550701 A7 B7 五、發明説明（1) 【發明之背景】 本發明係關於Pt、Ru、1]：、？2丁、1*1(〇2等 (請先閲讀背面之注意事項再填寫本頁) 難飽刻材之蝕刻方法，含有難蝕刻材之半導體積體電路裝 置及其製造方法、尤其是關於能有效將難鈾刻材之側壁以 幾近垂直形狀加以蝕刻之技術。 以往，以半導體元件之表面處理手段，已知有利用推 拔形狀或圓頭感光膠進行蝕刻之方法。 利用推拔形狀之光罩進行鈾刻之方法已揭露於 USP5818107 (JP - A - 10-214826 )及P — A— 1 0 — 223855。應用圓頭光阻材料進 行蝕刻之方法卻揭露於U S P 5 8 1 8 1 0 7 ( JP - A-l〇.- 214826)。 惟，不易蝕刻材料（以下簡稱爲難鈾刻材）之蝕刻， 乃在3 0 0 °C以上高溫進行，以致有時無法使用光阻材料 〇 【發明之槪要】 經濟部智慧財產局員工消費合作社印製 而，隨著半導體元件之精細化、動作高速化，更在進 行檢討以Μ〇S (metal-oxide-semiconductor)電晶體之閘 絕緣膜、閘電極、或存儲器一部分之電容器、電容電極使 用氧化鋁、氧化锆、氧化給、釕、白金、氧化鉅、B S T 、S B T、P Z T等材料。又，利用磁性之存儲器（ M R A Μ ; magnetic random access memory )等卻使用鐵、 鎳、鈷、錳或該等之合金。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -4- 550701 A7 B7 五、發明説明（2) 又，以難鈾刻材，可舉如以下者。 磁性體：（用途：磁碟、M R A Μ ) (請先閲讀背面之注意事項再填寫本頁)550701 A7 B7 V. Description of the invention (1) [Background of the invention] The present invention is about Pt, Ru, 1] :? 2 D, 1 * 1 (〇2, etc. (Please read the precautions on the back before filling in this page) Etching method of difficult to engraved materials, semiconductor integrated circuit devices containing difficult to etch materials, and their manufacturing methods, especially A technique for effectively etching the side wall of a hard uranium engraving material in a nearly vertical shape. In the past, a method of etching a push shape or a round-shaped photoresist is known as a surface treatment method of a semiconductor device. Uranium engraving method of photomask has been disclosed in USP5818107 (JP-A-10-214826) and P — A — 1 0 — 223855. The method of etching with a round head photoresist material has been disclosed in USP 5 8 1 8 1 0 7 (JP-Al〇.- 214826). However, the etching of materials that are not easily etched (hereinafter referred to as hard uranium engraving materials) is performed at a high temperature above 300 ° C, so that sometimes photoresist materials cannot be used. Important] Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, with the refinement of semiconductor components and high-speed operation, we are also reviewing the gate insulation film and gate of MOS (metal-oxide-semiconductor) transistors. Electrode, or The capacitors and capacitor electrodes of the device are made of alumina, zirconia, oxide, ruthenium, platinum, oxide, BST, SBT, PZT, etc. In addition, magnetic memory (MRA M; magnetic random access memory) is used. Iron, nickel, cobalt, manganese or alloys of this kind. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -4- 550701 A7 B7 V. Description of the invention (2) In addition, it is difficult to use engraved materials For example, the following: Magnetic body: (Use: magnetic disk, MRA Μ) (Please read the precautions on the back before filling in this page)
Fe、C〇、Mn、Ni 等 貴金屬：（用途：各種電極）Fe, Co, Mn, Ni and other precious metals: (Use: various electrodes)
Pt、Ru、Ru〇2、Ta、Ir、Ir〇2、〇s 、Pd、Ti 、丁 i〇x、SrRu〇3、 (La、Sr)Co〇3、Cu 等 高介電體：（用途：DRAM之電容器（存儲電荷） 等） B S T ： (Ba、Sr)Ti〇3，SR〇： S r T i 〇 a , BT〇：BaTi〇3、SrTa2〇6、 S r 2 T a 2 Ο 7，High dielectrics such as Pt, Ru, Ru〇2, Ta, Ir, Ir〇2, 〇s, Pd, Ti, but iox, SrRu〇3, (La, Sr) Co〇3, Cu: (Use : DRAM capacitors (stored charge, etc.) BST: (Ba, Sr) Ti〇3, SR〇: Sr T i 〇a, BT〇: BaTi〇3, SrTa206, Sr 2 T a 2 〇 7 ,
Zn〇、AI2〇3、Zr〇2、Hf〇2、Ta2〇5 等 鐵電體：（用品：FeRAM之電容器等） PZT:Pb(Zr、Ti)〇3，P Z T N ： P b ( Zr、Ti)Nb2〇8，P L Z T ： (Pb、La)( 經濟部智慧財產局員工消費合作社印製 Z r、T i ) 0 a , PTN： PbTiNbOx, SBT: S r B i 2 T a 2 0 9 , SBTN:Ferroelectrics such as Zn〇, AI203, Zr〇2, Hf〇2, Ta205 etc .: (supplies: capacitors of FeRAM, etc.) PZT: Pb (Zr, Ti) 〇3, PZTN: P b (Zr, Ti ) Nb208, PLZT: (Pb, La) (printed by Zr, T i, Consumer Cooperatives of Intellectual Property Bureau, Ministry of Economic Affairs) 0 a, PTN: PbTiNbOx, SBT: S r B i 2 T a 2 0 9, SBTN :
SrBi2(Ta、Nb)2〇9， BT〇：Bi4Ti3〇12、BiSi〇x， BLOT • B i4- xLaxT i3〇i2 等 化合物半導體：G a A s等 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29?公釐） -5- 550701 A7 _ B7_ _ 五、發明説明（3) I T〇其他·· I η T i〇等 (請先閱讀背面之注意事項再填寫本頁) 該等難蝕刻材料比起鋁、矽、氧化矽等不易鈾刻，尤 其欲將難鈾刻材料之側壁加工爲對基板呈垂直形狀頗困難 ，致成爲一問題。 上述任何眾知文件均無就將難蝕刻材料之側壁加工爲 對基板呈垂直形狀之點有任何之暗示。 繼之，就使用電漿對鐵、鈷、錳、鎳、白金、釕、鉅 、氧化鋁、氧化給、氧化銷、砷化鎵等之化學性安定材料 進行蝕刻時，在被蝕刻材料不易獲得垂直之蝕刻形狀之理 由加以說明如下。 經濟部智慧財產局員工消費合作社印製 在如上述難蝕刻材之不易蝕刻材料，由於蝕刻即形成 反應生成物，且該反應生成物自試樣表面以氣相跳出後， 卻有到達被鈾刻材料壁面即易附著之性質。因此，僅在被 蝕刻材之進行蝕刻位置附著反應生成物，實質上雖只會減 低蝕刻速度而已，惟實際上反應生成物會附著於被蝕刻材 之所有任意位置。亦即，被鈾刻材之殆不進行蝕刻側壁亦 會附著反應生成物，其結果，進行鈾刻之底面蝕刻與側壁 之附著物（deposition material)堆積同時進行，故在被鈾 刻材側壁無法獲得垂直於基板之形狀。以上乃是難蝕刻材 進行蝕刻時，其側壁無法獲得對於基板呈垂直蝕刻形狀之 原因。 茲參照圖1 A至圖2 G就上述被蝕刻材側壁無法獲得 垂直於基板之形狀之理由更加詳細說明之。 圖1 A '圖2 B爲處於蝕刻初期狀態，圖中右向之箭 本紙張尺度適财11@家樣準（〇阳）》4規格（2獻297公釐) '一-- -6- 550701 A7 ___ B7 五、發明説明（4 ) (請先閲讀背面之注意事項再填寫本頁) 頭顯示附著物堆積方向，下方之箭頭顯示鈾刻方向。在此 ，設光罩1 0側壁對於基板上面之角度（推拔角度）0爲 9 0度。自初期狀態經過微小單位時間△ t時，底面（曝 露於電漿之被鈾刻材2 0之上面2 1 )則僅被蝕刻△ e， 且光罩1 0及被蝕刻材2 0側壁只被堆積△ d之附著物 25 (圖IB、2B)。而實際上附著物之頂面部30亦 被進行鈾刻，因此該部分對於基板表面所成之角度（推拔 角度）0即由每單位時間之附著物堆積量（堆積率）△ d 與每單位時間之蝕刻量（鈾刻率）所予以決定。 又，光罩側壁直下部分3 2卻在附著物2 5開始堆積 於光罩側壁之瞬間，停止對於該光罩側壁之附著物底面部 3 3 (曝露於電漿之被蝕刻物2 0之頂面2 1 )之蝕刻。 惟，在該光罩側壁之附著物2 5側壁下部之被鈾刻物2 0 露出部經蝕刻而露出新的被鈾刻物2 0側壁瞬間，復對該 露出面進行堆積附著物。因此，蝕刻係沿斜下方進行（圖 1 C、2 C )。 經濟部智慧財產局員工消費合作社印製 接著，自圖1 C、2 C之狀態再經過單位時間△ t時 ，在附著物2 5側壁更進行附著物2 5之堆積同時，在附 著物2 5側壁下部之被蝕刻材2 0露出部亦進行蝕刻（圖 1 D、1 E、2 D〜2 F )。如是，依序沿斜下方進行蝕 刻，可獲得圖1 F、2 G所示之蝕刻形狀。於是，被鈾刻 物之側壁對於基板表面即呈推拔角度0 0 < 9 0度）。 本發明之目的乃在提供一種可消除上述習知技術之問 題點的難鈾刻材之蝕刻方法及使用它之半導體製造方法及 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 550701 A7 B7 五、發明説明（5) 裝置。 (請先閲讀背面之注意事項再填寫本頁) 本發明之另一目的則在提供一種爲因應半導體元件等 之精細要求，對多張晶圓能進行安定處理，或可獲得幾近 垂直之被蝕刻材推拔角度之試樣表面處理方法及裝置。 本發明之特徵係在將形成於基板之薄膜使用電漿予以 鈾刻時，利用推拔形狀之光罩進行鈾刻之試樣表面處理方 法。 即，依據本發明之一面，使用基板上所形成之難鈾刻 材薄膜與其上形成之光罩，以電漿鈾刻上述薄膜之方法， 卻具有使用上述光罩側壁對於上述基板表面之角度呈9 0 度未滿之光罩進行鈾刻之步驟。 因此，依據本發明，乃在側壁不易獲得垂直加工形狀 之材料之蝕刻，藉利用推拔狀光罩可獲得側壁幾近垂直之 蝕刻形狀，故能製造高功能之半導體裝置，或集體度高之 半導體裝置。 【圖示之簡單說明】 經濟部智慧財產局員工消費合作社印製 圖1 A〜1 F爲使用側壁垂直之光罩進行蝕刻處理說 明用剖面圖； 圖2 A〜2 G爲使用側壁垂直之光罩進行蝕刻處理說 明用剖面圖； 圖3爲適用本發明之電漿蝕刻裝置全體構成例示圖； 圖4 A〜4 D爲將光罩推拔角度設於9 0度未滿時之 鈾刻處理說明用剖面圖； 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -8- 550701 A7 B7 五、發明説明（6) (請先閲讀背面之注意事項再填寫本頁) 圖5 A〜5 D爲將光罩推拔角度自9 0度徐徐減少時 之光罩側壁附著物堆積狀態與被鈾刻材推拔角度0之關係 說明用剖面圖； 圖6爲光罩推拔角度與被鈾刻材推拔角度之關係顯示 圖； 圖7 A、7 B爲光罩推拔角度在臨界値未滿領域與在 臨界値以上領域之光罩推拔角度與被鈾刻材推拔角度之關 係顯示圖； 圖8 A〜8 E爲藉蝕刻瓦斯之成分或蝕刻壓力予以控 制光罩推拔角度之方法說明用圖； 圖9 A〜9 E爲藉濕式触刻予以控制光罩推拔角度之 方法說明用圖； 圖1 Ο A〜1 Ο I爲藉濕式蝕刻予以控制光罩推拔角 度之方法說明用圖； 圖1 1 A〜1 1 I爲藉濕式鈾刻予以控制光罩推拔角 度之其他方法說明用圖； 經濟部智慧財產局員工消費合作社印製 圖1 2 A〜1 2 D爲藉乾式蝕刻與濕式蝕刻予以控制 光罩推拔角度之方法說明用圖； 圖1 3 A〜1 3 D爲藉乾式鈾刻與濕式蝕刻予以控制 光罩推拔角度之其他方法說明用圖； 圖1 4A〜1 4 F爲利用推拔角度略9 0度之光罩而 可獲得實質上推拔狀光罩效果之方法說明用圖； 圖15A爲適用本案發明之半導體裝置之製造裝置構 成例方塊示意圖； 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -9 - 550701 A7 B7 五、發明説明（7) 圖1 5 B爲適用本案發明之半導體裝置之製造裝置其 他構成例方塊示意圖； (請先閱讀背面之注意事項再填寫本頁) 圖16A〜16D爲在鐵電體，使用推拔角度略90 度之光罩而可獲得實質上推拔狀光罩效果之方法說明用圖 9 圖1 7A〜1 7D爲在MRAM，使用推拔角度略 9 0度之光罩而可獲得實質上推拔狀光罩效果之方法說明 用圖； 圖1 8爲使用側壁垂直之光罩進行蝕刻處理之說明用 剖面圖。 主要元件對照表 10 光罩 2 0 被蝕刻物 2 1 頂面 2 5 附著物 30 附著物之頂面部 經濟部智慧財產局員工消費合作社印製 32 光罩側壁直下部分 33 附著物底面部 101 高頻電源 10 2 自動匹配器 10 3 線圏 104 真空容器 104a 放電部 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -10- 550701 Α7 Β7 五、發明説明（8) 104b 處理部 10 5 晶圓 (請先閲讀背面之注意事項再填寫本頁) 106 瓦斯導入部 107 排氣裝置 10 8 試樣 109 試樣台 110 偏壓電源 111 高通瀘波器 113 直流電源 114 低通濾波器 115 加熱器（負荷） 116 冷媒通路 118 靜電耦合天線 5 0 P t 50a，50b 凸部 5 1 遮光光罩材（氧化矽膜等） 52 光阻材料 經濟部智慧財產局員工消費合作社印製 6 1 導體膜（P t膜） 6 2 絕絕膜（P Z T膜） 6 3 導體膜（P t膜） 6 4 光罩 70 氧化矽膜 7 1，7 2 底材 7 3 F e Μ η 膜 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -11 - 550701 A 7 B7 五、發明説明（9) 7 4〜7 6 膜 (請先閱讀背面之注意事項再填寫本頁) 7 7 推拔光罩 9〇1，9〇1’ 鈾刻處理室 9 〇 2，9 0 2 ’ 附著物除去處理室 9 0 3 晶圓搬運用自動機 904 裝載鎖定室 905 卸載鎖定室 9 0 6 裝載機 907 儲藏室 9 0 8 卡盒 5 5，5 6 附著物（附著膜） 【具體之詳細描述】 以下，就本發明實施例參照所添附圖示加以詳細說明 〇 圖3爲適用本發明之電漿蝕刻裝置全體構成例顯示圖 。自高頻電源1 0 1介自動匹配器1 0 2 ( automatic 經濟部智慧財產局員工消費合作社印製 matching unit )向線圈1 〇 3供應高頻電流，促使真空容器 1 0 4內產生電漿。真空容器1 0 4則由絕緣材料所成放 電部1 0 4 a及被接地之處理部1 〇 4 b所成。該真空容 器1 0 4即介瓦斯導入部1 0 6被導入氯氣等蝕刻瓦斯， 該瓦斯卻藉排氣裝置1 0 7予以排出。 試樣1 0 8係被裝載於試樣台1 〇 9上。而爲增大射 入於試樣1 0 8之離子能量，該試樣台1 〇 9卻介高通濾 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12- 550701 A7 B7 五、發明説明（叫 (請先閲讀背面之注意事項再填寫本頁) 波器1 1 1連接有第二高頻電源之偏壓電源1 1 〇。該試 樣台1 0 9表面尙設有陶瓷等之絕緣膜1 1 2。又，試樣 台1 〇 9介低通濾波器1 1 4連接有直流電源1 i 3，藉 靜電力將試樣1 0 8保持於試樣台1 0 9。 且，爲調整試樣1 0 8溫度進行控制處埋，_亥f式樣台 1 09亦設有加熱器1 1 5及冷媒通路1 1 6。 使用本裝置，對鐵、銘、猛、鎳、白金、釕、|旦、氧 化銘、氧化給、氧化鍩、砷化鎵等化學性安定材料進行倉虫 刻時之典型條件即如下述。裝置之壓力爲〇 . 5pa，m 導入瓦斯主要爲氯氣。試樣1 0 8之溫度乃由對象之被餓 刻材而異，惟通常爲2 0 0 t以上5 0 0 t：以下。此雖因 所要求之蝕刻率或所製造之半導體裝置而被予以決定，但 比起蝕刻矽膜、鋁膜或氧化矽膜時之典型溫度爲〇它至 1 0 0 °C，試樣1 0 8之溫度則被保持於較高溫度。因此 ，以蝕刻之光罩材料無法有效使用感光膠之情形頗多，一 般多使用氧化矽或金屬之遮光光罩。 經濟部智慧財產局員工消費合作社印製 難蝕刻材之在蝕刻上之上述課題，亦即，欲進行可獲 得被蝕刻材推拔角度0對於基板表面呈幾近垂直角度之鈾 刻處理時，將附著於光罩側壁之附著物量加以抑制至爲重 要。 作爲如此壓制附著物堆積之方法，係可考慮降低反應 容器內之壓力，或提高導入於反應容器之瓦斯流量。惟， 壓力或瓦斯流量爲獲得較佳蝕刻特性以致被限定於適當範 圍之情形甚多，且壓力、流量由排氣功能決定其界限。因 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -13- 550701 A7 B7 五、發明説明（11) 此，欲由壓力、流量等抑制附著物之堆積至爲困難。 (請先閱讀背面之注意事項再填寫本頁) 其次，參照圖4 A〜5 D就藉使用推拔角度（光罩 1 0側壁對於基板頂面之角度）Θ被設呈9 0度未滿之光 罩（即，推拔狀光罩），而可獲得推拔角度（被蝕刻材側 壁對於基板頂面之角度）0幾近垂直之加工形狀之被蝕刻 材之理由加以說明。又，圖5 A爲將光罩之推拔角度設爲 9 0度之情形，且如圖1 A〜2 G所作說明附著物2 5係 沿光罩1 0側壁平行堆積。又，圖4 A爲顯示光罩之推拔 角度被設爲9 0度時之鈾刻前狀態。 經濟部智慧財產局員工消費合作社印製 首先，當決定工序條件時，試樣底面（曝露於電漿之 被鈾刻材表面2 1 )之蝕刻率即被決定。以氯氣爲主要蝕 刻瓦斯進行蝕刻時，試樣中之被蝕刻材氯化物（反應生成 物）乃自基板（資料）跳入鈾刻裝置（反應容器）內。而 跳入蝕刻裝置內之反應生成物再射入於基板，且射入於基 板之反應生成物中之若干則以附著物堆積於基板表面（光 罩側壁及被蝕刻材側壁）（圖4 B )。該附著物大多可予 以與各向同性近似。並將該附著物之堆積率（以下僅以附 著率（deposition rate)稱之）設爲r d。另，由於鈾刻主 要藉離子之工作進行，致鈾刻對象位置之離子射入方向會 大大地影響該位置之鈾刻率。單純地假設蝕刻率由離子之 流量所予以決定，且離子略垂直射入之試樣底面鈾刻率設 爲r e時，離子射入角度α之蝕刻率即爲r e X s i η α 。在此，r e爲附著物未堆積時之真正之蝕刻率。 即，光罩側壁對於基板表面呈垂直時，附著物之對於 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -14- 550701 Α7 Β7 五、發明説明（ (請先閲讀背面之注意事項再填寫本頁) 光罩側壁之附著率爲r d，而試樣底面2 1之表觀蝕刻率 爲r e - r d (參照圖4 D )。此時，被鈾刻材之推拔角 度0爲 tan^=(re — rd) / r d 又，如圖4 B、5 B所示，光罩側壁自垂直於基板表 面之方向稍微傾斜（光罩推拔角度未滿9 0度）時，由於 對於光罩側壁之附著率呈各向同性致爲r d，故光罩側壁 之鈾刻率爲rexcos0。因此，rd — rexcos<9 即爲光罩推拔角度0時之對於側壁之附著率。於是，被蝕 刻材之推拔角度0如圖4 D所示爲 tan0=(re — rd) / { (rd — rex cos0)xsin0} 如此在光罩側壁進行附著物堆積之條件下，光罩推拔 角度Θ愈小，蝕刻後之被蝕刻材之推拔角度0即愈大。又 ，圖4 C爲顯示經過如圖4 B所示鈾刻處理後之除去附著 物之狀態。 經濟部智慧財產局員工消費合作社印製 將光罩推拔角度β自9 0度予以逐漸趨小，且使推拔 角度0比圖5 Β更加以逐漸趨小時，如圖5 C所示，推拔 角度β即會與被飽刻材之推拔角度0 —致（0 = 0)。如 此狀態，係呈附著物對於光罩不進行附著之條件。亦即， 雖附著物附著於光罩，該附著物瞬間被蝕哿除去，故結果 附著物無法附著於光罩。設此時之光罩推拔角度爲0 0， 被蝕刻材之推拔角度爲0 m時，如圖5 D所示，就算更加 趨小光罩推拔角度0 (即β β 〇 )，被蝕刻材之推拔角 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -15- 550701 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（13) 度0亦不會比0rn更大。即，如圖5D所示，設ι9<0〇 時，變爲Θ < 0 m，因此，光罩推拔角度Θ 0爲將被蝕刻 材之推拔角度0設成最大（0m)之界限値。又，圖5D 之狀態乃是光罩或底質（被蝕刻材）呈露出狀態。 又，此種光罩之推拔角度Θ與被鈾刻材之推拔角度^ 之關係，卻如圖6所示。在此，r d / r e係由光罩、被 蝕刻材之材質、蝕刻條件（反應容器內之壓力、導入反應 容器內之瓦斯流量等）予以一種含義性地決定。一般，反 應容器內之壓力愈高r d / r e愈小，且導入反應容器內 之瓦斯流量愈大r d / r e愈小。 如圖6所示，假如r d / r e = 〇 . 5時，將光罩之 推拔角度0自9 0度予以減少，則與光罩之推拔角度0略 成反比，被鈾刻材之推拔角度0即增加。當光罩之推拔角 度Θ減少至約7 2度時，被鈾刻材之推拔角度0亦增加至 約7 2度（Θ二0 ),變爲圖5 C之狀態。即Θ = 0 0 = 0 = 0 m。因此，雖將光罩之推拔角度0再予以減少，被 蝕刻材之推拔角度0依然處於0 m原樣。 故，在圖6，線L爲顯示光罩推拔角度0之界限値 0 0。於是，領域A爲β 0 〇之領域，附著物乃附著於 光罩，被蝕刻材之推拔角度0卻由光罩推拔角度0予以決 定。另，領域Β爲0 $ 0 〇之領域，附著物乃不附著於光 罩，被蝕刻材之推拔角度/與光罩推拔角度0無關連而成 所定値0 m。因此，例如在r d / r e = 〇 . 4之情形， 欲被鈾刻材之推拔角度0設定於7 0度時，則將光罩推拔 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度通用中國國家標準（CNS ) A4規格（210X297公釐） -16- 550701 A7 B7 五、發明説明（ 角度0設爲約8 2度即可。 (請先閲讀背面之注意事項再填寫本頁) 接著，就側壁之推拔角度未滿9 0度之光罩形成方法 加以說明。 在此，即以一例示說明使用氧化矽之遮光光罩對P t 進行蝕刻之情形。 (a )首先，參照圖8 A〜8 E就藉蝕刻瓦斯成分或 鈾刻壓力進行控制作爲光罩之氧化矽膜側壁之推拔角度之 方法加以說明。即在P t 5 0上形成氧化砂膜或金屬膜等 之遮光光罩材5 1，再於其上予以圖案形成所疋圖案之光 阻材料5 2 (圖8 A )。其次主要使用碳氟化合物系瓦斯 或氧等之添加瓦斯，將氧化矽膜加以蝕刻呈推拔形狀（圖 8 B )。此時藉切換導入蝕刻處理室之瓦斯成分或改變蝕 刻壓力，而可實現將氧化矽膜加以蝕刻呈推拔形狀。 經濟部智慧財產局員工消費合作社印製 此種予以蝕刻爲推拔形狀，例如已在Vac. Sci. Technol. A14、1 832 ( 1 996)有記載。依據該文件，即記載有 將氧化矽膜之推拔角度藉蝕刻瓦斯成分或蝕刻壓力加以控 制之方法。具體爲使用推拔角度8 6度之光刻膠，在C F 4 之流量爲2 0 s c c m，旁通功率爲1 〇 〇 W之鈾刻條件 下，藉促使壓力自40mTo r r變化爲300 m T o r r，而可將所形成氧化矽膜之推拔角度自8 0度 予以變化爲5 1度。又，在壓力40mTo r I*、CHF3 與C F 4之總流量爲2 0 s c c m之鈾刻條件下，藉將其成 分比（CHFs in CF4(%))自〇%變化爲50 %，則能使氧化矽膜之推拔角度自6 6度變爲8 4度。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -17- 550701 A7 B7 五、發明説明（1$ (請先閲讀背面之注意事項再填寫本頁) 如是，可知藉利用針對氧化矽膜之橫向鈾刻速度與壓 力幾乎無關係，壓力愈增加縱向鈾刻速度愈減少，而能控 制氧化膜之推拔角度。 如將氧化矽膜之推拔角度形成爲9 0度未滿（圖8 B )，即予以除去光阻材料5 2 (圖8 C )。接著將該基板 搬運至鈾刻裝置內之所定位置加以蝕刻（圖8 D )，然後 再進行除去光罩51 (圖8E)。 欲將光罩推拔角度形成爲未滿9 0度之其他方法，已 在 U.S. Patent No. 5,856,239 有所揭露。 經濟部智慧財產局員工消費合作社印製 (b )其次，說明藉濕式蝕刻將作爲光罩之氧化矽之 推拔角度予以形成爲9 0度未滿之方法。此種方法例如在 Jpn. J· Appl. Phys· Vol.34 ( 1 995)，ρρ·21 32-21 36 已有開示。 即，如圖9 A所示，作爲蝕刻P t 5 0時之光罩係在氧化 矽膜5 1上予以形成所定圖案之多晶矽膜5 2，且以所定 條件將此浸漬於H F水溶液。其中，多晶矽膜5 2不被 H F水溶液所蝕刻，氧化矽膜5 1卻被H F水溶液加以各 向同性蝕刻，而形成爲如圖9 Β所示之推拔形狀。然後， 使用氯氣C i 2或氟F 2或六氟化氫S F 6等予以鈾刻多晶矽 膜5 2，最後即能形成爲具有圖9 C所示形狀之氧化矽光 罩5 1。因此，使用如此推拔形狀之光罩進行蝕刻（圖 9D)，然後，再進行除去光罩51 (圖9E) ° 圖1 0A〜1 3D爲形成相同幅度（尺寸）且推拔角 度相異之氧化矽膜光罩之若干方法示意圖。 首先，圖10A〜10D所示方法係以作爲光罩之氧 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -18- 550701 A7 _______ B7_ 五、發明説明（1弓 (請先閲讀背面之注意事項再填寫本頁) 化矽膜5 1膜厚與其對應之濕式蝕刻時間，進行形成相同 幅度（尺寸）且推拔角度相異之光罩者。例如，在圖 1 0A、1 0D、1 0G形成如各圖所示之不同厚度T1 、T 2、T 3之氧化矽膜5 1，然後，對應氧化矽膜之厚 度進行適當時間之H F濕式蝕刻時，即可形成如在圖 1 0Β、1 0 Ε、1 0Η各自所示之不同推拔角度之光罩 。因此，之後再予以除去多晶矽膜5 2時，乃可形成圖 10C、10F、101各自所示之相同幅度（尺寸）且 推拔角度爲0 1、02、Θ3 (在此，01>02> Θ 3 )之光罩。即，作爲光罩之氧化矽膜5 1膜厚愈大， 愈能將光罩之推拔角度予以設小。 經濟部智慧財產局員工消費合作社印製 圖1 1 Α〜1 1 I所示方法係爲以作爲光罩之多晶矽 膜膜厚與其對應之濕式蝕刻時間，予以形成相同幅度（尺 寸）且推拔角度相異之光罩者。例如，在1 1 A、1 1 D 、1 1 G形成如各圖所示之不同幅度（尺寸）wi 、W2 、W 3之形式及保護膜之多晶矽膜5 2，然後對應多晶矽 膜之幅度進行適當時間之H F濕式蝕刻時，即可形成如在 圖1 1Β、1 1 Ε、1 1Η各自所示之不同推拔角度之光 罩。因此，待後再予以除去多晶矽膜5 2時，乃可形成圖 lie、11F、11 I各自所示之相同幅度（尺寸）且 推拔角度爲Θ4、05、06 (在此，04>05>Θ6 )之光罩。即，多晶矽膜5 2之幅度（尺寸）愈小，愈能 將光罩之推拔角度加以設小。 圖1 2 Α〜1 2 D爲藉濕式鈾刻及乾式蝕刻予以控制 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 一 ~ -19- 550701 A7 __B7 _ 五、發明説明（1乃 光罩推拔角度之方法。 (請先閲讀背面之注意事項再填寫本頁) 在圖1 2 A〜1 2 C所示方法，則首先將多晶矽膜 5 2予以圖案形成爲所定幅度（尺寸）W4 (圖1 2A) ，然後，藉乾式鈾刻將氧化矽膜5 1 —部分予以切削略垂 直之厚度Thl (圖12 B)，之後，再進行濕式蝕刻在 氧化矽膜5 1形成推拔者（圖1 2 C )。 在圖1 3 A〜1 3D所不方法，卻是首先將多晶Ϊ夕膜 5 2予以圖案形成爲異於上述幅度（尺寸）W4之所定幅 度（尺寸）W5 (圖1 3A)，然後，藉乾式鈾刻將氧化 矽膜5 1 —部分予以切削異於略垂直之厚度T h 1之厚度 丁 h 2 (圖1 3 B ),之後，復進行濕式蝕刻在氧化矽膜 5 1形成推拔者（圖1 3 C )。 如此，假如圖1 2 A、1 3 A所用多晶矽膜5 2之厚 度均爲相同之T h時，多晶矽膜5 2之幅度（尺寸）愈小 愈可使光罩之推拔角度設定爲較小，氧化矽膜5 1之切削 厚度愈薄愈能將光罩之推拔角度設定於較小。 經濟部智慧財產局員工消費合作社印製 藉將上述之該等推拔光罩形成方法適當地加以組合， 亦可控制光罩之推拔角度。 在此參照圖1 8具體說明使用S i〇2之光罩以圖3之 蝕刻裝置加以蝕刻厚度0 . 5 // m之P t膜之情形。 如前述，蝕刻時所用瓦斯主要爲氯氣，且向晶圓施加 旁通電壓加以蝕刻，惟，此時S i 0 2之蝕刻速度與P t之 蝕刻速度爲相同程度，致S i 〇2光罩之厚度需爲P t之厚 度相同程度以上，在此即設爲0 . 5 // m。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -20- 550701 A7 B7 五、發明説明（18) (請先閲讀背面之注意事項再填寫本頁) 在圖1之裝置，能將電漿維持於穩定之條件乃是 r d / r e呈某所定値以上，在此其最小値設爲0 . 4。 此時，依據圖6，設S i 〇2光罩之推拔角度爲90度時， 藉蝕刻P t，該P t膜之推拔角度即呈5 7度。 即，P t之底面幅度y比起S i〇2光罩之幅度，各側 緣X 1、X 2分別大於約0 . 3 // m。此由X 1 = X 2 = 0 · 5//m + t = 0 · 5//m + t an57° 加以求 得。因此，將光罩全幅設爲0 · 5 // m，且將P t膜予以 蝕刻0 · 5//m時，P t之底面幅度y即呈y = 0 · 5 //m+xl + x2 = l . l#m〇 然，用上述任一方法在S i 〇2光罩予以形成8 0度之 推拔角度，並以同樣條件進行鈾刻時，蝕刻後之p t光罩 之推拔角度爲7 0度，且p t之底面幅度y比起光罩之幅 度，一側緣約大於0 . 2 // m。因此，P t之底面幅度y 約爲 0 · 9//m (0 , 5//m+〇 _ 2//m+0 . 2#m )° 經濟部智慧財產局員工消費合作社印製 如是藉將光罩之推拔角度予以趨小，則能使鈾刻後t P t光罩之推拔角度變大。換言之，藉光罩之推拔角度可 控制蝕刻形狀。 況且，將光罩之推拔角度趨小（例如6 0度）時，貪虫 刻之推拔角度雖變大，卻呈附著物不附著於光罩之條件， 故光罩可切削成爲問題。 因此，推拔角度變大，且欲將光罩底面保持於鈾刻前 之大小之條件，乃在將光罩之推拔角度設爲0 0。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） - 21 - 550701 A7 B7 五、發明説明（θ (請先閲讀背面之注意事項再填寫本頁) 該光罩之推拔角度0 〇即自使用垂直之光罩之蝕刻結 果可加以推想。亦即，使用垂直之光罩進行蝕刻之結果， 假設獲得0 (例如6 0度）。此時由圖6可推定其條件下 之rd/ re之値（0.37)。在上述蝕刻之推拔角度 預測式 tan^=(re-rd) / { (rd — rex cos(9)xsin6>} 予以代入推定爲r d/ r e之値（此時爲0 · 3 7) ，而求取能滿足0 = 0之（9 ( 7 7度）即可。 (c )其次，參照圖1 4 A〜1 4 F就使用側壁幾乎 垂直（即，推拔角度略爲9 0度）之氧化矽光罩，實質上 可獲得推拔光罩之效果之方法加以說明。首先，使用側壁 幾乎垂直之氧化矽5 1光罩，將被蝕刻材之P t 5 0之所 盼量中之所定量，例如一半予以蝕刻（圖1 4 B )。如上 述，如此狀態之氧化矽5 1光罩側壁即附著有附著物5 5 (圖1 4 B )。接著進行除去附著物（圖1 4 C )。該附 經濟部智慧財產局員工消費合作社印製 著物之除去方法卻以使用純水、氨水、硫酸、鹽酸、酒精 或該等混合物之濕式處理爲代表性。附著物5 5除去後， 被鈾刻材P t 5 0之凸部5 0 a之推拔角度即成爲0 1。 附著物除去後，則就P t 5 0再予以進行剩餘量之蝕刻， 以完成上述所盼量之蝕刻（圖1 4 D )。此時氧化矽5 1 光罩及P t 5 〇之凸部5 0 a之側壁乃堆積有附著膜5 6 ，該附著膜係與最初之附著膜5 5略同樣堆積。在第2次 蝕刻被切削之P t 5 0之凸部5 0 b側壁即露出P t。如 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -22- 550701 A7 B7 五、發明説明（2() 此所獲P t 5 0之凸部5 0 b之推拔角度則成爲0 2 (在 (請先閲讀背面之注意事項再填寫本頁) 此，0 1 < 0 2 )。如是，藉第1次蝕刻及其直後之附著 物除去，如圖1 4 C所示，可獲得由氧化矽5 1及 P t 5 0之凸部5 0 a所成之，推拔角度爲0 1之實質上 推拔光罩。藉使用如此實質上推拔光罩而能將被鈾刻材之 推拔角度予以形成爲幾近於垂直之角度。 又，藉多次反覆如此鈾刻與除去附著物，尙能將被鈾 刻材之推拔角度形成爲更加接近於垂直之角度。以鈾刻直 後所得形狀，側壁非爲附著物而是露出被蝕刻材之p t時 ，在過份蝕刻時P t即有馬上被蝕刻之優點。如露出附著 膜時，則在過份鈾刻時先蝕刻附著膜後，才蝕刻被蝕刻材 之P t。因此，乃有可縮短過份鈾刻之時間之優點。 繼之，就附著物之除去方法加以說明。 經濟部智慧財產局員工消費合作社印製 以附著物之除去方法，除了濕式處理之外，亦可考慮 使用超臨界狀態之水或C〇2之處理，及適當瓦斯系統之乾 式處理。該乾式處理亦可使用與P t之蝕刻處理相同之處 理裝置（同一反應容器）予以進行。且，某一梯次之鈾刻 與其他梯次之蝕刻可使用相同之蝕刻裝置（同一反應容器 )，亦可使用其他之蝕刻裝置（其他反應容器）。 以乾式處理，卻可導入例如氧、氫、氨、氯、氯化氫 、酒精促使產生電漿，而進行試樣之電漿處理亦無妨。 以濕式處理之其他方法，另有例如予以曝露於超臨界 狀態之二氧化碳添加氨、酒精、鹽酸、過氧化氫溶液等者 之方法，並藉此可除去附著於側壁之氯化物。 本紙張尺度逍用中國國家標準（CNS ) A4規格（210X297公釐） -23- 550701 A7 B7 五、發明説明（2》 (請先閲讀背面之注意事項再填寫本頁) 又，依需在附著物之除去工程前或後***乾燥工程亦 可。例如，以附著物之除去方法而進行使用藥液之濕式處 理時，其後復進行使用純水之淸洗處理，然後再進行乾燥 處理亦可。如此加以進行鈾刻時，光罩或被蝕刻材之側壁 途中即存在有推拔角度（急激）變化之點。或可在光罩或 被蝕刻材之側壁途中予以設置推拔角度明顯相異之部分。 又，大部分之金屬氯化物均爲水溶性。 接著就將本案發明適用於半導體裝置製造裝置之情形 ，參照圖1 5 A、1 5 B加以說明。 經濟部智慧財產局員工消費合作社印製 圖1 5 A所示半導體製造裝置爲多房式之半導體裝置 製造裝置，係具有蝕刻處理室9 0 1、晶圓搬運用自動機 9 0 3、裝載鎖定室9 0 4、卸載鎖定室9 0 5、裝載機 9 0 6、儲藏室9 0 7。該儲藏室9 0 7被放置卡盒 9 0 8。在處理室9 0 1進行處理晶圓時，乃將被裝入於 略爲大氣壓條件之卡盒9 0 8之晶圓1 0 5以裝載機 9 0 6予以搬至略爲大氣壓條件之裝載鎖定室9 0 4，並 封閉裝載鎖定室。且將裝載鎖定室9 0 4之壓力予以減壓 爲適當壓力後，以晶圓搬運用自動機9 0 3將晶圓1 0 5 搬運至處理室9 0 1，並加以蝕刻至途中。然後，以晶圓 搬運用自動機9 0 3將晶圓1 0 5搬運至附著物除去處理 室9 0 2，將附著於側壁之附著物予以除去。接著再次以 晶圓搬運用自動機9 0 3將晶圓1 0 5搬運至蝕刻處理室 9 0 1’ ，加以蝕刻所盼量。之後，將晶圓1 0 5搬運至 附著物除去處理室9 0 2 ’予以除去附著於側壁之附著物 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -24- 550701 A7 B7 五、發明説明（22) (請先閱讀背面之注意事項再填寫本頁) 。接著以晶圓搬運用自動機9 0 3將晶圓1 〇 5搬運至卸 載鎖定室9 0 5。而將卸載鎖定室9 0 5之壓力上昇至大 氣壓後，以裝載機9 0 6予以***於卡盒9 0 8內。 如是，圖15A係具有晶圓搬運裝置（9 0 3)，與 連接於該晶圓搬運裝置之多數處理室（90 1、90 1， )及多數後處理室（902、902，），與多數鎖定室 (9 04、9 0 5 )，與鄰接於該鎖定室之大氣搬運裝置 (906)，且該大氣搬運裝置爲可連接於上述多數鎖定 室及鄰接於該大氣搬運裝置之晶圓卡盒（9 0 8 )之半導 體製造裝置，將被處理材在上述多數處理室之任一經過蝕 刻後，並在上述多數後處理室之任一進行後處理，然後， 在上述多數處理室之任一予以蝕刻，更在上述多數後處理 室之任一進行後處理者。 又，圖1 5A之例示雖使用大氣卡盒，惟如圖1 5B 使用真空卡盒亦可。即，圖15B乃具有晶圓搬運裝置（ 903)，與連接於該晶圓搬運裝置之多數處理室（ 901、901’ ），與多數鎖定室（904、905) 經濟部智慧財產局員工消費合作社印製 ，與鄰接於該鎖定室之大氣搬運裝置（906)，且該大 氣搬運裝置爲可連接於上述多數鎖定室與鄰接於該大氣搬 運裝置之後處理室（9 0 2)以及晶圓卡盒（9 0 8)之 半導體製造裝置，將被處理材在上述多數處理室之任一*經 過鈾刻後，並在上述後處理室予以進行後處理，然後，在 上述多數處理室之任一加以鈾刻，更在上述後處理室之任 一予以進行後處理亦可。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -25- 550701 A7 B7 五、發明説明（23) 而，說明上，附著物除去處理雖以真空條件加以進行 ，惟在大氣壓條件進行亦無妨。 (請先閲讀背面之注意事項再填寫本頁) 又，上述例，雖將兩次蝕刻處理分別在蝕刻處理室 9 0 1與9 0 1’予以進行，惟僅在相同之處理室9 0 1 予以使用多數次亦可。以蝕刻處理室使用另別處理室之優 點，卻在欲飩刻疊層膜時，隨著各膜種能以不同條件加以 穩定地鈾刻。蝕刻與附著物除去處理亦可在同一室內進行 之。 其次，就使用上述圖1 4 A〜1 4 F所示方法，利用 實質性推拔狀之光罩對鐵電體存儲裝置之存儲部之 P t / P Z T / P t等疊層膜進行蝕刻之方法，參照圖 1 6 A〜1 6 D加以說明。此時，對圖1 6 A所示 P t / P Z T / P t膜6 1〜6 3進行一次蝕刻加工時， 必然會在該等層6 1〜6 3之側壁進行附著物堆積，成爲 圖1 6 D所示之形狀。即，光罩6 4尺寸與所獲被蝕刻材 尺寸之差變大。該尺寸差則成爲細微化之妨礙。 於是，在蝕刻位於絕緣膜（P Z T ) 6 2下之導體（ 經濟部智慧財產局員工消費合作社印製 例如P t )膜6 1前，中斷鈾刻予以進行除去附著物（圖 1 6 B )。則PZT/Pt膜62〜63之推拔角度變爲 0 3。其後，再進行蝕刻時，可獲得如圖1 6 C所示之形 狀。此時之P t膜6 1之推拔角度成爲0 4 (在此，分3 < 0 4 )。較有特徵性爲絕緣膜（P Z T ) 6 2之上下雖 形成有相同材質之導體（例如P t膜6 1、P t膜6 3 ) ，惟該等之推拔角度0 3、0 4卻相異。又，當然能將推 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -26- 550701 A7 B7 五、發明説明（24 拔角度0 4設定呈比圖1 6 D所示推拔角度0 5爲大。 (請先閲讀背面之注意事項再填寫本頁) 如此，藉第1次之鈾刻及其直後之附著物除去，可獲 得如圖1 6 C所示之由絕緣膜（p z T ) 6 2及導體（例 如P t )膜6 3所成之推拔角度爲0 3之實質上推拔光罩 。且藉使用此種實質上推拔光罩，而在疊層膜，能將被蝕 刻材之推拔角度形成爲幾近垂直之角度。 又，就使用上述圖14A〜14F所示方法（c)、 或上述1 6 A〜1 6 D所示方法，利用實質性推拔狀之光 罩對於以次世代存儲裝置所期待之M R A M ( magnetic random access memory)之疊層膜進行蝕刻之方法，參照圖 1 7 A〜1 7 D加以說明。 在MRAM係具有如圖17A所示之疊層膜。即，自 上向下分別爲強磁性材（例如C ◦) 7 6、絕緣膜（例如 A 1 2〇3 ) 7 5、強磁性材（例如C 〇 ) 7 4、反強磁性 材（例如F e Μ η ) 7 3、底材（例如C 〇與S i ) 7 2 、7 1。又，7 0爲例如氧化矽膜7 0。在M R A Μ，卻 被要求將該等膜7 1〜7 6使用一個光罩加以蝕刻。 經濟部智慧財產局員工消費合作社印製 此時，如果FeMn膜73之反應生成物之附著比起 其他材料之附著急激時，則在F e Μ η膜7 3之鈾刻開始 前，中斷鈾刻予以除去附著物（圖1 7 Β )。於是膜7 4 〜7 6之推拔角度成爲/ 6。然後，再加以蝕刻，乃能將 F e Μ η膜7 3鈾刻呈幾近於垂直之形狀（圖1 7 C )。 此時之FeMn膜73之推拔角度爲07，而06<必7 。如此，藉第1次蝕刻及其直後之附著物除去，與第2次 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -27- 550701 A7 B7 五、發明説明（2$ (請先閲讀背面之注意事項再填寫本頁) 鈾刻及其直後之附著物除去，係能獲得如圖1 7 C所示由 膜7 3〜7 6所成且在途中變化推拔角度之實質上推拔光 罩。藉使用如此實質上推拔光罩73〜77，在MRAM 等之疊層膜，能將被蝕刻材7 1、7 2之推拔角度0 8予 以形成爲幾近於垂直之角度（在此，06<^7<%8) 〇 又，作爲強磁性材料可考慮加以者，主要爲F e、 C 〇、N i 、Μ η或其化合物，該等以難蝕刻材被知悉。 而，圖中之符號77爲光罩。 以上之例示，雖爲促使被蝕刻材側壁呈略垂直形狀， 就對於光罩形狀或實質上推拔光罩形狀下工夫之方法加以 說明，但，下述說明之本案發明，則是藉蝕刻條件之變更 可使被鈾刻材側壁呈垂直形狀之方法。 如上述，蝕刻之推拔角度係由對於光罩或被蝕刻材側 壁之附著率r d與對於底面之蝕刻率r e之比所予以決定 ，r d / r e愈小愈能使被蝕刻材側壁之推拔角度接近於 垂直。 經濟部智慧財產局員工消費合作社印製 到目前雖在附著物不易附著於真空容器（圖3之 1 0 4 )壁面之條件下進行蝕刻，惟欲減少附著物之附著 ，如降低真空容器內反應生成物之濃度卻頗爲有效。在真 空容器壁面不易附著附著物之條件下，欲減少氣相中反應 生成物之濃度，乃僅有將氣相中反應生成物予以排出真空 容器外，或予以附著於光罩及被蝕刻材側壁之外，並無其 他方法。因此，實際上，在附著物不易附著於真空容器壁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -28- 550701 A7 B7 五、發明説明（2弓 面之條件下，氣相中之反應生成物濃度被保持於相當高。 (請先閲讀背面之注意事項再填寫本頁) 惟在圖3，藉降低負荷1 1 5之阻抗，促使流入靜電 耦合天線1 1 8之電流變少，而可使氣相中反應生成物容 易附著於真空容器壁面。此時，氣相中反應生成物藉附著 於真空容器壁面能減低其濃度，故自氣相射入於晶圓之反 應生成物量會減少。 其結果，減少對於光罩及被鈾刻材側壁之附著物堆積 ，於是雖使用側壁略9 0度之光罩，亦能獲得被鈾刻材側 壁幾近於垂直之形狀。 但，如果附著物附著於真空容器壁面時，由於電漿之 狀態會變化，或成爲發生粒子之原因，故需定期性除去附 著物。於是，例如每當完成一張或多張晶圓處理，即進行 附著物除去處理（即，趨大流入於靜電耦合天線1 1 8之 電流等處理）。 經濟部智慧財產局員工消費合作社印製 此時，藉將晶圓支承台（§式樣台）1 0 9之溫度設定 爲比蝕刻時高，俾使附著物不附著於晶圓支承台1 〇 9， 而予以迅速排出真空容器104外亦可。或者，反之，降 低晶圓支承台1 0 9之溫度，使附著物積極附著於支承台 或支承台裝載之晶圓，避免附著物自支承台或支承台裝載 之晶圓反射，以防止附著物再度附著於真空容器壁面，促 進附著物之排氣亦可。 依據本發明，係在側壁不易獲得垂直加工形狀之材半斗 之蝕刻，藉使用推拔狀光罩等可獲得側壁幾近於垂直之蝕 刻形狀，故能製成高功能之半導體裝置，或積體度高之半 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -29- 550701 A7 B7 五、發明説明（導體裝置。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）SrBi2 (Ta, Nb) 2〇9, BT〇: Bi4Ti3〇12, BiSi〇x, BLOT • B i4- xLaxT i3〇i2 and other compound semiconductors: G a As s, etc. This paper standard is applicable to China National Standard (CNS) A4 Specifications (210X29? Mm) -5- 550701 A7 _ B7_ _ V. Description of the invention (3) IT〇 Others · I η T i〇 etc. (Please read the precautions on the back before filling this page) These are difficult to etch Compared with aluminum, silicon, silicon oxide, etc., the material is not as easy to be engraved with uranium, and it is particularly difficult to process the side wall of the hardly engraved material into a vertical shape to the substrate, which has become a problem. None of the above-mentioned known documents has any suggestion that the side walls of the hard-to-etch material are processed to have a vertical shape to the substrate. Next, when plasma is used to etch chemically stable materials such as iron, cobalt, manganese, nickel, platinum, ruthenium, macro, alumina, oxidation feed, oxidation pins, gallium arsenide, etc., it is difficult to obtain the material to be etched. The reason for the vertical etching shape is explained below. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed on the hard-to-etch materials such as the hard-to-etch materials mentioned above, and formed a reaction product due to the etching, and the reaction product jumped out of the sample surface in the gas phase, but it was reached by uranium. The surface of the material is easy to attach. Therefore, attaching the reaction product only to the etching position of the material to be etched will substantially reduce the etching rate, but in fact, the reaction product will adhere to all arbitrary positions of the material to be etched. That is, the reaction product will be attached to the sidewall of the uranium carving material without etching. As a result, the etching of the bottom surface of the uranium carving and the deposition of the deposition material on the sidewall are performed simultaneously. A shape perpendicular to the substrate is obtained. The above is the reason why the side walls of the difficult-to-etch material cannot be etched vertically when the substrate is etched. The reason why the sidewall of the material to be etched cannot obtain a shape perpendicular to the substrate will be described in more detail with reference to FIGS. 1A to 2G. Figure 1 A 'Figure 2 B is in the initial state of etching, the right-handed arrow in the figure is paper size 11 @ 家 样 准 （〇 阳）》 4 specifications (2 297 mm)' a--6- 550701 A7 ___ B7 V. Description of the invention (4) (Please read the precautions on the back before filling out this page) The head shows the direction of deposit attachment, and the arrow below shows the direction of uranium engraving. Here, let the angle (push-out angle) 0 of the side wall of the mask 10 to the upper surface of the substrate 0 be 90 degrees. When a small unit time Δt has passed from the initial state, the bottom surface (the upper surface 2 1 of the uranium engraved material 20 exposed to the plasma) is only etched △ e, and the photomask 10 and the side wall of the etched material 20 are only etched. Attachments 25 of Δd were deposited (Figs. IB and 2B). In fact, the top surface 30 of the attachment is also engraved with uranium, so the angle (pushing angle) formed by the part on the surface of the substrate is 0, which is the accumulation amount of deposits (stacking rate) △ d per unit time and per unit The amount of time (etch rate of uranium) is determined. In addition, at the moment when the bottom part 3 2 of the photomask side wall started to accumulate on the photomask side wall, the bottom part 3 3 (the top of the object to be etched 20 exposed to the plasma) of the photomask side wall was stopped. Surface 2 1). However, at the moment when the exposed part of the engraved inscription 20 on the lower side of the side wall of the mask 25 was etched to expose the new engraved inscription 20 side wall, the attached surface was repeatedly deposited on the exposed surface. Therefore, the etching is performed obliquely downward (Fig. 1C, 2C). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. When the unit time Δt has elapsed from the state of Fig. 1 C and 2 C, deposits of attachments 2 5 are deposited on the side walls of attachments 5 and 5 The exposed part 20 of the material to be etched at the lower part of the side wall is also etched (Fig. 1 D, 1 E, 2 D to 2 F). If so, the etching is performed in an obliquely downward sequence in order to obtain the etched shapes shown in Figs. 1F and 2G. Therefore, the side wall of the inscribed uranium has a push angle of 0 0 to the substrate surface. < 90 degrees). The purpose of the present invention is to provide an etching method for a difficult uranium engraving material, a semiconductor manufacturing method using the same, and a paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm), which can eliminate the problems of the conventional technology. 550701 A7 B7 5. Description of the invention (5) Device. (Please read the precautions on the back before filling this page.) Another object of the present invention is to provide a method for stabilizing multiple wafers in response to the fine requirements of semiconductor devices, etc., or to obtain nearly vertical etched materials. Method and device for surface treatment of sample at pushing angle. A feature of the present invention is a sample surface treatment method for performing uranium engraving using a push-type mask when uranium engraving is performed on a thin film formed on a substrate using a plasma. That is, according to one aspect of the present invention, a method for engraving the above-mentioned film with plasma uranium using a thin uranium engraving material film formed on a substrate and a photomask formed thereon has the angle of the side wall of the photomask to the surface of the substrate. The step of engraving uranium is performed on a 90 degree sub-mask. Therefore, according to the present invention, it is not easy to etch a material with a vertical processing shape on the side wall. By using a push-type photomask, an almost vertical etched shape on the side wall can be obtained, so a highly functional semiconductor device or a high collective degree can be manufactured. Semiconductor device. [Brief description of the diagram] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Figures 1 ~ 1F are sectional views for explaining the etching process using a mask with vertical sidewalls; Figures 2 ~ 2G are using vertical sidewall light Sectional view for explaining the etching process of the mask; FIG. 3 is a diagram showing an example of the overall configuration of a plasma etching apparatus to which the present invention is applied; and FIGS. 4A to 4D are uranium etching processes when the photomask pushing angle is set to less than 90 degrees Sectional drawing for explanation; This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -8- 550701 A7 B7 V. Description of invention (6) (Please read the precautions on the back before filling this page) Figure 5 A ~ 5D are sectional views for explaining the relationship between the deposition state of the side wall of the mask and the pushing angle of 0 by the uranium carving material when the pushing angle of the mask is gradually decreased from 90 degrees; FIG. 6 is the pushing angle of the mask Figure 7 A and 7 B show the pushing angle of the mask in the critical radon underfill area and the pushing angle of the mask in the critical radon area and above. Angle relationship display; Figure 8 A ~ 8 E Figure 9 A to 9 E are illustrations of the method for controlling the mask push-out angle by wet touch engraving; Figure 1 〇 A ~ 1 Ο I The illustration of the method for controlling the pushing angle of the photomask by wet etching; Figure 1 1 ~ 1 1I is the illustration of the other methods of controlling the pushing angle of the photomask by wet uranium engraving; Intellectual Property of the Ministry of Economic Affairs Printed by the Consumer Cooperatives of the Bureau 1 2 A ~ 1 2 D are illustrations of the method for controlling the pushing angle of the photomask by dry etching and wet etching; Figure 1 3 A ~ 1 3 D are by dry uranium etching and wet Figures 4A ~ 1 4F are illustrations of methods that can be used to obtain a substantially push-out mask effect by using a mask with a push angle of approximately 90 degrees. Figures; Figure 15A is a block diagram of an example of a manufacturing device structure of a semiconductor device to which the invention of the present invention is applied; This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -9-550701 A7 B7 V. Description of the invention (7) 1 5 B is a semiconductor device to which the invention of the present invention is applied. Block diagram of other examples of the device; (Please read the precautions on the back before filling out this page) Figures 16A-16D are ferroelectric, using a mask with a push angle of approximately 90 degrees to obtain a substantially push-shaped mask The method of the effect is illustrated in FIG. 9. FIG. 1 7A to 17D are illustrations of the method for obtaining a substantially push-out mask effect in MRAM by using a mask with a push angle of slightly 90 degrees; FIG. 18 is used A cross-sectional view for explaining the etching treatment of a mask with a vertical sidewall. Main component comparison table 10 Photomask 2 0 Etched object 2 1 Top surface 2 5 Attachment 30 Top surface of the attachment Printed by the Ministry of Economic Affairs and Intellectual Property Bureau Employee Consumer Cooperative 32 Photomask side wall lower part 33 Attachment bottom surface 101 High frequency Power supply 10 2 Automatic matching device 10 3 Wire coil 104 Vacuum container 104a Discharge unit The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -10- 550701 A7 B7 V. Description of the invention (8) 104b Processing unit 10 5 Wafer (Please read the precautions on the back before filling in this page) 106 Gas introduction section 107 Exhaust device 10 8 Sample 109 Sample stage 110 Bias power supply 111 High-pass chirper 113 DC power supply 114 Low-pass filter 115 Heater (load) 116 Refrigerant path 118 Electrostatically coupled antenna 5 0 P t 50a, 50b Convex part 5 1 Light-shielding mask material (silicon oxide film, etc.) 52 Photoresist material Printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 6 1 Conductor Film (P t film) 6 2 Insulation film (PZT film) 6 3 Conductor film (P t film) 6 4 Photomask 70 Silicon oxide film 7 1, 7 2 Substrate 7 3 F e Μ η Film Applicable to this paper Chinese National Standard (CNS) Α4 specification (210X297 mm) -11-550701 A 7 B7 V. Description of the invention (9) 7 4 ~ 7 6 Film (Please read the precautions on the back before filling this page) 7 7 Push the photomask 9 〇1,9〇1 'Uranium engraving processing chamber 9 〇2,9 0 2' Attachment removal processing chamber 9 0 3 Wafer handling robot 904 Load lock chamber 905 Unload lock chamber 9 0 6 Loader 907 Storage chamber 9 0 8 Card box 5 5, 5 6 Attachment (adhesive film) [Detailed description] Hereinafter, the embodiment of the present invention will be described in detail with reference to the attached drawings. 0 FIG. 3 shows the overall configuration of a plasma etching apparatus to which the present invention is applied. Example display diagram. A high-frequency power source 101 supplies an automatic matching device 102 (printing matching unit printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs) to supply high-frequency current to the coil 103, causing a plasma to be generated in the vacuum container 104. The vacuum container 104 is composed of a discharge part 104a made of an insulating material and a grounded processing part 104b. The vacuum container 104, that is, the methane introduction section 106, is etched with gas such as chlorine gas, but the gas is discharged through the exhaust device 107. The sample 108 is mounted on the sample stage 109. In order to increase the ion energy injected into the sample 108, the sample table 1109 passes the high-pass filter. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -12-550701 A7 B7 V. Description of the invention (called (please read the precautions on the back before filling out this page) The wave device 1 1 1 is connected to the bias power supply 1 1 〇 of the second high-frequency power supply. The sample stand 1 9 is provided on the surface. An insulating film of ceramics 1 1 2. The sample stage 1 009 is connected to a DC power source 1 i 3 through a low-pass filter 1 1 4 and the sample 1 8 is held on the sample stage 1 0 9 by electrostatic force. In addition, in order to adjust the temperature of the sample 108 for control and burial, the _haif sample table 1 09 is also provided with a heater 1 1 5 and a refrigerant passage 1 1 6. Using this device, the iron, Ming, Meng, nickel , Platinum, ruthenium, | denier, oxidized oxide, oxidized to, dysprosium oxide, gallium arsenide and other chemically stable materials, the typical conditions when the worm is engraved are as follows. The pressure of the device is 0. 5pa, m The main introduction of gas is Chlorine gas. The temperature of the sample 108 is different depending on the material being cut, but it is usually more than 2 0 0 t and 5 0 0 t: the following. The etching rate or the semiconductor device to be manufactured is determined, but the typical temperature when etching a silicon film, an aluminum film, or a silicon oxide film is 0 to 100 ° C, and the temperature of the sample 108 is maintained. At higher temperatures. Therefore, it is often the case that the photoresist cannot be effectively used with the etched photomask material. Generally, a silicon oxide or metal light-shielding photomask is commonly used. In the above-mentioned problem in etching, that is, in order to obtain the uranium engraving treatment that can obtain the pushing angle 0 of the material to be etched, which is a nearly vertical angle to the substrate surface, it is important to suppress the amount of deposits attached to the side wall of the mask. In this way, the method for suppressing the accumulation of attachments can be considered to reduce the pressure in the reaction vessel or increase the gas flow rate introduced into the reaction vessel. However, pressure or gas flow rate is often limited to an appropriate range in order to obtain better etching characteristics. And the pressure and flow are determined by the exhaust function. Because this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -13- 550701 A7 B 7 V. Description of the invention (11) Therefore, it is difficult to suppress the accumulation of attachments by pressure, flow, etc. (Please read the precautions on the back before filling out this page) Second, refer to Figure 4 A ~ 5 D and use it. Pushing angle (angle of the side wall of the mask 10 with respect to the top surface of the substrate) Θ is set to a mask that is less than 90 degrees (ie, a push-shaped mask), and the push angle (the side of the etched material The angle of the top surface of the substrate) 0 almost vertical processing shape of the material to be etched will be explained. Also, Fig. 5A is a case where the pushing angle of the photomask is set to 90 degrees, and as shown in Fig. 1 A ~ 2 The description made by G is that the attachments 25 are stacked in parallel along the side walls of the mask 10. FIG. 4A shows the state before the uranium engraving when the pushing angle of the photomask is set to 90 degrees. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. First, when the process conditions are determined, the etching rate of the bottom surface of the sample (the surface of the uranium engraved material exposed to the plasma 2 1) is determined. When chlorine is used as the main etching gas, the chloride (reaction product) of the material to be etched in the sample jumps from the substrate (data) into the uranium engraving device (reaction container). The reaction products jumping into the etching device are then injected into the substrate, and some of the reaction products injected into the substrate are deposited on the surface of the substrate (the side wall of the mask and the side of the material to be etched) with attachments (Figure 4 B) ). Most of this attachment can be approximated isotropically. Let the deposition rate of the attached matter (hereinafter referred to as the deposition rate only) be r d. In addition, since the uranium carving is mainly performed by ions, the direction of the ion injection at the position of the uranium carving object will greatly affect the uranium carving rate at that position. It is simply assumed that the etching rate is determined by the flow rate of the ions, and when the uranium etch rate of the bottom surface of the sample where the ions are injected slightly perpendicularly is set to e, the etch rate of the ion injection angle α is r e X s i η α. Here, r e is the true etching rate when the deposits are not deposited. That is, when the sidewall of the mask is perpendicular to the surface of the substrate, the attached matter applies the Chinese National Standard (CNS) A4 specification (210X297 mm) for this paper size. -14- 550701 Α7 Β7 V. Description of the invention ((Please read the first Please fill in this page again.) The adhesion rate of the side wall of the photomask is rd, and the apparent etching rate of the bottom surface 21 of the sample is re-rd (see Figure 4D). At this time, the pushing angle of the uranium carving material is 0. It is tan ^ = (re — rd) / rd. As shown in Figs. 4B and 5B, when the side wall of the mask is slightly inclined from the direction perpendicular to the substrate surface (the mask pushing angle is less than 90 degrees), The adhesion rate of the mask side wall is isotropic and is rd, so the uranium engraving rate of the mask side wall is rexcos0. Therefore, rd — rexcos < 9 is the adhesion rate to the side wall when the reticle pushing angle is 0. Therefore, the pushing angle 0 of the material to be etched is shown in FIG. 4D as tan0 = (re — rd) / {(rd — rex cos0) xsin0}. Under the condition that the deposits are deposited on the side wall of the mask, the mask is pushed. The smaller the pulling angle Θ, the larger the pushing angle 0 of the material to be etched after etching. In addition, FIG. 4C is a view showing a state where the adhered matter is removed after the uranium etching process shown in FIG. 4B. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the pushing angle β of the mask is gradually reduced from 90 degrees, and the pushing angle 0 is gradually smaller than that in FIG. 5B, as shown in FIG. 5C. The pull-out angle β is equal to 0 (0 = 0). In this state, the conditions are such that the attachment is not attached to the photomask. That is, although the attached matter was attached to the photomask, the attached matter was instantly removed by erosion, and as a result, the attached matter could not be attached to the photomask. When the pushing angle of the mask at this time is 0 0 and the pushing angle of the material to be etched is 0 m, as shown in FIG. 5D, even if the pushing angle of the mask is smaller 0 (that is, β β 〇), Etching angle of etched material This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 × 297 mm) -15- 550701 A7 B7 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Will be bigger than 0rn. That is, as shown in FIG. 5D, let < 0〇 becomes Θ < 0 m. Therefore, the mask pushing angle Θ 0 is a limit 値 that sets the pushing angle 0 of the material to be etched to a maximum (0 m). In addition, the state of FIG. 5D is a state in which the photomask or substrate (material to be etched) is exposed. In addition, the relationship between the pushing angle Θ of such a mask and the pushing angle ^ of the engraved material is shown in FIG. 6. Here, r d / r e is meaningfully determined by the mask, the material of the material to be etched, and the etching conditions (pressure in the reaction vessel, gas flow rate into the reaction vessel, etc.). Generally, the higher the pressure in the reaction vessel is, the smaller r d / r e is, and the larger the gas flow rate introduced into the reaction vessel is, the smaller the r d / r e is. As shown in Figure 6, if rd / re = 0.5, the pushing angle 0 of the photomask is reduced from 90 degrees, it is slightly inversely proportional to the pushing angle 0 of the photomask, and it is pushed by the uranium carving material. Pulling angle 0 increases. When the pushing-out angle Θ of the photomask is reduced to about 72 degrees, the pushing-out angle 0 of the engraved material is also increased to about 72 degrees (Θ-20), and becomes the state shown in FIG. 5C. That is, Θ = 0 0 = 0 = 0 m. Therefore, although the pushing angle 0 of the photomask is reduced, the pushing angle 0 of the material to be etched is still at 0 m. Therefore, in FIG. 6, the line L is the limit 値 0 0 showing the mask pushing angle 0. Therefore, in the area of β 0 〇, the attachment is attached to the mask, and the pushing angle 0 of the material to be etched is determined by the pushing angle 0 of the mask. In addition, in the area B of 0 $ 0 〇, the attachment is not attached to the mask, and the pushing angle of the etched material / irrelevant to the mask pushing angle 0 is determined to be 0 m. Therefore, for example, in the case of rd / re = 0.4, if the pushing angle 0 of the uranium carving material is set to 70 degrees, push the photomask (please read the precautions on the back before filling this page) This paper is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) -16- 550701 A7 B7 V. Description of the invention (The angle 0 can be set to about 82 degrees. (Please read the precautions on the back before filling in this (Page) Next, a description will be given of a mask forming method in which the pushing angle of the side wall is less than 90 degrees. Here, an example will be described in which P t is etched using a light-shielding mask made of silicon oxide. (A) First, With reference to Figs. 8A to 8E, the method of controlling the pushing angle of the side wall of the silicon oxide film as a photomask by etching gas components or uranium etching pressure will be described. That is, an oxide sand film or a metal film is formed on Pt50. Wait for the light-shielding mask material 51, and then pattern it on the photoresist material 5 2 (Fig. 8A). Secondly, fluorocarbon-based gas or oxygen is added to the silicon oxide film. It is etched into a push shape (Figure 8B). At this time, it is introduced by switching The gas composition of the processing chamber can be etched or the etching pressure can be changed, so that the silicon oxide film can be etched into a push shape. This is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and etched into a push shape, for example, it has been etched in Vac. Sci Technol. A14, 1 832 (1 996). According to this document, it describes the method of controlling the pushing angle of the silicon oxide film by the etching gas component or etching pressure. Specifically, the pushing angle is 86 degrees. In the photoresist of CF 4 with a flow rate of 20 sccm and a bypass power of 1000W, the silicon oxide film can be formed by changing the pressure from 40mTo rr to 300 m T orr. The pushing angle was changed from 80 degrees to 51 degrees. Moreover, under the conditions of uranium engraving under the condition that the total flow of pressure 40mTo r I *, CHF3 and CF 4 is 20 sccm, the composition ratio (CHFs in CF4 (%)) Change from 0% to 50%, then the pushing angle of the silicon oxide film can be changed from 66 degrees to 84 degrees. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm)- 17- 550701 A7 B7 V. Description of the invention (1 $ (please read the note on the back first) Please fill in this page for further details.) If so, it can be seen that by using the lateral uranium engraving speed for the silicon oxide film, there is almost no relationship between pressure and pressure. As the pressure increases, the vertical uranium engraving speed decreases, and the pushing angle of the oxide film can be controlled. The pushing angle of the film is formed to be less than 90 degrees (Fig. 8B), and the photoresist material 5 2 (Fig. 8C) is removed. Then the substrate is transported to a predetermined position in the uranium etching device and etched (Fig. 8). D), and then the mask 51 is removed (FIG. 8E). Other methods for forming the pushing angle of the photomask to less than 90 degrees have been disclosed in U.S. Patent No. 5,856,239. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (b) Secondly, it explains the method of forming the pushing angle of the silicon oxide as a photomask by wet etching to less than 90 degrees. Such a method is disclosed, for example, in Jpn. J. Appl. Phys. Vol. 34 (1 995), ρρ 21 32-21 36. That is, as shown in FIG. 9A, a polycrystalline silicon film 5 2 having a predetermined pattern is formed on the silicon oxide film 51 as a mask when etching P t 50 0, and this is immersed in an H F aqueous solution under predetermined conditions. Among them, the polycrystalline silicon film 5 2 is not etched by the H F aqueous solution, but the silicon oxide film 51 is isotropically etched by the H F aqueous solution to form a push shape as shown in FIG. 9B. Then, the polycrystalline silicon film 5 2 is formed by uranium etching using chlorine gas C i 2 or fluorine F 2 or hydrogen hexafluoride S F 6 or the like, and finally a silicon oxide mask 51 having a shape as shown in FIG. 9C can be formed. Therefore, the mask with the shape pushed in this way is used for etching (Fig. 9D), and then the mask 51 is removed (Fig. 9E) ° Fig. 10A to 1 3D are formed with the same width (size) and the pushing angle is different Schematic diagrams of several methods of silicon oxide photomasks. First of all, the method shown in Figures 10A to 10D uses the oxygen of the paper as the mask. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -18- 550701 A7 _______ B7_ 5. Description of the invention (1 bow (please Read the notes on the back and fill in this page again.) Siliconized film 5 1 The thickness of the silicon film and its corresponding wet etching time are used to form a mask with the same width (size) and different push angles. For example, in Figure 10A, 1 0D, 1 0G form silicon oxide films 5 1 of different thicknesses T1, T2, and T3 as shown in the drawings. Then, when HF wet etching is performed for an appropriate time according to the thickness of the silicon oxide film, it can be formed as The masks with different pushing angles shown in Figs. 10B, 10E, and 10Η respectively. Therefore, when the polycrystalline silicon film 52 is removed later, the same widths as shown in Figs. 10C, 10F, and 101 can be formed. (Size), and the pushing angle is 0, 02, Θ3 (here, 01 > 02 > Θ3). That is, the larger the thickness of the silicon oxide film 51 as the mask, the more the mask can be used. The pushing angle should be set small. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 1 Α ~ 1 The method shown in 1 I is to form a photomask with the same width (size) and different push angles by using the polycrystalline silicon film thickness as the photomask and its corresponding wet etching time. For example, in 1 1 A, 1 1 D, 1 1 G forms a polycrystalline silicon film of different widths (sizes) wi, W2, and W3 as shown in the figure and a protective film of polycrystalline silicon film 5 2 and then performs HF wet etching at an appropriate time corresponding to the amplitude of the polycrystalline silicon film , You can form a mask with different push angles as shown in Figure 1 1B, 1 1 Ε, 1 1Η. Therefore, when the polycrystalline silicon film 5 2 is removed later, it can form Figures lie, 11F, 11 I masks with the same amplitude (size) shown by each and the pushing angles are Θ4, 05, 06 (here, 04 > 05 > Θ6). That is, the smaller the amplitude (size) of the polycrystalline silicon film 52, the more effective it is. Decrease the pushing angle of the photomask. Figure 1 2 Α ~ 1 2 D is controlled by wet uranium engraving and dry etching. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 19- 550701 A7 __B7 _ V. Description of the invention (1 is the method of pushing out the mask. (Please read first Note on the back, please fill in this page again.) In the method shown in Figures 1 2 A to 1 2 C, the polycrystalline silicon film 5 2 is first patterned to a predetermined width (size) W4 (Figure 1 2A). Then, dry uranium is borrowed. The silicon oxide film 51 is partially cut to a thickness of Thl (FIG. 12B), and then wet etching is performed on the silicon oxide film 51 to form a pusher (FIG. 12C). In the methods shown in FIGS. 1 3 A to 1 3D, the polycrystalline silicon film 5 2 is first patterned to a predetermined width (size) W5 different from the width (size) W4 (FIG. 1 3A), and then, The silicon oxide film 5 1 is partially cut by a dry uranium etch to a thickness that is different from the slightly vertical thickness T h 1 (Figure 1 3 B). After that, a wet etching is performed on the silicon oxide film 5 1 to form a pusher. Puller (Figure 1 3 C). In this way, if the thickness of the polycrystalline silicon film 5 2 used in Figures 12 A and 1 3 A is the same T h, the smaller the width (size) of the polycrystalline silicon film 52 can make the pushing angle of the photomask smaller. The thinner the cutting thickness of the silicon oxide film 51, the smaller the pushing angle of the photomask can be set. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs By appropriately combining the above-mentioned methods for forming the push-up masks, the push-out angle of the masks can also be controlled. Here, a case where a P t film with a thickness of 0.5 // m is etched by using the SiO 2 mask and the etching device of FIG. 3 will be specifically described with reference to FIG. 18. As mentioned above, the gas used in the etching is mainly chlorine gas, and a bypass voltage is applied to the wafer to etch. However, at this time, the etching speed of S i 0 2 is the same as the etching speed of P t, which results in a Si 02 mask. The thickness needs to be equal to or greater than the thickness of P t, which is set to 0. 5 // m here. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -20- 550701 A7 B7 V. Description of the invention (18) (Please read the precautions on the back before filling this page) The device in Figure 1 can The condition for maintaining the plasma to be stable is that rd / re is equal to or higher than a certain threshold, and here the minimum threshold is set to 0.4. At this time, according to FIG. 6, when the pushing angle of the Si02 mask is 90 degrees, by etching Pt, the pushing angle of the Pt film is 57 degrees. That is, the width y of the bottom surface of P t is larger than the width of the Si 102 mask, and each of the side edges X 1 and X 2 is larger than about 0.3 // m. This is obtained by X 1 = X 2 = 0 · 5 // m + t = 0 · 5 // m + t an57 °. Therefore, when the full width of the photomask is set to 0 · 5 // m and the P t film is etched to 0 · 5 // m, the width y of the bottom surface of P t becomes y = 0 · 5 // m + xl + x2 = l. l # m〇 Then, use any of the above methods to form a push angle of 80 degrees on the Si 〇2 mask, and perform uranium etching under the same conditions, the push angle of the pt mask after etching It is 70 degrees, and the width y of the bottom surface of pt is larger than that of the mask, and the edge of one side is greater than 0.2 / m. Therefore, the width y of the bottom surface of P t is approximately 0 · 9 // m (0, 5 // m + 〇_ 2 // m + 0. 2 # m) ° Decreasing the pushing angle of the photomask can increase the pushing angle of the t P t photomask after uranium engraving. In other words, the etched shape can be controlled by the pushing angle of the mask. Moreover, when the pushing-out angle of the photomask becomes smaller (for example, 60 degrees), although the pushing-in angle of the greedy worm is larger, the attached matter does not adhere to the photomask, so cutting of the photomask becomes a problem. Therefore, the condition that the pushing angle becomes larger and the bottom surface of the mask is to be maintained at the size before the uranium engraving is to set the pushing angle of the mask to 0 0. This paper size applies to Chinese National Standard (CNS) A4 specification (210X29 * 7mm)-21-550701 A7 B7 V. Description of the invention (θ (Please read the precautions on the back before filling this page) Pushing the photomask The angle 0 〇 can be inferred from the result of etching using a vertical mask. That is, the result of etching using a vertical mask is assumed to obtain 0 (for example, 60 degrees). At this time, the conditions can be estimated from FIG. 6. Rd / re 値 (0.37). In the above-mentioned etching, the prediction angle of tan ^ = (re-rd) / {(rd — rex cos (9) xsin6 >} is substituted into the presumed rd / re 値 ( At this time, it is 0 · 3 7), and it is sufficient to obtain (9 (7 7 degrees)) which can satisfy 0 = 0. (c) Secondly, referring to Figs. 1 4 A to 1 4 F, the side walls are almost vertical (that is, A silicon oxide mask with a pushing angle of slightly 90 degrees) will be explained in essence to obtain the effect of pushing the mask. First, a silicon oxide 51 mask with a side wall almost vertical will be used. The amount of the desired amount of t 5 0, for example, half is etched (Figure 1 4 B). As described above, the silicon oxide 5 1 mask side wall in this state That is, the attached matter 5 5 (Fig. 14B) is attached. Then the attached matter is removed (Fig. 14C). The removal method of the printed matter by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs uses pure water and ammonia water. The wet treatment of sulfuric acid, sulfuric acid, hydrochloric acid, alcohol, or these mixtures is typical. After the attachment 5 5 is removed, the pushing angle of the convex part 50 0 a by the uranium engraving material P t 50 0 becomes 0 1. The attachment After removal, the remaining amount of etching is performed on P t 50 to complete the above-mentioned desired amount of etching (Fig. 14 D). At this time, the silicon oxide 5 1 mask and the convex portion 50 of P t 5 0 An adhesion film 5 6 is deposited on the side wall of a, and the adhesion film is deposited similarly to the original adhesion film 5 5. P t is exposed on the side wall of the convex portion 5 0 b of P t 50 that is cut in the second etching. If this paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -22- 550701 A7 B7 V. Description of the invention (2 () The pushing angle of the convex part 5 0 b of P t 5 0 obtained here is Become 0 2 (in (Please read the precautions on the back before filling out this page) This, 0 1 < 0 2). If so, by the first etching and subsequent attachment removal, as shown in FIG. 14C, it can be obtained by the convex portion 5 0a of silicon oxide 5 1 and P t 50 0, and the pushing angle is 0. 1 essentially pushes out the photomask. By using such a substantially pushed-out photomask, the pushing-out angle of the engraved engraved material can be formed to a nearly vertical angle. In addition, by repeatedly repeating such uranium engraving and removing attachments, plutonium can form the pushing angle of the engraved engraved material to a more vertical angle. In the shape obtained after the uranium is straightened, when the sidewall is not an attachment but the p t of the material to be etched is exposed, the P t has the advantage of being etched immediately when the etching is excessive. If the attached film is exposed, the Pt of the material to be etched is etched after the attached film is etched when the uranium is etched excessively. Therefore, there is an advantage that the time for excessive uranium etching can be shortened. Next, a method for removing the adhered matter will be described. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In addition to wet treatment, in addition to wet treatment, the use of supercritical water or CO2 treatment and dry treatment with appropriate gas systems can be considered. This dry process can also be performed using the same processing apparatus (same reaction vessel) as the etching process of Pt. Moreover, the uranium engraving of a certain step and the etching of other steps can use the same etching device (the same reaction container), and other etching devices (other reaction containers) can also be used. In the dry process, the introduction of oxygen, hydrogen, ammonia, chlorine, hydrogen chloride, alcohol, etc. can be used to promote the generation of plasma, and the plasma treatment of the sample is not necessary. Other methods of wet treatment, for example, a method of adding ammonia, alcohol, hydrochloric acid, hydrogen peroxide solution, etc. to carbon dioxide exposed to a supercritical state, thereby removing chlorides adhering to the side wall. The size of this paper is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) -23- 550701 A7 B7 V. Description of the invention (2) (Please read the precautions on the back before filling this page) It is also possible to insert the drying process before or after the removal process of the object. For example, when the wet treatment using a chemical solution is performed by the removal method of the attachment, the washing process using pure water is followed by the drying process Yes. When uranium engraving is performed in this way, there is a point where the pushing angle (sharp) changes in the side wall of the mask or the material to be etched. The difference is that most of the metal chlorides are water-soluble. Next, the case where the invention of this case is applied to a semiconductor device manufacturing device will be described with reference to FIGS. 15A and 15B. Consumption by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative prints the semiconductor manufacturing device shown in Figure 15A is a multi-room semiconductor device manufacturing device, which has an etching processing chamber 9 0 1, a wafer transfer robot 9 0 3, and a load lock chamber 9 0 4. Unloading lock room 9 0 5, loader 9 0 6 and storage room 9 0 7. The storage room 9 0 7 is placed in a cassette 9 0 8. When processing wafers in the processing room 9 01, it will be The wafer 105 loaded into the cassette 9 0 8 with a slightly atmospheric pressure is transferred to the load lock chamber 9 0 4 with a slightly atmospheric pressure by a loader 9 0 6 and the load lock chamber is closed. The load is locked After the pressure in the chamber 9 4 is reduced to an appropriate pressure, the wafer transfer robot 9 0 3 transfers the wafer 105 to the processing chamber 9 01 and is etched halfway. Then, the wafer transfer is performed. The wafer 105 was transferred to the attachment removal processing chamber 9 02 using an automatic machine 9 0 3, and the attachment attached to the side wall was removed. Then, the wafer 1 0 was transferred again by the wafer transfer automatic machine 9 0 3. 5 Transfer to the etching processing room 9 0 1 'and add the desired amount of etching. After that, transfer the wafer 105 to the attachment removal processing room 9 0 2' to remove the attachments attached to the side wall. Standard (CNS) A4 specification (210X297 mm) -24- 550701 A7 B7 V. Description of invention (22) (Please read the note on the back first Please fill in this page again if necessary). Then transfer the wafer 105 to the unload lock chamber 9 0 5 by the wafer transfer robot 9 0. After increasing the pressure of the un lock chamber 9 05 to atmospheric pressure, The loader 9 06 is inserted into the cassette 908. If so, FIG. 15A has a wafer handling device (903), and most processing chambers (90 1, 90 1, ) And most post-processing chambers (902, 902,), and most lock chambers (904, 905), and an atmospheric transfer device (906) adjacent to the lock chamber, and the atmospheric transfer device can be connected to the above After the majority of the lock chambers and the semiconductor manufacturing device of the wafer cassette (9 0 8) adjacent to the atmospheric transfer device, the material to be processed is etched in any one of the above-mentioned processing chambers, and then in any of the above-mentioned post-processing chambers. After the post-treatment is performed, the etching is performed in any one of the plurality of processing chambers, and the post-processing is performed in any of the plurality of post-processing chambers. In addition, although the example of FIG. 5A uses an atmospheric cassette, the vacuum cassette as shown in FIG. 5B may be used. That is, FIG. 15B has a wafer handling device (903), most processing rooms (901, 901 ′) connected to the wafer handling device, and most lock rooms (904, 905). The consumer property cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed with an atmospheric transfer device (906) adjacent to the lock chamber, and the atmospheric transfer device is connectable to most of the above lock chambers and a post-processing chamber (920) and a wafer cassette adjacent to the atmospheric transfer device In the semiconductor manufacturing device (9 0 8), the material to be processed is subjected to uranium engraving in any one of the above-mentioned most processing chambers, and post-processed in the above-mentioned processing chamber, and then processed in any of the above-mentioned processing chambers. Uranium engraving may be post-processed in any of the above-mentioned post-processing chambers. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -25- 550701 A7 B7 V. Description of the invention (23) In addition, although the attachment removal treatment is performed under vacuum conditions, it is only at atmospheric pressure. It doesn't matter. (Please read the precautions on the back before filling in this page) In the above example, although the two etching processes are performed in the etching processing chambers 9 0 1 and 9 0 1 ', they are only performed in the same processing chamber 9 0 1 It can be used many times. The advantage of using a separate processing chamber in an etching processing chamber is that when a laminated film is to be etched, the uranium can be stably etched under different conditions with each film type. Etching and removal of attachments can be performed in the same chamber. Next, using the method shown in FIGS. 1 4 A to 1 4 F above, the laminated film such as P t / PZT / P t of the storage portion of the ferroelectric memory device is etched by using a substantially push-shaped photomask. The method will be described with reference to FIGS. 16A to 16D. At this time, when the P t / PZT / P t films 6 1 to 63 shown in FIG. 16A are subjected to an etching process, the deposits on the sidewalls of the layers 6 1 to 63 will inevitably be deposited, as shown in FIG. 1. 6 D shape. That is, the difference between the size of the mask 64 and the size of the material to be etched becomes large. This difference in size is an obstacle to miniaturization. Therefore, before etching the conductor 6 (printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, such as Pt) film 61 under the insulating film (PZT) 62, the uranium etching is interrupted to remove the attached matter (Fig. 16B). Then, the pushing angle of the PZT / Pt films 62 to 63 becomes 0.3. Thereafter, when etching is performed again, a shape as shown in FIG. 16C can be obtained. At this time, the pushing angle of the P t film 6 1 becomes 0 4 (here, divided into 3 < 0 4). It is more characteristic that although the conductors of the same material are formed above and below the insulating film (PZT) 6 2 (for example, P t film 6 1 and P t film 6 3), the pushing angles 0, 3, and 4 are similar. different. Also, of course, the paper size can be adapted to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -26- 550701 A7 B7 V. Description of the invention (24 drawing angle 0 4 setting is shown in Figure 1 6 D The pushing angle is 0 to 5. (Please read the precautions on the back before filling in this page.) So, by removing the first uranium incision and its subsequent attachments, you can get the insulation as shown in Figure 16C. The film (pz T) 6 2 and the conductor (for example, P t) film 6 3 have a push angle of 0 3 which substantially pushes the photomask. By using this type of substantially push photomask, the photomask is laminated. The film can form the pushing angle of the material to be etched to a nearly vertical angle. In addition, the method (c) shown in FIGS. 14A to 14F or the method shown in FIGS. 16A to 16D described above is used. A method of etching a laminated mask of a magnetic random access memory (MRAM) expected by a next-generation memory device will be described with reference to FIGS. 17A to 17D. The MRAM system has the following figure: The laminated film shown in 17A. That is, from top to bottom are ferromagnetic materials (such as C ◦) 7 6. Insulating films (such as A 1 2 〇3) 7 5. Ferromagnetic materials (such as C 〇) 7 4. Anti-ferromagnetic materials (such as F e M η) 7 3. Substrates (such as C 〇 and Si) 7 2, 7 1. And, 7 0 is, for example, a silicon oxide film 70. In MRA M, these films 7 1 to 7 6 are required to be etched using a photomask. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs at this time, if the FeMn film 73 When the adhesion of the reaction product is more rapid than that of other materials, the uranium etching is interrupted to remove the adhesion before the uranium etching of the Fe e η film 73 is started (Fig. 17B). Therefore, the films 7 4 to 76 The pushing angle is / 6. Then, after etching, the Fe e η film 7 3 uranium can be carved into a nearly vertical shape (Figure 1 7 C). The pushing angle of the FeMn film 73 at this time. For 07 and 06 < must be 7. In this way, by the first etching and subsequent attachment removal, and the second time this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -27- 550701 A7 B7 V. Description of the invention (2 $ ( Please read the precautions on the back before filling in this page.) The uranium engraving and subsequent attachment removal can obtain the essence of the film 7 3 ~ 76 as shown in Figure 1 7 C and changing the pushing angle along the way. Push the photomask upwards. By using the substantially push-ups of the photomasks 73 to 77 in this way, it is possible to form the push-up angle 0 8 of the material to be etched 7 1 and 7 2 to be almost vertical by using a laminated film of MRAM or the like Angle (here, 06 < ^ 7 <% 8) 〇 As ferromagnetic materials, Fe, C0, Ni, Mn, or a compound thereof can be considered as the main materials. These materials are known as hard-to-etch materials. The reference numeral 77 in the figure is a photomask. The above example illustrates the method of making a mask shape or substantially pushing the mask shape in order to make the side wall of the material to be etched to be slightly vertical. However, the invention described below is based on the etching conditions. Change the method of making the side wall of the engraved material into a vertical shape. As described above, the pushing angle of the etching is determined by the ratio of the adhesion rate rd to the photomask or the side wall of the material to be etched to the bottom surface etch rate re. The smaller the rd / re is, the more the side wall can be pushed. The angle is close to vertical. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, although the etching is performed under the condition that the attachment is not easily attached to the wall of the vacuum container (Fig. 3, 104), the purpose is to reduce the attachment of the attachment, such as reducing the reaction in the vacuum container. The concentration of the product is quite effective. Under the condition that the wall surface of the vacuum container is not easy to adhere, if the concentration of reaction products in the gas phase is to be reduced, the reaction products in the gas phase must be discharged out of the vacuum container, or attached to the photomask and the side wall of the material to be etched There is no other way. Therefore, in fact, the attached paper is not easily attached to the wall of the vacuum container. The paper size of the paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -28- 550701 A7 B7 V. Description of the invention (under the condition of 2 bows, gas The reaction product concentration in the phase is kept quite high. (Please read the precautions on the back before filling this page.) However, in Figure 3, by reducing the impedance of the load 1 1 5, the current flowing into the electrostatic coupling antenna 1 1 8 is promoted. The reaction product in the gas phase can be easily attached to the wall surface of the vacuum container. At this time, the reaction product in the gas phase can be reduced in concentration by adhering to the wall surface of the vacuum container. The amount of products will be reduced. As a result, the accumulation of deposits on the mask and the side wall of the carved uranium material is reduced. Therefore, although a mask with a side wall of about 90 degrees is used, the shape of the side wall of the carved uranium material can be almost vertical. However, if the attached matter is attached to the wall surface of the vacuum container, the state of the plasma may change or cause particles to occur, so the attached matter needs to be removed regularly. Therefore, for example, when one or more sheets are completed, Round treatment, that is, removal of attachments (ie, treatment of current flowing into the electrostatic coupling antenna 1 1 8 etc.). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. At this time, the wafer support table (§ The temperature of 109 is set to be higher than that at the time of etching, so that the adhered matter does not adhere to the wafer support table 10 and can be quickly discharged from the vacuum container 104. Alternatively, the wafer support table 1 may be lowered The temperature of 0 9 makes the attachment actively adhere to the supporting table or the wafer loaded on the supporting table, avoids the reflection of the attachment from the supporting table or the wafer loaded on the supporting table, so as to prevent the attachment from re-adhering to the wall of the vacuum container and promote the attachment. According to the present invention, the half-bucket etching of the vertical processing shape is difficult to obtain on the side wall, and the nearly vertical etching shape of the side wall can be obtained by using a push-type photomask, so it can be made with high functions Semi-conductor device, or half of the paper with a high degree of integration, applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -29- 550701 A7 B7 V. Description of the invention (conductor device. (Please first Note Complete this page and then read it back) Ministry of Economic Affairs Intellectual Property Office employees consumer cooperatives printed in this paper scale applicable Chinese National Standard (CNS) A4 size (210X297 mm)