TWI631988B - Multilayer film etching solution and etching concentrate and etching method - Google Patents
Multilayer film etching solution and etching concentrate and etching method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
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- C23F1/18—Acidic compositions for etching copper or alloys thereof
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
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Abstract
本發明提供在蝕刻銅與鉬的多層膜的蝕刻液,可降低使用量的蝕刻液。 The present invention provides an etching solution for etching a multilayer film of copper and molybdenum, which can reduce the amount of etching liquid used.
在使用雙氧水的蝕刻液,由於雙氧水會因銅離子分解,故需要補充多量的蝕刻液。包含:過氧化氫、酸性有機酸、胺化合物、過氧化氫分解抑制劑、唑類、及包含鋁鹽的析出防止劑,上述過氧化氫分解抑制劑,以0.4質量%以上5質量%以下的比例包含乙二醇單丁醚,上述胺化合物,係N,N-二乙基-1,3-丙二胺為特徵的多層膜用蝕刻液,即使銅離子增加,亦可抑制雙氧水分解速度,而可降低蝕刻液的總使用量。 In the etching solution using hydrogen peroxide, since hydrogen peroxide is decomposed by copper ions, it is necessary to add a large amount of etching liquid. Including: hydrogen peroxide, an acidic organic acid, an amine compound, a hydrogen peroxide decomposition inhibitor, an azole, and a precipitation preventive agent containing an aluminum salt, and the hydrogen peroxide decomposition inhibitor is 0.4% by mass or more and 5% by mass or less. The ratio includes ethylene glycol monobutyl ether, and the above amine compound, which is an etching solution for a multilayer film characterized by N,N-diethyl-1,3-propanediamine, can suppress the decomposition rate of hydrogen peroxide even if copper ions are increased. It can reduce the total amount of etchant used.
Description
本發明係關於用於蝕刻使用於液晶、有機EL等的平面顯示器的配線用的銅及鉬的多層膜時的多層膜用蝕刻液與蝕刻濃縮液及蝕刻方法。 The present invention relates to an etching solution for a multilayer film, an etching concentrate, and an etching method for etching a multilayer film of copper and molybdenum used for wiring of a flat panel display such as a liquid crystal or an organic EL.
液晶或有機EL(Electro-Luminescence:電致發光)等的平面顯示器(FPD)的TFT(Thin Film Transistor:薄膜電晶體),使用鋁作為配線材料。近幾年,大畫面而高解析度的FPD普及,在使用的配線材料,要求電阻較鋁低的材料。因此,近幾年使用較鋁低電阻的銅作為配線材料。 A TFT (Thin Film Transistor) of a flat panel display (FPD) such as liquid crystal or organic EL (Electro-Luminescence) uses aluminum as a wiring material. In recent years, large-screen and high-resolution FPD has become popular, and wiring materials used have required materials having lower electric resistance than aluminum. Therefore, in recent years, copper having a lower resistance than aluminum has been used as a wiring material.
使用銅作為配線材料,則會產生與基板之間的接著力,及對半導體基材的擴散的兩個問題。即,使用於閘極配線時,即使採用一般認為對基材的衝擊能較大的濺鍍法,在玻璃等的基板之間有接著力不充份的情形。此外,使用於源極.汲極配線時,附著的銅往成為底層的矽擴散,而發生改變半導體的電性設計值的問題。 When copper is used as the wiring material, there are two problems of adhesion between the substrate and diffusion of the semiconductor substrate. In other words, when it is used for the gate wiring, even if a sputtering method which is generally considered to have a large impact energy to the substrate is used, there is a case where there is insufficient adhesion between the substrates such as glass. In addition, used in the source. In the case of the drain wiring, the adhered copper diffuses toward the underlying germanium, and the problem of changing the electrical design value of the semiconductor occurs.
為解決此問題,現在是採用首先在半導體基材上,形成鉬膜,在其上形成銅膜的多層結構。 To solve this problem, it is now a multilayer structure in which a molybdenum film is first formed on a semiconductor substrate to form a copper film thereon.
FPD的配線,係將以濺鍍法形成的多層膜濕式蝕刻形成。由於可一口氣形成大面積,故可縮短步驟。在此,在 配線的濕式蝕刻,以下的點重要。 The wiring of the FPD is formed by wet etching a multilayer film formed by sputtering. Since a large area can be formed in one breath, the steps can be shortened. Here, in the wet etching of the wiring, the following points are important.
(1)加工精度高而一樣。 (1) The processing accuracy is high and the same.
(2)加工後的配線剖面係既定角度的順錐度。 (2) The wiring profile after processing is a straight taper of a predetermined angle.
(3)藉由包含銅離子,蝕刻速率不會變化(蝕刻浴壽命長)。 (3) The etching rate does not change by containing copper ions (the etching bath has a long life).
(4)析出物較少出現。 (4) Precipitates are less likely to appear.
滿足如此要求的蝕刻液,揭示在專利文獻1(日本特開2015-209568號公報)。 An etchant that satisfies such a requirement is disclosed in Patent Document 1 (JP-A-2015-209568).
在此,揭示一種多層膜用蝕刻液,其特徵在於包含:過氧化氫、酸性有機酸、胺化合物、過氧化氫分解抑制劑、唑類、及包含鋁鹽的析出防止劑。 Here, an etching liquid for a multilayer film comprising hydrogen peroxide, an acidic organic acid, an amine compound, a hydrogen peroxide decomposition inhibitor, an azole, and a precipitation preventing agent containing an aluminum salt are disclosed.
該蝕刻液,在銅(Cu)及鉬(Mo)的蝕刻速率、被蝕刻的邊界區域的錐度角、鉬(Mo)的底切、鉬(Mo)的殘渣、對過蝕刻的耐性、析出物、雙氧水分解速度等的評估,具有滿足用於現下的製造的水準的性能。 The etching rate of the etching solution in copper (Cu) and molybdenum (Mo), the taper angle of the boundary region to be etched, the undercut of molybdenum (Mo), the residue of molybdenum (Mo), the resistance to overetching, and the precipitate The evaluation of the hydrogen peroxide decomposition rate and the like has a performance that satisfies the level of production for the present.
另一方面,專利文獻1的蝕刻液,係以隨著使用,拋棄一定量的蝕刻液,追加新的蝕刻液(稱為新液。)使用作為前提。 On the other hand, the etching liquid of the patent document 1 is premised on the use which discards a certain amount of etching liquid, and adds a new etching liquid (referred to as a new liquid).
具體而言,如專利文獻1的實施例所示,以Cu濃度2000ppm為基準,將蝕刻液的一部分以新液替換。在如此的專利文獻1,將蝕刻液的一部分以新液替換,係由於蝕刻速率會隨著Cu濃度的上升使過氧化氫被分解而改變。 Specifically, as shown in the example of Patent Document 1, a part of the etching liquid was replaced with a new liquid based on a Cu concentration of 2000 ppm. In Patent Document 1 described above, a part of the etching liquid is replaced with a new liquid because the etching rate changes as the Cu concentration increases.
在行動終端機的普及之中,平面顯示器的需求,越來越多,製造工廠亦設立大規模的工廠,此外今後亦有預定設立。在如此的大規模工廠,為削減生產線的成本,期待削減蝕刻液的使用量。因為在製造階段的成本削減可降低最終產品的價格。 In the popularization of mobile terminals, there is an increasing demand for flat panel displays, and large-scale factories have been established in manufacturing plants. In addition, there are plans to set up in the future. In such a large-scale factory, in order to reduce the cost of the production line, it is expected to reduce the amount of etching liquid used. Because cost reductions in the manufacturing phase can lower the price of the final product.
在此,簡單說明關於上述蝕刻液的管理方法。鉬及銅被成膜,在抗蝕劑等描繪圖案的被處理物(玻璃基板等),係在蝕刻槽,一片一片處理,送到清洗步驟。此時,有與被處理物一起被帶出蝕刻槽的蝕刻液。因此,每當處理物從蝕刻槽搬出,需補充被帶出的部分的蝕刻液。 Here, a method of managing the above etching liquid will be briefly described. Molybdenum and copper are formed into a film, and the object to be processed (such as a glass substrate) drawn on a resist or the like is processed in an etching bath, and is sent to a cleaning step. At this time, there is an etchant that is carried out of the etching bath together with the object to be processed. Therefore, whenever the processed material is carried out from the etching bath, it is necessary to replenish the portion of the etching liquid that is carried out.
此外,隨著蝕刻液的使用蝕刻液中的銅離子濃度會變高。此係,由於會將蝕刻液中的過氧化氫分解,故銅離子達到一定濃度,需補充蝕刻液將銅離子濃度稀釋。此外,為補充分解的過氧化氫而補充蝕刻液。如此地,由此三個觀點追加蝕刻液。 Further, as the etching liquid is used, the concentration of copper ions in the etching liquid becomes high. In this system, since the hydrogen peroxide in the etching solution is decomposed, the copper ions reach a certain concentration, and the etching liquid is added to dilute the copper ion concentration. In addition, the etching liquid is replenished to supplement the decomposed hydrogen peroxide. In this way, the etching liquid is added by the three viewpoints.
然而,關於銅的蝕刻液,減低使用量的手法,已有先前的提案。專利文獻2(日本特開2013-184076號公報)、專利文獻3(日本特開2013-158707號公報),係由銅的蝕刻液中的酸回收銅,進行蝕刻液的再生,實現降低蝕刻液的使用。 However, regarding the etching solution of copper, the method of reducing the amount of use has been previously proposed. Patent Document 2 (JP-A-2013-184076), and Patent Document 3 (JP-A-2013-158707), which recovers copper from an acid in an etching solution of copper, and regenerates the etching solution to reduce the etching liquid. usage of.
此外,專利文獻4(日本特開2000-054167號公報),係在以氯化鐵蝕刻液對銅蝕刻處理時,適宜將氯化亞鐵及氯化亞銅氧化成氯化鐵及氯化銅,將蝕刻液的蝕刻能力維持一定而實現使用量的削減。 Further, in Patent Document 4 (JP-A-2000-054167), it is preferable to oxidize ferrous chloride and cuprous chloride into ferric chloride and copper chloride when etching copper with a ferric chloride etching solution. The etching ability of the etching liquid is maintained constant, and the amount of use is reduced.
[先前技術文獻] [Previous Technical Literature]
[專利文獻] [Patent Literature]
專利文獻1:日本特開2015-209568號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2015-209568
專利文獻2:日本特開2013-184076號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 2013-184076
專利文獻3:日本特開2013-158707號公報 Patent Document 3: Japanese Laid-Open Patent Publication No. 2013-158707
專利文獻4:日本特開2000-054167號公報 Patent Document 4: Japanese Laid-Open Patent Publication No. 2000-054167
以專利文獻1的蝕刻液,隨著處理的基板數量的增加,蝕刻液中的Cu濃度上升,則雙氧水的分解會進行,而為維持一定的蝕刻能力,需進行蝕刻液的追加。但是,被處理物所帶走的蝕刻液、銅離子濃度的稀釋、過氧化氫的濃度的維持,這三個觀點的追加是必要的,需要多量的蝕刻液。 In the etching liquid of Patent Document 1, as the number of substrates to be processed increases, the concentration of Cu in the etching liquid rises, and decomposition of hydrogen peroxide proceeds, and in order to maintain a constant etching ability, it is necessary to add an etching liquid. However, it is necessary to add the etching liquid, the dilution of the copper ion concentration, and the concentration of the hydrogen peroxide which are carried away by the object to be processed, and a large amount of etching liquid is required.
專利文獻2、3,係在蝕刻液使用酸,藉由從該酸回收銅離子以再生蝕刻液。因此,無法適用在使用過氧化氫的蝕刻液。 Patent Documents 2 and 3 use an acid in an etching solution to recover an etching liquid by recovering copper ions from the acid. Therefore, it is not applicable to an etching solution using hydrogen peroxide.
此外,專利文獻4,係藉由將蝕刻液中的銅離子氧化,而維持一定的蝕刻液的蝕刻能力,亦無法適用在使用過氧化氫的蝕刻液。因為在使用過氧化氫的蝕刻液,過氧化氫會分解,所無法完成蝕刻液的再生。 Further, Patent Document 4 is capable of maintaining a certain etching ability of an etching liquid by oxidizing copper ions in an etching solution, and is also not applicable to an etching liquid using hydrogen peroxide. Since the hydrogen peroxide is decomposed in the etching solution using hydrogen peroxide, the regeneration of the etching liquid cannot be completed.
本發明係為解決上述課題而想出,係藉由降低過氧化氫的分解速度,大幅減少用於維持過氧化氫濃度所追加的蝕刻液量,而可減低蝕刻液的使用量。 In order to solve the above problems, the present invention has been conceived to reduce the amount of etching liquid added to maintain the hydrogen peroxide concentration by reducing the decomposition rate of hydrogen peroxide, and to reduce the amount of etching liquid used.
具體而言,關於本發明的多層膜用蝕刻液,其特徵在於包含:過氧化氫、作為酸性有機酸之甘醇酸、丙二酸、及乳酸之中的至少1種、胺化合物、過氧化氫分解抑制劑、作為唑類之5-胺基-1H-四唑、及作為包含鋁鹽的析出防止劑之乳酸鋁,上述過氧化氫分解抑制劑,以0.4質量%以上5質量%以下的比例包含乙二醇單丁醚,上述胺化合物,係N,N-二乙基-1,3-丙二胺。再者,以後亦將乙二醇單丁醚稱為「BG」。 Specifically, the etching solution for a multilayer film of the present invention is characterized by comprising: hydrogen peroxide, at least one of glycolic acid, malonic acid, and lactic acid as an acidic organic acid, an amine compound, and peroxidation. a hydrogen decomposition inhibitor, 5-amino-1H-tetrazole as an azole, and aluminum lactate as a precipitation inhibitor containing an aluminum salt, and the hydrogen peroxide decomposition inhibitor is 0.4% by mass or more and 5% by mass or less. The ratio includes ethylene glycol monobutyl ether, and the above amine compound is N,N-diethyl-1,3-propanediamine. Furthermore, ethylene glycol monobutyl ether is also referred to as "BG" in the future.
此外,為解決上述課題,關於本發明的包含鉬與銅的多層膜用蝕刻液,其特徵在於包含:過氧化氫、作為酸性有機酸之甘醇酸、丙二酸、及乳酸之中的至少1種、胺化合物、過氧化氫分解抑制劑、作為唑類之5-胺基-1H-四唑、及作為包含鋁鹽的析出防止劑之乳酸鋁,上述過氧化氫分解抑制劑,以0.9質量%以上5質量%以下的比例包含乙二醇單丁醚,上述胺化合物係1-胺基-2-丙醇。 Further, in order to solve the above problems, the etching liquid for a multilayer film containing molybdenum and copper according to the present invention is characterized by comprising at least hydrogen peroxide, glycolic acid as an acidic organic acid, malonic acid, and lactic acid. One type, an amine compound, a hydrogen peroxide decomposition inhibitor, 5-amino-1H-tetrazole as an azole, and aluminum lactate as a precipitation inhibitor containing an aluminum salt, and the above-mentioned hydrogen peroxide decomposition inhibitor is 0.9 The ratio of the mass% or more and 5% by mass or less includes ethylene glycol monobutyl ether, and the above amine compound is 1-amino-2-propanol.
關於本發明的蝕刻液,相對於專利文獻1所揭示的蝕刻液,在Cu濃度2,000ppm以上會使雙氧水的分解速度上 升,即使在8,000ppm亦可維持非常低的雙氧水的分解速度。 The etching liquid of the present invention has a decomposition rate of hydrogen peroxide at a Cu concentration of 2,000 ppm or more with respect to the etching liquid disclosed in Patent Document 1. l, even at 8,000 ppm, the decomposition rate of very low hydrogen peroxide can be maintained.
因此,關於本發明的蝕刻液,可採取較長的用於補充過氧化氫的濃度下降的蝕刻液的追加間隔。結果,可得可降低蝕刻液的使用量的效果。Therefore, the etching liquid of the present invention can take a long additional interval of the etching liquid for replenishing the concentration of hydrogen peroxide. As a result, an effect of reducing the amount of use of the etching liquid can be obtained.
1‧‧‧基板 1‧‧‧Substrate
2‧‧‧Cu層 2‧‧‧Cu layer
3‧‧‧Mo層 3‧‧‧Mo layer
4‧‧‧抗蝕劑 4‧‧‧Resist
5‧‧‧錐度角 5‧‧‧ taper angle
6‧‧‧傾斜面 6‧‧‧Sloping surface
10‧‧‧逆錐度 10‧‧‧ inverse taper
圖1係表示蝕刻的配線的剖面的概念圖。 Fig. 1 is a conceptual diagram showing a cross section of an etched wiring.
圖2係表示模擬使用先前的蝕刻液時的使用量的結果的圖表。 Fig. 2 is a graph showing the results of simulating the amount of use when the previous etching solution was used.
圖3係表示使用關於本發明的多層膜用蝕刻液時的使用量的結果的圖表。 Fig. 3 is a graph showing the results of using the etching liquid for the multilayer film of the present invention.
圖4係表示BG的含量與雙氧水的分解速度的關係的圖表。 Fig. 4 is a graph showing the relationship between the content of BG and the decomposition rate of hydrogen peroxide.
以下說明關於本發明的多層膜用蝕刻液。再者,以下的說明係表示關於本發明的蝕刻液的一實施形態,在不脫離本發明的宗旨的範圍,以下的實施形態及實施例亦可變更。再者,在以下的說明,將數值範圍以「A~B」表示時,係「A以上、B以下」的意思。即,包含數值A而較大、且包含數值B而較小的範圍。 The etching liquid for a multilayer film of the present invention will be described below. In addition, the following description shows an embodiment of the etching liquid of the present invention, and the following embodiments and examples can be modified without departing from the scope of the invention. In the following description, when the numerical range is represented by "A to B", it means "A or more and B or less". That is, the range including the numerical value A is large and the numerical value B is included.
關於本發明的多層膜用蝕刻液,包含:過氧化氫、酸性有機酸、胺化合物、過氧化氫分解抑制劑、唑類、及包含鋁鹽的析出防止劑。以下詳細說明各個成分。 The etching liquid for a multilayer film of the present invention includes hydrogen peroxide, an acidic organic acid, an amine compound, a hydrogen peroxide decomposition inhibitor, an azole, and a precipitation preventing agent containing an aluminum salt. Each component is described in detail below.
<過氧化氫> <hydrogen peroxide>
銅的蝕刻,係銅被氧化成為氧化銅(CuO),而被酸(有機酸)溶解。此外,鉬的蝕刻,係被氧化成為氧化鉬(MoO3),而溶解於水。過氧化氫,係使用於作為氧化銅或鉬的氧化劑。再者,過氧化氫與雙氧水係同義語。過氧化氫,以蝕刻液全量的4.0質量%~5.8質量%為佳,以4.2質量%~5.6質量%更佳,以4.5質量%~5.3質量%最佳。 Copper is etched, and copper is oxidized to copper oxide (CuO) and dissolved by an acid (organic acid). Further, the etching of molybdenum is oxidized to molybdenum oxide (MoO 3 ) and dissolved in water. Hydrogen peroxide is used as an oxidizing agent for copper oxide or molybdenum. Furthermore, hydrogen peroxide is synonymous with hydrogen peroxide. The hydrogen peroxide is preferably 4.0% by mass to 5.8% by mass based on the total amount of the etching solution, more preferably 4.2% by mass to 5.6% by mass, and most preferably 4.5% by mass to 5.3% by mass.
<有機酸> <organic acid>
有機酸,係將銅膜蝕刻的同時,擔負調整被蝕刻的配線的剖面的錐度角的角色。此外,亦被認為具有某種程度的抑制過氧化氫分解的功能。在有機酸使用酸性的有機酸。再者,關於本發明的多層膜用蝕刻液,亦可包含中性的有機酸作為後述的析出防止劑。 The organic acid serves to etch the copper film and to adjust the taper angle of the cross section of the etched wiring. In addition, it is also considered to have a certain degree of function of suppressing decomposition of hydrogen peroxide. An acidic organic acid is used in the organic acid. In addition, the etching liquid for a multilayer film of the present invention may contain a neutral organic acid as a precipitation preventing agent to be described later.
有機酸,在碳數1~18的脂肪族羧酸、碳數6~10的芳香族羧酸之外,亦可良好地舉碳數1~10的胺基酸等。 The organic acid is preferably an aliphatic carboxylic acid having 1 to 18 carbon atoms or an aromatic carboxylic acid having 6 to 10 carbon atoms, and preferably an amino acid having 1 to 10 carbon atoms.
碳數1~18的脂肪族羧酸,可良好地舉蟻酸、酯酸、丙酸、乳酸、甘醇酸、二甘醇酸、丙酮酸、丙二酸、酪酸、羥酪酸、酒石酸、琥珀酸、蘋果酸、馬來酸、富馬酸、吉草酸、戊二酸、依康酸、己二酸、己酸、檸檬酸、丙烷三羧酸、逆式烏頭酸、庚酸、辛酸、月桂酸、十四烷酸、棕精酸、硬脂酸、油酸、亞油酸、亞麻酸等。 An aliphatic carboxylic acid having 1 to 18 carbon atoms, which can well be used for formic acid, ester acid, propionic acid, lactic acid, glycolic acid, diglycolic acid, pyruvic acid, malonic acid, butyric acid, hydroxybutyric acid, tartaric acid, succinic acid , malic acid, maleic acid, fumaric acid, oxalic acid, glutaric acid, isaconic acid, adipic acid, caproic acid, citric acid, propane tricarboxylic acid, trans-aconitic acid, heptanoic acid, octanoic acid, lauric acid , myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and the like.
碳數6~10的芳香族羧酸,可列舉,安息香酸、柳酸、扁桃酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸等為佳。 Examples of the aromatic carboxylic acid having 6 to 10 carbon atoms include benzoic acid, salicylic acid, mandelic acid, phthalic acid, isophthalic acid, and terephthalic acid.
此外,碳數1~10的胺基酸,可列舉胺基甲酸、丙胺酸、甘胺酸、天門冬胺、天門冬胺酸、肌胺酸、絲胺酸、麩醯胺酸、麩胺酸、4-胺基酪酸、亞胺二酪酸、精胺酸、白胺酸、異白胺酸、硝基三醋酸等為佳。 Further, examples of the amino acid having 1 to 10 carbon atoms include aminocarboxylic acid, alanine, glycine, asparagine, aspartic acid, sarcosine, serine, glutamic acid, and glutamic acid. 4-aminobutyric acid, imine dibutyric acid, arginine, leucine, isoleucine, nitrotriacetic acid, etc. are preferred.
上述有機酸之中,可良好地利用甘醇酸、丙二酸、乳酸作為酸性有機酸。特別是,甘醇酸、丙二酸、乳酸,可藉由同時並用三種,得到良好的特性。 Among the above organic acids, glycolic acid, malonic acid, and lactic acid can be favorably used as the acidic organic acid. In particular, glycolic acid, malonic acid, and lactic acid can be obtained by using three kinds at the same time to obtain good characteristics.
再者,甘醇酸係對蝕刻液全量,含有1.3質量%~3.3質量%為佳,以1.8質量%~2.8質量%更佳,以2.1質量%~2.5質量%最佳。 Further, the glycolic acid is preferably contained in an amount of from 1.3% by mass to 3.3% by mass based on the total amount of the etching liquid, more preferably from 1.8% by mass to 2.8% by mass, and most preferably from 2.1% by mass to 2.5% by mass.
此外,丙二酸,對蝕刻液全量,含有3.0質量%~5質量%為佳,以3.5質量%~4.5質量%更佳,以3.8質量%~4.2質量%最佳。 Further, the malonic acid is preferably 3.0% by mass to 5% by mass based on the total amount of the etching liquid, more preferably 3.5% by mass to 4.5% by mass, and most preferably 3.8 % by mass to 4.2% by mass.
此外,乳酸,對蝕刻液全量,含有0.4質量%~1.6質量%為佳,以0.6質量%~1.4質量%更佳,以0.8質量%~1.2質量%最佳。 Further, lactic acid is preferably 0.4% by mass to 1.6% by mass based on the total amount of the etching liquid, more preferably 0.6% by mass to 1.4% by mass, and most preferably 0.8% by mass to 1.2% by mass.
此外,酸性有機酸全體,對蝕刻液全量,含有4.7質量%~9.9質量%為佳,以5.9質量%~8.7質量%更佳,以6.7質量%~7.9質量%最佳。 Further, the total amount of the acidic organic acid is preferably 4.7 mass% to 9.9% by mass, more preferably 5.9% by mass to 8.7% by mass, and most preferably 6.7% by mass to 7.9% by mass.
<胺化合物> <amine compound>
胺化合物係擔負蝕刻液的pH調整。胺化合物,可良好地利用碳數2~10的化合物。更具體可舉,乙二胺、三亞甲基二胺、四亞甲基二胺、1,2-丙二胺、1,3-丙二胺、N,N-二甲基-1,3-丙二胺、N,N-二乙基-1,3-丙二胺、1,3-二胺基丁烷、2,3-二胺基丁烷、五亞甲基胺、2,4-二胺基戊烷、六亞甲基二胺、七亞甲基二胺、八亞甲基二胺、九亞甲基二胺、N-甲基乙二胺、N,N-二甲基乙二胺、三甲基乙二胺、N-乙基乙二胺、N,N-二乙基乙二胺、三乙基乙二胺、1,2,3-三胺基丙烷、聯胺、三(2-胺基乙基)胺、四(胺基甲基)甲烷、二亞乙基三胺、三亞乙基四胺、四乙基五胺、七亞乙基八胺、九亞乙基十胺、二氮雜二環十一烯等的多胺;乙醇胺、N-甲基乙醇胺、N-甲基二乙醇胺、N-乙基乙醇胺、N-胺基乙基乙醇胺、N-丙基乙醇胺、N-丁基乙醇胺、二乙醇胺、三乙醇胺、1-胺基-2-丙醇、N-甲基異丙醇胺、N-乙基異丙醇胺、N-丙基異丙醇胺、2-胺基丙-1-醇、N-甲基-2-胺基丙-1-醇、N-乙基-2-胺基丙-1-醇、1-胺基丙-3-醇、N-甲基-1-胺基丙-3-醇、N-乙基-1-胺基丙-3-醇、1-胺基丁-2-醇、N-甲基-1-胺基丁-2-醇、N-乙基-1-胺基丁-2-醇、2-胺基丁-1-醇、N-甲基-2-胺基丁-1-醇、N-乙基-2-胺基丁-1-醇、3-胺基丁-1-醇、N-甲基-3-胺基丁-1-醇、N-乙基-3-胺基丁-1-醇、1-胺基丁-4-醇、N-甲基-1-胺基丁-4-醇、N-乙基-1-胺基丁-4-醇、1-胺基-2-甲基丙-2-醇、2-胺基-2-甲基丙-1-醇、1-胺基戊-4-醇、2-胺基-4-甲基戊-1-醇、2-胺基己-1-醇、3-胺基庚-4-醇、1-胺基辛-2-醇、5-胺基辛-4-醇、1-胺基丙-2,3-二醇、2-胺基丙-1,3-二醇、三(氧甲基)胺基甲烷、1,2-二胺基丙-3-醇、1,3-二胺基丙-2-醇、2-(2-胺基乙氧基)乙醇、2-(2-胺基乙基胺基)乙醇、二甘醇胺等的烷醇胺為佳,該等可以單獨或組合複數使用。 The amine compound is responsible for the pH adjustment of the etching solution. As the amine compound, a compound having 2 to 10 carbon atoms can be favorably used. More specifically, ethylenediamine, trimethylenediamine, tetramethylenediamine, 1,2-propylenediamine, 1,3-propanediamine, N,N-dimethyl-1,3- Propylenediamine, N,N-diethyl-1,3-propanediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentamethyleneamine, 2,4- Diaminopentane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, ninethylenediamine, N-methylethylenediamine, N,N-dimethyl B Diamine, trimethylethylenediamine, N-ethylethylenediamine, N,N-diethylethylenediamine, triethylethylenediamine, 1,2,3-triaminopropane, hydrazine, Tris(2-aminoethyl)amine, tetrakis(aminomethyl)methane, diethylenetriamine, triethylenetetramine, tetraethylpentamine, heptaethylene octaamine, nonaethylene Polyamines such as decaamine, diazabicycloundecene, etc.; ethanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, N-aminoethylethanolamine, N-propylethanolamine , N-butylethanolamine, diethanolamine, triethanolamine, 1-amino-2-propanol, N-methylisopropanolamine, N-ethylisopropanolamine, N-propyl isopropanolamine, 2-Aminopropan-1-ol, N-methyl-2-aminopropan-1-ol, N- Ethyl-2-aminopropan-1-ol, 1-aminopropan-3-ol, N-methyl-1-aminopropan-3-ol, N-ethyl-1-aminopropyl-3 - alcohol, 1-aminobutan-2-ol, N-methyl-1-aminobutan-2-ol, N-ethyl-1-aminobutan-2-ol, 2-aminobutyrate-1 - alcohol, N-methyl-2-aminobutan-1-ol, N-ethyl-2-aminobutan-1-ol, 3-aminobutan-1-ol, N-methyl-3- Aminobutan-1-ol, N-ethyl-3-aminobutan-1-ol, 1-aminobutan-4-ol, N-methyl-1-aminobutan-4-ol, N- Ethyl-1-aminobutan-4-ol, 1-amino-2-methylpropan-2-ol, 2-amino-2-methylpropan-1-ol, 1-aminopenta-4 - alcohol, 2-amino-4-methylpentan-1-ol, 2-aminohexan-1-ol, 3-aminoheptan-4-ol, 1-aminooctin-2-ol, 5- Aminooctyl-4-ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris(oxymethyl)aminomethane, 1,2-diamine Propyl-3-ol, 1,3-diaminopropan-2-ol, 2-(2-aminoethoxy)ethanol, 2-(2-aminoethylamino)ethanol, diethylene glycol An alkanolamine such as an amine is preferred, and these may be used singly or in combination.
該等之中,以1-胺基-2-丙醇(CAS編碼78-96-6:以下亦稱為「1A2P」。)或N,N-二乙基-1,3-丙二胺(CAS編號104-78-9:以下亦稱為「NNDPA」。)特佳。此外,胺化合物,對蝕刻液全量,以2.0質量%~3.2質量%為佳,以2.2質量%~3.0質量%更佳,以2.4~2.8質量%最佳。 Among these, 1-amino-2-propanol (CAS code 78-96-6: hereinafter also referred to as "1A2P") or N,N-diethyl-1,3-propanediamine ( CAS No. 104-78-9: The following is also referred to as "NNDPA".) Excellent. Further, the amine compound is preferably 2.0% by mass to 3.2% by mass based on the total amount of the etching liquid, more preferably 2.2% by mass to 3.0% by mass, and most preferably 2.4% by mass to 2.8% by mass.
<過氧化氫分解抑制劑> <Hydrogen peroxide decomposition inhibitor>
關於本發明的多層膜用蝕刻液,利用過氧化氫作為氧化劑。過氧化氫,由於會自我分解,故追加抑制該分解的分解抑制劑。過氧化氫分解抑制劑,亦稱為過氧化氫穩定劑(或「雙氧水穩定劑」)。 Regarding the etching solution for a multilayer film of the present invention, hydrogen peroxide is used as the oxidizing agent. Since hydrogen peroxide decomposes by itself, a decomposition inhibitor that suppresses the decomposition is added. Hydrogen peroxide decomposition inhibitors, also known as hydrogen peroxide stabilizers (or "hydrogen peroxide stabilizers").
特別是在關於本發明的蝕刻液的情形,需要使蝕刻速率,即使Cu濃度到8,000ppm仍變化些微。在本發明,可良好地使用乙二醇單丁醚(CAS編號111-76-2:以下亦稱為「BG」。)。 Particularly in the case of the etching liquid of the present invention, it is necessary to make the etching rate slightly small even if the Cu concentration is 8,000 ppm. In the present invention, ethylene glycol monobutyl ether (CAS No. 111-76-2: hereinafter also referred to as "BG") can be preferably used.
先前,過氧化氫分解抑制劑,在苯基尿素、烯丙基尿素、1,3-二甲基尿素、硫代尿素等的尿素系過氧化氫分解抑制劑之外,亦可良好地使用苯基醋酸醯胺、苯基乙二醇或1-丙醇、2-丙醇等的低級醇等。但是,發現BG,即使Cu濃度到8,000ppm以上的高濃度,可發揮抑制雙氧水的分解的顯著效果。 Previously, the hydrogen peroxide decomposition inhibitor was used in addition to urea-based hydrogen peroxide decomposition inhibitors such as phenyl urea, allyl urea, 1,3-dimethyl urea, and thiourea. A lower alcohol such as decylamine acetate, phenylethylene glycol, 1-propanol or 2-propanol. However, it has been found that BG exhibits a remarkable effect of suppressing decomposition of hydrogen peroxide even at a high concentration of Cu concentration of 8,000 ppm or more.
再者,如後所述,BG係藉由對蝕刻液放入一定量以上而有效,即使放入多量亦會飽和。只又可確保其他必要成分的量,即使放入多量,亦可發揮作為蝕刻液的效果。但是,多加BG,會提高成本。考慮效果與價格,BG追加超過5質量%並無意義。 Further, as will be described later, BG is effective by placing a certain amount or more of the etching liquid, and is saturated even if a large amount is placed. Only the amount of other necessary components can be ensured, and even if it is put in a large amount, it can exert the effect as an etching liquid. However, adding more BG will increase the cost. Considering the effect and price, it is meaningless to add more than 5% by mass to BG.
此外,BG根據共存的胺化合物而含量有所不同。例如,利用可良好地使用於作為唑類的NNDPA時,作為過氧化氫分解抑制劑的BG,對蝕刻液全量,含有0.4質量%~5.0質量%為佳。 Further, BG differs in content depending on the coexisting amine compound. For example, when NNDPA which is used as an azole is used satisfactorily, BG which is a hydrogen peroxide decomposition inhibitor is preferably contained in an amount of 0.4% by mass to 5.0% by mass based on the total amount of the etching liquid.
此外,以同樣地可良好地利用作為唑類的1A2P時,作為過氧化氫分解抑制劑的BG,對蝕刻液全量,含有0.9質量%~5.0質量%為佳。 In addition, when 1A2P which is an azole is used in the same manner, BG which is a hydrogen peroxide decomposition inhibitor is preferably contained in an amount of 0.9% by mass to 5.0% by mass based on the total amount of the etching liquid.
又,先前使用於作為過氧化氫分解抑制劑的苯基尿素,對蝕刻液全量,含有超過0.2質量%,則苯基會與過氧化氫反應,產生別於唑類與過氧化氫的反應物的析出物。但是,BG並不會發生如此的析出物。因此,由抑制析出物的點而言,亦係良好的過氧化氫分解抑制劑(雙氧水穩定劑)。 Further, when phenyl urea which has been used as a hydrogen peroxide decomposition inhibitor is contained in an amount of more than 0.2% by mass based on the total amount of the etching liquid, the phenyl group reacts with hydrogen peroxide to produce a reactant different from the azole and hydrogen peroxide. The precipitate. However, BG does not have such precipitates. Therefore, a point of suppressing precipitates is also a good hydrogen peroxide decomposition inhibitor (hydrogen peroxide stabilizer).
<唑類> <azoles>
關於本發明的多層膜用蝕刻液,含有抑制Cu的蝕刻速率,用於去除Mo的殘渣的唑類。唑類,可良好地利用***類、四唑類、咪唑類、噻唑類等。更具體而言,可舉如下。 The etching solution for a multilayer film of the present invention contains an azole for suppressing the etching rate of Cu and for removing the residue of Mo. As the azole, triazoles, tetrazoles, imidazoles, thiazoles and the like can be preferably used. More specifically, it can be mentioned as follows.
***類,可良好地利用1H-苯並***、5-甲基-1H-苯並***、3-胺基-1H-***等。 As the triazole, 1H-benzotriazole, 5-methyl-1H-benzotriazole, 3-amino-1H-triazole or the like can be preferably used.
四唑類,可良好地利用1H-四唑、5-甲基-1H-四唑、5-苯基-1H-四唑、5-胺基-1H-四唑等。此外,咪唑類,可良好地利用1H-咪唑,1H-苯並咪唑等。此外,噻唑類,可良好地利用1,3-噻唑、4-甲基噻唑等。 As the tetrazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole or the like can be preferably used. Further, as the imidazole, 1H-imidazole, 1H-benzimidazole or the like can be preferably used. Further, as the thiazole, 1,3-thiazole, 4-methylthiazole or the like can be preferably used.
此外,該等之中,四唑類,蝕刻速率抑制效果高,特別是以5-胺基-1H-四唑(CAS編號4418-61-5:以後亦稱為「5A1HT」。)為佳。 Further, among these, the tetrazolium has a high etching rate suppressing effect, and particularly preferably 5-amino-1H-tetrazole (CAS No. 4418-61-5: hereinafter also referred to as "5A1HT").
該等唑類,對蝕刻液全量,含有0.04質量%~0.16質量%為佳,以0.06質量%~0.14質量%更佳,以0.08質量%~0.12質量%最佳。 The azoles are preferably contained in an amount of from 0.04% by mass to 0.16% by mass based on the total amount of the etchant, more preferably from 0.06% by mass to 0.14% by mass, and most preferably from 0.08% by mass to 0.12% by mass.
<析出防止劑> <Precipitation inhibitor>
如已敘述,使過氧化氫為主體的蝕刻液含有有機酸,可調 整被蝕刻的配線的剖面的錐度角度。但是,有機酸係以過氧化氫氧化分解生成草酸。該草酸與被蝕刻而存在於蝕刻液中的銅離子生成草酸銅,成為析出物。鋁離子比銅容易形成與草酸的錯合物且溶解度較草酸銅高。 As described above, the etching liquid containing hydrogen peroxide as a main component contains an organic acid, and the taper angle of the cross section of the etched wiring can be adjusted. However, the organic acid is decomposed by hydrogen peroxide to form oxalic acid. The oxalic acid and the copper ions which are etched and are present in the etching liquid form copper oxalate and become precipitates. Aluminum ions are more likely to form complexes with oxalic acid than copper and have higher solubility than copper oxalate.
因此,在關於本發明的蝕刻液,預先使之含有鋁鹽,即使是藉由蝕刻而發生銅離子,亦不會變成析出物(草酸銅)。鋁鹽,可良好地利用硫酸鋁、硝酸鋁、氯化鋁等的無機鹽,或乳酸鋁、醋酸鋁、碳酸鋁等的有機鹽等。 Therefore, in the etching liquid of the present invention, an aluminum salt is contained in advance, and even if copper ions are generated by etching, they do not become precipitates (copper oxalate). As the aluminum salt, an inorganic salt such as aluminum sulfate, aluminum nitrate or aluminum chloride, or an organic salt such as aluminum lactate, aluminum acetate or aluminum carbonate can be preferably used.
析出防止劑,對蝕刻液全量,含有0.05質量%~0.7質量%為佳,以0.1質量%~0.5質量%更佳,以0.2質量%~0.4質量%最佳。 The precipitation preventing agent is preferably contained in an amount of 0.05% by mass to 0.7% by mass based on the total amount of the etching liquid, more preferably 0.1% by mass to 0.5% by mass, and most preferably 0.2% by mass to 0.4% by mass.
<銅離子> <copper ion>
通常的多層膜用蝕刻液,藉由追加稀釋用的蝕刻液,使Cu離子濃度在2,000ppm到4,000ppm的程度。因為雙氧水的分解速度會變快,而雙氧水濃度會降低。但是,關於本發明的蝕刻液,由於可抑制雙氧水的分解速度,故即使Cu離子濃度變得更高,亦無需追加用於稀釋Cu離子的蝕刻液。更具體而言,蝕刻液的Cu濃度到8,000ppm,無需追加用於稀釋的蝕刻液。 In the usual etching liquid for a multilayer film, the etching liquid for dilution is added to have a Cu ion concentration of about 2,000 ppm to 4,000 ppm. Because the decomposition rate of hydrogen peroxide will increase, and the concentration of hydrogen peroxide will decrease. However, since the etching liquid of the present invention can suppress the decomposition rate of hydrogen peroxide, even if the Cu ion concentration is higher, it is not necessary to add an etching liquid for diluting Cu ions. More specifically, the Cu concentration of the etching liquid is 8,000 ppm, and it is not necessary to add an etching liquid for dilution.
<其他> <Other>
本發明的多層膜用蝕刻液,在該等成分之外,亦可追加水、及在不阻礙蝕刻性能的範圍,通常使用的各種追加劑。在蝕刻,由於係以精密加工為目標,故在水中不存在異物為佳。以純水或超純水為佳。此外,上述所說明的各成分的含有比例的範圍,當然可分別適宜調整使蝕刻液總量成100質量%。 In addition to these components, the etching liquid for a multilayer film of the present invention may be added with water or various additional agents which are generally used without departing from the etching performance. In etching, since it is aimed at precision processing, it is preferable that no foreign matter exists in water. Pure water or ultrapure water is preferred. Further, it is needless to say that the range of the content ratio of each component described above can be appropriately adjusted so that the total amount of the etching liquid becomes 100% by mass.
<pH、溫度> <pH, temperature>
關於本發明的多層膜用蝕刻液,pH為2~6,以在pH3~4.5的範圍使用為佳。此外,蝕刻液,可在20℃至40℃之間使用。以25℃至35℃更佳,以30℃~35℃最佳。 The etching solution for a multilayer film of the present invention preferably has a pH of 2 to 6, and is preferably used in the range of pH 3 to 4.5. Further, the etching solution can be used between 20 ° C and 40 ° C. More preferably from 25 ° C to 35 ° C, and most preferably from 30 ° C to 35 ° C.
<儲存> <storage>
關於本發明的多層膜用蝕刻液,使用過氧化氫。過氧化氫會自我分解。因此,在蝕刻液,包含過氧化氫分解抑制劑。但是,儲存時,可將過氧化氫(或過氧化氫水)其他的液體分開儲存。此外,亦可僅將過氧化氫(或過氧化氫水)、水及銅離子以外的原料(稱為「蝕刻液原料」。)一起儲存。再者,在蝕刻液原料,可存在液體與粉狀物。即,關於本發明的多層膜用蝕刻液,亦可將蝕刻液原料、與水、過氧化氫(或過氧化氫水)混在一起將之完成。 Hydrogen peroxide is used as the etching solution for a multilayer film of the present invention. Hydrogen peroxide will decompose itself. Therefore, the etching solution contains a hydrogen peroxide decomposition inhibitor. However, when storing, other liquids of hydrogen peroxide (or hydrogen peroxide) can be stored separately. Further, only raw materials other than hydrogen peroxide (or hydrogen peroxide water), water, and copper ions (referred to as "etching liquid materials") may be stored together. Further, in the etching liquid raw material, a liquid and a powder may be present. That is, the etching liquid for a multilayer film of the present invention may be obtained by mixing an etching liquid raw material with water or hydrogen peroxide (or hydrogen peroxide water).
此外,亦可將蝕刻液原料與水混合,製作蝕刻液原料的溶液。該溶液,水的比例可為較後述實施例所示蝕刻液的水的比例少。將蝕刻液原料與水製作的蝕刻液原料的溶液稱為「蝕刻濃縮液」。蝕刻濃縮液,與蝕刻液相比,由於少了過氧化氫的部分所以體積小,故儲存及搬送時較方便。因此,本發明的多層膜用蝕刻液,可藉由混合蝕刻濃縮液、水及過氧化氫而完成。 Further, the etching liquid raw material may be mixed with water to prepare a solution of the etching liquid raw material. The ratio of the solution and the water may be smaller than the ratio of the water of the etching liquid shown in the later-described embodiment. A solution of an etching liquid raw material and an etching liquid raw material made of water is referred to as an "etching concentrated liquid". Since the concentrated liquid is etched, the volume of the hydrogen peroxide is smaller than that of the etching liquid, so that it is convenient to store and transport. Therefore, the etching solution for a multilayer film of the present invention can be completed by mixing an etching concentrate, water, and hydrogen peroxide.
在此,蝕刻濃縮液的水,只要具有可溶解蝕刻液原料的量即可。即,考慮過氧化氫係以水溶液的過氧化氫水提供,則本發明的多層膜用蝕刻液,可藉由將蝕刻濃縮液、水及過氧化氫水等三個混在一起完成。 Here, the water for etching the concentrate may be any amount as long as it can dissolve the raw material of the etching liquid. In other words, in consideration of the fact that hydrogen peroxide is supplied as hydrogen peroxide water in an aqueous solution, the etching solution for a multilayer film of the present invention can be obtained by mixing three etching solutions, water, and hydrogen peroxide water.
此外,水只要包含在蝕刻濃縮液或過氧化氫水 裡,則亦可藉由將蝕刻濃縮液與過氧化氫水的兩個混在一起完成。此外,在本說明書,蝕刻濃縮液的各成分比例,係以對完成蝕刻液時的全量的比例表示。因此,蝕刻濃縮液的各成分的合計,不到100質量%。 Further, water may be contained in the etching concentrate or hydrogen peroxide water by mixing the etching concentrate with two of hydrogen peroxide water. Further, in the present specification, the ratio of each component of the etching concentrate is expressed as a ratio of the total amount when the etching liquid is completed. Therefore, the total amount of each component of the etching concentrate is less than 100% by mass.
<蝕刻方法> <etching method>
關於本發明的多層膜用蝕刻液的對象,係鉬在下層,而銅為上層的銅/鉬多層膜。下層的鉬的厚度,較上層的銅的厚度薄。使下層的厚度為t0,使上層的厚度為t1,則t0/t1的範圍,係0.01至0.2的範圍的構成。t0/t1的範圍由該範圍偏離,而Mo層過厚,則容易發生Mo層的殘渣,相反地過薄,則無法發揮作為Cu層的底層的作用。 The object of the etching liquid for a multilayer film of the present invention is a copper/molybdenum multilayer film in which molybdenum is in the lower layer and copper is in the upper layer. The thickness of the lower layer of molybdenum is thinner than the thickness of the upper layer of copper. When the thickness of the lower layer is t0 and the thickness of the upper layer is t1, the range of t0/t1 is a range of 0.01 to 0.2. The range of t0/t1 is deviated from this range, and when the Mo layer is too thick, the residue of the Mo layer tends to occur, and if it is too thin, it does not function as a bottom layer of the Cu layer.
本發明的多層膜用蝕刻液,在儲存時,藉由將過氧化氫與蝕刻液原料及水分開儲存,可長期儲存。因此,實際使用時,將該等調配完成蝕刻液。調配的方法,只要過氧化氫的濃度最終成為既定的濃度,則無特別限定。 The etching solution for a multilayer film of the present invention can be stored for a long period of time by storing hydrogen peroxide separately from the etching liquid raw material and water during storage. Therefore, in actual use, the etchant is completed. The method of blending is not particularly limited as long as the concentration of hydrogen peroxide eventually becomes a predetermined concentration.
表示一例,則先調製對一定量的水混蝕刻液原料的蝕刻濃縮液。過氧化氫,通常以較關於本發明的多層膜用蝕刻液的過氧化氫濃度高的濃度的過氧化氫水供給。在此,將過氧化氫水與蝕刻濃縮液按既定量調配。亦可將該步驟稱為調配多層膜用蝕刻液的步驟。 As an example, an etching concentrate for a predetermined amount of water-mixing etching liquid raw material is prepared. Hydrogen peroxide is usually supplied in a hydrogen peroxide water having a higher concentration of hydrogen peroxide than the etching liquid for a multilayer film of the present invention. Here, the hydrogen peroxide water and the etching concentrate are dosed together. This step can also be referred to as a step of preparing an etching solution for a multilayer film.
進行蝕刻時,如上所述,以pH2~6,20℃至40℃的條件使用蝕刻液。因此,蝕刻的被處理基板,亦預熱為該溫度為佳。使被處理基板與蝕刻液接觸的方法,並無特別限定。可如淋浴式將蝕刻液由上方對被處理基板散佈,亦可將被處理 基板浸漬在蝕刻液池的方法。亦可將此稱為使被處理基板接觸多層膜用蝕刻液的步驟。 When etching is performed, as described above, the etching liquid is used under the conditions of pH 2 to 6, 20 ° C to 40 ° C. Therefore, the etched substrate to be processed is also preheated to have a temperature of this. The method of bringing the substrate to be processed into contact with the etching liquid is not particularly limited. The etchant may be sprayed from above to the substrate to be processed, or the substrate to be processed may be immersed in the etchant bath. This may also be referred to as a step of bringing the substrate to be processed into contact with the etching liquid for a multilayer film.
再者,所謂被處理基板,係指在玻璃等的基材上層積鉬層及銅層,在該層積膜形成有用於形成圖案的抗蝕劑圖案的狀態的基板。 In addition, the substrate to be processed refers to a substrate in which a molybdenum layer and a copper layer are laminated on a substrate such as glass, and a resist pattern for forming a pattern is formed on the laminated film.
接著,在圖2、圖3表示簡單的模擬結果,顯示關於本發明的蝕刻液的效果。模擬的條件係如下所示。總處理片數(在玻璃基板上蒸鍍銅)為3,000片,各玻璃基板上的銅的膜厚為300nm。蝕刻槽的容量為2,600L。1片基板的蝕刻液帶出量為1L。因此,蝕刻液的補充量亦對每1片基板追加1L。 Next, a simple simulation result is shown in Figs. 2 and 3, and the effect of the etching liquid of the present invention is shown. The conditions for the simulation are as follows. The total number of processed sheets (copper deposited on a glass substrate) was 3,000 sheets, and the thickness of copper on each glass substrate was 300 nm. The etching tank has a capacity of 2,600 liters. The etching liquid of one substrate was taken out in an amount of 1 L. Therefore, the amount of the etching liquid to be replenished is also 1 L per one substrate.
再者,圖2、圖3的各圖表的橫軸係表示基板的處理片數(片),設有0至3,000的刻度。3,000片的部分以縱箭頭表示。此外,各縱軸係由零開始,在圖表中表示最大刻度。 In addition, the horizontal axis of each graph of FIG. 2 and FIG. 3 shows the number of sheets (pieces) of the board|substrate, and the scale of 0-3,000 is provided. The 3,000-piece portion is indicated by a vertical arrow. In addition, each vertical axis starts from zero and represents the maximum scale in the graph.
蝕刻液的雙氧水濃度維持在5.3質量%至5.25質量%之間。此外,為提高雙氧水濃度所追加的蝕刻液的雙氧水濃度為10質量%。 The hydrogen peroxide concentration of the etching solution is maintained between 5.3 mass% and 5.25 mass%. Further, the hydrogen peroxide concentration of the etching liquid added to increase the hydrogen peroxide concentration was 10% by mass.
再者,基板的處理時間,每1片定為140秒。此外,蝕刻液中的Cu濃度的初期值係由2,000ppm開始。再者,雙氧水的分解速度係設定為銅離子濃度在8,000ppm時為0.2質量%/hr。 Furthermore, the processing time of the substrate was set to 140 seconds per sheet. Further, the initial value of the Cu concentration in the etching liquid starts from 2,000 ppm. Further, the decomposition rate of the hydrogen peroxide was set to 0.2% by mass/hr when the copper ion concentration was 8,000 ppm.
在圖2的(a)至(f),表示使用先前(專利文獻1的情形)的蝕刻液時的變化等。Cu濃度維持在2,900ppm至3,500ppm之間。在全圖表中橫軸係處理片數。圖2(a)係表示蝕刻槽內的蝕刻液的Cu濃度的變化。縱軸係銅離子濃度(ppm)。最初由 2,000ppm開始的銅離子濃度,大約在第400片處理物呈3,500ppm。為稀釋Cu離子濃度,追加蝕刻液。 (a) to (f) of FIG. 2 show changes in the etching liquid used in the prior (in the case of Patent Document 1). The Cu concentration is maintained between 2,900 ppm and 3,500 ppm. The number of slices is processed in the horizontal axis in the full chart. Fig. 2(a) shows a change in Cu concentration of the etching liquid in the etching bath. The vertical axis is the copper ion concentration (ppm). The copper ion concentration initially starting at 2,000 ppm was approximately 3,500 ppm at the 400th treatment. To dilute the Cu ion concentration, an etching solution is added.
圖2(c),縱軸係表示對蝕刻槽追加的蝕刻液的總量(L)。處理片數在第400片,追加500L的蝕刻液。再次參照圖2(a),藉由追加該蝕刻液,銅離子濃度下降至2,900ppm(參照箭頭A)。之後,反覆此狀態。 2(c), the vertical axis indicates the total amount (L) of the etching liquid added to the etching bath. The number of processed sheets was 400, and 500 L of etching liquid was added. Referring again to Fig. 2(a), by adding this etching liquid, the copper ion concentration is lowered to 2,900 ppm (see arrow A). After that, repeat this state.
圖2(b),係縱軸表示蝕刻液中的雙氧水濃度(記載為「wt%」。與質量%同義。)的變化。最初的雙氧水的比例為5.3質量%,雙氧水會被圖2(a)所示銅離子分解。在大約100片的處理,雙氧水濃度呈5.25質量%。因此,為提升雙氧水濃度,加入包含10質量%雙氧水的蝕刻液(別的組成亦相同。)。 2(b), the vertical axis represents the change in the concentration of hydrogen peroxide in the etching solution (described as "wt%", which is synonymous with mass%). The ratio of the initial hydrogen peroxide is 5.3% by mass, and the hydrogen peroxide is decomposed by the copper ions shown in Fig. 2(a). In a treatment of about 100 sheets, the hydrogen peroxide concentration was 5.25 mass%. Therefore, in order to increase the hydrogen peroxide concentration, an etching solution containing 10% by mass of hydrogen peroxide is added (the other compositions are also the same).
圖2(d),係表示用於調整雙氧水濃度所追加的10質量%雙氧水的蝕刻液的總添加量的圖表。縱軸係總添加量(L)。在100片的處理,追加50L。再次參照圖2(b),藉由追加該含有10質量%雙氧水的蝕刻液,蝕刻槽中的雙氧水濃度再度回到5.3質量%(參照箭頭B)。 Fig. 2 (d) is a graph showing the total amount of addition of an etching liquid for adjusting 10% by mass of hydrogen peroxide added to the hydrogen peroxide concentration. The vertical axis is the total addition amount (L). In the processing of 100 pieces, 50L is added. Referring again to Fig. 2(b), by adding the etching liquid containing 10% by mass of hydrogen peroxide, the hydrogen peroxide concentration in the etching bath is again returned to 5.3% by mass (see arrow B).
圖2(e),係表示被基板帶走的蝕刻液的補充的變化。縱軸係其追加量(L)。在此,表示每1片追加1L的蝕刻液的情形。 Fig. 2(e) shows a modification of the etchant carried away by the substrate. The vertical axis is the additional amount (L). Here, the case where 1 L of etching liquid is added per one piece is shown.
將根據如上變化的蝕刻液的追加的總量示於圖2(f)。縱軸係總量(L),縱軸刻度刻到10,000L。根據該模擬,在處理3,000片之間所追加的蝕刻液的總量需要10,000L以上。 The additional total amount of the etching liquid according to the above change is shown in Fig. 2(f). The vertical axis is the total amount (L), and the vertical axis is engraved to 10,000L. According to this simulation, the total amount of the etching liquid added between the processing of 3,000 sheets needs to be 10,000 L or more.
圖3係關於本發明的蝕刻液之情形。(a)至(f)係對應圖2的圖。參照圖3(a)。在本發明,直到蝕刻液中的銅離子 濃度達8,000ppm,無需稀釋。因此,蝕刻液中的銅離子濃度會上升到3,000片的處理片數。 Figure 3 is a view of the etching liquid of the present invention. (a) to (f) correspond to the diagram of Fig. 2 . Refer to Figure 3(a). In the present invention, it is not necessary to dilute until the copper ion concentration in the etching solution reaches 8,000 ppm. Therefore, the concentration of copper ions in the etching solution rises to the number of processed sheets of 3,000 sheets.
再者,蝕刻液中的銅離子濃度上升,則由於包含被基板帶走的蝕刻液中的銅亦會增加,故包含在蝕刻槽中的蝕刻液中的銅離子濃度,隨著處理片數的增加,上升傾向較和緩。 Further, when the concentration of copper ions in the etching solution increases, the amount of copper in the etching liquid contained in the etching bath increases, so the concentration of copper ions in the etching liquid contained in the etching bath increases with the number of sheets processed. Increase, the tendency to rise is more moderate.
圖3(c),係表示用於稀釋銅離子濃度所追加的蝕刻液量。在關於本發明的蝕刻液,由於直到銅離子濃度達8,000ppm,無需稀釋,故以此觀點所追加的蝕刻液為零。此外,此時的雙氧水分解速度在8,000ppm時,速率為0.16質量%/hr。 Fig. 3(c) shows the amount of etching liquid added for diluting the copper ion concentration. In the etching liquid of the present invention, since the copper ion concentration is up to 8,000 ppm, no dilution is required, and thus the etching liquid added from this viewpoint is zero. Further, at a time when the decomposition rate of hydrogen peroxide at this time was 8,000 ppm, the rate was 0.16 mass%/hr.
圖3(b)係雙氧水濃度的變化。隨著銅離子濃度的增加,雙氧水的分解速度會變快。因此,隨著處理片數的增加,追加的間隔會變短。因此,含有10質量%雙氧水的蝕刻液的總添加量(參照圖3(d))變得較圖2的情形大。在圖2(d),雖然最大刻度為1,200L,在圖3(d)為2,000L。圖3(e)所示基板所帶出的部分的補充係每1片1L,與圖2的情形相同。 Figure 3 (b) shows the change in hydrogen peroxide concentration. As the concentration of copper ions increases, the decomposition rate of hydrogen peroxide becomes faster. Therefore, as the number of processed sheets increases, the additional interval becomes shorter. Therefore, the total addition amount of the etching liquid containing 10% by mass of hydrogen peroxide (refer to FIG. 3(d)) becomes larger than that in the case of FIG. In Fig. 2(d), although the maximum scale is 1,200L, it is 2,000L in Fig. 3(d). The portion of the substrate shown in Fig. 3(e) is supplemented by 1 L per piece, which is the same as in the case of Fig. 2.
圖3(f)係處理3,000片時的蝕刻液的總追加量(L)。縱軸的刻度最大為4,000L。由此以關於本發明的蝕刻液,則為處理3,000片,使用大約5,000L的蝕刻液。此可估算為圖2(f)所示10,000L的一半的程度。 Fig. 3(f) shows the total amount (L) of the etching liquid when 3,000 sheets are processed. The vertical axis has a scale of up to 4,000L. Thus, in the case of the etching liquid of the present invention, 3,000 sheets were processed, and about 5,000 L of an etching liquid was used. This can be estimated to be half the 10,000 L shown in Fig. 2(f).
如此地,抑制雙氧水分解速度,即使銅離子濃度變高亦無需稀釋蝕刻液,則可大幅降低蝕刻液的使用量。 As described above, the rate of decomposition of hydrogen peroxide is suppressed, and even if the concentration of copper ions is high, it is not necessary to dilute the etching liquid, and the amount of the etching liquid used can be greatly reduced.
實施例 Example
<各種評估方法的說明> <Explanation of various evaluation methods>
對關於本發明的多層膜用蝕刻液,以銅及鉬的蝕刻速率 (nm/min)、蝕刻的配線的剖面的錐度角(°)、鉬層的底切、殘留在基板上的鉬層(亦稱為「Mo殘渣」。)、過蝕刻耐性、有無析出物、過氧化氫分解速度(質量%/18hr)的項目進行評估。 The etching solution for a multilayer film of the present invention has an etching rate (nm/min) of copper and molybdenum, a taper angle (°) of a cross section of the etched wiring, an undercut of the molybdenum layer, and a molybdenum layer remaining on the substrate ( Also known as "Mo residue".), over-etching resistance, presence or absence of precipitates, and decomposition rate of hydrogen peroxide (% by mass / 18 hr) were evaluated.
蝕刻速率,係如下測定。首先,在形成100nm熱氧化膜的矽晶圓上,以濺鍍法,分別以銅300nm、鉬150nm的厚度形成單層膜。將該銅膜及鉬膜,與30℃(根據比較例亦有35℃的情形)的蝕刻液接觸20秒至60秒。 The etching rate was measured as follows. First, a single-layer film was formed on a tantalum wafer on which a 100 nm thermal oxide film was formed by sputtering to a thickness of 300 nm of copper and 150 nm of molybdenum. The copper film and the molybdenum film were brought into contact with an etching solution at 30 ° C (in the case of 35 ° C according to a comparative example) for 20 seconds to 60 seconds.
將蝕刻前後的膜的電阻值,使用定電流施加模式的4端子4探針法電阻率計(Mitsubishi Chemical Analytech製:MCP-T610型)測定。由該電阻值的變化算出膜厚變化,計算蝕刻速率。 The resistance value of the film before and after the etching was measured using a 4-terminal 4-probe method resistivity meter (manufactured by Mitsubishi Chemical Analytech: MCP-T610 type) in a constant current application mode. The change in film thickness was calculated from the change in the resistance value, and the etching rate was calculated.
再者,銅的蝕刻速率只要在250nm/min~350nm/min,則判定為圈(○)。此外,鉬的蝕刻速率只要在60nm/min~120nm/min,則判定為圈(○)。除此以外,則係在規定範圍外而判定為叉(×)。 Further, the etching rate of copper is determined to be a circle (○) as long as it is in the range of 250 nm/min to 350 nm/min. Further, the etching rate of molybdenum is determined to be a circle (○) as long as it is from 60 nm/min to 120 nm/min. Otherwise, it is judged to be a fork (×) outside the predetermined range.
由於銅與鉬的膜厚比大約為10:1,故鉬的蝕刻速率似乎看起來過快,但鉬層係構成作為銅膜的下層,故若不使蝕刻速率為上述程度的比例,則無法使外觀上以相同速度蝕刻。再者,「圈」係指在規格範圍內、成功或合格,「叉」係指規格範圍外、失敗或不合格的意思。以下的評估亦相同。 Since the film thickness ratio of copper to molybdenum is about 10:1, the etching rate of molybdenum seems to be too fast, but the molybdenum layer is formed as a lower layer of the copper film, so if the etching rate is not made to the above ratio, Etching the appearance at the same speed. In addition, "circle" means successful or qualified within the scope of the specification, and "fork" means outside the specification range, failure or failure. The following assessments are also the same.
錐度角,係如下測定。首先,在玻璃基板上,以濺鍍法,將鉬成膜20nm的厚度,在其上,繼續將銅成膜300nm的厚度,製作Cu/Mo的多層膜樣品。形成在該銅膜上形成配線形狀圖案的阻劑,作為錐度角評估用的基材。即,基材,係由 基板、鉬膜及其上的銅膜、及銅膜上的圖形化成配線形狀的阻劑層所組成。將該基材浸漬在蝕刻液,可剛好蝕刻的時間之間,進行蝕刻。將蝕刻後的樣品清洗,使之乾燥之後,將配線部分切斷,觀察切斷面。 The taper angle is determined as follows. First, on the glass substrate, molybdenum was deposited by a sputtering method to a thickness of 20 nm, and copper was continuously formed into a film having a thickness of 300 nm to prepare a multilayer film sample of Cu/Mo. A resist for forming a wiring pattern on the copper film was formed as a substrate for taper angle evaluation. That is, the substrate is composed of a substrate, a molybdenum film and a copper film thereon, and a resist layer patterned on the copper film to form a wiring. The substrate is immersed in an etching solution, and etching can be performed just between the etching time. After the etched sample was washed and dried, the wiring portion was cut and the cut surface was observed.
切斷面的觀測,係使用SEM(日立製:SU8020型),加速電壓1kV,30,000~50,000倍的條件進行。再者,剛好蝕刻,係從蝕刻開始至膜可使光穿透之前的時間。膜可使光穿透的時點,係以目視確認。 The observation of the cut surface was carried out under the conditions of an SEM (Hitachi: SU8020 type), an acceleration voltage of 1 kV, and 30,000 to 50,000 times. Again, just etching is the time from the start of etching until the film can penetrate the light. The time at which the film can penetrate light is visually confirmed.
將切斷面形狀示於圖1。如圖1(a)所示,使基板1與蝕刻的傾斜面6所形成的角度5作為錐度角(°)。錐度角5,只要在30~60°,則判定為圈(○)。在該角度的範圍外,則判定為叉(×)。再者,在圖1(a),Mo層係以符號3,Cu層係以符號2,阻劑係以符號4表示。 The shape of the cut surface is shown in Fig. 1. As shown in Fig. 1(a), the angle 5 formed by the substrate 1 and the etched inclined surface 6 is taken as a taper angle (°). The taper angle 5 is determined to be a circle (○) as long as it is 30 to 60°. Outside the range of the angle, it is judged to be a fork (x). Further, in Fig. 1(a), the Mo layer is denoted by reference numeral 3, the Cu layer is denoted by reference numeral 2, and the resister is denoted by reference numeral 4.
鉬層的底切,係如圖1(b)的符號10所示,鉬層3與基板1之間較快被蝕刻的狀態(逆錐度)。評估,可與錐度角5的評估時同時進行。由SEM的30,000倍至50,000倍的觀測,沒有發現鉬層的底切,則判定為圈(○),可發現則判定為叉(×)。 The undercut of the molybdenum layer is a state in which the molybdenum layer 3 and the substrate 1 are etched faster (reverse taper) as indicated by reference numeral 10 in Fig. 1(b). The evaluation can be performed simultaneously with the evaluation of the taper angle 5. From the observation of 30,000 times to 50,000 times of the SEM, if the undercut of the molybdenum layer was not found, it was judged to be a circle (○), and it was found to be a fork (×).
Mo殘渣,係以光學顯微鏡與SEM的觀察中,確認到殘渣則判定為叉(×),沒有確認到則判定為圈(○)。再者,光學顯微鏡係以100倍左右的倍率,以明視野觀察及暗視野觀察,觀察之。此外,SEM係以30,000倍至50,000倍觀察。 In the observation of the optical microscope and the SEM, the Mo residue was judged to be a fork (×), and if it was not confirmed, it was determined to be a circle (○). Further, the optical microscope was observed at a magnification of about 100 times in a bright field observation and a dark field observation. Further, the SEM was observed at 30,000 times to 50,000 times.
所謂過蝕刻耐性(亦稱為「O.E.耐性」。),係觀察以剛好蝕刻的時間的2倍的時間蝕刻時的錐度角、鉬層的底切、Mo殘渣,均為「圈」評估則判定為圈(○)。只要有任何 一個為「叉」評估則判定為叉(×)。 The over-etching resistance (also referred to as "OE resistance") is determined by observing the taper angle at the time of etching twice, the undercut of the molybdenum layer, and the Mo residue. It is a circle (○). As long as any one is evaluated as a "fork", it is judged to be a fork (×).
有無析出物,係在調配蝕刻液之後,在瓶中以室溫放置既定時間(3小時),以目視判定是否在瓶內發生淺藍色的析出物。沒有析出物被目視觀測,則判定為圈(○),以目視確認到時判定為叉(×)。 The presence or absence of precipitates was set in the bottle at room temperature for a predetermined time (3 hours) after the preparation of the etching solution, and it was visually judged whether or not a light blue precipitate occurred in the bottle. When no precipitate was visually observed, it was judged to be a circle (○), and it was judged to be a fork (×) when visually confirmed.
過氧化氫分解速度,係對調配的蝕刻液,分別加入Cu離子及Mo離子呈8,000ppm、800ppm,將以35℃經過既定時間之後(18hr(小時))的過氧化氫濃度,使用過錳酸鉀作為滴定試劑,以自動滴定裝置(Mitsubishi Chemical Analytech製GT-200)測定。然後,由過氧化氫濃度的變化量,算出分解速度(質量%/hr)。過氧化氫的分解速度,只要在0.16質量%/hr以下,則可認為在量產規模沒有問題。此外,如以模擬所作粗略估計,亦可充分降低蝕刻液的使用量。 The decomposition rate of hydrogen peroxide is 8,000 ppm and 800 ppm of Cu ions and Mo ions, respectively, and the peroxymanganic acid concentration is used after 35 ° C for a predetermined period of time (18 hr (hours)). Potassium was used as a titration reagent and was measured by an automatic titration apparatus (GT-200, manufactured by Mitsubishi Chemical Analytech). Then, the decomposition rate (% by mass/hr) was calculated from the amount of change in the concentration of hydrogen peroxide. When the decomposition rate of hydrogen peroxide is 0.16 mass%/hr or less, it is considered that there is no problem in the mass production scale. In addition, if a rough estimate is made by simulation, the amount of etching liquid used can be sufficiently reduced.
(實施例1) (Example 1)
將由1.90質量%甘醇酸、3.40質量%丙二酸、0.80質量%乳酸 Will be composed of 1.90 mass% glycolic acid, 3.40 mass% malonic acid, 0.80 mass% lactic acid
作為酸性有機酸;以2.20質量%1-胺基-2-丙醇 As an acidic organic acid; 2.20% by mass of 1-amino-2-propanol
作為胺化合物;以90質量%BG As an amine compound; at 90% by mass BG
作為雙氧水穩定劑;以0.08質量%5-胺基-1H-四唑 As a hydrogen peroxide stabilizer; 0.08 mass% 5-amino-1H-tetrazole
作為唑類, 以0.26質量%乳酸鋁 As an azole, 0.26 mass% aluminum lactate
作為析出防止劑;所組成的蝕刻液原料,與75.32質量%的水調配,調製蝕刻濃縮液。再者,在蝕刻濃縮液的各成分比例,係以與後述的過氧化氫水混合完成蝕刻液時的總量的比例表示。關於以下的實施例及比較例亦相同。 As a precipitation preventing agent; the etchant raw material composed of the composition was prepared by mixing with 75.32 mass% of water to prepare an etching concentrate. In addition, the ratio of each component in the etching concentrate is represented by the ratio of the total amount at the time of completion of the etching liquid mixed with the hydrogen peroxide water mentioned later. The same applies to the following examples and comparative examples.
將15.14質量%的35%過氧化氫水(對蝕刻液全量,過氧化氫為5.3質量%及水分為9.84質量%)與蝕刻濃縮液混合,調製過氧化氫濃度為5.3質量%的蝕刻液。再者,水對全量為85.16質量%。再者,加上乳酸銅將銅離子濃度調整為8,000ppm。此外,加上鉬粉末將鉬濃度調整為800ppm。此外,液溫使用35℃。將佔蝕刻液全體的各成分濃度,與各評估事項的結果示於表1。 15.14% by mass of 35% hydrogen peroxide water (the total amount of the etching solution, 5.3% by mass of hydrogen peroxide and 9.84% by mass of water) was mixed with the etching concentrate to prepare an etching liquid having a hydrogen peroxide concentration of 5.3% by mass. Furthermore, the total amount of water was 85.16 mass%. Further, copper lactate was added to adjust the copper ion concentration to 8,000 ppm. Further, molybdenum powder was added to adjust the molybdenum concentration to 800 ppm. In addition, the liquid temperature was 35 °C. The concentration of each component in the entire etching liquid and the results of each evaluation item are shown in Table 1.
(實施例2) (Example 2)
將以1.90質量%甘醇酸、3.40質量%丙二酸、0.80質量%乳酸 Will be 1.90% by mass of glycolic acid, 3.40% by mass of malonic acid, 0.80% by mass of lactic acid
作為酸性有機酸;以2.20質量%1-胺基-2-丙醇 As an acidic organic acid; 2.20% by mass of 1-amino-2-propanol
作為胺化合物;以2.00質量%BG As an amine compound; at 2.00% by mass BG
作為雙氧水穩定劑;以0.08質量%5-胺基-1H-四唑 As a hydrogen peroxide stabilizer; 0.08 mass% 5-amino-1H-tetrazole
作為唑類,以0.26質量%乳酸鋁 As an azole, 0.26 mass% aluminum lactate
作為析出防止劑;所組成的蝕刻液原料,與74.22質量%的水調配,調製蝕刻濃縮液。 As a precipitation preventing agent; the etchant raw material composed of the composition was mixed with 74.22% by mass of water to prepare an etching concentrate.
將15.14質量%的35%過氧化氫水(對蝕刻液全量,過氧化氫為5.3質量%及水分為9.84質量%)與蝕刻濃縮液混合,調製過氧化氫濃度為5.3質量%的蝕刻液。再者,水對全量為84.06質量%。再者,加上乳酸銅將銅離子濃度調整為8,000ppm。此外,加上鉬粉末將鉬濃度調整為800ppm。此外,液溫使用35℃。將佔蝕刻液全體的各成分濃度,與各評估事項的結果示於表1。 15.14% by mass of 35% hydrogen peroxide water (the total amount of the etching solution, 5.3% by mass of hydrogen peroxide and 9.84% by mass of water) was mixed with the etching concentrate to prepare an etching liquid having a hydrogen peroxide concentration of 5.3% by mass. Furthermore, the total amount of water is 84.06 mass%. Further, copper lactate was added to adjust the copper ion concentration to 8,000 ppm. Further, molybdenum powder was added to adjust the molybdenum concentration to 800 ppm. In addition, the liquid temperature was 35 °C. The concentration of each component in the entire etching liquid and the results of each evaluation item are shown in Table 1.
(實施例3) (Example 3)
將由1.90質量%甘醇酸、3.40質量%丙二酸、0.80質量%乳酸 Will be composed of 1.90 mass% glycolic acid, 3.40 mass% malonic acid, 0.80 mass% lactic acid
作為酸性有機酸;以2.20質量%NNDPA As an acidic organic acid; at 2.20 mass% NNDPA
作為胺化合物;以0.40質量%BG As an amine compound; at 0.40% by mass BG
作為雙氧水穩定劑;以0.08質量%5-胺基-1H-四唑 As a hydrogen peroxide stabilizer; 0.08 mass% 5-amino-1H-tetrazole
作為唑類,以0.26質量%乳酸鋁 As an azole, 0.26 mass% aluminum lactate
作為析出防止劑;所組成的蝕刻液原料,與75.82質量%的水調配,調製蝕刻濃縮液。 As a precipitation preventive agent, the composition of the etching liquid was prepared by mixing with 75.82% by mass of water to prepare an etching concentrate.
將15.14質量%的35%過氧化氫水(對蝕刻液全 量,過氧化氫為5.3質量%及水分為9.84質量%)與蝕刻濃縮液混合,調製過氧化氫濃度為5.3質量%的蝕刻液。再者,水對全量為85.66質量%。再者,加上乳酸銅將銅離子濃度調整為8,000ppm。此外,加上鉬粉末將鉬濃度調整為800ppm。此外,液溫使用35℃。將佔蝕刻液全體的各成分濃度,與各評估事項的結果示於表1。 15.14% by mass of 35% hydrogen peroxide water (the total amount of the etching solution, 5.3% by mass of hydrogen peroxide and 9.84% by mass of water) was mixed with the etching concentrate to prepare an etching liquid having a hydrogen peroxide concentration of 5.3% by mass. Furthermore, the total amount of water was 85.66 mass%. Further, copper lactate was added to adjust the copper ion concentration to 8,000 ppm. Further, molybdenum powder was added to adjust the molybdenum concentration to 800 ppm. In addition, the liquid temperature was 35 °C. The concentration of each component in the entire etching liquid and the results of each evaluation item are shown in Table 1.
(實施例4) (Example 4)
將由1.90質量%甘醇酸、3.40質量%丙二酸、0.80質量%乳酸 Will be composed of 1.90 mass% glycolic acid, 3.40 mass% malonic acid, 0.80 mass% lactic acid
作為酸性有機酸;以2.20質量%NNDPA As an acidic organic acid; at 2.20 mass% NNDPA
作為胺化合物;以0.90質量%BG As an amine compound; at 0.90% by mass BG
作為雙氧水穩定劑;以0.08質量%5-胺基-1H-四唑 As a hydrogen peroxide stabilizer; 0.08 mass% 5-amino-1H-tetrazole
作為唑類,以0.26質量%乳酸鋁 As an azole, 0.26 mass% aluminum lactate
作為析出防止劑;所組成的蝕刻液原料,與75.32質量%的水調配,調製蝕刻濃縮液。 As a precipitation preventing agent; the etchant raw material composed of the composition was prepared by mixing with 75.32 mass% of water to prepare an etching concentrate.
將15.14質量%的35%過氧化氫水(對蝕刻液全量,過氧化氫為5.3質量%及水分為9.84質量%)與蝕刻濃縮液混合,調製過氧化氫濃度為5.3質量%的蝕刻液。再者,水對全量為85.16質量%。再者,加上乳酸銅將銅離子濃度調整為 8,000ppm。此外,加上鉬粉末將鉬濃度調整為800ppm。此外,液溫使用35℃。將佔蝕刻液全體的各成分濃度,與各評估事項的結果示於表1。 15.14% by mass of 35% hydrogen peroxide water (the total amount of the etching solution, 5.3% by mass of hydrogen peroxide and 9.84% by mass of water) was mixed with the etching concentrate to prepare an etching liquid having a hydrogen peroxide concentration of 5.3% by mass. Furthermore, the total amount of water was 85.16 mass%. Further, copper lactate was added to adjust the copper ion concentration to 8,000 ppm. Further, molybdenum powder was added to adjust the molybdenum concentration to 800 ppm. In addition, the liquid temperature was 35 °C. The concentration of each component in the entire etching liquid and the results of each evaluation item are shown in Table 1.
(實施例5) (Example 5)
將由1.90質量%甘醇酸、3.40質量%丙二酸、0.80質量%乳酸 Will be composed of 1.90 mass% glycolic acid, 3.40 mass% malonic acid, 0.80 mass% lactic acid
作為酸性有機酸;以2.20質量%NNDPA As an acidic organic acid; at 2.20 mass% NNDPA
作為胺化合物;以2.00質量%BG As an amine compound; at 2.00% by mass BG
作為雙氧水穩定劑;以0.08質量%5-胺基-1H-四唑 As a hydrogen peroxide stabilizer; 0.08 mass% 5-amino-1H-tetrazole
作為唑類,以0.26質量%乳酸鋁 As an azole, 0.26 mass% aluminum lactate
作為析出防止劑;所組成的蝕刻液原料,與74.22質量%的水調配,調製蝕刻濃縮液。 As a precipitation preventing agent; the etchant raw material composed of the composition was mixed with 74.22% by mass of water to prepare an etching concentrate.
將15.14質量%的35%過氧化氫水(對蝕刻液全量,過氧化氫為5.3質量%及水分為9.84質量%)與蝕刻濃縮液混合,調製過氧化氫濃度為5.3質量%的蝕刻液。再者,水對全量為84.06質量%。再者,加上乳酸銅將銅離子濃度調整為8,000ppm。此外,加上鉬粉末將鉬濃度調整為800ppm。此外,液溫使用35℃。將佔蝕刻液全體的各成分濃度,與各評估事項的結果示於表1。 15.14% by mass of 35% hydrogen peroxide water (the total amount of the etching solution, 5.3% by mass of hydrogen peroxide and 9.84% by mass of water) was mixed with the etching concentrate to prepare an etching liquid having a hydrogen peroxide concentration of 5.3% by mass. Furthermore, the total amount of water is 84.06 mass%. Further, copper lactate was added to adjust the copper ion concentration to 8,000 ppm. Further, molybdenum powder was added to adjust the molybdenum concentration to 800 ppm. In addition, the liquid temperature was 35 °C. The concentration of each component in the entire etching liquid and the results of each evaluation item are shown in Table 1.
(比較例1) (Comparative Example 1)
將由1.90質量%甘醇酸、3.40質量%丙二酸、0.80質量%乳酸 Will be composed of 1.90 mass% glycolic acid, 3.40 mass% malonic acid, 0.80 mass% lactic acid
作為酸性有機酸;以2.20質量%1-胺基-2-丙醇 As an acidic organic acid; 2.20% by mass of 1-amino-2-propanol
作為胺化合物;以0.30質量%BG As an amine compound; at 0.30 mass% BG
作為雙氧水穩定劑;以0.08質量%5-胺基-1H-四唑 As a hydrogen peroxide stabilizer; 0.08 mass% 5-amino-1H-tetrazole
作為唑類,以0.26質量%乳酸鋁 As an azole, 0.26 mass% aluminum lactate
作為析出防止劑;所組成的蝕刻液原料,與75.92質量%的水調配,調製蝕刻濃縮液 As a precipitation preventing agent; the etchant raw material composed is formulated with 75.92% by mass of water to prepare an etching concentrate
將15.14質量%的35%過氧化氫水(對蝕刻液全量,過氧化氫為5.3質量%及水分為9.84質量%)與蝕刻濃縮液混合,調製過氧化氫濃度為5.3質量%的蝕刻液。再者,水對全量為85.76質量%。再者,加上乳酸銅將銅離子濃度調整為8,000ppm。此外,加上鉬粉末將鉬濃度調整為800ppm。此外,液溫使用35℃。將佔蝕刻液全體的各成分濃度,與各評估事項的結果示於表2。 15.14% by mass of 35% hydrogen peroxide water (the total amount of the etching solution, 5.3% by mass of hydrogen peroxide and 9.84% by mass of water) was mixed with the etching concentrate to prepare an etching liquid having a hydrogen peroxide concentration of 5.3% by mass. Furthermore, the total amount of water was 85.76 mass%. Further, copper lactate was added to adjust the copper ion concentration to 8,000 ppm. Further, molybdenum powder was added to adjust the molybdenum concentration to 800 ppm. In addition, the liquid temperature was 35 °C. The concentration of each component in the entire etching liquid and the results of each evaluation item are shown in Table 2.
(比較例2) (Comparative Example 2)
將由1.90質量%甘醇酸、3.40質量%丙二酸、 0.80質量%乳酸 Will be 1.90% by mass of glycolic acid, 3.40% by mass of malonic acid, 0.80% by mass of lactic acid
作為酸性有機酸;以2.20質量%1-胺基-2-丙醇 As an acidic organic acid; 2.20% by mass of 1-amino-2-propanol
作為胺化合物;以0.40質量%BG As an amine compound; at 0.40% by mass BG
作為雙氧水穩定劑;以0.08質量%5-胺基-1H-四唑 As a hydrogen peroxide stabilizer; 0.08 mass% 5-amino-1H-tetrazole
作為唑類,以0.26質量%乳酸鋁 As an azole, 0.26 mass% aluminum lactate
作為析出防止劑;所組成的蝕刻液原料,與75.82質量%的水調配,調製蝕刻濃縮液 As a precipitation preventing agent; the etchant raw material composed is formulated with 75.82% by mass of water to prepare an etching concentrate
將15.14質量%的35%過氧化氫水(對蝕刻液全量,過氧化氫為5.3質量%及水分為9.84質量%)與蝕刻濃縮液混合,調製過氧化氫濃度為5.3質量%的蝕刻液。再者,水對全量為85.66質量%。再者,加上乳酸銅將銅離子濃度調整為8,000ppm。此外,加上鉬粉末將鉬濃度調整為800ppm。此外,液溫使用35℃。將佔蝕刻液全體的各成分濃度,與各評估事項的結果示於表2。 15.14% by mass of 35% hydrogen peroxide water (the total amount of the etching solution, 5.3% by mass of hydrogen peroxide and 9.84% by mass of water) was mixed with the etching concentrate to prepare an etching liquid having a hydrogen peroxide concentration of 5.3% by mass. Furthermore, the total amount of water was 85.66 mass%. Further, copper lactate was added to adjust the copper ion concentration to 8,000 ppm. Further, molybdenum powder was added to adjust the molybdenum concentration to 800 ppm. In addition, the liquid temperature was 35 °C. The concentration of each component in the entire etching liquid and the results of each evaluation item are shown in Table 2.
(比較例3) (Comparative Example 3)
將由1.90質量%甘醇酸、3.40質量%丙二酸、0.80質量%乳酸 Will be composed of 1.90 mass% glycolic acid, 3.40 mass% malonic acid, 0.80 mass% lactic acid
作為酸性有機酸;以2.20質量%NNDPA As an acidic organic acid; at 2.20 mass% NNDPA
作為胺化合物;以0.30質量%BG As an amine compound; at 0.30 mass% BG
作為雙氧水穩定劑;以0.08質量%5-胺基-1H-四唑 As a hydrogen peroxide stabilizer; 0.08 mass% 5-amino-1H-tetrazole
作為唑類,以0.26質量%乳酸鋁 As an azole, 0.26 mass% aluminum lactate
作為析出防止劑;所組成的蝕刻液原料,與75.92質量%的水調配,調製蝕刻濃縮液 As a precipitation preventing agent; the etchant raw material composed is formulated with 75.92% by mass of water to prepare an etching concentrate
將15.14質量%的35%過氧化氫水(對蝕刻液全量,過氧化氫為5.3質量%及水分為9.84質量%)與蝕刻濃縮液混合,調製過氧化氫濃度為5.3質量%的蝕刻液。再者,水對全量為85.76質量%。再者,加上乳酸銅將銅離子濃度調整為8,000ppm。此外,加上鉬粉末將鉬濃度調整為800ppm。此外,液溫使用35℃。將佔蝕刻液全體的各成分濃度,與各評估事項的結果示於表2。 15.14% by mass of 35% hydrogen peroxide water (the total amount of the etching solution, 5.3% by mass of hydrogen peroxide and 9.84% by mass of water) was mixed with the etching concentrate to prepare an etching liquid having a hydrogen peroxide concentration of 5.3% by mass. Furthermore, the total amount of water was 85.76 mass%. Further, copper lactate was added to adjust the copper ion concentration to 8,000 ppm. Further, molybdenum powder was added to adjust the molybdenum concentration to 800 ppm. In addition, the liquid temperature was 35 °C. The concentration of each component in the entire etching liquid and the results of each evaluation item are shown in Table 2.
(比較例4) (Comparative Example 4)
將由1.87質量%甘醇酸、3.41質量%丙二酸、0.69質量%乳酸 Will be composed of 1.87 mass% glycolic acid, 3.41 mass% malonic acid, 0.69 mass% lactic acid
作為酸性有機酸;以2.20質量%1-胺基-2-丙醇 As an acidic organic acid; 2.20% by mass of 1-amino-2-propanol
作為胺化合物;以0.10質量%苯基尿素 As an amine compound; 0.10% by mass of phenylurea
作為雙氧水穩定劑; 以0.12質量%5-胺基-1H-四唑 As a hydrogen peroxide stabilizer; 0.12 mass% 5-amino-1H-tetrazole
作為唑類,以0.28質量%硝酸鋁 As an azole, 0.28 mass% aluminum nitrate
作為析出防止劑;所組成的蝕刻液原料,與76.19質量%的水調配,調製蝕刻濃縮液 As a precipitation preventing agent; the etchant raw material composed is prepared by mixing with 76.19% by mass of water to prepare an etching concentrate
將15.14質量%的35%過氧化氫水(對蝕刻液全量,過氧化氫為5.3質量%及水分為9.84質量%)與蝕刻濃縮液混合,調製過氧化氫濃度為5.3質量%的蝕刻液。再者,水對全量為86.03質量%。再者,加上乳酸銅將銅離子濃度調整為8,000ppm。此外,加上鉬粉末將鉬濃度調整為800ppm。此外,液溫使用35℃。將佔蝕刻液全體的各成分濃度,與各評估事項的結果示於表2。 15.14% by mass of 35% hydrogen peroxide water (the total amount of the etching solution, 5.3% by mass of hydrogen peroxide and 9.84% by mass of water) was mixed with the etching concentrate to prepare an etching liquid having a hydrogen peroxide concentration of 5.3% by mass. Furthermore, the total amount of water is 86.03% by mass. Further, copper lactate was added to adjust the copper ion concentration to 8,000 ppm. Further, molybdenum powder was added to adjust the molybdenum concentration to 800 ppm. In addition, the liquid temperature was 35 °C. The concentration of each component in the entire etching liquid and the results of each evaluation item are shown in Table 2.
(比較例5) (Comparative Example 5)
將由1.87質量%甘醇酸、3.41質量%丙二酸、0.69質量%乳酸 Will be composed of 1.87 mass% glycolic acid, 3.41 mass% malonic acid, 0.69 mass% lactic acid
作為酸性有機酸;以2.20質量%1-胺基-2-丙醇 As an acidic organic acid; 2.20% by mass of 1-amino-2-propanol
作為胺化合物;以0.10質量%尿素 As an amine compound; with 0.10% by mass of urea
作為雙氧水穩定劑;以0.12質量%5-胺基-1H-四唑 As a hydrogen peroxide stabilizer; 0.12 mass% 5-amino-1H-tetrazole
作為唑類,以0.22質量%乳酸鋁 As an azole, 0.22% by mass of aluminum lactate
作為析出防止劑;所組成的蝕刻液原料,與76.25質量%的水調配,調製蝕刻濃縮液。 As a precipitation preventive agent, the etchant raw material composed was prepared by mixing with 76.25 mass% of water to prepare an etching concentrate.
將15.14質量%的35%過氧化氫水(對蝕刻液全量,過氧化氫為5.3質量%及水分為9.84質量%)與蝕刻濃縮液混合,調製過氧化氫濃度為5.3質量%的蝕刻液。再者,水對全量為86.09質量%。再者,加上乳酸銅將銅離子濃度調整為8,000ppm。此外,加上鉬粉末將鉬濃度調整為800ppm。此外,液溫使用35℃。將佔蝕刻液全體的各成分濃度,與各評估事項的結果示於表2。 15.14% by mass of 35% hydrogen peroxide water (the total amount of the etching solution, 5.3% by mass of hydrogen peroxide and 9.84% by mass of water) was mixed with the etching concentrate to prepare an etching liquid having a hydrogen peroxide concentration of 5.3% by mass. Furthermore, the total amount of water is 86.09 mass%. Further, copper lactate was added to adjust the copper ion concentration to 8,000 ppm. Further, molybdenum powder was added to adjust the molybdenum concentration to 800 ppm. In addition, the liquid temperature was 35 °C. The concentration of each component in the entire etching liquid and the results of each evaluation item are shown in Table 2.
(比較例6) (Comparative Example 6)
將由1.87質量%甘醇酸、3.41質量%丙二酸、0.69質量%乳酸 Will be composed of 1.87 mass% glycolic acid, 3.41 mass% malonic acid, 0.69 mass% lactic acid
作為酸性有機酸;以2.20質量%1-胺基-2-丙醇 As an acidic organic acid; 2.20% by mass of 1-amino-2-propanol
作為胺化合物;以0.10質量%苯基尿素 As an amine compound; 0.10% by mass of phenylurea
作為雙氧水穩定劑;以0.12質量%5-胺基-1H-四唑 As a hydrogen peroxide stabilizer; 0.12 mass% 5-amino-1H-tetrazole
作為唑類,以0.56質量%β丙胺酸、0.28質量%硝酸鋁 As an azole, 0.56 mass% beta alanine, 0.28 mass% aluminum nitrate
作為析出防止劑;所組成的蝕刻液原料,與75.63質量%的水調配,調製蝕刻濃縮液 As a precipitation preventing agent; the etchant raw material composed is formulated with 75.63 mass% of water to prepare an etching concentrate
將15.14質量%的35%過氧化氫水(對蝕刻液全量,過氧化氫為5.3質量%及水分為9.84質量%)與蝕刻濃縮液混合,調製過氧化氫濃度為5.3質量%的蝕刻液。再者,水對全量為85.47質量%。再者,加上乳酸銅將銅離子濃度調整為8,000ppm。此外,加上鉬粉末將鉬濃度調整為800ppm。此外,液溫使用35℃。將佔蝕刻液全體的各成分濃度,與各評估事項的結果示於表2。 15.14% by mass of 35% hydrogen peroxide water (the total amount of the etching solution, 5.3% by mass of hydrogen peroxide and 9.84% by mass of water) was mixed with the etching concentrate to prepare an etching liquid having a hydrogen peroxide concentration of 5.3% by mass. Furthermore, the total amount of water was 85.47 mass%. Further, copper lactate was added to adjust the copper ion concentration to 8,000 ppm. Further, molybdenum powder was added to adjust the molybdenum concentration to 800 ppm. In addition, the liquid temperature was 35 °C. The concentration of each component in the entire etching liquid and the results of each evaluation item are shown in Table 2.
(比較例7) (Comparative Example 7)
將由1.87質量%甘醇酸、3.41質量%丙二酸、0.69質量%乳酸 Will be composed of 1.87 mass% glycolic acid, 3.41 mass% malonic acid, 0.69 mass% lactic acid
作為酸性有機酸;以2.20質量%1-胺基-2-丙醇 As an acidic organic acid; 2.20% by mass of 1-amino-2-propanol
作為胺化合物;以0.10質量%苯基尿素 As an amine compound; 0.10% by mass of phenylurea
作為雙氧水穩定劑;以0.12質量%5-胺基-1H-四唑 As a hydrogen peroxide stabilizer; 0.12 mass% 5-amino-1H-tetrazole
作為唑類,以0.56質量%β丙胺酸、以0.22質量%乳酸鋁 As the azole, 0.56 mass% β alanine, 0.22 mass% aluminum lactate
作為析出防止劑;所組成的蝕刻液原料,與75.69質量%的水調配,調製蝕刻濃縮液。 As a precipitation preventive agent, the etchant raw material composed was prepared by mixing with 75.69 mass% of water to prepare an etching concentrate.
將15.14質量%的35%過氧化氫水(對蝕刻液全量,過氧化氫為5.3質量%及水分為9.84質量%)與蝕刻濃縮液 混合,調製過氧化氫濃度為5.3質量%的蝕刻液。再者,水對全量為85.53質量%。再者,加上乳酸銅將銅離子濃度調整為8,000ppm。此外,加上鉬粉末將鉬濃度調整為800ppm。此外,液溫使用35℃。將佔蝕刻液全體的各成分濃度,與各評估事項的結果示於表2。 15.14% by mass of 35% hydrogen peroxide water (the total amount of the etching solution, 5.3% by mass of hydrogen peroxide and 9.84% by mass of water) was mixed with the etching concentrate to prepare an etching liquid having a hydrogen peroxide concentration of 5.3% by mass. Furthermore, the total amount of water was 85.53 mass%. Further, copper lactate was added to adjust the copper ion concentration to 8,000 ppm. Further, molybdenum powder was added to adjust the molybdenum concentration to 800 ppm. In addition, the liquid temperature was 35 °C. The concentration of each component in the entire etching liquid and the results of each evaluation item are shown in Table 2.
參照表2,比較例1、2、3均包含BG作為雙氧水穩定劑。但是,任一情形雙氧水分解速度均高於0.16質量%。在圖4,表示比較例1、2、3與實施例1至5的雙氧水分解速度的圖表。橫軸係BG的含量(質量%),縱軸係雙氧水分解速度(質量%/hr)。 Referring to Table 2, Comparative Examples 1, 2, and 3 all contained BG as a hydrogen peroxide stabilizer. However, in any case, the decomposition rate of hydrogen peroxide is higher than 0.16 mass%. Fig. 4 is a graph showing the hydrogen peroxide decomposition rates of Comparative Examples 1, 2, and 3 and Examples 1 to 5. The content of the horizontal axis BG (% by mass) and the vertical axis are the rate of decomposition of hydrogen peroxide (% by mass/hr).
黑四角係使用1A2P作為胺化合物的情形,黑圓係使用NNDPA作為胺化合物的情形。再者,在比較例1、2、3, 以在黑四角及黑圓之中放入小白圓的符號。 The black tetragonal system uses 1A2P as the amine compound, and the black circle system uses NNDPA as the amine compound. Further, in Comparative Examples 1, 2, and 3, a symbol of a small white circle was placed in the black square and the black circle.
參照圖4,1A2P的情形及NNDPA的情形,均當雙氧水穩定劑的BG的量增加,則雙氧水分解速度會下降。此外,使用NNDPA雙氧水分解速度較1A2P更低。 Referring to Fig. 4, in the case of 1A2P and the case of NNDPA, when the amount of BG of the hydrogen peroxide stabilizer is increased, the decomposition rate of hydrogen peroxide is lowered. In addition, the use of NNDPA hydrogen peroxide decomposition rate is lower than 1A2P.
再次參照表2,比較例4至7係使用先前使用的苯基尿素作為雙氧水穩定劑之情形。比較例4至7(使用1A2P作為胺化合物時),雙氧水分解速度快,即使是最慢的比較例7,亦為0.219質量%/hr。 Referring again to Table 2, Comparative Examples 4 to 7 used the case where the previously used phenyl urea was used as the hydrogen peroxide stabilizer. In Comparative Examples 4 to 7 (when 1A2P was used as the amine compound), the hydrogen peroxide decomposition rate was fast, and even the slowest Comparative Example 7 was 0.219% by mass/hr.
再次參照圖4,將比較例7的情形的雙氧水分解速度,以一點虛線表示。由圖4可知,使用1A2P作為胺化合物時,作為雙氧水穩定劑的BG,需要0.9質量%以上。此外,使用NNDPA作為胺化合物時,作為雙氧水穩定劑的BG,含有0.4質量%以上即可。 Referring again to Fig. 4, the hydrogen peroxide decomposition rate in the case of Comparative Example 7 is indicated by a dotted line. As is clear from Fig. 4, when 1A2P is used as the amine compound, the BG as the hydrogen peroxide stabilizer needs to be 0.9% by mass or more. Further, when NNDPA is used as the amine compound, BG as a hydrogen peroxide stabilizer may be contained in an amount of 0.4% by mass or more.
另一方面,雙氧水穩定劑的添加,即使對蝕刻液全量混入2.0質量%以上,其效果(雙氧水分解速度的下降)幾乎飽和。再者,在實施例,省略BG的含量在2.0質量%以上的例。因此,在圖4的圖表,亦沒有BG濃度在2.0質量%以上的繪圖點。 On the other hand, even if the total amount of the etching solution is 2.0% by mass or more, the effect of the addition of the hydrogen peroxide stabilizer is almost saturated. In the examples, the example in which the content of BG is 2.0% by mass or more is omitted. Therefore, in the graph of Fig. 4, there is no plot point where the BG concentration is 2.0% by mass or more.
綜合以上,在實施例,顯示胺化合物為NNDPA時,BG以0.4質量%~2.0質量%為佳,以0.9質量%~2.0質量%更佳,以2.0質量%最佳。此外,胺化合物為1-胺基-2-丙醇時,BG以0.9質量%~2.0質量%為佳,以2.0質量%更佳。 In summary, in the examples, when the amine compound is NNDPA, BG is preferably 0.4% by mass to 2.0% by mass, more preferably 0.9% by mass to 2.0% by mass, and most preferably 2.0% by mass. Further, when the amine compound is 1-amino-2-propanol, BG is preferably 0.9% by mass to 2.0% by mass, more preferably 2.0% by mass.
另一方面,如已說明,BG含有超過5質量%並沒有意義。因此,BG的範圍可如下所說。胺化合物為NNDPA 時,BG以0.4質量%~5.0質量%為佳,以0.9質量%~5.0質量%更佳,以2.0質量%~5.0質量%最佳。此外,胺化合物為1-胺基-2-丙醇時,BG為0.9質量%~5.0質量%為佳,以2.0質量%~5.0質量%更佳。 On the other hand, as already explained, it does not make sense for BG to contain more than 5% by mass. Therefore, the scope of BG can be as follows. When the amine compound is NNDPA, BG is preferably 0.4% by mass to 5.0% by mass, more preferably 0.9% by mass to 5.0% by mass, and most preferably 2.0% by mass to 5.0% by mass. Further, when the amine compound is 1-amino-2-propanol, BG is preferably 0.9% by mass to 5.0% by mass, more preferably 2.0% by mass to 5.0% by mass.
【產業上的可利性】 [Industry profitability]
關於本發明的蝕刻液,可良好地利用在蝕刻鉬與銅的多層膜之情形。特別是,即使銅離子濃度變得非常的高,亦可抑制過氧化氫水的分解速度,故可長期維持既定的蝕刻速率的範圍。 Regarding the etching liquid of the present invention, the case of etching a multilayer film of molybdenum and copper can be favorably utilized. In particular, even if the copper ion concentration is extremely high, the decomposition rate of the hydrogen peroxide water can be suppressed, so that the predetermined etching rate can be maintained for a long period of time.
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CN114318340B (en) * | 2021-12-22 | 2023-09-29 | 惠州达诚微电子材料有限公司 | Etching solution composition and preparation method thereof |
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JP2015209568A (en) * | 2014-04-25 | 2015-11-24 | パナソニックIpマネジメント株式会社 | Etching liquid and etching concentrated liquid for multilayer film containing molybdenum and copper and etching method |
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