201237546 々、發明說明： 【發明所屬之技術領域】 本發明係關於做為多階調使用之半多 白光罩及半色調光罩之製造方法。邑5周先罩、半色調空 【先前技術】 在液晶面板、電漿顯示器等電子機器中，、 氣配線、彩色滤光片等圖案化而使用光罩。、斤了將〔、电 降低光罩之製造成本，而使用可減少光罩使用== 調光罩。多階調光罩為在透光性基 數之4 量不同之區域之光罩，典型而言，除了透成^3以上透光 外，還具有半透過部。 矛、了透過部及遮光部以 就形成多階調光罩之半透過部之方 成=白光罩之半透過部之處蝴像 之:透過_。 及「下置型」兩種。上置型奇指㈣「上置型」 另-方面再將半透過_案化之方法。 空白光罩彳在半透频均翁遮光膜之 白先罩後’分卿遮絲及半透顧加工之方法。 過二由於藉著將遮光膜圖案上所形成之半透 過膜過部、半透過部及遮光部，所以半透 步驟其反面’由於將圖案化步驟與成臈 問題。另付需要長步驟’在短期間形成光罩上有 罩，然而由於半透:雖然容易於短期間形成光 膜之綱液具有耐性之材料形成半透過臈，在半透過膜 4/28 201237546 之材料設計上有困難。 其中，在下置型之光罩中，已知在遮光膜與半透過膜 之間没置蝕刻終止層之方法。例如在下述專利文獻丨、2中 揭示.为別於遮光膜及半透過膜使用Cr(鉻）系材料，於蝕 刻終止層❹SiQ魏切)膜錢㈣㈣(SQG (spin on glass))膜之光罩。然而在此情況，由於在酬終止層之姓刻上 ，須為乾麵或混合氟酸之濕铜，所以有成本非常高之問 題。 上、另方面’下述專利文獻3中記載具有蝕刻終止層之半色 调光罩，顧刻終止層含有Ni(鎳）、&(鐵）、等元素。 此種侧終止層由於可用魏系之藥液進行侧，所以具有可 減低其圖案化所需成本之優點 形成透過部、半透過部及遮光部後，用洗淨液洗淨基材。 已知在此種光罩洗淨步驟巾，除使㈣洗或強超音波 trr)等ΐ物理性洗淨步驟之外，尚有使用酸系或驗系藥 =子11洗乎步'驟。其中酸系藥液對基板之濕潤性高，光阻 =殘餘物之溶解性高。就酸系藥液而言，經常使用室溫的 艰石瓜i欠、經過加熱之熱濃硫酸等。 [先前技術文獻] [專利文獻] [專利文獻1] [專利文獻2] [專利文獻3] 【發明内容】 [發明之概要] 曰本專利特開2002-189281號公報 曰本專利特開2006-154122號公報 W〇2〇〇9/O5766〇 號公報 [發明所欲解決之課題] 5/28 201237546 丨I專利讀3中所記载之半色調料β巾，已判明 其ΐ層容綠縣洗淨步射所制之雜酸溶解。因此 ^光罩洗淨過程中_終止層會進行側面姓刻，而有發生遮 祕等之虞。結果，麵無細高射度地製造 具有微細圖案之半色調光罩。 鑑於以上情事，本發明之目的係提供—種半色調光罩、半 2空白鮮及半色調光罩之製造方法，其在伽濃硫酸之洗 驟中，可抑制蝕刻終止層之側面蝕刻。 [解決課題之手段] 為達成上述目的，本發明之一態樣之半色調光罩具備 透過部、半透過部及遮光部。 上述透過部包含透光性基材。 上述半透過部包含上述基材、及設置於上述基材上 之由Cr或Cr化合物所形成之半透過層。 上述遮光部包含上述基材、上述半透過層、及設置 於上述半透過層上之由Cr或Cr化合物所形成之遮光 層、及設置於上述半透過層與上述遮光層之間之蝕刻終 止層。上述蝕刻終止層含有第1元素及第2元素。上述 第1元素係由選自Mo及w所組成之群中之至少一種元素 所構成，且具有6.4莫耳％以上38.2莫耳。/。以下之組成比。 上述第2元素係由選自Zr、Nb、Hf及仏所組成之群中之 至少一種元素所構成。 本發明之一態樣之半色調空白光罩具備透光性基材、 半透過層、遮光層及餘刻終止層。 上述半透過層係設置於上述基材上，且係由Cr或 Cr化合物所形成。 6/28 201237546 上述遮光層係設置於上述半透過層上，且係由Cr 或Cr化合物所形成。 上述蝕刻終止層含有第1元素及第2元素。上述第 1凡素係由選自M〇(鉬)及％(鎢)所組成之群中之至少一種 疋素所構成，且具有6.4莫耳％以上38.2莫耳％以下之組成 匕上述第2元素係由選自Zr(鍅）、Nb(鈮）、Hf(铪)及Ta(钽) 成之群中之至4 -種it素所構成。上述餘刻終止層係 S又置於上述半透過層與上述遮光層之間。 本發明之-態樣之半色調光罩之製造方法，包含將由 或Cr化合物所形成之半透過層成膜在透光性基材上 之步驟。 、…將含有第1 70素及第2元素之㈣終止層成膜在上 迟半透過層上。上述第丨元素係由選自M〇及w所組成 =群中之至少-種兀素所構成，且具有6 4莫耳％以上如 莫耳％以下之組成比。上述第2元素係由選自Zr、灿、班 及Ta所組成之群中之至少一種元素所構成。 將由&或&化合物所形成之遮光層成膜在上述蝕 刻終止層上。 〜藉由將在上述遮光層上所形成之光阻圖案做為光罩進 行蝕刻，分別形成包含上述基材之透過部，包含上述基材 及上述半透過層之半透過部，以及包含上述基材、上 透過層及上述遮光層之遮光部。 使用硫酸系藥液除去該基材。 【實施方式】 本發明之-實施態樣之丰色調光罩具備透過部 透過部及遮光部。 7/28 201237546 上述透過部包含透光性之基材。 上述半透過部包含上述基材及設置於該基材上之由 Cr或Cr化合物所形成半透過層； 上述遮光部包含上述基材、上述半透過層、設置於 上述半透過層上之由Cr或Cr化合物所形成之遮光層， 及設置於上述半透過層與上述遮光層之間之蝕刻終止 層。上述蝕刻終止層含有第1元素及第2元素。上述第 1元素係由選自Mo及W所組成之群中之至少一種元素所 構成且具有6.4莫耳％以上38.2莫耳％以下之組成比。上述 第2元素係由選自Zr、Nb、Hf及Ta所組成之群中之至少 一種元素所構成。 上述半色調光罩中，蝕刻終止層因含有第丨元素，而提高 對濃硫酸之耐溶解性。亦即第丨元素顯示難溶於濃硫酸中之傾 向。因此第1元素之組成比越高，越能減少濃硫酸所造成之钱 刻終止層之溶解量。藉此可抑制使用濃硫酸洗淨時蝕刻終止層 之側面蝕刻，並可防止遮光膜之剝蝕或缺陷等。 曰 第2元素雖然對濃硫酸只呈現稍微難溶之傾向，但是蝕刻 終止層對—酸之耐溶祕受到第丨元素之組成比之影響 大。因此，第2元素之組成比(含量)係依據第丨元素之組成二 是否可實施使用濃硫酸之洗淨處理之判斷，可以用使银 ^止層在1G(rc濃硫酸中浸潰1G分鐘時之侧面侧量為」 ^列如側面_量為〇如以下時，判斷為可實施使用息 酉夂之洗淨處理。細侧量為α3μηι時 辛 喜4料/。，第2讀之組成比為3.4莫耳％。因此，在第卜 素之組成比為6.4莫耳％以上，望7201237546 发明, 发明发明: [Technical Field] The present invention relates to a method of manufacturing a half-white mask and a halftone mask used as a multi-tone tone.邑5 weeks of hood and halftone empty [Prior Art] In an electronic device such as a liquid crystal panel or a plasma display, a gas mask, a color filter, or the like is patterned to use a photomask. It will reduce the manufacturing cost of the mask, and the use of the mask can reduce the use of the mask == dimming cover. The multi-step dimming cover is a photomask having a different amount of light transmissive base, and typically has a semi-transmissive portion in addition to transparency of 3 or more. The spear, the transmissive portion and the light-shielding portion form a semi-transmissive portion of the multi-step dimming cover = a half-transmissive portion of the white mask: a transmitted image. And "lower type". The upper type is odd (4) "upper type" and the other side will be semi-transparent. The blank mask is placed behind the white hood of the semi-transmission-averaged light-shielding film. In the second case, since the semi-transmissive film, the semi-transmissive portion, and the light-shielding portion formed on the light-shielding film pattern are formed, the reverse side of the semi-transparent step is a problem due to the patterning step. In addition, a long step is required to form a mask on the mask during a short period of time. However, due to the semi-transparent: a material that is resistant to short-term formation of a film of light film to form a semi-transmissive crucible, in a semi-permeable membrane 4/28 201237546 There are difficulties in material design. Among them, in the underlying type photomask, a method in which an etching stopper layer is not provided between the light shielding film and the semi-transmissive film is known. For example, it is disclosed in the following patent documents 丨 and 2. For the light-shielding film and the semi-transmissive film, a Cr (chromium)-based material is used, and in the etching stop layer ❹SiQ Wei cut), the light of the SQG (spin on glass) film is used. cover. However, in this case, since the surname of the reward layer is required to be dry or mixed with wet copper of hydrofluoric acid, there is a problem of very high cost. Further, the following Patent Document 3 describes a halftone dimming cover having an etching stopper layer, and the stopper layer contains elements such as Ni (nickel), & (iron). Since the side termination layer can be side-formed by the Wei-based chemical solution, it has the advantage of reducing the cost required for patterning. After forming the transmissive portion, the semi-transmissive portion, and the light-shielding portion, the substrate is washed with a cleaning solution. It is known that in such a reticle cleaning step, in addition to the physical cleaning step such as (four) washing or strong ultrasonic wave trr), it is also known to use an acid system or a test drug = sub-step 11 step. Among them, the acid-based liquid has high wettability to the substrate, and the photoresist = high solubility of the residue. In the case of an acid-based liquid, it is often used at room temperature, and the heated hot concentrated sulfuric acid. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] [Patent Document 2] [Patent Document 3] [Summary of the Invention] [Summary of the Invention] Patent Publication No. 2002-189281, Japanese Patent Laid-Open No. 2006- 154122 Bulletin W〇2〇〇9/O5766〇号 [Problems to be Solved by the Invention] 5/28 201237546 The halftone material β towel described in 丨I Patent Reading 3 has been identified as its The miscellaneous acid produced by the washing step is dissolved. Therefore, during the reticle cleaning process, the _ termination layer will be engraved on the side, and there will be occlusions such as occlusion. As a result, a halftone mask having a fine pattern was produced without a fine high-radiance. In view of the above, it is an object of the present invention to provide a method for producing a halftone mask, a half blank and a halftone mask which can suppress side etching of the etch stop layer in the sulphuric acid wash. [Means for Solving the Problem] In order to achieve the above object, a halftone mask according to an aspect of the present invention includes a transmissive portion, a semi-transmissive portion, and a light shielding portion. The transmissive portion includes a light-transmitting substrate. The semi-transmissive portion includes the substrate and a semi-transmissive layer formed of Cr or a Cr compound provided on the substrate. The light shielding portion includes the substrate, the semi-transmissive layer, a light shielding layer formed of a Cr or Cr compound provided on the semi-transmissive layer, and an etching stop layer provided between the semi-transmissive layer and the light shielding layer . The etching stopper layer contains a first element and a second element. The first element is composed of at least one element selected from the group consisting of Mo and w, and has 6.4 mol% or more and 38.2 mol. /. The composition ratio below. The second element is composed of at least one element selected from the group consisting of Zr, Nb, Hf and hydrazine. A halftone blank mask according to an aspect of the present invention includes a light transmissive substrate, a semi-transmissive layer, a light shielding layer, and a residual stop layer. The semi-transmissive layer is provided on the substrate and is formed of a Cr or Cr compound. 6/28 201237546 The above-mentioned light shielding layer is provided on the semi-transmissive layer and is formed of a Cr or Cr compound. The etching stopper layer contains a first element and a second element. The first first element is composed of at least one element selected from the group consisting of M〇 (molybdenum) and % (tungsten), and has a composition of 6.4 mol% or more and 38.2 mol% or less. The element is composed of a group selected from Zr (鍅), Nb (铌), Hf (铪), and Ta (钽) to 4-input. The above-mentioned residual termination layer S is further disposed between the semi-transmissive layer and the light-shielding layer. The method for producing a halftone mask of the present invention comprises the step of forming a semi-transmissive layer formed of a Cr compound or a Cr compound on a light-transmitting substrate. The film of the (4) termination layer containing the 1 70th element and the 2nd element is formed on the upper semi-transmissive layer. The above-mentioned third element is composed of at least one species of halogen selected from the group consisting of M〇 and w, and has a composition ratio of 6 4 mol% or more, such as mol% or less. The second element is composed of at least one element selected from the group consisting of Zr, Can, Ban and Ta. A light-shielding layer formed of a & or & compound is formed on the above-described etch stop layer. And etching the photoresist pattern formed on the light shielding layer as a mask to form a transmissive portion including the substrate, a semi-transmissive portion including the substrate and the semi-transmissive layer, and the base a material, an upper transmission layer, and a light shielding portion of the light shielding layer. The substrate was removed using a sulfuric acid-based solution. [Embodiment] The rich-tone mask of the embodiment of the present invention includes a transmissive portion transmissive portion and a light blocking portion. 7/28 201237546 The above-mentioned transmissive portion contains a light-transmitting substrate. The semi-transmissive portion includes the base material and a semi-transmissive layer formed of Cr or a Cr compound provided on the base material, and the light shielding portion includes the base material, the semi-transmissive layer, and Cr disposed on the semi-transmissive layer Or a light shielding layer formed of a Cr compound, and an etch stop layer disposed between the semi-transmissive layer and the light shielding layer. The etching stopper layer contains a first element and a second element. The first element is composed of at least one element selected from the group consisting of Mo and W and has a composition ratio of 6.4 mol% or more and 38.2 mol% or less. The second element is composed of at least one element selected from the group consisting of Zr, Nb, Hf and Ta. In the above-described halftone mask, the etching stop layer contains a ruthenium element to improve the solubility resistance to concentrated sulfuric acid. That is, the third element shows the tendency to be insoluble in concentrated sulfuric acid. Therefore, the higher the composition ratio of the first element, the more the amount of dissolution of the stop layer caused by concentrated sulfuric acid can be reduced. Thereby, the side etching of the etching stopper layer at the time of washing with concentrated sulfuric acid can be suppressed, and the etching or defects of the light shielding film can be prevented.曰 Although the second element tends to be slightly insoluble to concentrated sulfuric acid, the resistance of the etching stop layer to acid is greatly affected by the composition ratio of the second element. Therefore, the composition ratio (content) of the second element can be judged by whether or not the composition of the second element can be subjected to a washing treatment using concentrated sulfuric acid, and the silver layer can be used to impregnate 1 G minutes in 1 G (rc concentrated sulfuric acid). When the amount of the side surface is "", if the amount of the side surface is less than or equal to the following, it is judged that the cleaning treatment can be carried out using the application. The amount of the fine side is α3μηι, when Xin Xi 4 material /., the composition of the second reading The ratio is 3.4 mol%. Therefore, the composition ratio of the diazepam is 6.4 mol% or more.
关开上弟2几素之組成比為3.4莫J 8/28 201237546 4以上之情況，適合貫施使用濃硫酸之洗淨處理。 第1元素之組成比為6.4莫耳％以上，38.2莫耳。以下。 若第1元素之組成比小於6.4莫耳％時，難以確保對濃硫酸之 良好耐溶解性。又，若第丨元素之組成比超過π』莫耳％，如 後所述，明顯地會造成蝕刻終止層成膜用之濺射標靶 (spattering target)之加工性降低，蝕刻終止層之蝕刻速率降低， 對Cr蝕刻溶液之耐溶解性降低。 蝕刻終止層可藉由例如濺射(spattering)法而成膜。對於濺 射所使用之標乾，可使用由侧終止層之構成材料所形成之合 金材料。《了確保良好之加工性，標革巴之硬度越低越好，藉此 可?低加从本。另—方面，第1元素及第2元素，其組二匕 越高’則標乾變得越硬’加工性越降低。於是，將第i及第） 凡素之組成比之和設為5〇莫耳％以下。藉此可轉對濃硫酸 之耐溶解性，而且確保標靶之良好加工性。 另一方面，上述半色調光罩，在半透過層及遮光層係使用 Cr或Cr化合物。就Cr化合物而言，可列舉&之氧化物、氡 化物、碳化物、氧化氮化物、氧化碳化物、氮化碳化物、氧氮 化碳化合鱗。蝴終止層由於在遮光層及半透之圖案餘 刻時會與Cr |虫刻溶液接觸’在Cr侧溶液中之溶解量必須 少。侧終止層最好是即使在Cr钱刻溶液中浸潰3〇分鐘以上 後仍殘存於基材上者。就&_溶_言，主要可使用俩 鈽(iv)銨溶液與過氣酸之混合物等含有硝酸筛(ιν)之钱刻液。 其中’構成姓刻終止層之第i元素，其組成比越高，則呈 現因硝酸_〇錢溶液的溶解量有變得越多之傾向；相對於 此’第2 7G素，其組献_，則呈現該騎量有減少之傾向。 如上所述’為了提高钱刻終止層對濃硫酸之耐溶解性，第i元 9/28 201237546 素之=成比雖然越高越好，然而從確保韻刻終止層對W虫刻 觀點而言’第1元素之組成比可由第2元素之 二為須精度良好地進行各層 刻終止層必須容易溶解於其之钱刻液。 要 以止層係使用含有硝酸之鞋刻液來進行_，刻終 ^層^峨可為顧，或在俩中混合有乙酸、草酸、 而成之侧液，亦可為在俩中混合有魏、硫 中夂、、曰過乳化風水溶液等而成之_液。再者，在硫酸 硝酸^=、曱酸、檸檬酸等紐之情況，以使用低濃度之 姓刻終止層之I虫刻液亦可為在確酸中混合有鹽之敍刻 _液。再者，'過氣酸鹽等而成之 時間π成朗者’再者綱咖越短越好。 構成餘刻終止層之第丨元素含量 止⑽速率越大’第二=Ξ 層之良之傾向。為了得糊終止 第70素軚佳係至少含有6莫耳％以上。 10/28 201237546 再者，當進行半色調光罩之製作時，各層之圖案化步驟可 使用光Μ影(photolithography)技術。在使用光微影技術之圖案 =步驟中，在光阻之顯像·娜或光罩之洗料上常使用驗性 /合液。就提咼圖案化之精確度而言，要求蝕刻終止層對鹼性溶 液之耐溶解性高。構紐祕止層之第丨元姐第2元素之任 一者均呈現容倾雜溶液溶解之傾向。因此為雜朗終止 層對驗性溶液之耐雜性，將第丨及第2元素之總和設為例如 70莫耳％以下。 上祕刻終止層，可進一步含有第3元素，該第3元素係 由選自Ab Ti、v、Fe、Ni、Co及Cu所組成之群中之至少一 種疋素所構成。此時，上述第3元素之組姐為5G莫耳％以 上90.2莫耳％以下。 舉一例，在加溫至KKTC之濃硫酸中浸潰1〇分鐘時之側 =飯刻量為0.3陴町，可高精確度_統、對㈣刻液 =驗性溶液之耐溶解性高、標㈣工性良好之侧終止層之組 成比為1丨元素為1U莫耳％以上226莫耳％以下，第2 =素為3.6莫耳％以上7.4莫耳％以下，帛3元素 %以上85.3莫耳％以下。 旲斗 本發明之-實施態樣之半色調空白光罩具備透光性 土材、半透過層、遮光層及蝕刻終止層。 上述半透過層係設㈣上述基材上，且係由c & 化合物形成。 上述遮光層係設置於上述半透過層上，且係由& Cr化合物形成 一亡述蝕刻終止層包含第1元素及第2元素。上述第 疋素係由選自施及〜所組成之群中之至少-種元素所 11/28 201237546 構成且具有6.4莫耳％以上μ.2莫耳％以下之組成比。 第2元素係由選自Zr、Nb、Hf及&所組成之群中之至少 -種7L素所構成。上述㈣終止層係設置於上 層與上述遮光層之間。 ^ 若藉由上述半色調空白光罩，可抑制使用濃硫酸洗淨 時兹刻終止層之側面_ ’可防止遮光層之她或缺陷等 此可谷易地製造尚精確度之半色調光罩。 本發明之-實施態樣之半色調料之製造方法 將由Cr或CiMt合物卿紅半透過層賴在透光性基材 上之步驟。 述丰：ΐί第1元素及第2元素之崎止層成膜在上 述+透過層上。上述第i元素係由選自⑽及w所組成 =群中之至少-種元素所構成，且具有Μ莫耳％以上％ 2 旲耳。/。以下之組成比。上述第2元素係由選自&、灿、班 及Ta所組成之群中之至少一種元素所構成。 終止=化合物所形成之遮光層成獏在上述钱刻 藉由將在上㈣光層上卿狀紐_做為光 =虫刻’可分別形成包含上述基材之透過部，包含 2上述半透過層之半透過部，包含上述基材、上述半透 過層及上述遮光層之遮光部。 使用硫酸系之藥劑除去上述基材。 列炊fr照上職造方法’由於可㈣制濃硫酸洗淨時餘The composition ratio of the two brothers is 3.4 Mo J 8/28 201237546 4 or more, which is suitable for the treatment of concentrated sulfuric acid. The composition ratio of the first element was 6.4 mol% or more, and 38.2 mol. the following. When the composition ratio of the first element is less than 6.4 mol%, it is difficult to ensure good solubility resistance to concentrated sulfuric acid. Further, if the composition ratio of the second element exceeds π"mol%, as will be described later, the workability of the sputtering target for the film formation of the etch stop layer is remarkably lowered, and the etching stop layer is etched. The rate is lowered and the solubility resistance to the Cr etching solution is lowered. The etch stop layer can be formed by, for example, a sputtering method. For the standard dryness used for the sputtering, an alloy material formed of a constituent material of the side termination layer may be used. "To ensure good processability, the hardness of the standard leather bar is as low as possible, so that it can be reduced." On the other hand, in the first element and the second element, the higher the group size, the harder the standard dryness is, and the lower the workability. Therefore, the sum of the composition ratios of the i-th and the third-order elements is set to 5 〇 mol% or less. This allows conversion to concentrated sulfuric acid and ensures good processability of the target. On the other hand, in the above-described halftone mask, Cr or a Cr compound is used for the semi-transmissive layer and the light-shielding layer. Examples of the Cr compound include oxides, tellurides, carbides, oxynitrides, oxidized carbides, carbonitrides, and oxynitride sulphate scales. The butterfly termination layer must be dissolved in the Cr-side solution due to contact with the Cr | insect solution solution during the shading layer and the semi-transparent pattern. Preferably, the side termination layer remains on the substrate even after being immersed in the Cr solution for more than 3 minutes. In the case of &_dissolved, it is mainly possible to use a solution of a nitric acid sieve (ιν) such as a mixture of an ammonium (iv) ammonium solution and a peroxyacid. Among them, 'the i-th element that constitutes the end-of-sequence layer, the higher the composition ratio, the more the amount of dissolution of the nitric acid-salt solution becomes more and more; compared to the '2 7G prime, its group _ , there is a tendency for the ride to decrease. As described above, in order to improve the solubility resistance of the end layer to concentrated sulfuric acid, the i-element 9/28 201237546 ratio is higher, but the better, from the viewpoint of ensuring the rhyme-terminating layer to the W-worm The composition ratio of the first element can be made by the second element of the second element, and the layer engraving layer must be easily dissolved in the layer. It is necessary to use the shoe polish containing nitric acid to carry out the _, the end of the layer can be used for care, or the mixture of acetic acid, oxalic acid, or the side liquid, or a mixture of the two Wei, sulphur, sputum, sputum, emulsified air, etc. Further, in the case of sulfuric acid, nitric acid, citric acid, citric acid, etc., it is also possible to use a low-concentration I-terminating layer to terminate the layer of the insect-like liquid. In addition, the time of π gasification is the same as that of the sulphuric acid salt. The content of the second element constituting the terminating stop layer is greater (10). The higher the rate of the second = 层 layer. In order to obtain a paste, the 70th prime quality system contains at least 6 mol% or more. 10/28 201237546 Furthermore, when fabricating a halftone mask, the patterning step of each layer can use photolithography. In the pattern = step using photolithography, it is often used in the imaging of the photoresist or the photographic mask. In terms of the accuracy of patterning, the etching stop layer is required to have high resistance to alkali solution. Any of the second elements of the second element of the dynasty secret layer of the structure is a tendency to dissolve the mixed solution. Therefore, the heterogeneity of the layer to the test solution is terminated, and the sum of the second and second elements is, for example, 70 mol% or less. The top secreting layer may further contain a third element composed of at least one halogen selected from the group consisting of Ab Ti, v, Fe, Ni, Co, and Cu. At this time, the group of the third element is at least 90.2% by volume of 5G moles. For example, when the temperature is immersed in concentrated sulfuric acid of KKTC for 1 minute, the side = the amount of rice is 0.3 陴, which can be highly accurate, and the liquid is inferior to the (4) etch solution. The composition ratio of the side termination layer with good workability is (1) 1丨 element is 1U mol% or more and 226 mol% or less, and 2nd element is 3.6 mol% or more and 7.4 mol% or less, 帛3 element% or more 85.3 Mole% or less. The halftone blank mask of the embodiment of the present invention comprises a light transmissive earth material, a semi-transmissive layer, a light shielding layer, and an etch stop layer. The semi-transmissive layer is provided on the substrate (4) and is formed of a c & compound. The light shielding layer is provided on the semi-transmissive layer and is formed of a & Cr compound. The etch stop layer includes a first element and a second element. The above-mentioned diterpene is composed of at least one element selected from the group consisting of ~~2012 201237546 and has a composition ratio of 6.4 mol% or more and μ.2 mol% or less. The second element is composed of at least one species of 7L selected from the group consisting of Zr, Nb, Hf, and & The (4) termination layer is disposed between the upper layer and the light shielding layer. ^ If the above-mentioned halftone blank mask is used, it is possible to suppress the side of the layer from being etched when the concentrated sulfuric acid is used _ 'can prevent her or defects of the light shielding layer, etc., which can easily produce a halftone mask of precise precision. . The method for producing a halftone material according to an embodiment of the present invention comprises the step of applying a Cr or a CiMt composition to a translucent substrate.述: The film of the first element and the second element of the sacrificial layer is formed on the above + permeation layer. The above i-th element is composed of at least one element selected from the group consisting of (10) and w, and has more than 2% by mole of Μmol. /. The composition ratio below. The second element is composed of at least one element selected from the group consisting of &, Can, Ban and Ta. Termination = the formation of the light-shielding layer of the compound. In the above-mentioned money, the transmissive portion including the substrate may be separately formed by using the upper layer on the upper (four) light layer as The semi-transmissive portion of the layer includes the base material, the semi-transmissive layer, and the light-shielding portion of the light-shielding layer. The above substrate was removed using a sulfuric acid-based agent. Lennon fr, according to the method of production, because of the (four) system of concentrated sulfuric acid wash
之側面1 虫刻’不造成遮光層之熱或缺陷等，可高声 精確地製造半色調光罩。 X 以下在參考圖式下，說明本發明之實施態樣。 12/28 201237546 <第1之實施態樣> 圖1(A)〜(F)及圖2(A)〜(F)為說明根據本發明之一實施 態樣之半色調光罩之製造方法之步驟圖。 、 [半色調空白光罩] 首先，如圖1(A)所示，製作半色調空白光罩14。半 色調空白光罩14具有基材S、半透過層u、蝕刻終止 層12與遮光層π之積層構造。 基材s典型地由玻璃基板所構成。半透過層n及 遮光層13係由Cr系材料所構成。&系材料意指& ^屬或Cr化合物，Cr化合物包含α之氧化物、瓦化物、 石反化物、氧化氮化物、氧化碳化物、氮化碳化物 氮化礙 化物等。 钱刻終止層η含有第！元素及第2元素。第！元 :係由選自Mo及W所組成之群中之至少一種元素所構 弟1疋素之組成比為6.4莫耳％以上38 。 第二元f由選自-，、班及Ta所組成之群中之至少 :種兀素所構成。第2元素之組成 莫耳°/。以下。 夫卄/。以上ιζ.δ :=層12可進一步含有第3元素。第3元素係由選 i戶二π、广、Ni、c。及cu所組成之群中之至少一種元 ;。 $讀之組觀為5G莫耳％以上9G.2莫耳％以 將半透過層11、蝕刻終止層12及 ;，基材s上。半透過層11、 ㈣射法、高頻_射法、二 由離子束濺射法等成臈。 13/28 201237546 在本實施態樣中，半锈 光層13分別藉由濺射二層二1㈣終止層12及遮 係使用含有上述第終止層12之成膜中’ 中所導入之氣體，可使材料之餘。在成膜 NO、N2〇、N2〇2 等。 4、N2、〇2、C〇2、c〇、 成可學^^之個別厚度並無特別限定，設定 言，設舉—例’就半賴11而 度到聽〜透過率之厚 度，終…亦 可設刻終止要求之機= 之半色Μ*/、-凋光罩17，係藉由在如上述構成 ΤΑ、半^^ 所設定之_上分卿成透過部 部ΤΑ星有^ ΗΑ及遮光部ΡΑ而製作（圖2(F))。透過 s盘半透ί:二 層構造，半透過部^具有基材 半透過層“二積：：。遮光部ΡΑ具有基材S、 以下〜止層12及遮光層13之積層構造。 下本實施態樣之半色調光罩17之製造方法。 色凋光罩之製造方法】 光阻，麵光層13上形成第1光阻層15。第1 旋轉:布有機光阻材料所構成’將液狀之光阻材料藉由 上狹縫塗布法或毛細管塗布法等塗布在遮光層η 可由乾則1姐層15除概阻外，亦 繼而’如圖1(〇所示’藉由對於第1光阻層15施行曝光 14/28 201237546 處理及顯像處理，形成具有用於形成透過部TA之開口 15a之 第1光阻圖案15P。曝光處理係使用雷射曝光裝置等曝光裝 置，顯像處理係使贱氧化_、氫氧化鈉、氫氧化四曱基錢等 驗性溶液。 繼而，如圖1(D)所示，以第1光阻圖案15P做為光罩， _遮光層13。藉此，形成與開口 15a對應之第i遮光開口 13a。遮綠13之侧液’係使㈣酸解v)銨與過氣酸之混 合液等含有硝酸渐no之侧液(以下，稱為第丨侧液）。 此時’關終止層12之—部分雖驗由第丨遮光開口以 而暴露於第i侧液，但並未被第！钮刻液實質上紐。因此 層12使第1㈣液所進行之深度方向侧在 止層12之表層實質上停止。 、 繼而’如圖1(E)所示，經由第丨遮来 ί:=:==::合液(一 口丨3a之第1終止開：層12形成對應於第1遮光開 古而^夺嗜絲刻終止層12之第1元素，隨著其含有率择 阿而使第2钱刻液所達成之钱刻速率增加 有革曰 其含有率增高而使蝕刻速率減低 ^ 疋素’隨著 照第1元辛m Γ 钱刻終止層12係依 刻。’、之個別含量而以期望之朗速率被钱 繼而，如圖1(F)所示，經由第丨 開口仏，將露出外部之半透過層二=⑶及第1終止 進行韻刻，在半透過層„上 二。=第1 _液 第1終止一之第〗半透二^ ua。错此，在基材8上 15/28 201237546 形成透過部ΤΑ。 S進行洗淨^成^卩ΤΑ之基材_於洗淨液，將基材 殘餘物等除去。就二„ S上殘留於表面之異物或光阻 溶液。洗淨液d =而可使用例如濃硫酸之含硫酸水 液之加溫，度可為室溫’亦可加溫至設定之溫度。洗淨 =皿度無特別限定，例如為1〇叱以下。 褥成钱刻終止層穿 藉此可抑制洗淨處理中钱酸具有耐溶解性。 刻終止層12之3^ 之側祕刻，阻止因钱 ㈣之讀細侧終止層丨2之侵麵造成之遮光 造成之層】=丄==高由可使濃硫酸 層】2含有6.4莫耳％以上之^本^態射，由於侧終止 酸中浸、、賫10八^上之弟1兀素，所以可將在loot濃硫 ^貝10刀騎之側祕刻量抑制於α3μιη以下。 濃硫西=如f 所7^ ’對璃基板s全_給驗性溶液或 遮光層13將苐1光阻圖案i5p除去。錄终止 -:===侵 之 r::二 =二繼而’如圖取)所示，對於第2先二= 繼而’如圖2(D)所示，以第2光阻圖案府 :吏=:刻液刪細。藉此，形成與開口祕對應 遮先開口 Ub。此時，钱刻終止層】2與第！遮光開口 J6/28 201237546 13a形成_樣地，由於並未勤第〗_液進行 造成之深度方㈣刻，在-_ :如：2_示，經由第2遮光開口 遮光開二之止止層12上形成對應於第2 鹼性溶液等伴至美材s於疋，如圖2(F)所示’將 芦13上Μ ' 王士將第2光阻圖案16?從遮光 此，在基材S上形成透過部一部 第：===:其含有，使 率:高而使崎率減低。因:，磁二止=== 苐2騎之侧含量《敏之侧速率植ΐ據弟 s ’以濃硫酸所構成：淨【遮光:。Α之基材 美材<^夕μ主工 尹夜進仃洗淨處理。猎此，將殘留於 ^ 上表面之異物或光阻殘餘物等除去。The side 1 insects can produce a halftone mask with high precision and without causing heat or defects of the light shielding layer. X Hereinafter, an embodiment of the present invention will be described with reference to the drawings. 12/28 201237546 <First embodiment of the invention> Figs. 1(A) to (F) and Figs. 2(A) to (F) are diagrams for explaining the manufacture of a halftone mask according to an embodiment of the present invention. Step diagram of the method. [Half-tone blank mask] First, as shown in FIG. 1(A), a halftone blank mask 14 is produced. The halftone blank mask 14 has a laminated structure of a substrate S, a semi-transmissive layer u, an etch stop layer 12, and a light shielding layer π. The substrate s is typically composed of a glass substrate. The semi-transmissive layer n and the light-shielding layer 13 are made of a Cr-based material. The & material means & ^ or Cr compound, and the Cr compound contains α oxide, silicate, stone cyanide, oxynitride, oxidized carbide, carbonitride nitriding inhibitor, and the like. Money engraved termination layer η contains the first! Element and second element. The first! Element: The composition ratio of at least one element selected from the group consisting of Mo and W is 6.4 mol% or more 38. The second element f is composed of at least: a species of alizarin selected from the group consisting of -, , and Ban. The composition of the second element Moer ° /. the following.卄 卄 /. The above ι ζ := layer 12 may further contain a third element. The third element is selected from the two households π, 广, Ni, c. And at least one element of the group consisting of cu; The reading group view is 5G mol% or more and 9G.2 mol% to be the semi-transmissive layer 11, the etch stop layer 12 and the substrate s. The semi-transmissive layer 11, the (four) emission method, the high-frequency emission method, and the second ion beam sputtering method are used. 13/28 201237546 In the present embodiment, the semi-rust layer 13 is formed by sputtering a two-layer two (four) termination layer 12 and using a gas introduced in the film formation of the first termination layer 12, respectively. Make the material. In the film formation NO, N2 〇, N2 〇 2 and so on. 4, N2, 〇2, C〇2, c〇, Cheng can learn ^^ the individual thickness is not particularly limited, set the statement, the example - the case 'is half to 11 to listen to ~ the thickness of the transmission, the end ... can also be set to terminate the required machine = half-color Μ * /, - withering cover 17, by setting the ΤΑ, half ^ ^ as set above _ _ _ _ _ _ _ _ _ _ _ _ _ ΗΑ and opaque parts are produced (Fig. 2(F)). Through the s-disk semi-transparent ί: two-layer structure, the semi-transmissive portion has a substrate semi-transmissive layer "two-product:: the light-shielding portion ΡΑ has a laminated structure of the substrate S, the lower-stop layer 12, and the light-shielding layer 13. A method of manufacturing a halftone mask 17 of the embodiment. A method of manufacturing a color ray mask] A photoresist, a first photoresist layer 15 is formed on the surface layer 13. The first rotation: the organic photoresist material is formed. The liquid photoresist material is coated on the light shielding layer η by the upper slit coating method or the capillary coating method, etc., and may be removed by the dry layer 1 layer, and then 'as shown in FIG. 1 (shown by 1 The photoresist layer 15 is subjected to exposure 14/28 201237546 processing and development processing to form a first photoresist pattern 15P having an opening 15a for forming the transmissive portion TA. The exposure processing is performed by using an exposure device such as a laser exposure device. The treatment system is an inspective solution such as ruthenium oxide, sodium hydroxide or tetrahydrocarbyl hydroxide. Then, as shown in Fig. 1(D), the first photoresist pattern 15P is used as a mask, and the light shielding layer 13 is used. Thereby, the ith light-shielding opening 13a corresponding to the opening 15a is formed. The side liquid of the green cover 13 is made by (4) acid hydrolysis v) ammonium and The mixture of gas and acid contains a side liquid of nitric acid (hereinafter referred to as a side liquid). At this time, the portion of the "off-stop layer 12" is exposed to the i-side liquid by the second light-shielding opening. However, the layer is not substantially etched by the first button. Therefore, the layer 12 causes the depth direction side of the first (four) liquid to substantially stop at the surface layer of the stopper layer 12. Then, as shown in Fig. 1(E),丨 来 ί : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : The rate of selection is increased, and the rate of money enriched by the second money engraving is increased. The content of the engraving is increased and the etching rate is reduced. Engraved. ', the individual content is followed by the expected rate of money, as shown in Figure 1 (F), through the first opening 仏, will expose the outer semi-transmission layer two = (3) and the first termination rhyme, In the semi-transmissive layer „上二.=1st _liquid 1st terminates the first 〗 〖Semi-transparent 2^ ua. In this case, on the substrate 8 15/28 201237546 to form a transmissive section ΤΑ. The substrate of the net is formed into a cleaning liquid, and the substrate residue or the like is removed. The foreign matter or the photoresist solution remaining on the surface of the second layer S. The temperature of the sulfuric acid-containing water solution can be room temperature and can be warmed to the set temperature. The washing degree = the degree of the dish is not particularly limited, for example, 1 〇叱 or less. In the washing process, the acidity of the acid has solubility resistance. The side of the 3* side of the engraving layer 12 is secreted to prevent the layer caused by the shading caused by the intrusion of the fine side stop layer 丨2 of the money (4)] = 丄 == high It can make the concentrated sulfuric acid layer 2 contain 6.4 mol% or more of the ^ morphism, due to the side-stop acid immersion, and the 賫10 八 上 之 弟 , , , , , , , loo loo loo loo loo loo loo loo loo The amount of the secret of the knife ride is suppressed below α3μιη. Concentrated sulphur ===================================================================== Record termination -:===invasion r::two=two and then 'as shown in the figure', for the second first two = then 'as shown in Figure 2 (D), to the second photoresist pattern: 吏=: The engraved liquid is cut. Thereby, the opening Ub corresponding to the opening secret is formed. At this point, the money is ending the layer] 2 and the first! The shading opening J6/28 201237546 13a forms a _ sample ground, because the depth is not caused by the _ liquid, the depth is square (four) engraved, in the -_: such as: 2_, the second shading opening through the second shading opening 12 is formed corresponding to the second alkaline solution, etc., accompanied by the US material s in the 疋, as shown in Fig. 2(F) 'will be the 13th 芦 王 ' Wang Shi will be the second photoresist pattern 16? A part of the transmissive portion is formed on the material S: ===: it is contained, so that the rate is high and the zigzag rate is lowered. Because:, magnetic two stop === 苐2 riding side content "Min's side rate planting ΐ s ‘ with concentrated sulfuric acid: net [shading:.基材 基材 美 美 美 美 美 美 美 ^ ^ ^ ^ ^ ^ ^ 主 主 主 主 主 主 主Hunting this, remove foreign matter or photoresist residue remaining on the upper surface of ^.
由於=!^17，照本實施態樣， =之洗淨處理時；_=;== ^吏_終止層12之圖案變細等發生而能以期望曰 :=半 ，'I Π/28 201237546 將半透過層n、_i 第紘祕同樣地，依序 f作半色卞〜ί 層12及遮光層13成膜在基材s上， 、^白光罩14。繼而’將光阻材料塗布在遮光層u 由將該光阻材料預烘烤，形成第3光阻層21。 雷射=裝 21 絲Γ &置之曝域理，及使贱鉀、氫氧 圖案ϋ魏四？基鱗齡絲之雜4理，形成第3光阻 =’抑相_成透獅ΤΑ之區軌狀形成 之區域照射不同曝光量之曝光光線。例如，在用於形 之區域中’係沿著第3光阻層21之整個深度方向， ^光阻材料。又，在用於形成半透過部ΗΑ之區財，係除 去從苐3光阻芦21夕本js r·— '、’、 1 層至深度方向之一半為止之光阻材 域具有用於形成透過粒之第丨凹部瓜及用於 =+透過部HA之第2凹部m之第3光阻圖案2ip。第！ 2凹部鳥深之凹部’其係貫穿第3光阻層 21至遮光層13之表層為止之貫通孔。 21ρΓΓ2=_示/藉由在遮光層13以第3光阻圖案 第1 _ 9丨，貝贼用帛1餘刻液之姓刻處理，形成對應於 第凹邓21a之第1遮光開口 13a。繼而 ，# 由在蝕刻終止層12經由第〗遮光 二 不，稭 ‘先開口 13a，貫施使用第2蝕 祕之細處理，形成對應於第1遮光開口 13a之第i終止開 口 12a。繼而，如圖3(F)所+ -，^ 終止開_，實施層11經由第1 第！遮光開口 13a及第丨终止^理’形成對應於 此在基材s上，形成透過部^ 半透過開口⑴。藉 18/28 201237546 繼而，如圖4⑷所示，在基材s之全部上，施行使第2 凹部2ib之底部到達遮光層13之灰化(ashing)處理。繼而，如 圖4⑻所示，藉由在遮光層13以第3光阻圖案2ip做為光罩， 貫施使用第1侧液之_處理，形成對應於第2 第1遮光開口 13b。 此時，蝕刻終止層12，與形成第1遮光開口 13a時-樣， 由於不會被第U虫刻液實質上侵钱，所以第u虫刻液所造成之 殊度方向之_在細終止層12之表層實質上停止。 繼而’如圖4(C)所示’在餘刻終止層12上，藉著經由 2 ^光開口 13b，實施使用第2 _液之侧 於第2遮光開口 13b之第2終止開口⑶。於是，如圖成= 所示，將紐溶_餅至整錄材s，以 從遮光層13上除去。鋅吐，左苴, 遮光部ρΑ。’、 Μ在基材S上形成半透過部ha及 μ構祕刻終止層12之第1元素，隨著其含有率變高，使 成之钱刻速率增加，而第2元素係隨著其含有 速率減少。因此，侧終止層12可依照第丨 素及第2 70素之個別含量，以期望之_速率進行則。 可，部TA、半透過部HA及遮光部pa之基材s， 成之洗淨液進行洗淨處理，藉此，可將殘留 ;土 上表面之異物及光阻殘餘物除去。 由於細炊I作半色錢罩17。若轉本實施態樣， ==12對濃硫酸具有耐溶解性，在使用濃硫酸之 土材S之洗淨處理中，可抑制钱刻終止層！ 不會發生飯刻終止層12之图旬M U猎此， 確度域透過部ΤΑ、半透過部ΗΑ及遮光部ΡΑ。 19/28 201237546 [實施例] (實施例1) 在玻璃基板上，藉由DC濺射法將含有Cr之半透過層(於 波長436nm之透過率為30%)成膜後，將以Ni — n i "莫耳 /〇Τι—3.6莫耳％>11)—11.1莫耳％]\4〇所構成之蝕刻終止層成 膜，再將含有Cr與Cr化合物之遮光層成膜。在遮光層上塗布 光阻(Electronic Materials公司製「ΑΖ15〇0」），曝光後’藉由 鹼性溶液顯像。然後，藉由硝酸鈽(IV)銨與過氣酸之混合溶液 將遮光層蝕刻’藉由硝酸與過氧化氫水溶液之混合溶液將蝕刻 終止層姓刻，藉由硝酸鈽(IV)録與過氣酸之混合溶液將半透過 層蝕刻，藉由鹼性溶液除去光阻，形成透過部。然後，在加溫 至100C之濃硫酸中將上述基板浸潰120分鐘，此時钱刻終止 層之側面餘刻量為〇.13μιη。 在上述基板上再度塗布光阻(Electronic Materials公司製 「AZ1500」)’曝光後’藉由鹼性溶液顯像。再藉由硝酸飾(ιν) 銨與過氣酸之混合溶液將遮光層钱刻，藉由硝酸與過氧化氫水 溶液之混合溶液將蝕刻終止層蝕刻，藉由鹼性溶液除去光阻， 形成半透過部。 (實施例2) 在玻璃基板上，藉由DC藏射法將含有Cr之半透過層(於 波長436mn之透過率為70%)成膜後，將以Ni__107莫耳。/(^__ 6.5莫耳％Nb—9.5莫耳％Mo所構成之蝕刻終止層成膜，再將 含有Cr與Cr化合物之遮光層成膜。在遮光層上塗布光阻 (Electronic Materials公司製「AZ1500」），曝光後，藉由鹼性 溶液顯像。然後，藉由硝酸鈽(IV)銨與過氯酸之混合溶液將遮 光層蝕刻’藉由硝酸與過氧化氫水溶液之混合溶液將蝕刻終止 20/28 201237546 層蝕刻，藉由硝酸鈽(ιν)銨與過氣酸之混合溶液將半透過層餘 刻’藉由驗性溶液除去光阻’形成透過部。然後，在室溫之濃 硫酸中將上述基板浸潰10分鐘，此時蝕刻終止層之側面蝕刻 量為 0.22μιη。 在上述基板上再度塗布光阻(Electronic Materials公司製 「AZ1500」），曝光後，藉由鹼性溶液顯像。再藉由硝酸鈽(IV) 銨與過氣酸之混合溶液將遮光層餃刻，藉由硝酸與過氧化氮水 溶液之混合溶液將蝕刻終止層蝕刻，藉由鹼性溶液除去光阻， 形成半透過部。 (實施例3) 在玻璃基板上，藉由DC濺射法將含有Cr之半透過層(於 波長436nm之透過率為30%)成膜後，將以Ni—1〇 7莫耳％Ώ— 1〇.7莫耳°獅-19.3莫耳％Mo構成之钱刻終止層成膜，再將 含有Cr與Cr化合物之遮光層成膜。在遮光層上塗布光阻 (Electronic Materials公司製「AZ1500」），曝光後，藉由驗性 溶液顯像。然後，藉由确酸錦(IV)!安與過氣酸之混合溶液將遮 光層侧，藉由雜及過氧化氫水溶液之混合溶賴侧終止 層蝕刻，藉由硝酸鈽(IV)銨與過氯酸之混合溶液將半透過層蝕 刻，藉由鹼性溶液除去光阻，形成透過部。然後，在室溫之濃 ，酸中將上縣板浸潰120分鐘，此時_終止層之側面侧 量為Ομιη。 在上述基板上再度塗布光阻(Electr〇nic施纪她公司製 「AZ150G」），曝光後’藉由驗性溶液顯像。再藉㈣酸飾㈤ 銨與過氣酸之混合溶液將遮光層_，藉由猶與過氧化氮水 溶液之混合溶液將侧終止層侧，藉由陳溶液除去光阻， 形成半透過部。 21/28 201237546 (實施例4) 在玻璃基板上，藉由DC濺射法將含有Cr之半透過層(於 波長436nm之透過率為52%)成膜後，將以Νί—1〇 7莫耳％丁卜 9.8莫耳％1^—·15.6莫耳％界構成之蝕刻終止層成膜，再將含 有Cr與Cr化合物之遮光層成膜。在遮光層上塗布光阻 (Electronic Materials公司製「AZ1500」）’曝光後’藉由鹼性 溶液顯像。然後，藉由硝酸鈽(IV)銨與過氯酸之混合溶液將遮 光層蝕刻，藉由硝酸與過氧化氫水溶液之混合溶液將蝕刻終止 層蝕刻，藉由硝酸鈽(IV)銨與過氯酸之混合溶液將半透過層蝕 刻，藉由鹼性溶液除去光阻’形成透過部。然後，在加^至 100°C之濃硫財將上述絲浸潰12Q分鐘，此時蝴終止層 之側面蚀刻量為〇.〇2pm。 在上述基板上再度塗布光阻(Electr〇nic Materials公司製 ^ΑΖ1500」），曝光後，藉甴鹼性溶液顯像。再藉由硝酸鈽^乂) 銨與過氣酸之混合溶液將遮光層I虫刻，藉由硝酸與過氧化氫水 溶液之混合溶液絲祕止層㈣，藉由驗性溶液除去光阻， 形成半透過部。 (實施例5) 在玻璃基板上，藉由DC賤射法將含有Cr之半透過層(於 波長436nm之透過率為52%)成膜後，將以丨2.丨莫耳 23.8莫耳〇擔構成之钱刻終止層成膜，再將含有&與&化合 物之遮紐細。在遮光層上塗布光阻(細祕聽她公 司製「AZ1·」），曝光後’藉由驗性溶液顯像。狹後，藉由 硝酸錦(IV)銨與過氣酸之混合溶液將遮光層綱，藉由硝酸盘 過氧化氫水雜之混合騎絲祕止層_，藉由硝酸姉 (IV)録與·酸之混合驗將半透綱，藉祕性溶液除 22/28 201237546 ^阻，形成透過部。然後，在加溫至靴之漠硫酸中將上 述基板浸潰12〇分鐘，此時姓刻終止層之側面敍刻量騎⑺。 在上述基板上再度塗布級(Ele伽nie麻她公司製 「AZ1500」），曝光後’藉由鹼性溶液顯像。再藉由硝酸鋪 錄與過氯酸之混合溶㈣遮光層_，藉由俩與過氧化氯水 溶液之混合驗職刻終止層_，藉由鹼性溶液除 ， 形成半透過部。 (實施例6) 在玻璃基板上，藉由DC賤射法將含有&之半透過層(於 波長436nm之透過率為52%)成膜後，將以Ni—13莫耳娜」 26.3莫耳％施構成之侧終止層成膜，再將含有&與^化 層成膜。在遮光層上塗布光阻㈤咖nie麻祕 a 3衣AZ1500」）’曝光後’藉由驗性溶液顯像。然後，料 由猶_，與過氯酸之混合溶液將遮光層侧，藉由石^ ”過氧化氣水减之混合雜將侧終止層 ，過氣酸之混合溶液將半透過糊，藉二^ ，=，形成透過部。然後’在加溫至觸。C之濃硫酸中將上Since =!^17, according to the embodiment, when the cleaning process is performed; _=;== ^吏_The pattern of the termination layer 12 is thinned, etc., and can be expected 曰:=half, 'I Π/28 201237546 The semi-transmissive layer n, _i 纮 纮 同样 同样 同样 同样 同样 同样 同样 同样 同样 ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί 及 及 及 及 及Then, the photoresist material is applied to the light shielding layer u, and the photoresist material is prebaked to form the third photoresist layer 21. Laser = installed 21 silk Γ & set the exposure domain, and make the 贱 potassium, hydrogen and oxygen pattern ϋ Wei four? The base of the squamous silk is formed into a third light-resistance = 'suppressed phase _ into the area formed by the orbital region of the lion's owl. The exposure light of different exposure amounts is irradiated. For example, in the region for the shape, the photoresist is applied along the entire depth direction of the third photoresist layer 21. Further, in the area for forming the semi-transmissive portion, the photoresist region is removed from the j3 photoresist Ru 21, the layer of js r·-, ', 1 and one half of the depth direction. The third resist pattern 2ip of the second recess m for the pass-through portion of the grain and the second recess m of the pass-through portion HA. The first! The recessed portion of the concave portion of the bird is a through hole extending through the surface layer of the third photoresist layer 21 to the light shielding layer 13. 21 ΓΓ = 2 = _ shows / by the third photoresist pattern in the light-shielding layer 13 _ 9 丨, the thief is treated with the nick 1 etched to form the first light-shielding opening 13a corresponding to the first concave 21a. Then, # is formed by the etch stop layer 12 through the first light-shielding, the straw ‘first opening 13a, and the second etching is used to form the ith termination opening 12a corresponding to the first light-shielding opening 13a. Then, as shown in Fig. 3(F), + -, ^ terminates on _, and the implementation layer 11 passes through the first! The light-shielding opening 13a and the second end stop are formed corresponding to the substrate s to form a transmissive portion semi-transmissive opening (1). 18/28 201237546 Then, as shown in Fig. 4 (4), the ashing process of the bottom portion of the second concave portion 2ib to the light shielding layer 13 is performed on all of the substrate s. Then, as shown in Fig. 4 (8), the third light-shielding pattern 13ip is used as the mask in the light-shielding layer 13, and the first first liquid-shielding opening 13b is formed by the use of the first side liquid. At this time, the etching stopper layer 12 is similar to the case where the first light-shielding opening 13a is formed, and since the U-worm engraving liquid does not substantially invade the money, the direction of the special degree caused by the u-worm engraving liquid is finely terminated. The surface layer of layer 12 is substantially stopped. Then, as shown in Fig. 4(C), the second termination opening (3) on the side of the second light-shielding opening 13b using the second liquid is applied to the residual stopper layer 12 via the 2^ light opening 13b. Then, as shown in Fig. =, the cake is melted to the entire recording material s to be removed from the light shielding layer 13. Zinc spit, left 苴, shading ρΑ. ', Μ forming the semi-transmissive portion ha and the first element of the structuring layer 12 on the substrate S, and as the content ratio becomes higher, the rate of the engraving is increased, and the second element is followed by The rate of inclusion is reduced. Therefore, the side stop layer 12 can be carried out at a desired rate according to the individual contents of the dioxin and the 270th. The base material s of the portion TA, the semi-transmissive portion HA, and the light-shielding portion pa can be washed by the cleaning liquid, whereby the foreign matter on the upper surface of the soil and the photoresist residue can be removed. Because of the fine 炊 I made a half-color money cover 17. If it is transferred to this embodiment, ==12 has solubility resistance to concentrated sulfuric acid, and in the washing treatment of soil S using concentrated sulfuric acid, it can suppress the end of the layer! There is no such thing as the end of the meal stop layer 12, and the accuracy is transmitted through the sputum, the semi-transmissive part, and the opaque part. 19/28 201237546 [Examples] (Example 1) On a glass substrate, a semi-transmissive layer containing Cr (having a transmittance of 30% at a wavelength of 436 nm) was formed by a DC sputtering method, and then Ni was used. The etch stop layer formed of ni "mole/〇Τι-3.6 mol%>11)-11.1 mol%]\4〇 was formed into a film, and a light-shielding layer containing a Cr and a Cr compound was formed into a film. A photoresist ("15 〇 15" manufactured by Electronic Materials Co., Ltd.) was applied to the light-shielding layer, and after exposure, it was developed by an alkaline solution. Then, the light-shielding layer is etched by a mixed solution of cerium (IV) ammonium nitrate and a peroxyacid. The etch-stop layer is etched by a mixed solution of nitric acid and an aqueous hydrogen peroxide solution, and recorded by cerium nitrate (IV). The mixed solution of gas and acid is etched through the semi-transmissive layer, and the photoresist is removed by an alkaline solution to form a transmissive portion. Then, the substrate was immersed in concentrated sulfuric acid heated to 100 C for 120 minutes, at which time the side of the layer was 〇13 μιη. Further, a photoresist ("AZ1500" manufactured by Electronic Materials Co., Ltd.) was applied to the substrate, and the image was developed by an alkaline solution. Then, the light-shielding layer is etched by a mixed solution of nitric acid (ιν) ammonium and peroxyacid, and the etching stopper layer is etched by a mixed solution of nitric acid and an aqueous hydrogen peroxide solution, and the photoresist is removed by an alkaline solution to form a half. Through the department. (Example 2) On a glass substrate, a semi-transmissive layer containing Cr (having a transmittance of 70% at a wavelength of 436 nm) was formed by a DC deposition method, and then Ni__107 was used. /(^__ 6.5 mol% Nb - 9.5 mol % Mo is formed by forming an etch stop layer, and then forming a light-shielding layer containing Cr and Cr compounds. Coating a photoresist on the light-shielding layer ("Electronic Materials" AZ1500"), after exposure, is developed by an alkaline solution. Then, the light-shielding layer is etched by a mixed solution of cerium (IV) ammonium nitrate and perchloric acid, which is etched by a mixed solution of nitric acid and an aqueous hydrogen peroxide solution. Terminate 20/28 201237546 layer etching, and pass through the semi-transmissive layer by removing the semi-transmissive layer by removing the semi-transmissive layer of yttrium nitrate (ιν) ammonium and peroxyacid to form a transmissive portion. Then, at room temperature The substrate was immersed in sulfuric acid for 10 minutes, and the etching amount of the etching stopper layer was 0.22 μm. The photoresist was again applied to the substrate ("AZ1500" manufactured by Electronic Materials Co., Ltd.), and exposed to an alkaline solution after exposure. Then, the light-shielding layer is dumped by a mixed solution of cerium (IV) ammonium nitrate and a peroxy acid, and the etching stopper layer is etched by a mixed solution of nitric acid and an aqueous solution of nitrogen peroxide, and the photoresist is removed by an alkaline solution. Form a semi-transmissive part. Example 3) On a glass substrate, a semi-transmissive layer containing Cr (having a transmittance of 30% at a wavelength of 436 nm) was formed by a DC sputtering method, and then Ni-1 〇7 mol% Ώ-1 〇.7莫耳°lion-19.3 mol% Mo is formed by the formation of a film, and a light-shielding layer containing Cr and a Cr compound is formed into a film. The photoresist is coated on the light-shielding layer ("AZ1500" manufactured by Electronic Materials Co., Ltd." After exposure, the solution is developed by an assay solution. Then, by using a mixed solution of acid (IV)! and a mixture of peroxyacids, the side of the light-shielding layer is mixed with the aqueous solution of hydrogen peroxide. To terminate the layer etching, the semi-transmissive layer is etched by a mixed solution of cerium (IV) ammonium nitrate and perchloric acid, and the photoresist is removed by an alkaline solution to form a transmissive portion. Then, at room temperature, the acid is added. The plate was immersed for 120 minutes. At this time, the amount of the side surface of the _stop layer was Ομιη. The photoresist was again coated on the substrate (Electr〇nic Shiji Her Co., Ltd. "AZ150G"), and the exposure was followed by an experimental solution. Like, borrow (4) acid decoration (5) mixed solution of ammonium and peroxyacid will be the light-shielding layer _, by mixing with the aqueous solution of nitrogen peroxide The solution was placed on the side termination layer side, and the photoresist was removed by the aging solution to form a semi-transmissive portion. 21/28 201237546 (Example 4) A semi-transmissive layer containing Cr was deposited by a DC sputtering method on a glass substrate. The transmittance at a wavelength of 436 nm is 52%. After the film formation, an etch stop layer composed of Ν — 〇 莫 莫 莫 9.8 9.8 9.8 9.8 9.8 9.8 9.8 9.8 9.8 9.8 , , , , , , , A film was formed on the light-shielding layer of the Cr compound, and a photoresist ("AZ1500" manufactured by Electronic Materials Co., Ltd.) was applied to the light-shielding layer to "develop after exposure" by an alkaline solution. Then, the light shielding layer is etched by a mixed solution of cerium (IV) ammonium nitrate and perchloric acid, and the etching stopper layer is etched by a mixed solution of nitric acid and an aqueous hydrogen peroxide solution, by ammonium (IV) nitrate and perchloric acid. The mixed solution of the acid is etched through the semi-transmissive layer, and the photoresist is removed by an alkaline solution to form a transmissive portion. Then, the above filaments were immersed for 12Q minutes at a concentration of 100 ° C, and the side etching amount of the mating layer was 〇. 〇 2 pm. A photoresist (manufactured by Electron Co., Ltd., ΑΖ1500) was applied to the substrate, and after exposure, it was developed by an alkaline solution. Then, the light-shielding layer I is inscribed by a mixed solution of ammonium and peroxyacid, and the photoresist is removed by an inert solution by a mixture solution of nitric acid and an aqueous hydrogen peroxide solution (4). Semi-transmission section. (Example 5) On a glass substrate, a semi-transmissive layer containing Cr (having a transmittance of 52% at a wavelength of 436 nm) was formed by a DC sputtering method, and then 丨2.丨莫耳23.8莫〇 The constitutive money is used to terminate the film formation, and the mask containing the && compound is fine. A photoresist was applied to the light-shielding layer (see "AZ1·" by her company), and after exposure, it was developed by an assay solution. After narrowing, the light-shielding layer is obtained by a mixed solution of ammonium (IV) nitrate and peroxy acid, and the mixture is occluded by a nitrate disk of hydrogen peroxide, and is recorded by cerium nitrate (IV). · The combination of acid will be semi-transparent, and the secret solution will be removed by 22/28 201237546. Then, the substrate was immersed for 12 minutes in the sulfuric acid heated to the boot, at which time the side of the surname was terminated to ride the amount (7). On the substrate, the grade was again applied ("AZ1500" manufactured by Ele Ganesha Co., Ltd.), and after exposure, it was developed by an alkaline solution. Then, by dissolving the mixed solution of perchloric acid with nitric acid (four) light-shielding layer _, the layer _ is terminated by the mixing of the two with the aqueous solution of chlorine peroxide, and the semi-transmissive portion is formed by the removal of the alkaline solution. (Example 6) On a glass substrate, a semi-transmissive layer containing a & semi-transmissive layer (having a transmittance of 52% at a wavelength of 436 nm) was formed by a DC sputtering method, and Ni-13 moiré was used. The side termination layer formed by the ear % is formed into a film, and then the film containing & Applying a photoresist to the light-shielding layer (5) coffee nie hemp a 3 garment AZ1500") after exposure" was developed by an assay solution. Then, the material is mixed with a mixture of perchloric acid and the side of the light-shielding layer, and the side-stop layer is mixed with the mixed gas of the peroxidized gas, and the mixed solution of the peroxyacid is semi-permeable. ^ , =, forming the transmissive part. Then 'in the warmth to the touch. C in the concentrated sulfuric acid will be on
述基板浸潰12G分鐘，㈣侧終止狀側面 (λΟΙμηι。 、J 「在上述基板上再度塗布光阻(Electr〇nic黯她公司製 r）’曝光後，藉由驗性溶液顯像。再藉由硝酸飾(IV) 义、過贼之混合溶液將遮光層似彳，藉㈣酸與過氧化） 祕糊终止層綱，#祕⑽錄去光阻， (比較例1) 在玻璃基板上，藉由DC濺射法將含有Cr之半透過層(於 23/28 201237546 波長436nm之透過率為71%)成膜後，將以Ni—12.8%Ti構成 之蝕刻終止層成臈，再將含有Q·與&化合物之遮光層成膜。 在遮光層上塗布光阻(Electronic Materials公司製「AZ1500」）， 曝光後，藉由鹼性溶液顯像。然後，藉由硝酸鈽(IV)銨與過氯 酸之混合溶液將遮光層蝕刻，藉由硝酸與過氧化氫水溶液之混 合溶液將蝕刻終止層蝕刻，藉由硝酸鈽(IV)銨與過氣酸之混合 /合液將半透過層蝕刻，藉由鹼性溶液除去光阻，形成透過部。 然後，在室溫之濃硫酸中將上述基板浸;責12〇分鐘，此時姓刻 終土層之側面蝕刻量為4.26μηι。 在上述基板上再度塗布光阻(E】ectr〇nic Maierials公司製 AZ1500」）’曝光後’藉由驗性溶液顯像。再藉由硝酸鈽(iv) ，與過氣酸之混合溶液將遮光層⑽，藉由顧與過氧化氮水 浴液之混合溶液將蝴終止層細，藉由雌溶液除去光阻， 形成半透過部。 (比較例2) 在玻璃基板上，藉由賤射法將含有之半透過層(於 波長436nm之透過率為71%)成膜後，將以Ni—構成 之侧終止層細，再將含有&與&化合物之遮光層成膜。 在遮光層上塗布光阻(EleetrGnie胸如也公司製「az 1 」）， 曝光後’藉由驗性溶液顯像。然後，藉由猶鈽(IV)銨與過氣 @夂=合浴液將遮光層侧，藉由硝酸與過氧化氫水溶液之混 二液將侧終止層钱刻，藉由硝酸鈽㈣銨與過氣酸之混合 冷液將半透過層勤卜n由驗性溶液除去光阻，形成透過部。 然後，在加溫至靴之濃硫酸中將上述基板浸潰10分鐘， 此時遮光層消失’只殘留半透過部。 乂上關於本發明之實施態樣加以說明，然而本發明並不 24/28 201237546 /、=之限定’根據本翻之技術思想可有各種形式之變更。 本、类、^在以上之實施態樣中，雖係舉例說明在基材s上具有 及綱終止層12各1層之半色概罩17，然而 芦及齡ίΓ本發财可顧於基材s上具有複數層半透過 ^讀之所謂多色賊罩。衫色調光罩之情 透耶層12之上可進—步交互形成至少1層追加半 列t 11層追加勤1終止層。再者，於最上層之追加钱 刻終止層之上形成遮光層13。 【圖式簡單說明】 之一實施態樣之半色調 之一實施態樣之半色調 圖1(A)〜(F)係說明根據本發明 光罩之製造方法之步驟圖。 圖2(A)〜(F)係說明根據本發明 光罩之製造方法之步驟圖。 ϋ〜(F)係朗根縣發明之其他實《樣之半色 兩光罩之製造方法之步驟圖。 【主要元件符號說明】 …圖4(A)〜(D)係說明根據本發明之其他實施態樣之 調光罩之製造方法之步驟圖。 11 半透過層 11a 第l半透過開 12 蝕刻終止層 12a 第1終止開口 12b 第2終止開口 13 遮光層 13a 第1遮光開口 13b 第2遮光開口 25/28 201237546 14 半色調空白光罩 15P、16P、21P 光阻圖案 16b 半透過部HA用之開口 17 半色調光罩 21a 第1凹部 21b 第2凹部 HA 半透過部 PA 遮光部 TA 透過部 S 基材 26/28The substrate was immersed for 12 G minutes, and the (4) side-terminated side surface (λΟΙμηι, J "recoated photoresist on the substrate (Electr〇nic黯 her company r)' exposure, and then developed by an experimental solution. The light-shielding layer is similar to yttrium by the mixed solution of nitric acid (IV) and the thief. By means of (4) acid and peroxidation), the layer is terminated, #秘(10) is recorded, (Comparative Example 1) On the glass substrate, After forming a semi-transmissive layer containing Cr (71% transmittance at a wavelength of 436 nm at 23/28 201237546) by DC sputtering, an etch stop layer made of Ni-12.8% Ti is formed and then contained. Q. A film was formed on the light-shielding layer of the & compound. A photoresist ("AZ1500" manufactured by Electronic Materials Co., Ltd.) was applied onto the light-shielding layer, and after exposure, it was developed by an alkaline solution. Then, the light shielding layer is etched by a mixed solution of cerium (IV) ammonium nitrate and perchloric acid, and the etching stopper layer is etched by a mixed solution of nitric acid and an aqueous hydrogen peroxide solution, by ammonium cerium (IV) nitrate and over gas. The acid mixture/liquid mixture is etched by the semi-transmissive layer, and the photoresist is removed by an alkaline solution to form a transmissive portion. Then, the substrate was immersed in concentrated sulfuric acid at room temperature; for 12 minutes, the side etching amount of the final layer was 4.26 μm. Further, a photoresist (AZ1500 manufactured by Eectro 〇nic Maierials Co., Ltd.) was applied to the substrate, and the image was developed by an assay solution. Then, by using a mixed solution of cerium nitrate (iv) and a peroxyacid, the light-shielding layer (10) is thinned by a mixed solution of a nitrogen peroxide water bath, and the photoresist is removed by the female solution to form a semi-transmissive layer. unit. (Comparative Example 2) On the glass substrate, a semi-transmissive layer (71% transmittance at a wavelength of 436 nm) was formed by a sputtering method, and then the side termination layer made of Ni- was finely formed, and then contained. & filming with the light-shielding layer of & compound. A photoresist (EleetrGnie chest "az 1" manufactured by Seiko Co., Ltd.) was applied to the light-shielding layer, and after exposure, it was developed by an assay solution. Then, the side of the light-shielding layer is passed through the mixture of the ammonium (IV) ammonium and the over-gas @夂= bath, and the side-stop layer is engraved by the mixed solution of the nitric acid and the aqueous hydrogen peroxide solution, by using ammonium cerium (tetra) nitrate and The mixed cold liquid of the peroxygen acid removes the photoresist from the test solution by the semi-transparent layer to form a transmissive portion. Then, the substrate was immersed in concentrated sulfuric acid heated to the boot for 10 minutes, at which time the light-shielding layer disappeared, and only the semi-transmissive portion remained. While the embodiments of the present invention have been described, the present invention is not limited to the scope of the present invention. In the above embodiments, although the half-color mask 17 having one layer and one layer of the termination layer 12 on the substrate s is exemplified, the Lu and the age of the money can be taken into consideration. The material s has a so-called multi-color thief cover with a plurality of layers of semi-transmission. The color of the mask is opaque. On the layer 12, the layer can be alternately formed to form at least one layer of additional half column t 11 layer additional layer 1 termination layer. Further, a light shielding layer 13 is formed on the uppermost layer of the additional layer. BRIEF DESCRIPTION OF THE DRAWINGS A halftone of one embodiment of the present invention. Figs. 1(A) to (F) are diagrams showing the steps of a method of manufacturing a photomask according to the present invention. 2(A) to (F) are diagrams showing the steps of a method of manufacturing a photomask according to the present invention. ϋ~(F) is a step diagram of the manufacturing method of the other half-color two-masks invented by Langen County. [Description of Main Element Symbols] Fig. 4 (A) to (D) are diagrams showing the steps of a method of manufacturing a dimming cover according to another embodiment of the present invention. 11 semi-transmissive layer 11a first half-transmission opening 12 etch-stop layer 12a first end opening 12b second end opening 13 light-shielding layer 13a first light-shielding opening 13b second light-shielding opening 25/28 201237546 14 halftone blank mask 15P, 16P 21P photoresist pattern 16b opening for semi-transmissive portion HA 17 halftone mask 21a first recess 21b second recess HA semi-transmissive portion PA light blocking portion TA transmitting portion S substrate 26/28