raw liquid supply tube (6) and the dilution water supply tube (7) are supplied to the developing tank and the pure water to the brewing tank (1). Or, a new developing liquid is supplied to the brewing tank (1) through the new liquid supply pipe (8), and the alkali concentration is adjusted by the above operation. In the present invention, as described above, the alkali concentration of the developing solution, the carbonate concentration in the developing solution, and the dissolved resin concentration are measured, and the alkali concentration and the carbonate concentration and the dissolution which can exhibit the solubility of the enthalpy of the CD 根据 are exhibited. The relationship between the resin concentration and the previously prepared relationship adjusts the alkali concentration. Thereby, the dissolution energy of the developing solution to the photoresist, that is, the developing speed can be further maintained constant. Therefore, according to the present invention, it is possible to further improve the dimensional accuracy and film thickness precision of the photoresist pattern produced by the image processing. As described above, according to the present invention, since the dimensional accuracy and film thickness precision of the photoresist pattern can be further improved in the development processing, higher-quality development processing can be performed. As a result, it is possible to form a pattern with higher precision on the substrate by uranium engraving. Further, since the alkali concentration is gradually increased in response to an increase in the concentration of the carbonate in the developing liquid, the circulation rate of the developing liquid can be increased, and the development program can be made more stable. Further, according to the modulating device of the present invention, it is possible to modulate a developing liquid which can perform higher-quality developing processing by using the used developing liquid recovered by the developing program. Further, since the developing liquid obtained by the concentration adjusting method and the modulating device of the present invention maintains a constant developing speed for the resist, -27-200837513 can perform high-quality developing processing. By the way, use a freshly prepared developer solution without carbonate (the actual concentration used 2. 38% by weight of TMAH) was subjected to a prescribed development process, and when the obtained photoresist pattern was confirmed, CD値 was 4. 00 μπι. On the other hand, several types of used developing liquids having a carbonate concentration of 100 to 2000 ppm are prepared, the TMAH concentration is adjusted according to the relationship of the above formula (II), and the same development as described above is performed using each developing liquid. As a result of the treatment, in the case of using any of the developing liquids, the CD 値 is 4. 00 μπι. By this, it was confirmed that the alkali concentration can be adjusted according to the relationship between the mathematical formulas (I) and (Π) (the relationship shown in Fig. 1), whereby a certain amount of dissolved energy can be maintained. Further, the prepared carbonate concentration is 100 to 2000 ppm, and the dissolved resin concentration is 〇 〜2. The used imaging liquid of the Oabs type adjusts the TMAH concentration according to the relationship of the above formula (IV). Then, the same development process as described above was carried out using each of the developing liquids, and in the case of using any of the developing liquids, the CD 値 was 4·00 μm. As a result, it has been confirmed that the developer can be maintained at a constant concentration by adjusting the alkali concentration according to the relationship between the mathematical formulas (ΙΠ) and (IV). BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the relationship between the carbonate concentration and the alkali concentration to the shortage of the reference concentration, and the relationship between the carbonate concentration and the alkali concentration which can exhibit a predetermined solubility. Fig. 2 is a graph showing the effect of the carbonate concentration in the developing solution on the line width (CD値) of the photoresist pattern obtained by the developing process. -28- 200837513 Fig. 3 is a graph showing the influence of the dissolved resin concentration in the developing solution on the line width (CD値) of the photoresist pattern obtained by the developing treatment. Fig. 4 is a flow chart showing the main structural elements of a modulating device for a developing liquid of the present invention. [Description of main component symbols] 1 : Modulation tank 2 : Supply pipe 21 : Pump 3 : Recovery pipe 4 : Recirculation flow path 41 : Pump 5 : Concentration meter 6 : Raw liquid supply pipe 6 1 : Flow regulating valve 7 : Dilution water Supply pipe 7 1 : Flow regulating valve 8 = New liquid supply pipe 8 1 : Flow regulating valve 9 : Developing device A : Raw liquid supply mechanism B : Dilution water supply mechanism C = New liquid supply mechanism -29 -