TW201817917A - Etchant composition - Google Patents

Etchant composition Download PDF

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TW201817917A
TW201817917A TW106135312A TW106135312A TW201817917A TW 201817917 A TW201817917 A TW 201817917A TW 106135312 A TW106135312 A TW 106135312A TW 106135312 A TW106135312 A TW 106135312A TW 201817917 A TW201817917 A TW 201817917A
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acid
group
etchant composition
parts
compound
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TW106135312A
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TWI733924B (en
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李明翰
安鎬源
金世訓
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南韓商易案愛富科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/10—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a boron compound
    • 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
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • ing And Chemical Polishing (AREA)
  • Weting (AREA)

Abstract

Provided is an etchant composition including: hydrogen peroxide; a cyclic or aromatic compound containing any one or two or more selected from the group consisting of oxygen, sulfur and nitrogen in a molecule; an aminocarboxylic or aminophosphoric acid-based compound; any one or two or more compounds selected from the group consisting of an organic acid, an inorganic acid and a salt thereof; an undercut inhibitor; and a C4 or more alkylamine. The etchant composition of the present invention controls over-etching of an interface of copper and molybdenum layers during an etching process, thereby allowing a stable etching process, and improving etching characteristics.

Description

蝕刻劑組成物    Etchant composition   

以下揭露內容關於一種蝕刻劑組成物，且更具體地，關於一種用於TFT-LCD顯示器的電極中的蝕刻劑組成物。 The following disclosure relates to an etchant composition, and more specifically, to an etchant composition used in an electrode of a TFT-LCD display.

在半導體裝置中的基板上形成金屬佈線的製程一般包括用於形成金屬層的濺射製程、藉由光阻劑塗覆具有所欲圖案的光阻劑形成製程、曝光和顯影、以及在形成佈線後，去除不需要的光阻劑的剝離製程。 A process for forming a metal wiring on a substrate in a semiconductor device generally includes a sputtering process for forming a metal layer, a photoresist forming process with a photoresist coating having a desired pattern, exposure and development, and wiring formation After that, an unnecessary photoresist is removed by a peeling process.

為了製造半導體裝置和TFT-LCD的基板，通常使用鋁或鋁合金層作為用於TFT(薄膜電晶體)的柵極和資料線電極的佈線材料。然而，為了實現大型顯示器，減少用於電極的佈線的電阻是必要的。為此，已經有使用具有低電阻的金屬銅來形成佈線的嘗試。 In order to manufacture a semiconductor device and a substrate of a TFT-LCD, an aluminum or aluminum alloy layer is generally used as a wiring material for a gate and a data line electrode of a TFT (thin film transistor). However, in order to realize a large display, it is necessary to reduce the resistance of the wiring for the electrodes. For this reason, there have been attempts to form wiring using metallic copper having a low resistance.

然而，使用銅層進行佈線形成的製程具有與矽絕緣膜的黏著強度差的問題。為了彌補銅層的缺點，使用鈦、鉬、鈦/鉬合金等作為下層障壁金屬層。 However, the process of forming a wiring using a copper layer has a problem of poor adhesion strength with a silicon insulating film. In order to make up for the shortcomings of the copper layer, titanium, molybdenum, titanium / molybdenum alloy, etc. are used as the lower barrier metal layer.

在障壁金屬是鈦/鉬的合金的情況下，由於鈦的化學性質，只能使用某些離子或在一定條件下進行蝕刻。在障壁金屬是鉬的情況下，對於蝕刻製程是有利的， 但是與銅/鈦和銅/鉬合金層相比，銅層與鉬層之間的黏著強度差。特別是，由於蝕刻劑會滲透到銅層與鉬層之間的黏著強度差的部分而會加劇過度蝕刻。 In the case where the barrier metal is a titanium / molybdenum alloy, due to the chemical nature of titanium, only certain ions can be used or etching under certain conditions. In the case where the barrier metal is molybdenum, it is advantageous for the etching process, but compared with the copper / titanium and copper / molybdenum alloy layers, the adhesion strength between the copper layer and the molybdenum layer is poor. In particular, overetching is exacerbated because the etchant penetrates to the portion where the adhesive strength between the copper layer and the molybdenum layer is poor.

關於可用於銅層和鉬合金層的蝕刻劑組成物，韓國專利登記號10-1495619揭露一種過氧化氫-基底蝕刻劑。然而，該蝕刻劑係用於鉬合金層，且在銅/鉬合金層的情況下，不考慮銅與障壁層之間的黏著強度差的部分的界面保護，因此在銅/鉬層的界面上存在過蝕刻問題。另外，特別是環狀胺化合物與在銅層蝕刻期間產生的銅離子結合的情況下，在此情況下，當在蝕刻劑組成物中存在氯離子時，氯離子和結合到銅離子上的化合物會反應並產生微溶的沉澱。 Regarding an etchant composition that can be used for a copper layer and a molybdenum alloy layer, Korean Patent Registration No. 10-1495619 discloses a hydrogen peroxide-based etchant. However, this etchant is used for the molybdenum alloy layer, and in the case of the copper / molybdenum alloy layer, the interface protection of the portion where the adhesion strength between copper and the barrier layer is poor is not taken into account, and therefore, the There is an over-etching problem. In addition, particularly in the case where a cyclic amine compound is combined with copper ions generated during the etching of the copper layer, in this case, when chloride ions are present in the etchant composition, the chloride ions and the compounds bound to the copper ions Reacts and produces a slightly soluble precipitate.

因此，目前需要一種技術來改善由銅層和鉬層的低黏著強度引起的界面的過度蝕刻問題。 Therefore, a technology is currently needed to improve the problem of over-etching of the interface caused by the low adhesion strength of the copper layer and the molybdenum layer.

[相關先前技術文獻] [Related prior technical literature]

[專利文獻] [Patent Literature]

韓國專利登記號10-1495619(2015年2月16日)。 Korean Patent Registration No. 10-1495619 (February 16, 2015).

本發明之一實施例旨在提供一種能夠在蝕刻銅層和鉬層時控制銅層和鉬層的界面的過度蝕刻的蝕刻劑組成物，從而具有優異和穩定的蝕刻性能，並能改善蝕刻特性。 An embodiment of the present invention aims to provide an etchant composition capable of controlling over-etching of an interface between a copper layer and a molybdenum layer when etching a copper layer and a molybdenum layer, thereby having excellent and stable etching performance and improving etching characteristics. .

在一個態樣中，一種蝕刻劑組成物包括：過氧化氫；含有選自由分子中的氧、硫及氮所組成之群組中之任一種或二種或更多種的環狀化合物或芳香族化合物；胺基羧酸系化合物或胺基磷酸系化合物；選自由有機酸、無機酸及其鹽所組成之群組中之任一種或二種或更多種的化合物；底切抑制劑；以及C4或更多碳數的烷基胺。 In one aspect, an etchant composition includes: hydrogen peroxide; a cyclic compound or an aromatic compound containing any one or two or more selected from the group consisting of oxygen, sulfur, and nitrogen in a molecule; Family compounds; aminocarboxylic acid-based compounds or aminophosphoric acid-based compounds; any one or two or more compounds selected from the group consisting of organic acids, inorganic acids, and salts thereof; undercut inhibitors; And C 4 or more carbon amines.

基於100重量份的該過氧化氫，根據本發明之示例性實施例的蝕刻劑組成物可包括0.1重量份至50重量份的該環狀化合物或該芳香族化合物；0.1重量份至50重量份的該胺基羧酸系化合物或該胺基磷酸系化合物；0.1重量份至50重量份的該選自由有機酸、無機酸及其鹽所組成之群組中之任一種或二種或更多種的化合物；0.01重量份至20重量份的該底切抑制劑；以及0.1重量份至50重量份的該烷基胺。 Based on 100 parts by weight of the hydrogen peroxide, the etchant composition according to an exemplary embodiment of the present invention may include the cyclic compound or the aromatic compound in an amount of 0.1 to 50 parts by weight; 0.1 to 50 parts by weight The aminocarboxylic acid-based compound or the aminophosphoric acid-based compound; 0.1 to 50 parts by weight of any one or two or more selected from the group consisting of organic acids, inorganic acids, and salts thereof A compound of a species; 0.01 to 20 parts by weight of the undercut inhibitor; and 0.1 to 50 parts by weight of the alkylamine.

根據本發明之示例性實施例的蝕刻劑組成物可進一步包括氟化合物。 The etchant composition according to the exemplary embodiment of the present invention may further include a fluorine compound.

根據本發明之示例性實施例的氟化合物可基於100重量份的該過氧化氫以0.01重量份至20重量份被添加。 The fluorine compound according to an exemplary embodiment of the present invention may be added at 0.01 to 20 parts by weight based on 100 parts by weight of the hydrogen peroxide.

根據本發明之示例性實施例的C4或更多碳數的烷基胺可以是C4至C16直鏈或支鏈的烷基胺化合物。 The C 4 or more carbon number alkylamine according to an exemplary embodiment of the present invention may be a C 4 to C 16 linear or branched alkylamine compound.

根據本發明之示例性實施例的C4或更多碳數的烷基胺可以是選自由丁胺、戊胺、己胺、庚胺、辛胺及 2-乙基-1-己胺所組成之群組中的任一種或兩種或更多種的混合物。 A C 4 or more carbon number alkylamine according to an exemplary embodiment of the present invention may be selected from the group consisting of butylamine, pentylamine, hexylamine, heptylamine, octylamine, and 2-ethyl-1-hexylamine Any one or a mixture of two or more of the groups.

根據本發明之示例性實施例的環狀化合物或芳香族化合物可以是選自由噁唑(oxazole)、咪唑、吡唑(pyrazole)、***、四唑、5-胺基四唑、甲基四唑、哌嗪(piperazine)、甲基哌嗪、羥乙基哌嗪、苯并咪唑、苯并吡唑、甲基苯并***、氫甲基苯并***及羥甲基苯并***所組成之群組中的任一種或兩種或更多種的混合物。 The cyclic compound or the aromatic compound according to an exemplary embodiment of the present invention may be selected from the group consisting of oxazole, imidazole, pyrazole, triazole, tetrazole, 5-aminotetrazole, methyl tetra Azole, piperazine, methylpiperazine, hydroxyethylpiperazine, benzimidazole, benzopyrazole, methylbenzotriazole, hydromethylbenzotriazole, and hydroxymethylbenzotriazole Any one or a mixture of two or more of the groups formed.

根據本發明之示例性實施例的胺基羧酸系化合物或胺基磷酸系化合物可包括在分子中具有胺基的羧酸基或膦酸基。 The aminocarboxylic acid-based compound or the aminophosphoric acid-based compound according to an exemplary embodiment of the present invention may include a carboxylic acid group or a phosphonic acid group having an amine group in a molecule.

根據本發明之示例性實施例的胺基羧酸系化合物或胺基磷酸系化合物可以是選自由亞胺基二乙酸、氮基三乙酸、乙二胺四乙酸、二伸乙三胺五乙酸、胺基參(亞甲基膦酸)、(1-羥基乙烷-1,1-二基)雙(亞膦酸)、乙二胺肆(亞甲基膦酸)、二伸乙基三胺五(亞甲基膦酸)、丙胺酸、麩胺酸、胺基丁酸及甘胺酸等所組成之群組中的任一種或兩種或更多種的混合物。 The aminocarboxylic acid-based compound or the aminophosphoric acid-based compound according to an exemplary embodiment of the present invention may be selected from the group consisting of iminodiacetic acid, nitrotriacetic acid, ethylenediaminetetraacetic acid, diethylene glycol triaminepentaacetic acid, Amine reference (methylene phosphonic acid), (1-hydroxyethane-1,1-diyl) bis (phosphinic acid), ethylene diamine (methylene phosphonic acid), diethylene triamine Any one or a mixture of two or more of the group consisting of penta (methylenephosphonic acid), alanine, glutamic acid, aminobutyric acid, and glycine.

根據本發明之示例性實施例的無機酸可以是選自由硫酸、硝酸及磷酸所組成之群組中的任一種或兩種或更多種的混合物。 The inorganic acid according to an exemplary embodiment of the present invention may be any one or a mixture of two or more selected from the group consisting of sulfuric acid, nitric acid, and phosphoric acid.

有機酸可以是選自由乙酸、甲酸、丁酸、檸檬酸、乙醇酸、草酸、丙二酸、戊酸、丙酸、酒石酸、蘋果酸、葡萄糖酸、醛糖酸及琥珀酸等所組成之群組中的任 一種或兩種或更多種的混合物。 The organic acid may be selected from the group consisting of acetic acid, formic acid, butyric acid, citric acid, glycolic acid, oxalic acid, malonic acid, valeric acid, propionic acid, tartaric acid, malic acid, gluconic acid, aldonic acid, and succinic acid. Any one or a mixture of two or more of the groups.

無機酸鹽和有機酸鹽可以是選自由磷酸氫鉀、磷酸氫鈉、磷酸氫銨、磷酸鈉、過磷酸鈉、磷酸鉀、過磷酸鉀、磷酸銨及過磷酸銨等所組成之群組中的任一種或兩種或更多種的混合物。 The inorganic acid salt and the organic acid salt may be selected from the group consisting of potassium hydrogen phosphate, sodium hydrogen phosphate, ammonium hydrogen phosphate, sodium phosphate, sodium superphosphate, potassium phosphate, potassium superphosphate, ammonium phosphate, and ammonium superphosphate. Any one or a mixture of two or more.

根據本發明之示例性實施例的氟化合物可以是選自由HF、NaF、KF、AlF3、HBF4、NH4HF2、NaHF2、KHF2及NH4BF4所組成之群組中的任一種或兩種或更多種的混合物。 The fluorine compound according to an exemplary embodiment of the present invention may be any one selected from the group consisting of HF, NaF, KF, AlF 3 , HBF 4 , NH 4 HF 2 , NaHF 2 , KHF 2 and NH 4 BF 4 . One or a mixture of two or more.

根據本發明之示例性實施例的底切抑制劑可以是選自由腺嘌呤、鳥糞嘌呤、異鳥糞嘌呤、次黃嘌呤、黃嘌呤、可可鹼、咖啡因及尿酸等所組成之群組中的任一種或兩種或更多種的混合物。 The undercut inhibitor according to an exemplary embodiment of the present invention may be selected from the group consisting of adenine, guanopurine, isoguanosine, hypoxanthine, xanthine, theobromine, caffeine, and uric acid Any one or a mixture of two or more.

根據本發明之示例性實施例的蝕刻劑組成物可進一步包括選自由過氧化氫穩定劑、蝕刻穩定劑及玻璃蝕刻抑制劑所組成之群組中的任一種或兩種或更多種的混合物。 The etchant composition according to the exemplary embodiment of the present invention may further include any one or a mixture of two or more selected from the group consisting of a hydrogen peroxide stabilizer, an etching stabilizer, and a glass etching inhibitor. .

根據本發明之蝕刻劑組成物可控制銅層和鉬層的界面的過度蝕刻，並可增加蝕刻劑組成物的穩定性，從而允許優異和穩定的蝕刻製程。 The etchant composition according to the present invention can control the excessive etching of the interface between the copper layer and the molybdenum layer, and can increase the stability of the etchant composition, thereby allowing an excellent and stable etching process.

另外，與傳統的蝕刻劑組成物相比，本發明之蝕刻劑組成物可在蝕刻製程期間保護界面，從而改善蝕刻特性諸如錐角、CD損失和視覺線性度(vision linearity)， 並且有效降低缺陷率。 In addition, compared with the conventional etchant composition, the etchant composition of the present invention can protect the interface during the etching process, thereby improving etching characteristics such as taper angle, CD loss and vision linearity, and effectively reducing defects. rate.

圖1是使用根據本發明之實例1的蝕刻劑組成物對銅層和鉬層進行蝕刻，然後藉由掃描型電子顯微鏡觀察傾斜試樣的剖面所獲得的照片。 FIG. 1 is a photograph obtained by etching a copper layer and a molybdenum layer using an etchant composition according to Example 1 of the present invention, and then observing a cross section of the inclined sample by a scanning electron microscope.

圖2是使用根據本發明之實例6的蝕刻劑組成物對銅層和鉬層進行蝕刻，然後藉由掃描型電子顯微鏡觀察傾斜試樣的剖面所獲得的照片。 FIG. 2 is a photograph obtained by etching a copper layer and a molybdenum layer using an etchant composition according to Example 6 of the present invention, and then observing a cross section of the inclined sample by a scanning electron microscope.

圖3是使用根據本發明之實例11的蝕刻劑組成物對銅層和鉬層進行蝕刻，然後藉由掃描型電子顯微鏡觀察傾斜試樣的剖面所獲得的照片。 FIG. 3 is a photo obtained by etching a copper layer and a molybdenum layer using an etchant composition according to Example 11 of the present invention, and then observing a cross section of the inclined sample by a scanning electron microscope.

圖4是使用根據本發明之比較例1的蝕刻劑組成物對銅層和鉬層進行蝕刻，然後藉由掃描型電子顯微鏡觀察傾斜試樣的剖面所獲得的照片。 FIG. 4 is a photograph obtained by etching a copper layer and a molybdenum layer using an etchant composition according to Comparative Example 1 of the present invention, and then observing a cross section of the inclined sample by a scanning electron microscope.

圖5是使用根據本發明之比較例6的蝕刻劑組成物對銅層和鉬層進行蝕刻，然後藉由掃描型電子顯微鏡觀察傾斜試樣的剖面所獲得的照片。 FIG. 5 is a photograph obtained by etching a copper layer and a molybdenum layer using an etchant composition according to Comparative Example 6 of the present invention, and then observing a cross section of the inclined sample by a scanning electron microscope.

圖6是使用根據本發明之實例1的蝕刻劑組成物對銅層和鉬層進行蝕刻，然後藉由掃描型電子顯微鏡觀察試樣的剖面所獲得的照片。 FIG. 6 is a photo obtained by etching a copper layer and a molybdenum layer using an etchant composition according to Example 1 of the present invention, and then observing a cross section of the sample by a scanning electron microscope.

圖7是使用根據本發明之比較例6的蝕刻劑組成物對銅/鉬層進行蝕刻，然後藉由掃描型電子顯微鏡觀察試樣的剖面所獲得的照片。 FIG. 7 is a photograph obtained by etching a copper / molybdenum layer using an etchant composition according to Comparative Example 6 of the present invention, and then observing a cross section of the sample by a scanning electron microscope.

在下文中，將詳細描述根據本發明之示例性實施例的蝕刻劑組成物。 Hereinafter, an etchant composition according to an exemplary embodiment of the present invention will be described in detail.

本發明提供一種蝕刻劑組成物，包括：過氧化氫；含有選自由分子中的氧、硫及氮所組成之群組中之任一種或二種或更多種的環狀化合物或芳香族化合物；胺基羧酸系化合物或胺基磷酸系化合物；選自由有機酸、無機酸及其鹽所組成之群組中之任一種或二種或更多種的化合物；底切抑制劑；以及C4或更多碳數的烷基胺。 The invention provides an etchant composition comprising: hydrogen peroxide; a cyclic compound or an aromatic compound containing any one or two or more selected from the group consisting of oxygen, sulfur and nitrogen in a molecule; ; Aminocarboxylic acid-based compounds or aminophosphoric acid-based compounds; any one or two or more compounds selected from the group consisting of organic acids, inorganic acids, and salts thereof; undercut inhibitors; and C 4 or more carbon amines.

該蝕刻劑組成物可包括以下所有：過氧化氫；含有選自由分子中的氧、硫及氮所組成之群組中之任一種或二種或更多種的環狀化合物或芳香族化合物；胺基羧酸系化合物或胺基磷酸系化合物；選自由有機酸、無機酸及其鹽所組成之群組中之任一種或二種或更多種的化合物；底切抑制劑；以及C4或更多碳數的烷基胺，從而有效地蝕刻銅層和鉬層兩者。此外，可以抑制銅層和鉬層的界面的過度蝕刻，使得可以有效地控制蝕刻劑滲透到具有較差黏著強度的銅層和鉬層的部分的過度蝕刻。此外，蝕刻劑組成物具有藉由控制過度蝕刻來執行穩定的蝕刻製程及保護銅層和鉬層的界面的特性，從而能顯著地改善蝕刻特性。 The etchant composition may include all of the following: hydrogen peroxide; containing any one or two or more cyclic compounds or aromatic compounds selected from the group consisting of oxygen, sulfur, and nitrogen in a molecule; Aminocarboxylic acid-based compounds or aminophosphoric acid-based compounds; any one or two or more compounds selected from the group consisting of organic acids, inorganic acids, and salts thereof; undercut inhibitors; and C 4 Or more carbon amines, effectively etching both the copper layer and the molybdenum layer. In addition, the excessive etching of the interface between the copper layer and the molybdenum layer can be suppressed, so that the excessive etching of the portion where the etchant penetrates into the copper layer and the molybdenum layer with poor adhesion strength can be effectively controlled. In addition, the etchant composition has the characteristics of performing a stable etching process by controlling over-etching and protecting the interface between the copper layer and the molybdenum layer, thereby significantly improving the etching characteristics.

如本文所用“銅層和鉬層”是指銅層和鉬層，且除了銅層和鉬層以外的銅和鉬的合金層可以被排除。 The "copper layer and molybdenum layer" as used herein refers to a copper layer and a molybdenum layer, and an alloy layer of copper and molybdenum other than the copper layer and the molybdenum layer may be excluded.

由於鉬合金層具有比銅層和鉬層更佳的銅層與障壁層之間的黏著強度，所以可能不考慮C4或更多碳數 的烷基胺。 Since the molybdenum alloy layer has better adhesion strength between the copper layer and the barrier layer than the copper layer and the molybdenum layer, a C 4 or more carbon number alkylamine may not be considered.

基於100重量份的該過氧化氫，根據本發明之示例性實施例的蝕刻劑組成物可包括0.1重量份至50重量份的環狀化合物或芳香族化合物；0.1重量份至50重量份的胺基羧酸系化合物或胺基磷酸系化合物；0.1重量份至50重量份的選自由有機酸、無機酸及其鹽所組成之群組中之任一種或二種或更多種的化合物；0.01重量份至20重量份的底切抑制劑；以及0.1重量份至50重量份的烷基胺。在此範圍內，銅層和鉬層的界面的過度蝕刻控制效果優異。 Based on 100 parts by weight of the hydrogen peroxide, the etchant composition according to an exemplary embodiment of the present invention may include a cyclic compound or an aromatic compound in an amount of 0.1 to 50 parts by weight; and an amine in an amount of 0.1 to 50 parts by weight. Carboxylic acid-based compound or amino phosphoric acid-based compound; 0.1 to 50 parts by weight of any one or two or more compounds selected from the group consisting of organic acids, inorganic acids, and salts thereof; 0.01 Underweight inhibitor to 20 parts by weight; and alkylamine from 0.1 to 50 parts by weight. Within this range, the effect of excessive etching control at the interface between the copper layer and the molybdenum layer is excellent.

更佳地，基於100重量份的該過氧化氫，根據本發明之示例性實施例的蝕刻劑組成物可包括1重量份至20重量份的環狀化合物或芳香族化合物；1重量份至20重量份的胺基羧酸系化合物或胺基磷酸系化合物；1重量份至20重量份的選自由有機酸、無機酸及其鹽所組成之群組中之任一種或二種或更多種的化合物；0.1重量份至20重量份的底切抑制劑；以及1重量份至20重量份的烷基胺。在此範圍內，可以更有效地控制銅層和鉬層的界面的過度蝕刻，並且可以有效地改善蝕刻特性諸如錐角、CD損失和視覺線性度。 More preferably, based on 100 parts by weight of the hydrogen peroxide, the etchant composition according to an exemplary embodiment of the present invention may include a cyclic compound or an aromatic compound from 1 to 20 parts by weight; 1 to 20 parts by weight Parts by weight of aminocarboxylic acid-based compounds or aminophosphoric acid-based compounds; 1 to 20 parts by weight of any one or two or more selected from the group consisting of organic acids, inorganic acids, and salts thereof A compound; 0.1 to 20 parts by weight of an undercut inhibitor; and 1 to 20 parts by weight of an alkylamine. Within this range, the excessive etching of the interface between the copper layer and the molybdenum layer can be more effectively controlled, and the etching characteristics such as taper angle, CD loss, and visual linearity can be effectively improved.

特別佳地，基於100重量份的該過氧化氫，根據本發明之示例性實施例的蝕刻劑組成物可包括2重量份至10重量份的環狀化合物或芳香族化合物；5重量份至15重量份的胺基羧酸系化合物或胺基磷酸系化合物；1重量份至10重量份的選自由有機酸、無機酸及其鹽所組成之群組 中之任一種或二種或更多種的化合物；1重量份至5重量份的底切抑制劑；以及1重量份至10重量份的烷基胺。在此範圍內，可以顯著地改善銅層和鉬層的界面的過度蝕刻控制效果，並且可以確保優異蝕刻特性諸如錐角、CD損失和視覺線性度。 Particularly preferably, the etchant composition according to the exemplary embodiment of the present invention may include a cyclic compound or an aromatic compound in an amount of 2 to 10 parts by weight based on 100 parts by weight of the hydrogen peroxide; 5 to 15 parts by weight Part by weight of aminocarboxylic acid-based compound or aminophosphoric acid-based compound; 1 to 10 parts by weight of any one or two or more selected from the group consisting of organic acids, inorganic acids, and salts thereof A compound; 1 to 5 parts by weight of an undercut inhibitor; and 1 to 10 parts by weight of an alkylamine. Within this range, the effect of excessive etching control at the interface of the copper layer and the molybdenum layer can be significantly improved, and excellent etching characteristics such as taper angle, CD loss, and visual linearity can be ensured.

在下文中，將以具體實例描述根據本發明之示例性實施例的蝕刻劑組成物的每個組分。 Hereinafter, each component of the etchant composition according to an exemplary embodiment of the present invention will be described with a specific example.

a)過氧化氫。 a) Hydrogen peroxide.

根據本發明之示例性實施例的過氧化氫可以用作銅和鉬或銅層和鉬層的主要氧化劑。 Hydrogen peroxide according to an exemplary embodiment of the present invention may be used as a main oxidant of copper and molybdenum or a copper layer and a molybdenum layer.

相對於蝕刻劑組成物，根據本發明之示例性實施例的過氧化氫可以10重量%至30重量%被包括在內，且更佳是以15重量%至25重量%被包括在內。當過氧化氫以少於10重量%被包括在內時，則銅和鉬的氧化力不足，使得不能進行蝕刻，且當過氧化氫以超過30重量%被包括在內時，則蝕刻速率太快，使得製程控制困難。在該範圍內，過氧化氫可以實施較佳的蝕刻速率以防止蝕刻殘留物和蝕刻缺陷。此外，它可以降低CD損失，並允許簡單的製程調整。 With respect to the etchant composition, hydrogen peroxide according to an exemplary embodiment of the present invention may be included in an amount of 10% to 30% by weight, and more preferably included in an amount of 15% to 25% by weight. When hydrogen peroxide is included at less than 10% by weight, the oxidizing power of copper and molybdenum is insufficient so that etching cannot be performed, and when hydrogen peroxide is included at more than 30% by weight, the etching rate is too high. Fast, making process control difficult. Within this range, hydrogen peroxide may implement a better etch rate to prevent etch residues and etch defects. In addition, it reduces CD losses and allows simple process adjustments.

b)含有選自由分子中的氧、硫及氮所組成之群組中之任一種或二種或更多種的環狀化合物或芳香族化合物。 b) A cyclic compound or an aromatic compound containing any one or two or more members selected from the group consisting of oxygen, sulfur, and nitrogen in a molecule.

根據本發明之示例性實施例，該含有選自由分子中的氧、硫及氮所組成之群組中之任一種或二種或更 多種的環狀化合物或芳香族化合物可以調整銅和鉬的蝕刻速率，從而降低CD損失的模式。此外，該含有選自由分子中的氧、硫及氮所組成之群組中之任一種或二種或更多種的環狀化合物或芳香族化合物可以增加製程幅度(margin)，並且允許獲得具有適當錐角的蝕刻輪廓。 According to an exemplary embodiment of the present invention, the cyclic compound or aromatic compound containing any one or two or more members selected from the group consisting of oxygen, sulfur, and nitrogen in a molecule can adjust copper and molybdenum Etching rate, which reduces the mode of CD loss. In addition, the cyclic compound or aromatic compound containing any one or two or more members selected from the group consisting of oxygen, sulfur, and nitrogen in the molecule can increase the margin of the process and allow obtaining Etched contour with proper cone angle.

作為具體實例，該含有選自由分子中的氧、硫及氮所組成之群組中之任一種或二種或更多種的環狀化合物或芳香族化合物可以是選自由噁唑、咪唑、吡唑、***、四唑、5-胺基四唑、甲基四唑、哌嗪、甲基哌嗪、羥乙基哌嗪、苯并咪唑、苯并吡唑、甲基苯并***、氫甲基苯并***及羥甲基苯并***所組成之群組中的任一種或兩種或更多種的混合物，但不限於此。 As a specific example, the cyclic compound or aromatic compound containing any one or two or more members selected from the group consisting of oxygen, sulfur, and nitrogen in the molecule may be selected from the group consisting of oxazole, imidazole, and pyridine Azole, triazole, tetrazole, 5-aminotetrazole, methyltetrazole, piperazine, methylpiperazine, hydroxyethylpiperazine, benzimidazole, benzopyrazole, methylbenzotriazole, Any one or a mixture of two or more of the group consisting of hydromethylbenzotriazole and hydroxymethylbenzotriazole, but is not limited thereto.

較佳是，基於100重量份的該過氧化氫，本發明之含有選自由分子中的氧、硫及氮所組成之群組中之任一種或二種或更多種的環狀化合物或芳香族化合物係以0.1重量份至50重量份被包括在內，且更佳是以1重量份至20重量份被包括在內，又更佳是以2重量份至10重量份被包括在內。在該範圍內，該含有選自由氧、硫及氮所組成之群組中之任一種或二種或更多種的環狀化合物或芳香族化合物可保持適當的蝕刻速率。 Preferably, based on 100 parts by weight of the hydrogen peroxide, the present invention contains any one or two or more cyclic compounds or aromatic compounds selected from the group consisting of oxygen, sulfur and nitrogen in a molecule. The family compound is included in an amount of 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight, and even more preferably 2 to 10 parts by weight. Within this range, the cyclic compound or aromatic compound containing any one or two or more members selected from the group consisting of oxygen, sulfur, and nitrogen can maintain an appropriate etching rate.

當該含有選自由分子中的氧、硫及氮所組成之群組中之任一種或二種或更多種的環狀化合物或芳香族化合物以少於0.1重量份被包括在內時，難以調整蝕刻速率，調整錐角的能力可能會降低，並且製程幅度很小，從 而降低大量生產率。此外，當該含有選自由分子中的氧、硫及氮所組成之群組中之任一種或二種或更多種的環狀化合物或芳香族化合物以超過50重量份被包括在內時，蝕刻速率降低，因此無效率(inefficient)。 When the cyclic compound or aromatic compound containing any one or two or more members selected from the group consisting of oxygen, sulfur, and nitrogen in a molecule is included in less than 0.1 parts by weight, it is difficult Adjusting the etch rate, the ability to adjust the cone angle may be reduced, and the process width is small, which reduces a lot of productivity. In addition, when the cyclic compound or aromatic compound containing any one or two or more members selected from the group consisting of oxygen, sulfur, and nitrogen in a molecule is included in more than 50 parts by weight, The etching rate is reduced and therefore inefficient.

c)胺基羧酸系化合物或胺基磷酸系化合物。 c) Aminocarboxylic acid-based compound or aminophosphoric acid-based compound.

根據本發明之示例性實施例的胺基羧酸系化合物或胺基磷酸系化合物與在蝕刻製程期間產生的金屬離子諸如銅離子和鉬離子形成螯合物以使離子去活性，從而防止由這些金屬引起的副作用。結果，即使在重複的蝕刻製程中，蝕刻特性也可以被維持。 An aminocarboxylic acid-based compound or an aminophosphoric acid-based compound according to an exemplary embodiment of the present invention forms a chelate with metal ions such as copper ions and molybdenum ions generated during the etching process to deactivate the ions, thereby preventing these ions from being deactivated. Side effects caused by metals. As a result, the etching characteristics can be maintained even in repeated etching processes.

特別地，在銅層的情況下，當銅離子大量存在於蝕刻劑組成物中時，它們形成被氧化的鈍化層，從而防止蝕刻。然而，藉由添加胺基羧酸系化合物或胺基磷酸系化合物，可以防止由銅離子形成鈍化層。此外，胺基羧酸系化合物或胺基磷酸系化合物可以防止過氧化氫本身的分解反應，從而增加蝕刻劑的穩定性。 Particularly, in the case of a copper layer, when copper ions are present in a large amount in the etchant composition, they form an oxidized passivation layer, thereby preventing etching. However, by adding an aminocarboxylic acid-based compound or an aminophosphoric acid-based compound, the formation of a passivation layer by copper ions can be prevented. In addition, the aminocarboxylic acid-based compound or aminophosphoric acid-based compound can prevent the decomposition reaction of hydrogen peroxide itself, thereby increasing the stability of the etchant.

在沒有將胺基羧酸系化合物或胺基磷酸系化合物添加到蝕刻劑組成物中的情況下，在蝕刻製程期間中氧化的金屬離子被活化，使得蝕刻劑的蝕刻特性容易變化，且會促進過氧化氫的分解反應引起著火和***。 Without the addition of an aminocarboxylic acid-based compound or an aminophosphoric acid-based compound to the etchant composition, the oxidized metal ions are activated during the etching process, so that the etching characteristics of the etchant are easily changed and promoted. The decomposition reaction of hydrogen peroxide causes fire and explosion.

因此，本發明之胺基羧酸系化合物或胺基磷酸系化合物可以與在蝕刻製程中產生的金屬離子螯合以抑制過氧化氫的分解，並且用於在儲存蝕刻劑組成物時增加穩定性。 Therefore, the aminocarboxylic acid-based compound or aminophosphoric acid-based compound of the present invention can chelate with metal ions generated in the etching process to suppress the decomposition of hydrogen peroxide, and is used to increase the stability when the etchant composition is stored. .

根據本發明之示例性實施例的胺基羧酸系化合物或胺基磷酸系化合物可以包括在分子中具有胺基的羧酸基或膦酸基。 The aminocarboxylic acid-based compound or the aminophosphoric acid-based compound according to an exemplary embodiment of the present invention may include a carboxylic acid group or a phosphonic acid group having an amine group in a molecule.

作為具體實例，該胺基羧酸系化合物或胺基磷酸系化合物可以是選自由亞胺基二乙酸、氮基三乙酸、乙二胺四乙酸、二伸乙三胺五乙酸、胺基參(亞甲基膦酸)、(1-羥基乙烷-1,1-二基)雙(亞膦酸)、乙二胺肆(亞甲基膦酸)、二伸乙基三胺五(亞甲基膦酸)、丙胺酸、麩胺酸、胺基丁酸及甘胺酸所組成之群組中的任一種或兩種或更多種的混合物，但不限於此。 As a specific example, the aminocarboxylic acid-based compound or aminophosphoric acid-based compound may be selected from the group consisting of imine diacetic acid, nitrogen triacetic acid, ethylene diamine tetraacetic acid, diethylene glycol triamine pentaacetic acid, and amino parameters ( Methylene phosphonic acid), (1-hydroxyethane-1,1-diyl) bis (phosphinic acid), ethylenediamine (methylenephosphonic acid), diethylene triamine penta (methylene Any one or a mixture of two or more of the group consisting of aminophosphonic acid), alanine, glutamic acid, aminobutyric acid, and glycine, but is not limited thereto.

較佳是，基於100重量份的該過氧化氫，該胺基羧酸系化合物或胺基磷酸系化合物係以0.1重量份至50重量份被包括在內，且更佳是以1重量份至20重量份被包括在內，又更佳是以5重量份至15重量份被包括在內。在該範圍內，金屬離子可以優異的效率去活性，並且可以抑制與金屬離子的副反應。 Preferably, based on 100 parts by weight of the hydrogen peroxide, the aminocarboxylic acid-based compound or aminophosphoric acid-based compound is included in an amount of 0.1 to 50 parts by weight, and more preferably 1 to 50 parts by weight. 20 parts by weight is included, and even more preferably 5 to 15 parts by weight is included. Within this range, metal ions can be deactivated with excellent efficiency, and side reactions with metal ions can be suppressed.

當該胺基羧酸系化合物或胺基磷酸系化合物以少於0.1重量份被包括在內時，待去活性的金屬離子的量過小，使得控制過氧化氫的分解反應的能力可能下降，並且當以超過50重量份被包括在內時，可能不期望會藉由形成另外的螯合物使金屬去活性，因此無效率。 When the aminocarboxylic acid-based compound or aminophosphoric acid-based compound is included in less than 0.1 parts by weight, the amount of metal ions to be deactivated is too small, so that the ability to control the decomposition reaction of hydrogen peroxide may be reduced, and When included in more than 50 parts by weight, it may not be desirable to deactivate the metal by forming another chelate, and thus is inefficient.

d)選自由有機酸、無機酸及其鹽所組成之群組中之任一種或二種或更多種的化合物。 d) a compound selected from any one or two or more of the group consisting of an organic acid, an inorganic acid, and a salt thereof.

根據本發明之示例性實施例的選自由有機 酸、無機酸及其鹽所組成之群組中之任一種或二種或更多種的化合物用作銅和鉬的輔助氧化劑，並可改善錐形輪廓。 According to an exemplary embodiment of the present invention, any one or two or more compounds selected from the group consisting of organic acids, inorganic acids, and salts thereof are used as auxiliary oxidants for copper and molybdenum, and can improve the cone Shaped silhouette.

作為具體實例，該無機酸可以是選自由硫酸、硝酸及磷酸等所組成之群組中的任一種或兩種或更多種的混合物，但不限於此。 As a specific example, the inorganic acid may be any one selected from the group consisting of sulfuric acid, nitric acid, phosphoric acid, and the like, or a mixture of two or more, but is not limited thereto.

作為具體實例，該有機酸可以是選自由乙酸、甲酸、丁酸、檸檬酸、乙醇酸、草酸、丙二酸、戊酸、丙酸、酒石酸、蘋果酸、葡萄糖酸、醛糖酸及琥珀酸等所組成之群組中的任一種或兩種或更多種的混合物，但不限於此。 As a specific example, the organic acid may be selected from the group consisting of acetic acid, formic acid, butyric acid, citric acid, glycolic acid, oxalic acid, malonic acid, valeric acid, propionic acid, tartaric acid, malic acid, gluconic acid, aldonic acid, and succinic acid. Any one or a mixture of two or more in the group consisting of but is not limited thereto.

作為具體實例，作為其鹽的無機酸鹽和有機酸鹽可以是磷酸鹽，並且可以是選自由磷酸氫鉀、磷酸氫鈉、磷酸氫銨、磷酸鈉、過磷酸鈉、磷酸鉀、過磷酸鉀、磷酸銨及過磷酸銨等所組成之群組中的任一種或兩種或更多種的混合物，且較佳是具有優異的蝕刻特性改善效果的磷酸氫銨，但不限於此。 As a specific example, the inorganic acid salt and organic acid salt as its salt may be a phosphate, and may be selected from the group consisting of potassium hydrogen phosphate, sodium hydrogen phosphate, ammonium hydrogen phosphate, sodium phosphate, sodium superphosphate, potassium phosphate, potassium superphosphate Any one or a mixture of two or more of the group consisting of ammonium phosphate, ammonium phosphate, and ammonium superphosphate, etc., and ammonium hydrogen phosphate having an excellent etching property improvement effect is preferred, but is not limited thereto.

較佳是，基於100重量份的該過氧化氫，該選自由有機酸、無機酸及其鹽所組成之群組中之任一種或二種或更多種的化合物係以0.1重量份至50重量份被包括在內，且更佳是以1重量份至20重量份被包括在內，且又更佳是以1重量份至10重量份被包括在內。在該範圍內，由於使用該選自由有機酸、無機酸及其鹽所組成之群組中之任一種或二種或更多種的化合物所致的錐形輪廓改善效果可以是優異的，並且可以抑制蝕刻特性的劣化。 Preferably, based on 100 parts by weight of the hydrogen peroxide, the compound selected from any one or two or more of the group consisting of organic acids, inorganic acids, and salts thereof is 0.1 to 50 parts by weight. The parts by weight are included, and more preferably, they are included in 1 to 20 parts by weight, and even more preferably, they are included in 1 to 10 parts by weight. Within this range, a cone profile improvement effect due to using any one or two or more compounds selected from the group consisting of an organic acid, an inorganic acid, and a salt thereof may be excellent, and It is possible to suppress deterioration of the etching characteristics.

e)底切抑制劑。 e) Undercut inhibitor.

為了在同時蝕刻銅層和鉬層時控制鉬層的底切蝕刻，可以調節氟化合物和含有選自由分子中的氧、硫及氮所組成之群組中之任一種或二種或更多種的環狀化合物或芳香族化合物的含量。然而，當氟化合物的含量少時，則可能產生鉬殘餘物，且當含有選自由分子中的氧、硫及氮所組成之群組中之任一種或二種或更多種的環狀化合物或芳香族化合物的含量增加時，則銅的蝕刻速率會顯著地降低，因而難以進行蝕刻處理。 In order to control the undercut etching of the molybdenum layer when the copper layer and the molybdenum layer are etched at the same time, the fluorine compound and any one or two or more kinds selected from the group consisting of oxygen, sulfur and nitrogen in the molecule can be adjusted Content of cyclic compounds or aromatic compounds. However, when the content of the fluorine compound is small, a molybdenum residue may be generated, and when it contains any one or two or more cyclic compounds selected from the group consisting of oxygen, sulfur, and nitrogen in the molecule When the content of the aromatic compound is increased, the etching rate of copper is significantly reduced, and it is difficult to perform the etching treatment.

為此，本發明包括底切抑制劑，藉此防止產生鉬層殘餘物並降低銅的蝕刻速率。 To this end, the present invention includes an undercut inhibitor, thereby preventing the occurrence of molybdenum layer residues and reducing the etching rate of copper.

根據本發明之示例性實施例的底切抑制劑可以是含有選自由嘧啶和咪唑的縮合結構中的胺基、羥基、羰基和甲基所組成之群組中的任一種或複數種官能基的化合物。 The undercut inhibitor according to an exemplary embodiment of the present invention may be any one or a plurality of functional groups selected from the group consisting of an amine group, a hydroxyl group, a carbonyl group, and a methyl group in a condensation structure of pyrimidine and imidazole. Compound.

該底切抑制劑含有在嘧啶和咪唑的縮合結構中的胺基、羥基、羰基和甲基所組成之群組中的任一種或複數種官能基，因而底切抑制效果大，且可以發揮優異的蝕刻特性改善效果。 The undercut inhibitor contains any one or a plurality of functional groups in a group consisting of an amine group, a hydroxyl group, a carbonyl group, and a methyl group in a condensation structure of a pyrimidine and an imidazole, so the undercut suppression effect is large and excellent Effect of improving the etching characteristics.

作為具體實例，該底切抑制劑可以是嘌呤鹼，其是選自由腺嘌呤、鳥糞嘌呤、異鳥糞嘌呤、次黃嘌呤、黃瞟呤、可可鹼、咖啡因及尿酸等所組成之群組中的任一種或兩種或更多種的混合物，且較佳是腺嘌呤、鳥糞嘌呤及異鳥糞嘌呤，但不限於此。 As a specific example, the undercut inhibitor may be a purine base, which is selected from the group consisting of adenine, guanine, isoguanosine, hypoxanthine, xanthine, theobromine, caffeine, and uric acid. Any one or a mixture of two or more, and is preferably, but not limited to, adenine, guanine, and isoguanine.

較佳是，基於100重量份的該過氧化氫，該底切抑制劑係以0.01重量份至20重量份被包括在內，更佳是以0.1重量份至20重量份被包括在內，又更佳是以1重量份至5重量份被包括在內。在該範圍內，由於使用該底切抑制劑的改善效果可能是優異的，並且蝕刻速率可能不會降低。 Preferably, the undercut inhibitor is included in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the hydrogen peroxide, and more preferably is included in an amount of 0.1 to 20 parts by weight. It is more preferably included in an amount of 1 to 5 parts by weight. Within this range, the improvement effect due to the use of the undercut inhibitor may be excellent, and the etching rate may not be reduced.

f)C4或更多碳數的烷基胺。 f) C 4 or more carbon amines.

當同時蝕刻銅層和鉬層時，由於銅層和鉬層的化學性質，會發生具有黏著強度差的部分。在此情況下，在蝕刻過程期間，該具有黏著強度差的部分可能會被蝕刻劑滲透。 When the copper layer and the molybdenum layer are etched at the same time, due to the chemical properties of the copper layer and the molybdenum layer, a portion having a poor adhesion strength occurs. In this case, during the etching process, the portion having poor adhesive strength may be penetrated by the etchant.

當不能控制滲透時，由於銅層和鉬層的界面的過度蝕刻導致降低的輪廓例如錐角差和佈線短路，可能會導致增加的缺陷率。 When the penetration cannot be controlled, reduced contours such as a difference in taper angle and wiring shorts due to excessive etching of the interface between the copper layer and the molybdenum layer may result in an increased defect rate.

為此，本發明使用C4或更多碳數的烷基胺，因而控制銅層和鉬層的界面的過度蝕刻以改善蝕刻輪廓，並且有效地降低缺陷率。 For this reason, the present invention uses an alkylamine having a carbon number of C 4 or more, thereby controlling excessive etching of the interface between the copper layer and the molybdenum layer to improve the etching profile and effectively reduce the defect rate.

具體地，該C4或更多碳數的烷基胺可以是C4至C16，較佳是C4至C8的直鏈或支鏈的烷基胺化合物。在該範圍內，該化合物可以選擇性地吸附在銅層和鉬層的黏著強度差的界面上，因而抑制蝕刻劑滲透到界面以控制銅層和鉬層的界面的過度蝕刻。此外，由於蝕刻劑組成物不具有氣泡，因此更佳為C4至C8烷基胺。然而，C3或低級烷基胺化合物可能不會抑制蝕刻劑滲透。 Specifically, the C 4 or more carbon number alkylamine may be a C 4 to C 16 , preferably C 4 to C 8 linear or branched alkylamine compound. Within this range, the compound can be selectively adsorbed on the interface with poor adhesion strength between the copper layer and the molybdenum layer, thereby suppressing the etchant from penetrating the interface to control the excessive etching of the interface between the copper layer and the molybdenum layer. In addition, since the etchant composition does not have bubbles, it is more preferably a C 4 to C 8 alkylamine. However, C 3 or lower alkylamine compounds may not inhibit the etchant penetration.

作為具體實例，該C4或更多碳數的烷基胺可 以是選自由丁胺、戊胺、己胺、庚胺、辛胺及2-乙基-1-己胺所組成之群組中的任一種或兩種或更多種的混合物。 As a specific example, the C 4 or more carbon number alkylamine may be selected from the group consisting of butylamine, pentylamine, hexylamine, heptylamine, octylamine, and 2-ethyl-1-hexylamine Any one or a mixture of two or more.

較佳是，基於100重量份的該過氧化氫，該C4或更多碳數的烷基胺係以0.1重量份至50重量份被包括在內，更佳是以1重量份至20重量份被包括在內，又更佳是以1重量份至10重量份被包括在內。在該範圍內，由於界面保護導致的界面的過度蝕刻控制效果可能是優異的。此外，不會產生鉬殘餘物，因而不會由於殘餘物導致電短路、佈線不良，且亮度不會降低。 Preferably, based on 100 parts by weight of the hydrogen peroxide, the alkylamine having C 4 or more carbon atoms is included in an amount of 0.1 to 50 parts by weight, and more preferably 1 to 20 parts by weight. Parts are included, and even more preferably from 1 to 10 parts by weight. Within this range, the excessive etching control effect of the interface due to the interface protection may be excellent. In addition, no molybdenum residue is generated, and thus no electrical short circuit or defective wiring is caused by the residue, and the brightness is not reduced.

g)氟化合物。 g) Fluorine compounds.

本發明可進一步在蝕刻劑組成物中包括氟化合物。該氟化合物在同時蝕刻銅層和鉬層時可以改善鉬層的蝕刻速率，因而降低尾部長度，並且用於移除蝕刻期間不可避免產生的鉬殘餘物。鉬的增加的尾部可能降低亮度，並且當殘餘物保留在基板和下層中時，會電短路、佈線不良和亮度降低，因此，較佳是必須移除該尾部。 The present invention may further include a fluorine compound in the etchant composition. The fluorine compound can improve the etching rate of the molybdenum layer when the copper layer and the molybdenum layer are etched at the same time, thereby reducing the tail length, and is used to remove the molybdenum residue inevitably generated during the etching. The increased tail of molybdenum may reduce the brightness, and when the residue remains in the substrate and the lower layer, it may be electrically short-circuited, the wiring is poor, and the brightness is reduced, so it is preferable to remove the tail.

根據本發明之示例性實施例的氟化合物可以是能夠解離產生F-或HF2 -的化合物。 The fluorine compound according to an exemplary embodiment of the present invention may be capable of dissociating to produce F - compound - or HF 2.

作為具體實例，該氟化合物可以是選自由HF、NaF、KF、AlF3、HBF4、NH4HF2、NaHF2、KHF2及NH4BF4所組成之群組中的任一種或兩種或更多種的混合物，但不限於此。 As a specific example, the fluorine compound may be any one or two selected from the group consisting of HF, NaF, KF, AlF 3 , HBF 4 , NH 4 HF 2 , NaHF 2 , KHF 2 and NH 4 BF 4 Or more, but not limited to this.

較佳是，基於100重量份的該過氧化氫，該氟化合物係以0.01重量份至20重量份被包括在內。在該範圍 內，鉬殘餘物可以被有效地移除，並且可以抑制諸如玻璃基板的下膜的蝕刻。 Preferably, the fluorine compound is included in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the hydrogen peroxide. Within this range, the molybdenum residue can be effectively removed, and the etching of the lower film such as a glass substrate can be suppressed.

h)水。 h) water.

本發明之蝕刻劑組成物可進一步包括水，且包含在該蝕刻劑組成物中的水不受特別限制，但是較佳可以是去離子水。作為具體實例，更佳是具有18MΩ/cm或更高電阻率值的去離子水，其中該電阻率是去除水中離子的程度。基於100重量份的過氧化氫，水可以200重量份至1000重量份被添加，更佳為以250重量份至800重量份被添加，又更佳為以300重量份至500重量份被添加。 The etchant composition of the present invention may further include water, and the water contained in the etchant composition is not particularly limited, but it may be deionized water. As a specific example, more preferred is deionized water having a resistivity value of 18 MΩ / cm or more, where the resistivity is a degree of removing ions in the water. Based on 100 parts by weight of hydrogen peroxide, water may be added at 200 to 1,000 parts by weight, more preferably at 250 to 800 parts by weight, and even more preferably at 300 to 500 parts by weight.

i)其他添加劑。 i) other additives.

根據本發明之示例性實施例的蝕刻劑組成物可進一步包括蝕刻劑組成物中通常使用的用於改善蝕刻性能的視需要的添加劑。作為添加劑，任一種或兩種或更多種的添加劑選自由過氧化氫穩定劑、蝕刻穩定劑及玻璃蝕刻抑制劑等所組成之群組。 The etchant composition according to the exemplary embodiment of the present invention may further include optional additives generally used in the etchant composition for improving etching performance. As the additive, any one or two or more additives are selected from the group consisting of a hydrogen peroxide stabilizer, an etching stabilizer, a glass etching inhibitor, and the like.

當蝕刻劑中的金屬離子含量由於重複的蝕刻製程而高時，該過氧化氫穩定劑可以用於控製過氧化氫分解反應。 When the metal ion content in the etchant is high due to the repeated etching process, the hydrogen peroxide stabilizer can be used to control the hydrogen peroxide decomposition reaction.

作為具體實例，該過氧化氫穩定劑可以是選自由磷酸、乙二醇和胺所組成之群組中的任一種或兩種或更多種的混合物。具體地，可以包括聚乙二醇，但不限於此。 As a specific example, the hydrogen peroxide stabilizer may be any one or a mixture of two or more selected from the group consisting of phosphoric acid, ethylene glycol, and amines. Specifically, polyethylene glycol may be included, but is not limited thereto.

在過氧化氫穩定劑包含在蝕刻劑組成物中的 情況下，基於100重量份的過氧化氫，其可以0.1重量份至30重量份被添加，更佳以1重量份至20重量份被添加，又更佳以5重量份至15重量份被添加。在該範圍內，過氧化氫穩定劑對過氧化氫分解反應具有優異的控制效果，並且不會降低蝕刻能力。 In the case where the hydrogen peroxide stabilizer is contained in the etchant composition, it may be added in an amount of 0.1 to 30 parts by weight, and more preferably 1 to 20 parts by weight, based on 100 parts by weight of hydrogen peroxide. And, more preferably, 5 to 15 parts by weight is added. Within this range, the hydrogen peroxide stabilizer has an excellent control effect on the hydrogen peroxide decomposition reaction without reducing the etching ability.

蝕刻穩定劑可以是同時具有醇基和胺基的化合物。作為具體實例，可以是選自由甲醇胺、乙醇胺、丙醇胺、丁醇胺、二乙醇胺、三乙醇胺、二甲基乙醇胺和N-甲基乙醇胺所組成之群組中的任一種或兩種或更多種的混合物，但不限於此。 The etching stabilizer may be a compound having both an alcohol group and an amine group. As a specific example, it may be any one or two or selected from the group consisting of methanolamine, ethanolamine, propanolamine, butanolamine, diethanolamine, triethanolamine, dimethylethanolamine, and N-methylethanolamine, or More kinds of mixtures, but not limited to this.

較佳是，基於100重量份的該過氧化氫，該蝕刻穩定劑係以0.01重量份至10重量份被添加，更佳是以0.05重量份至7重量份被添加，又更佳是以0.1重量份至5重量份被添加。在該範圍內，蝕刻穩定劑可以有效地抑制金屬殘餘物的產生。 Preferably, based on 100 parts by weight of the hydrogen peroxide, the etching stabilizer is added in an amount of 0.01 to 10 parts by weight, more preferably 0.05 to 7 parts by weight, and even more preferably 0.1. Part by weight to 5 parts by weight are added. Within this range, the etching stabilizer can effectively suppress the generation of metal residues.

玻璃蝕刻抑制劑可以是選自由氫氟硼酸和氫氟硼酸鹽所組成之群組中的任一種或複數種的混合物。作為具體實例，其可以是選自由HBF4、NaBF4、KBF4及NH4BF4所組成之群組中的任一種或兩種或更多種的混合物，但不限於此。 The glass etching inhibitor may be any one or a mixture of a plurality of members selected from the group consisting of hydrofluoric acid and hydrofluoroborate. As a specific example, it may be any one selected from the group consisting of HBF 4 , NaBF 4 , KBF 4 and NH 4 BF 4 or a mixture of two or more, but is not limited thereto.

較佳是，基於100重量份的該過氧化氫，該玻璃蝕刻抑制劑的含量是0.01重量份至10重量份，更佳是0.05重量份至7重量份，又更佳是0.1重量份至5重量份。在該範圍內，玻璃蝕刻抑制效果可能優異，並且蝕刻速率可 能不會降低。 Preferably, based on 100 parts by weight of the hydrogen peroxide, the content of the glass etching inhibitor is 0.01 to 10 parts by weight, more preferably 0.05 to 7 parts by weight, and still more preferably 0.1 to 5 parts by weight. Parts by weight. Within this range, the glass etching suppression effect may be excellent, and the etching rate may not be reduced.

具有上述組成物的本發明之蝕刻劑組成物在蝕刻銅層和鉬層時保護銅層和鉬層的界面，從而控制該界面上的過度蝕刻發生，以允許穩定的蝕刻製程。結果，可以改善諸如錐角、CD損失和視覺線性度的蝕刻特性。此外，可以容易地執行蝕刻速率調整。 The etchant composition of the present invention having the above composition protects the interface between the copper layer and the molybdenum layer when the copper layer and the molybdenum layer are etched, thereby controlling the occurrence of excessive etching on the interface to allow a stable etching process. As a result, etching characteristics such as taper angle, CD loss, and visual linearity can be improved. In addition, the etching rate adjustment can be easily performed.

因此，當使用銅層和鉬層作為構成液晶顯示器的薄膜電晶體(TFT)的柵極、源極或汲極電極的金屬佈線材料時，該蝕刻劑組成物可有效地用作用於形成金屬佈線圖案的蝕刻劑組成物。 Therefore, when a copper layer and a molybdenum layer are used as a metal wiring material for a gate, source, or drain electrode of a thin film transistor (TFT) constituting a liquid crystal display, the etchant composition can be effectively used for forming metal wiring Patterned etchant composition.

根據本發明之示例性實施例的銅層和鉬層可以是其中一個或複數個銅(Cu)層和一個或複數個鉬(Mo)層交替堆疊的多層，並且該多層可以包括銅(Cu)/鉬(Mo)雙層、以及銅(Cu)/鉬(Mo)/銅(Cu)或鉬(Mo)/銅(Cu)/鉬(Mo)三層，但不限於此。層順序可以根據基板的材質和黏合性質適當地調整。 The copper layer and the molybdenum layer according to an exemplary embodiment of the present invention may be multiple layers in which one or more copper (Cu) layers and one or more molybdenum (Mo) layers are alternately stacked, and the multiple layers may include copper (Cu) / Molybdenum (Mo) double layer, and copper (Cu) / molybdenum (Mo) / copper (Cu) or molybdenum (Mo) / copper (Cu) / molybdenum (Mo) three layers, but is not limited thereto. The layer order can be appropriately adjusted according to the material and adhesive properties of the substrate.

使用根據本發明之示例性實施例的蝕刻劑組成物的銅層和鉬層的蝕刻方法可以根據常規方法來進行。 The etching method of the copper layer and the molybdenum layer using the etchant composition according to the exemplary embodiment of the present invention may be performed according to a conventional method.

具體地，銅層和鉬層的蝕刻方法包括：在基板上沉積銅/鉬層。 Specifically, the etching method of the copper layer and the molybdenum layer includes: depositing a copper / molybdenum layer on the substrate.

在該銅層和鉬層上形成光阻劑層，並圖案化該光阻劑層。 A photoresist layer is formed on the copper layer and the molybdenum layer, and the photoresist layer is patterned.

可進行使用本發明之蝕刻劑組成物來蝕刻其上形成有圖案化的光阻劑層的銅層和鉬層。此處，形成在 基板上的銅/鉬層的堆疊順序沒有特別限制。 The use of the etchant composition of the present invention may be performed to etch a copper layer and a molybdenum layer on which a patterned photoresist layer is formed. Here, the stacking order of the copper / molybdenum layers formed on the substrate is not particularly limited.

此外，蝕刻方法可包括在基板與銅層和鉬層之間，亦即在基板與銅層之間，或者在基板與鉬層之間形成半導體結構。 In addition, the etching method may include forming a semiconductor structure between the substrate and the copper layer and the molybdenum layer, that is, between the substrate and the copper layer, or between the substrate and the molybdenum layer.

該半導體結構可以是用於諸如液晶顯示器和電漿顯示面板的顯示器的半導體結構。 The semiconductor structure may be a semiconductor structure used for displays such as a liquid crystal display and a plasma display panel.

具體地，該半導體結構可包括選自由介電膜、導電膜以及諸如非晶質或多晶膜的矽膜所組成之群組中的一層或複數層。該半導體結構可以根據常規方法製造。 Specifically, the semiconductor structure may include one or more layers selected from the group consisting of a dielectric film, a conductive film, and a silicon film such as an amorphous or polycrystalline film. The semiconductor structure can be manufactured according to a conventional method.

在下文中，將藉由以下實例更詳細地描述根據本發明之蝕刻劑組成物及其製備方法。然而，下文的實例僅是用於詳細描述本發明的參考，並且本發明不限於此，且可以各種形式實施。 Hereinafter, the etchant composition according to the present invention and a preparation method thereof will be described in more detail by the following examples. However, the following examples are merely references for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

此外，除非另外定義，否則所有技術術語和科學術語具有與本案所屬技術領域中具有通常知識者通常理解的那些相同的含義。本文使用的術語僅用於有效地描述特定的示例性實施例，而不意欲在限制本發明。 In addition, unless otherwise defined, all technical and scientific terms have the same meaning as those commonly understood by those having ordinary knowledge in the technical field to which this case belongs. The terminology used herein is used merely to effectively describe a specific exemplary embodiment, and is not intended to limit the present invention.

此外，下文提供的圖式藉由舉例的方式提供，使得本發明的思想可以被充分地傳遞給本案所屬技術領域中具有通常知識者。因此，本發明不限於下文提供的圖式，而是可以許多不同的形式進行修改。此外，為了清楚本發明的精神和範圍，下文提供的圖式將被誇大。 In addition, the drawings provided below are provided by way of example, so that the idea of the present invention can be fully transferred to those with ordinary knowledge in the technical field to which this case belongs. Therefore, the present invention is not limited to the drawings provided below, but may be modified in many different forms. In addition, in order to clarify the spirit and scope of the present invention, the drawings provided below will be exaggerated.

此外，除非在上下文中另外指出，否則說明書和隨附的申請專利範圍中使用的單數形式亦可意欲包括 複數形式。 In addition, the singular forms used in the specification and the scope of the appended patent application may also be intended to include the plural forms unless otherwise indicated in the context.

[實例1至實例29、以及比較例1至比較例13] [Examples 1 to 29, and Comparative Examples 1 to 13]

以下表1中列出的組分含量(重量%)混合各組分，從而製備根據本發明之蝕刻劑組成物。 The component contents (% by weight) listed in Table 1 below are mixed with each other to prepare an etchant composition according to the present invention.

上表1中列出的組分如下。 The components listed in Table 1 above are as follows.

作為含有選自由分子中的氧、硫及氮所組成之群組中之任一種或二種或更多種的環狀化合物或芳香族化合物，使用以ATZ表示的5-胺基四唑。 As a cyclic compound or an aromatic compound containing any one or two or more members selected from the group consisting of oxygen, sulfur, and nitrogen in a molecule, 5-aminotetrazole represented by ATZ is used.

作為胺基羧酸系化合物或胺基磷酸系化合物，使用以IDA表示的亞胺基二乙酸。 As the aminocarboxylic acid-based compound or aminophosphoric acid-based compound, imine diacetic acid represented by IDA is used.

作為選自由有機酸、無機酸及其鹽之任一種或二種或更多種的化合物，使用以AHP表示的磷酸氫銨。 As a compound selected from any one or two or more of an organic acid, an inorganic acid, and a salt thereof, ammonium hydrogen phosphate represented by AHP is used.

作為氟化合物，使用NH4HF2。作為底切抑制劑，使用鳥糞嘌呤。 As the fluorine compound, NH 4 HF 2 was used . As an undercutting inhibitor, guanine was used.

作為C4或更多碳數的烷基胺，使用丁胺、戊胺、己胺、庚胺、辛胺和2-乙基-1-己胺。 As the alkylamine having C 4 or more carbon numbers, butylamine, pentylamine, hexylamine, heptylamine, octylamine, and 2-ethyl-1-hexylamine are used.

丁胺以b-AM表示，戊胺以pn-AM表示，己胺以hx-AM表示，庚胺以hp-AM表示，辛胺以o-AM表示，以及2-乙基-1-己胺以2-e-1-hx-A表示。 Butylamine is represented by b-AM, pentylamine is represented by pn-AM, hexylamine is represented by hx-AM, heptylamine is represented by hp-AM, octylamine is represented by o-AM, and 2-ethyl-1-hexylamine Expressed as 2-e-1-hx-A.

在比較例中，使用丙胺、乙胺和環己胺作為烷基胺，且該丙胺、該乙胺和該環己胺分別以pr-AM、e-AM和cyhx-AM表示。 In the comparative examples, propylamine, ethylamine, and cyclohexylamine were used as the alkylamines, and the propylamine, the ethylamine, and the cyclohexylamine were respectively represented by pr-AM, e-AM, and cyhx-AM.

[實驗例：蝕刻性能評估] [Experimental example: Evaluation of etching performance]

在玻璃基板上，分別依次沉積具有5500Å的厚度的銅層和鉬層以製造試樣。對該試樣進行光蝕刻製程以形成圖案化的光阻膜，並分別使用實例1至實例29和比較例1至比較例13的蝕刻劑組成物對銅層和鉬層進行蝕刻。此處，使用可噴射設備(小型蝕刻機ME-001)在32℃下進行120秒的蝕刻製程。 On the glass substrate, a copper layer and a molybdenum layer each having a thickness of 5500Å were sequentially deposited to produce a sample. The sample is subjected to a photo-etching process to form a patterned photoresist film, and the copper and molybdenum layers are etched using the etchant compositions of Examples 1 to 29 and Comparative Examples 1 to 13, respectively. Here, an etching process was performed using a sprayable device (small etching machine ME-001) at 32 ° C for 120 seconds.

在完成蝕刻之後，測量蝕刻終點。此外，使用掃描型電子顯微鏡(Hitachi,S-4800)，觀察蝕刻的銅層和鉬層的蝕刻特性，諸如CD損失、錐角、或銅層和鉬層的界面的過度蝕刻的存在或不存在等。該銅層和鉬層的界面的過度蝕刻的存在或不存在可以藉由傾斜該試樣使用掃描型電子顯微鏡來確認。結果顯示在下表2。 After the etching is completed, the etching end point is measured. In addition, using a scanning electron microscope (Hitachi, S-4800), the etching characteristics of the etched copper layer and the molybdenum layer were observed, such as the CD loss, the taper angle, or the presence or absence of over-etching of the interface between the copper layer and the molybdenum layer. Wait. The presence or absence of excessive etching at the interface between the copper layer and the molybdenum layer can be confirmed by using a scanning electron microscope by tilting the sample. The results are shown in Table 2 below.

上表2表示蝕刻性能評估。如上表2所示，與比較例1至比較例13的蝕刻劑組成物相比，根據本發明之實例1至實例29的蝕刻劑組成物含有C4或更多碳數的烷基胺，因而在所有蝕刻偏差、CD損失、錐角方面均表現優異的結果。 Table 2 above shows the evaluation of the etching performance. As shown in Table 2 above, the etchant compositions according to Examples 1 to 29 of the present invention contain C 4 or more alkylamines, as compared with the etchant compositions of Comparative Examples 1 to 13, and therefore, Excellent results in all etching deviations, CD losses, and taper angles.

特別地，當將實例4、實例6、實例11、實例 17和實例25與未添加氟化合物的實例5、實例7、實例12、實例19和實例23進行比較時，實例4、實例6、實例11、實例17和實例25具有改善的鉬層的蝕刻速率且沒有惡化過度蝕刻控制效果，因此具有降低的尾部長度，且能有效地從其中移除鉬殘餘物。 Specifically, when comparing Example 4, Example 6, Example 11, Example 17 and Example 25 with Examples 5, Example 7, Example 12, Example 19 and Example 23 without the addition of a fluorine compound, Example 4, Example 6, Example 23 11. Examples 17 and 25 have an improved etch rate of the molybdenum layer without deteriorating the effect of the over-etch control, and thus have a reduced tail length and can effectively remove molybdenum residues therefrom.

比較例1至比較例7包括C3丙胺，因而不能抑制蝕刻劑滲透到銅層和鉬層界面，結果存在過度蝕刻。此外，比較例8包括C2乙胺，因而引起過度蝕刻。 Since Comparative Examples 1 to 7 included C 3 propylamine, it was impossible to suppress the etchant from penetrating to the interface between the copper layer and the molybdenum layer, and as a result, there was excessive etching. In addition, Comparative Example 8 included C 2 ethylamine, and thus caused excessive etching.

比較例9不包括作為含有選自由分子中的氧、硫及氮所組成之群組中之任一種或二種或更多種的環狀化合物或芳香族化合物的5-胺基四唑，使得難以控制蝕刻速率，且錐形的形式差。比較例10不包括作為胺基羧酸系化合物或胺基磷酸系化合物的亞胺基二乙酸(IDA)，因此導致過度蝕刻的過氧化氫分解反應的控制能力差。比較例11不包括作為選自由有機酸、無機酸及其鹽之任一種或二種或更多種的化合物的磷酸氫銨(AHP)，因而具有高錐角值。比較例12不包括作為底切抑制劑的鳥糞嘌呤，因而產生鉬殘餘物，具具有高錐角。比較例13包括作為環狀胺化合物的環己胺，因而不能控制導致過度蝕刻的過度蝕刻抑制。 Comparative Example 9 does not include 5-aminotetrazole as a cyclic compound or an aromatic compound containing any one or two or more members selected from the group consisting of oxygen, sulfur, and nitrogen in a molecule such that It is difficult to control the etching rate and the form of the cone is poor. Comparative Example 10 did not include imino diacetic acid (IDA) as an amino carboxylic acid-based compound or an amino phosphoric acid-based compound, and therefore the control ability of the hydrogen peroxide decomposition reaction that caused excessive etching was poor. Comparative Example 11 does not include ammonium hydrogen phosphate (AHP) as a compound selected from any one or two or more of an organic acid, an inorganic acid, and a salt thereof, and thus has a high cone angle value. Comparative Example 12 did not include guanopurine as an undercut inhibitor, and thus produced a molybdenum residue with a high cone angle. Comparative Example 13 includes cyclohexylamine, which is a cyclic amine compound, and thus cannot suppress excessive etching suppression that causes excessive etching.

此外，為了觀察在銅層與鉬層之間是否發生界面過度蝕刻，使用實例1、實例6和實例11、以及比較例1和比較例6的蝕刻劑組成物來蝕刻銅層和鉬層，並使用掃描型電子顯微鏡傾斜和觀察該銅層和鉬層的試樣的剖面。結果顯示在圖1、圖2、圖3、圖4和圖5。 In addition, in order to observe whether an interface over-etching occurred between the copper layer and the molybdenum layer, the etchant composition of Example 1, Example 6, and Example 11, and Comparative Examples 1 and 6 was used to etch the copper layer and the molybdenum layer, and A cross section of the sample of the copper layer and the molybdenum layer was tilted and observed using a scanning electron microscope. The results are shown in Figures 1, 2, 3, 4, and 5.

圖1、圖2和圖3示出分別使用根據實例1、實例6和實例11的蝕刻劑組成物蝕刻銅層和鉬層，然後使用掃描型電子顯微鏡傾斜從側面觀察的試樣的剖面所獲得的照片。 FIG. 1, FIG. 2 and FIG. 3 show obtained by etching a copper layer and a molybdenum layer using an etchant composition according to Example 1, Example 6, and Example 11, respectively, and then obliquely cutting a cross section of a sample viewed from the side using a scanning electron microscope Photo.

圖4和圖5示出分別使用根據比較例1和比較例6的蝕刻劑組成物蝕刻銅層和鉬層，然後使用掃描型電子顯微鏡傾斜觀察的試樣的剖面所獲得的照片。 4 and 5 show photographs obtained by etching a copper layer and a molybdenum layer using an etchant composition according to Comparative Examples 1 and 6, respectively, and then obliquely observing a cross section of a sample using a scanning electron microscope.

如圖1、圖2和圖3所示，使用本發明之實例1、實例6和實例11的蝕刻劑組成物蝕刻該等層的結果，證實沒有觀察到銅/鉬層界面的過度蝕刻。 As shown in FIGS. 1, 2 and 3, the results of etching the layers using the etchant compositions of Examples 1, 6 and 11 of the present invention confirmed that no over-etching of the copper / molybdenum interface was observed.

然而，當使用比較例1和比較例6的蝕刻劑組成物時，可證實不佳的視覺輪廓，這是因在銅和鉬層界面上發生過度蝕刻以擴大界面間隙，如圖4和圖5所示。 However, when the etchant compositions of Comparative Examples 1 and 6 were used, poor visual contours could be confirmed due to excessive etching at the interface of the copper and molybdenum layers to expand the interfacial gap, as shown in FIGS. 4 and 5 As shown.

此外，藉由掃描型電子顯微鏡觀察被蝕刻以確認蝕刻特性的銅層和鉬層的試樣的部面。結果顯示在圖6和圖7。 In addition, a scanning electron microscope was used to observe the surface of a sample of a copper layer and a molybdenum layer that had been etched to confirm the etching characteristics. The results are shown in Figures 6 and 7.

圖6示出使用根據實例1的蝕刻劑組成物蝕刻銅層和鉬層之後，藉由掃描型電子顯微鏡觀察到試樣的剖面的照片，而圖7示出使用根據比較例6的蝕刻劑組成物蝕刻銅/鉬層之後，藉由掃描型電子顯微鏡觀察到試樣的剖面的照片。 FIG. 6 shows a photograph of a cross section of a sample observed by a scanning electron microscope after etching a copper layer and a molybdenum layer using the etchant composition according to Example 1, and FIG. 7 shows a composition using the etchant according to Comparative Example 6 After the copper / molybdenum layer was etched, a photograph of a cross section of the sample was observed with a scanning electron microscope.

如圖6所示，當使用實例1的蝕刻劑組成物時，蝕刻特性優異。 As shown in FIG. 6, when the etchant composition of Example 1 is used, the etching characteristics are excellent.

如圖7所示，當使用比較例6的蝕刻劑組成物 時，藉由銅和鉬層界面的過度蝕刻顯示出倒錐形的形式的不佳蝕刻特性。 As shown in Fig. 7, when the etchant composition of Comparative Example 6 was used, excessive etching by the copper and molybdenum layer interface showed poor etching characteristics in the form of an inverted cone.

如上所述，當蝕刻銅層和鉬層時，根據本發明之蝕刻劑組成物藉由控制銅和鉬層界面的過度蝕刻允許穩定的蝕刻製程。此外，如結果，證實了改善蝕刻特性諸如錐角、CD損失和視覺線性度。 As described above, when the copper layer and the molybdenum layer are etched, the etchant composition according to the present invention allows a stable etching process by controlling excessive etching at the interface of the copper and molybdenum layers. Further, as a result, it was confirmed that the etching characteristics such as taper angle, CD loss, and visual linearity were improved.

在上文中，儘管已經描述本發明的較佳示例性實施例，然而，各種修改和等同物可被用於本發明，顯然上述實例可被適當地修改和相同地應用。因此，上述說明不受限於以下申請專利範圍定義的本發明的範圍。 In the above, although the preferred exemplary embodiment of the present invention has been described, various modifications and equivalents can be used for the present invention, and it is apparent that the above-mentioned examples can be appropriately modified and applied the same. Therefore, the above description is not limited to the scope of the present invention defined by the scope of the following patent applications.

Claims (13)

一種蝕刻劑組成物，包括：過氧化氫；含有選自由分子中的氧、硫及氮所組成之群組中之任一種或二種或更多種的環狀化合物或芳香族化合物；胺基羧酸系化合物或胺基磷酸系化合物；選自由有機酸、無機酸及其鹽所組成之群組中之任一種或二種或更多種的化合物；底切抑制劑；以及C 4或更多碳數的烷基胺。 An etchant composition comprising: hydrogen peroxide; a cyclic compound or an aromatic compound containing any one or two or more members selected from the group consisting of oxygen, sulfur, and nitrogen in a molecule; an amine group A carboxylic acid-based compound or an amino-phosphoric acid-based compound; a compound selected from any one or two or more of the group consisting of organic acids, inorganic acids, and salts thereof; undercut inhibitors; and C 4 or more Multi-carbon alkylamine. 如請求項1所記載之蝕刻劑組成物，其中，基於100重量份的該過氧化氫，該蝕刻劑組成物包括0.1重量份至50重量份的該環狀化合物或該芳香族化合物；0.1重量份至50重量份的該胺基羧酸系化合物或該胺基磷酸系化合物；0.1重量份至50重量份的該選自由有機酸、無機酸及其鹽所組成之群組中之任一種或二種或更多種的化合物；0.01重量份至20重量份的該底切抑制劑；以及0.1重量份至50重量份的該烷基胺。     The etchant composition according to claim 1, wherein the etchant composition includes the cyclic compound or the aromatic compound in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the hydrogen peroxide; Parts to 50 parts by weight of the amino carboxylic acid-based compound or the amino phosphate-based compound; 0.1 to 50 parts by weight of any one selected from the group consisting of an organic acid, an inorganic acid, and a salt thereof, or Two or more compounds; 0.01 to 20 parts by weight of the undercut inhibitor; and 0.1 to 50 parts by weight of the alkylamine.     如請求項1所記載之蝕刻劑組成物，其進一步包括氟化合物。     The etchant composition according to claim 1, further comprising a fluorine compound.     如請求項3所記載之蝕刻劑組成物，其中，基於100重量份的該過氧化氫，該氟化合物係以0.01重量份至20重量份被添加。     The etchant composition according to claim 3, wherein the fluorine compound is added in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the hydrogen peroxide.     如請求項1所記載之蝕刻劑組成物，其中，該C 4或更多碳數的烷基胺係C 4至C 16直鏈或支鏈的烷基胺化合物。 The etchant composition according to claim 1, wherein the C 4 or more carbon amine alkylamine is a C 4 to C 16 linear or branched alkyl amine compound. 如請求項5所記載之蝕刻劑組成物，其中，該C 4或更多碳數的烷基胺係選自由丁胺、戊胺、己胺、庚胺、辛胺及2-乙基-1-己胺所組成之群組中的任一種或兩種或更多種的混合物。 The etchant composition according to claim 5, wherein the C 4 or more alkyl amine is selected from the group consisting of butylamine, pentylamine, hexylamine, heptylamine, octylamine, and 2-ethyl-1 -Any one or a mixture of two or more of the group consisting of hexylamine. 如請求項1所記載之蝕刻劑組成物，其中，該環狀化合物或該芳香族化合物係選自由噁唑、咪唑、吡唑、***、四唑、5-胺基四唑、甲基四唑、哌嗪、甲基哌嗪、羥乙基哌嗪、苯并咪唑、苯并吡唑、甲基苯并***、氫甲基苯并***及羥甲基苯并***所組成之群組中的任一種或兩種或更多種的混合物。     The etchant composition according to claim 1, wherein the cyclic compound or the aromatic compound is selected from the group consisting of oxazole, imidazole, pyrazole, triazole, tetrazole, 5-aminotetrazole, and methyltetrazol. Azole, piperazine, methylpiperazine, hydroxyethylpiperazine, benzimidazole, benzopyrazole, methylbenzotriazole, hydromethylbenzotriazole, and hydroxymethylbenzotriazole Any one or a mixture of two or more in a group.     如請求項1所記載之蝕刻劑組成物，其中，該胺基羧酸系化合物或該胺基磷酸系化合物包括在分子中具有胺基的羧酸基或膦酸基。     The etchant composition according to claim 1, wherein the aminocarboxylic acid-based compound or the aminophosphoric acid-based compound includes a carboxylic acid group or a phosphonic acid group having an amine group in a molecule.     如請求項1所記載之蝕刻劑組成物，其中，該胺基羧酸系化合物或該胺基磷酸系化合物係選自由亞胺基二乙酸、氮基三乙酸、乙二胺四乙酸、二伸乙三胺五乙酸、胺基參(亞甲基膦酸)、(1-羥基乙烷-1,1-二基)雙(亞膦酸)、乙二胺肆(亞甲基膦酸)、二伸乙基三胺 五(亞甲基膦酸)、丙胺酸、麩胺酸、胺基丁酸及甘胺酸所組成之群組中的任一種或兩種或更多種的混合物。     The etchant composition according to claim 1, wherein the aminocarboxylic acid-based compound or the aminophosphoric acid-based compound is selected from the group consisting of iminodiacetic acid, nitrogen triacetic acid, ethylenediaminetetraacetic acid, and diethylene glycol. Ethylene triamine pentaacetic acid, amino reference (methylene phosphonic acid), (1-hydroxyethane-1,1-diyl) bis (phosphinic acid), ethylene diamine (methylene phosphonic acid), Any one or a mixture of two or more of the group consisting of diethylenetriaminepenta (methylenephosphonic acid), alanine, glutamic acid, aminobutyric acid, and glycine.     如請求項1所記載之蝕刻劑組成物，其中，該有機酸係選自由乙酸、甲酸、丁酸、檸檬酸、乙醇酸、草酸、丙二酸、戊酸、丙酸、酒石酸、蘋果酸、葡萄糖酸、醛糖酸及琥珀酸所組成之群組中的任一種或兩種或更多種的混合物；該無機酸係選自由硫酸、硝酸及磷酸所組成之群組中的任一種或兩種或更多種的混合物；該無機酸鹽和該有機酸鹽係選自由磷酸氫鉀、磷酸氫鈉、磷酸氫銨、磷酸鈉、過磷酸鈉、磷酸鉀、過磷酸鉀、磷酸銨及過磷酸銨所組成之群組中的任一種或兩種或更多種的混合物。     The etchant composition according to claim 1, wherein the organic acid is selected from the group consisting of acetic acid, formic acid, butyric acid, citric acid, glycolic acid, oxalic acid, malonic acid, valeric acid, propionic acid, tartaric acid, malic acid, Any one or a mixture of two or more of the group consisting of gluconic acid, aldonic acid and succinic acid; the inorganic acid is selected from any one or two of the group consisting of sulfuric acid, nitric acid and phosphoric acid A mixture of two or more; the inorganic acid salt and the organic acid salt are selected from the group consisting of potassium hydrogen phosphate, sodium hydrogen phosphate, ammonium hydrogen phosphate, sodium phosphate, sodium superphosphate, potassium phosphate, potassium superphosphate, ammonium phosphate and Any one or a mixture of two or more of the group consisting of ammonium phosphate.     如請求項3所記載之蝕刻劑組成物，其中，該氟化合物係選自由HF、NaF、KF、AlF 3、HBF 4、NH 4HF 2、NaHF 2、KHF 2及NH 4BF 4所組成之群組中的任一種或兩種或更多種的混合物。 The etchant composition according to claim 3, wherein the fluorine compound is selected from the group consisting of HF, NaF, KF, AlF 3 , HBF 4 , NH 4 HF 2 , NaHF 2 , KHF 2 and NH 4 BF 4 Any one or a mixture of two or more in a group. 如請求項1所記載之蝕刻劑組成物，其中，該底切抑制劑係選自由腺嘌呤、鳥糞嘌呤、異鳥糞嘌呤、次黃嘌呤、黃嘌呤、可可鹼、咖啡因及尿酸所組成之群組中的任一種或兩種或更多種的混合物。     The etchant composition according to claim 1, wherein the undercut inhibitor is selected from the group consisting of adenine, guanine, isoguanine, hypoxanthine, xanthine, theobromine, caffeine, and uric acid Any one or a mixture of two or more of the groups.     如請求項1所記載之蝕刻劑組成物，其進一步包括選自由過氧化氫穩定劑、蝕刻穩定劑及玻璃蝕刻抑制劑所組成之群組中的任一種或兩種或更多種的混合物。     The etchant composition according to claim 1, further comprising any one or a mixture of two or more selected from the group consisting of a hydrogen peroxide stabilizer, an etching stabilizer, and a glass etching inhibitor.    
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