TWI433909B - Etchant for thin film transistor-liquid crystal displays - Google Patents

Etchant for thin film transistor-liquid crystal displays Download PDF

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TWI433909B
TWI433909B TW097108299A TW97108299A TWI433909B TW I433909 B TWI433909 B TW I433909B TW 097108299 A TW097108299 A TW 097108299A TW 97108299 A TW97108299 A TW 97108299A TW I433909 B TWI433909 B TW I433909B
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weight
compound
acid
group
etching
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TW200844215A (en
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Jong Hyun Choung
Hong Sick Park
Sun Young Hong
Bong Kyun Kim
Ji Sun Lee
Byeong Jin Lee
Ki Beom Lee
Sam Young Cho
Byung Soo Ku
Hyun Cheol Shin
Won Guk Seo
Kwi Hong Park
Tae Sung Ha
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Dongjin Semichem Co Ltd
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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
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • 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
    • 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
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
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  • Metallurgy (AREA)
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  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
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  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Weting (AREA)
  • ing And Chemical Polishing (AREA)

Description

用於薄膜電晶體液晶顯示裝置之蝕刻液組成物Etching liquid composition for thin film transistor liquid crystal display device 發明領域Field of invention

本發明係有關用於薄膜電晶體液晶顯示裝置之蝕刻液組成物者，更詳細言之，係有關薄膜電晶體液晶顯示裝置(thin film transistor－liquid crystal display device，TFT－LCD device)的製造步驟中所用之蝕刻液組成物。The present invention relates to an etchant composition for a thin film transistor liquid crystal display device, and more particularly, a manufacturing process for a thin film transistor-liquid crystal display device (TFT-LCD device) The etchant composition used in the process.

發明背景Background of the invention

液晶顯示元件(liquid crystal display device，LCD device)係藉由優良之解像度以提供鮮明之映像，由於具有電力消耗少，可使顯示畫面薄層化之特性，在平板顯示裝置之中最備受注目者。最近作為驅動此類液晶顯示裝置之電子回路的代表者，非薄膜電晶體(thin film transistor，TFT)回路莫屬。在TFT－LCD製造時，首先，在玻璃基板上以閘極及源極/汲極(source/drain)作為電極用配線材料，將金屬層積層，隨後就進行該金屬層以具腐蝕性之氣體或溶液蝕刻，以實現期望之電氣回路的線路之蝕刻(etching)製程。A liquid crystal display device (LCD device) provides a clear image with excellent resolution, and has a characteristic of thinning the display screen due to low power consumption, and is most attracting attention among flat panel display devices. By. Recently, as a representative of an electronic circuit that drives such a liquid crystal display device, a non-thin film transistor (TFT) circuit is a necessity. In the manufacture of a TFT-LCD, first, a gate layer and a source/drain are used as electrode wiring materials on a glass substrate, and a metal layer is laminated, and then the metal layer is subjected to a corrosive gas. Or solution etching to achieve the etching process of the desired electrical circuit trace.

TFT基板上由於置有許多之薄膜、薄層，在該等之間，為防止發生電力的短路，在已蝕刻基板之橫切面側面，即，蝕刻輪廓(profile)呈均等地傾斜成之下方寬過上方，以呈顯緩緩的錐形(taper)形狀為佳。蝕刻輪廓如成為緩緩的錐形形狀，係在於減少所形成的複數薄膜層之間的段差。閘極金屬之蝕刻模式無法達到均勻且精密時，會發生TFT－LCD映 像之解像度降低且色彩不正確之問題。蝕刻方法中雖有利用氣體之乾式蝕刻及利用蝕刻液之濕式蝕刻，但不拘於濕式蝕刻所具之缺點，由於對於製程所需之設備投資費用低、對於蝕刻環境不需維持之於高真空狀態，對於遮蔽及基板，均具有優良的蝕刻選擇性之長處，因此對於濕式蝕刻液之需要仍持續存在。Since a plurality of thin films and thin layers are disposed on the TFT substrate, in order to prevent short-circuiting of electric power, the side surface of the cross-section of the etched substrate, that is, the etching profile is uniformly inclined downward to be wide. Over the top, it is better to have a slowly tapered shape. The etched profile, such as a tapered shape, is designed to reduce the step difference between the plurality of formed thin film layers. When the etching mode of the gate metal cannot be uniform and precise, a TFT-LCD image will occur. Like the problem of reduced resolution and incorrect color. Although the etching method uses dry etching using a gas and wet etching using an etching liquid, it does not deviate from the disadvantages of wet etching, because the investment cost for the equipment required for the process is low, and the etching environment is not required to be maintained high. The vacuum state has excellent etch selectivity advantages for both the mask and the substrate, so the need for a wet etchant persists.

回路之小型化、積層化為電子業界之一貫潮流，TFT中雖亦無例外，但回路之小型化、積層化愈進步回線愈細，產生電阻相對地增加愈大之問題點。由於電阻係引起RC信號延遲之主要因子。特別於TFT時，業界之傾向雖趨重於面板之大小愈增大且解像度提高之方向，而電阻可否維持於低值是成為面板大小之增大及解像度之實現的關鍵。因此，為要實現TFT－LCD之大型化中所必須要求之減少RC信號延遲，雖有必須開發具低電阻之物質，但以往作為回線材料以使用鉻、鉬、鋁及該等之合金為主，其電阻值較大，故不適於作為未來之大型TFT－LCD電極配線。The miniaturization and stratification of the circuit has always been the trend of the electronics industry. Although there are no exceptions in the TFT, the miniaturization and stratification of the circuit are becoming more and more fine, and the problem that the resistance is relatively increased is larger. The main factor of the RC signal delay due to the resistance. Especially in the case of TFTs, the trend in the industry tends to increase the size of the panel and increase the resolution, and whether the resistance can be maintained at a low value is the key to the increase of the panel size and the realization of the resolution. Therefore, in order to reduce the RC signal delay required to achieve a large-scale TFT-LCD, it is necessary to develop a material having a low resistance. However, in the past, chromium, molybdenum, aluminum, and the like have been mainly used as the return material. , its resistance value is large, so it is not suitable for future large TFT-LCD electrode wiring.

另一方面，銅係導電率優良且儲藏量豐富之金屬，銅膜使用於TFT配線時，其電阻顯著地比鋁膜或鉻膜低且具有對環境更為親和之長處。但，由於銅對於氧化劑之抵抗性高於鋁或鉻，故必須使用含有更強烈的氧化劑之蝕刻液。此類之氧化劑有過氧化氫(H2 O2 )及高鐵【Fe(III)】等廣被使用。On the other hand, a copper-based metal having excellent conductivity and a large amount of storage, when used for a TFT wiring, has a significantly lower electrical resistance than an aluminum film or a chromium film and has a more affinity for the environment. However, since copper is more resistant to oxidizing agents than aluminum or chromium, it is necessary to use an etching solution containing a stronger oxidizing agent. Such oxidizing agents are widely used such as hydrogen peroxide (H 2 O 2 ) and high-iron [Fe(III)].

具體而言，過氧化氫時，在下述專利文獻1對於作為銅膜之蝕刻溶液，揭示有過氧化氫與無機酸或中性鹽之混合 物；下述專利文獻2揭示有過氧化氫、銅反應抑制劑、水合物穩定化劑、氟化離子之組成物；下述專利文獻3揭示有在過氧化氫中添加含有氟化合物、有機分子等5種添加劑的構成。Specifically, in the case of hydrogen peroxide, in the following Patent Document 1, a mixture of hydrogen peroxide and a mineral acid or a neutral salt is disclosed as an etching solution for a copper film. Patent Document 2 discloses a composition of hydrogen peroxide, a copper reaction inhibitor, a hydrate stabilizer, and a fluoride ion; Patent Document 3 listed below discloses the addition of a fluorine compound or an organic molecule to hydrogen peroxide. The composition of five kinds of additives.

高鐵氧化劑時，下述專利文獻4揭示有氯化鐵(III)6水合物及氟化氫酸之混合物。一方面，作為含銅多層膜之蝕刻溶液，在下述專利文獻5亦揭示有使用磷酸、硝酸、醋酸之通用蝕刻液之構成。In the case of a high-iron oxidizing agent, Patent Document 4 below discloses a mixture of iron (III) chloride 6 hydrate and hydrogen fluoride. On the other hand, as an etching solution for a copper-containing multilayer film, a configuration using a general-purpose etching liquid of phosphoric acid, nitric acid, or acetic acid is also disclosed in Patent Document 5 below.

但是，該蝕刻液引起銅膜與其他的金屬層積層形成之半導體基板之蝕刻速度過快，引起被蝕刻的金屬膜之錐形輪廓超過90度等不良蝕刻之問題點。尤其是廣被使用之過氧化氫，特別由於在銅及鐵離子存在下，引起不均化作用(disproportionation)而分解為水及氧(參照下述專利文獻6)，會產生發熱及激烈之組成變化，因此於製程範圍及穩定性發生很多問題。為解決此種之問題，雖使用添加有水合物穩定化劑，由於價格高昂成為費用提高之原因。However, the etching liquid causes the etching speed of the semiconductor substrate formed by laminating the copper film and other metal layers to be too fast, causing problems such as poor etching such as a tapered profile of the etched metal film exceeding 90 degrees. In particular, hydrogen peroxide which is widely used is decomposed into water and oxygen in particular in the presence of copper and iron ions, and is decomposed into water and oxygen (see Patent Document 6 below), which causes heat generation and intense composition. Changes, so there are many problems in the scope and stability of the process. In order to solve such a problem, although the use of a hydrate-stabilizing agent is added, the cost is increased because of the high price.

【專利文獻1】大韓民國公開專利第2000－079355號 【專利文獻2】大韓民國公開專利第2005－000682號 【專利文獻3】大韓民國公開專利第2006－064881號 【專利文獻4】大韓民國公開專利第2000－032999號 【專利文獻5】大韓民國公開專利第1999－017836號 【專利文獻6】美國登錄專利第4140772號[Patent Document 1] Republic of Korea Open Patent No. 2000-079355 [Patent Document 2] Republic of Korea Open Patent No. 2005-000682 [Patent Document 3] Republic of Korea Open Patent No. 2006-064881 [Patent Document 4] Republic of Korea Open Patent No. 2000-032999 [Patent Document 5] Republic of Korea Open Patent No. 1999-017836 [Patent Document 6] U.S. Patent No. 4140772

發明揭示Invention

本發明之目的在於提供一種優良蝕刻液，可保障穩定性高及製程範圍，且將含銅金屬層作成均等的錐形蝕刻。本發明係藉由提供不使用過氧化氫之蝕刻液，以解決製程範圍及穩定性、添加水合物穩定化劑等一類之問題點，藉由選擇性地添加無機鹽類氧化調節劑以確保優良的蝕刻輪廓。SUMMARY OF THE INVENTION It is an object of the present invention to provide an excellent etching solution which ensures high stability and a range of processes, and which makes the copper-containing metal layer uniform in cone etching. The present invention provides excellent problems by providing an etching solution which does not use hydrogen peroxide to solve the problem of process range and stability, addition of a hydrate stabilizing agent, etc., by selectively adding an inorganic salt oxidation regulator. Etched outline.

根據本發明之蝕刻液組成物，含有過硫酸銨【(NH4 )2 S2 O8 ；ammonium persulfate】及吡咯(azole)系化合物。The etching liquid composition according to the present invention contains ammonium persulfate [(NH 4 ) 2 S 2 O 8 ; ammonium persulfate] and an azole compound.

前述過硫酸銨係含有蝕刻液之重量對比0.1%至50%。前述吡咯系化合物係含有蝕刻液之重量對比0.01%至5%。The above ammonium persulfate-containing etchant has a weight ratio of 0.1% to 50%. The above pyrrole-based compound contains 0.01% to 5% by weight of the etching solution.

前述蝕刻液組成物，可更含有氟化物系化合物。The etching liquid composition may further contain a fluoride-based compound.

前述蝕刻液組成物，可更包含一個選自於由含有硝酸或硝酸鹽之第1化合物、含有硫酸或硫酸鹽之第2化合物、含有磷酸或磷酸鹽之第3化合物，及含有乙酸或乙酸鹽之第4化合物所構成之群之化合物。The etching liquid composition may further comprise one selected from the group consisting of a first compound containing nitric acid or a nitrate, a second compound containing sulfuric acid or a sulfate, a third compound containing phosphoric acid or a phosphate, and containing acetic acid or acetate. A compound of the group consisting of the fourth compound.

前述蝕刻液組成物，可更含有磺酸系化合物。The etching liquid composition may further contain a sulfonic acid compound.

前述蝕刻液組成物，可更含有螯合劑。The etching liquid composition may further contain a chelating agent.

根據此類之蝕刻液組成物，由於未使用過氧化氫，故無發熱現象或降低蝕刻液之穩定性、無需添加昂貴的穩定化劑一類之問題點，而具有可將銅以良好的速度形成錐形 蝕刻之長處。以本發明之蝕刻液組成物形成銅配線時，確保蝕刻液之穩定性且可長期維持蝕刻液之性能，具有充分保障蝕刻製程上之範圍而降低費用之效果。According to such an etching liquid composition, since hydrogen peroxide is not used, there is no problem of heat generation or stability of the etching liquid, no need to add an expensive stabilizer, and copper can be formed at a good speed. Cone The strength of etching. When the copper wiring is formed by the etching liquid composition of the present invention, the stability of the etching liquid is ensured and the performance of the etching liquid can be maintained for a long period of time, and the effect on the etching process is sufficiently ensured and the cost is reduced.

實施發明之最佳形態Best form for implementing the invention

本發明係提供由過硫酸銨【(NH4 )2 S2 O8 ；ammonium persulfate】及吡咯(azole)系化合物，及相當於殘餘部分之水所構成之蝕刻液。The present invention provides an etching solution comprising ammonium persulfate [(NH 4 ) 2 S 2 O 8 ; ammonium persulfate] and an azole compound, and water corresponding to a residual portion.

本發明中之水，雖未明確地提及，相對於全體之蝕刻液中，佔有除水外之其他成分的重量%合計為100%之殘餘部分。在本發明蝕刻液中所使用之水，以使用半導體用等級之水或超純水(ultrapure water)為佳。The water in the present invention, although not explicitly mentioned, accounts for 100% of the total weight% of the components other than water in the entire etching liquid. The water used in the etching liquid of the present invention is preferably water or ultrapure water of a semiconductor grade.

蝕刻液組成物Etching solution composition

本發明之過硫酸銨係氧化劑，且係蝕刻含銅金屬層之主要成分。過硫酸銨以使用具有半導體工程用之純度者為佳。本發明之蝕刻液中，過硫酸銨係蝕刻液之重量對比佔有0.1%至50%。The ammonium persulfate-based oxidizing agent of the present invention is a main component for etching a copper-containing metal layer. It is preferred that ammonium persulfate is used in a purity for semiconductor engineering. In the etching liquid of the present invention, the weight ratio of the ammonium persulfate-based etching liquid is 0.1% to 50%.

本發明之吡咯系化合物，係含有以氮作為元素之至少1個以上的非碳原子，具備於環中之5角雜環稱之。雖無特別限制，在本發明之吡咯系化合物，可舉例如苯并***(benzotriazole)、胺基四唑(aminotetrazole)、咪唑(imidazole)、吡唑(pyrazole)等。本發明之蝕刻液中，吡咯系化合物係以全體蝕刻液作為重量比佔有0.01%~5%。吡咯系化合物於前述含銅金屬層中抑制銅之蝕刻，且於含有前 述銅之金屬層的上部及/或下部，銅及其他的金屬層形成之多層膜中，擔任調節前述銅及其他金屬之間的蝕刻速度之任務。前述銅及其他金屬層例如可含鈦。前述吡咯系化合物係藉由減少金屬配線之切斷尺寸損失(cut dimension loss)，將金屬配線作為閘極及數據配線使用。吡咯系化合物不添加本發明之蝕刻液時，不但無法調節對銅之蝕刻速度，切斷尺寸損失增大，配線之直進性亦降低，在量產製程適用時可引起嚴重問題。The pyrrole compound of the present invention contains at least one or more non-carbon atoms containing nitrogen as an element, and is represented by a 5-membered heterocyclic ring in the ring. The pyrrole compound of the present invention is not particularly limited, and examples thereof include benzotriazole, aminotetrazole, imidazole, and pyrazole. In the etching solution of the present invention, the pyrrole-based compound accounts for 0.01% to 5% by weight of the entire etching solution. The pyrrole compound inhibits etching of copper in the copper-containing metal layer, and before being contained The upper and/or lower portion of the copper metal layer serves as a task for adjusting the etching rate between the copper and other metals in the multilayer film formed of copper and other metal layers. The aforementioned copper and other metal layers may, for example, comprise titanium. The pyrrole-based compound uses a metal wiring as a gate and a data wiring by reducing a cut dimension loss of a metal wiring. When the azole liquid of the present invention is not added to the azole solution, the etching rate for copper can not be adjusted, the size loss of the cut is increased, and the straightness of the wiring is also lowered, which can cause serious problems when the mass production process is applied.

前述蝕刻液可更含有含氟之氟化物系化合物。本發明之蝕刻液中，前述氟化物系化合物係以全體蝕刻液作為重量比佔有0.01%~10%。前述氟化物系化合物係作為前述蝕刻液之氧化輔助劑，可提高前述含銅金屬層之蝕刻速度。又，前述氟化物系化合物可蝕刻含有前述鈦之金屬層。前述氟化物系化合物，例如可含有氫氟酸(hydrofluoric acid)、氟化銨(ammoniun fluoride)、二氟化銨(ammoniun bifluoride)、氟化鉀(potassiun fluoride)、氟化鈉(sodiun fluoride)等。The etching solution may further contain a fluorine-containing fluoride-based compound. In the etching solution of the present invention, the fluoride-based compound accounts for 0.01% to 10% by weight of the entire etching solution. The fluoride compound is used as an oxidation aid of the etching liquid, and the etching rate of the copper-containing metal layer can be improved. Further, the fluoride-based compound can etch a metal layer containing the titanium. The fluoride-based compound may, for example, contain hydrofluoric acid, ammoniun fluoride, ammoniun bifluoride, potassiun fluoride, sodun fluoride, or the like. .

本發明更於前述過硫酸銨及吡咯系化合物中，可更含有4種類類型之氧化調節劑。該4種類類型之氧化調節劑全部未被使用，包括全部使用時在內，全部之可能組合皆可使用。該4種類類型之氧化調節劑分別係含有硝酸或硝酸鹽之第1化合物、含有硫酸或硫酸鹽之第2化合物、含有磷酸或磷酸鹽之第3化合物、及含有乙酸或乙酸鹽之第4化合物。Further, in the present invention, the ammonium persulfate and the pyrrole compound may further contain four types of oxidation regulators. All of the four types of oxidation regulators are not used, including all possible combinations, all possible combinations. The four types of oxidation regulators are respectively a first compound containing nitric acid or nitrate, a second compound containing sulfuric acid or sulfate, a third compound containing phosphoric acid or phosphate, and a fourth compound containing acetic acid or acetate. .

本發明之前述第1化合物，係於蝕刻液內釋出硝酸離子 (NO3 － )之物質。本發明之蝕刻液中，選擇性構成成分之前述第1化合物，係以重量比佔有0%至10%。前述第1化合物例如可含有硝酸鐵(III)【Fe(NO3 )3 】、硝酸鉀、硝酸銨、硝酸鋰等。The first compound of the present invention is a substance which releases nitrate ions (NO 3 - ) in an etching liquid. In the etching solution of the present invention, the first compound of the selective constituent component is contained in an amount of from 0% by weight to 10% by weight. The first compound may contain, for example, iron (III) nitrate [Fe(NO 3 ) 3 ], potassium nitrate, ammonium nitrate, lithium nitrate or the like.

本發明之前述第2化合物，係於蝕刻液內釋出硫酸離子(SO4 2－ )或硫酸氫離子(HSO4 2－ )之化合物。本發明之選擇性構成成分之前述第2化合物，係以全體蝕刻液作為重量比佔有0%至10%。根據本發明之金屬配線蝕刻溶液中，前述第2化合物於含銅金屬層之蝕刻液中，使之形成適宜之錐形角(30∘至60∘)，一方面，不但使後製程時膜之被覆(step coverage)良好而有助於收率提高，同時提高銅之蝕刻速度而有助於提高蝕刻工程之生產性。本發明之蝕刻溶液中，排除前述第2化合物時雖亦可進行銅之蝕刻，不過使用前述第2化合物時，則可維持錐形角於適當的水準，防止後續膜之被覆性降低之現象以預防不良之發生。前述第2化合物例如可含有硫酸、硫酸氫銨(NH4 HSO4 )、硫酸氫鉀(KHSO4 )、硫酸鉀(K2 SO4 )等。The second compound of the present invention is a compound which releases sulfate ions (SO 4 2- ) or hydrogen sulfate ions (HSO 4 2- ) in an etching solution. The second compound of the selective constituent of the present invention accounts for 0% to 10% by weight of the entire etching solution. According to the metal wiring etching solution of the present invention, the second compound is formed in an etching liquid of the copper-containing metal layer to form a suitable taper angle (30 Å to 60 Å), on the one hand, not only the film in the post-process A good coverage of the coating contributes to an increase in yield while increasing the etching rate of copper to help improve the productivity of the etching process. In the etching solution of the present invention, copper etching may be performed when the second compound is excluded. However, when the second compound is used, the taper angle can be maintained at an appropriate level, and the coating property of the subsequent film can be prevented from being lowered. Prevent the occurrence of maladjustment. The second compound may contain, for example, sulfuric acid, ammonium hydrogen sulfate (NH 4 HSO 4 ), potassium hydrogen sulfate (KHSO 4 ), potassium sulfate (K 2 SO 4 ), or the like.

本發明中前述第3化合物，係於蝕刻液內放出磷酸離子(PO4 3－ )、磷酸氫離子(HPO4 2－ )、磷酸二氫離子(H2 PO4 3－ )之化合物。本發明之選擇性構成成分之前述第3化合物，係以全體蝕刻液作為重量比佔有0%至10%。前述第3化合物例如可含有磷酸、磷酸銨【(NH4 )3 PO4 】、磷酸氫銨【(NH4 )2 HPO4 】、磷酸二氫銨【(NH4 )2 H2 PO4 】、磷酸鉀(K3 PO4 )、磷酸氫鉀(K2 HPO4 )、磷酸二氫鉀(KH2 PO4 )、磷酸 鈉(Na3 PO4 )、磷酸氫鈉(Na2 HPO4 )及磷酸二氫鈉(NaH2 PO4 )等。含有適當的前述第3化合物之蝕刻液，可使含銅金屬層形成均等之錐形蝕刻。In the present invention, the third compound is a compound which releases phosphate ions (PO 4 3- ), hydrogen phosphate ions (HPO 4 2- ), and dihydrogen phosphate ions (H 2 PO 4 3- ) in the etching solution. The third compound of the selective constituent component of the present invention accounts for 0% to 10% by weight of the entire etching solution. The third compound may contain, for example, phosphoric acid, ammonium phosphate [(NH 4 ) 3 PO 4 ], ammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], ammonium dihydrogen phosphate [(NH 4 ) 2 H 2 PO 4 ], Potassium phosphate (K 3 PO 4 ), potassium hydrogen phosphate (K 2 HPO 4 ), potassium dihydrogen phosphate (KH 2 PO 4 ), sodium phosphate (Na 3 PO 4 ), sodium hydrogen phosphate (Na 2 HPO 4 ), and phosphoric acid Sodium dihydrogen (NaH 2 PO 4 ) and the like. The etchant containing the appropriate third compound allows the copper-containing metal layer to be uniformly tapered.

本發明中前述第4化合物，係於蝕刻液內放出乙酸離子(CH3 COO－ )之物質。本發明之選擇性構成成分之前述第4化合物以重量比佔有0%至10%。前述第4化合物例如可含有乙酸、乙酸銨、乙酸鉀、乙酸鈉、亞胺二乙酸【HN(CH2 COOH)2 ；iminodiacetic acid；IDA】等。前述第4化合物可提高蝕刻液之第1化合物之安全性，維持蝕刻能力。In the present invention, the fourth compound is a substance which releases acetic acid ions (CH 3 COO - ) in an etching solution. The aforementioned fourth compound of the selective constituent of the present invention accounts for 0% to 10% by weight. The fourth compound may contain, for example, acetic acid, ammonium acetate, potassium acetate, sodium acetate, iminodiacetic acid [HN(CH 2 COOH) 2 ; iminodiacetic acid; IDA]. The fourth compound can improve the safety of the first compound of the etching solution and maintain the etching ability.

前述蝕刻液可更含有含磺酸之磺酸化合物。在本發明之蝕刻液中，前述氟化物系化合物係以全體蝕刻液作為重量比佔有0.01%至10%。前述磺酸化合物係藉由對於蝕刻含有前述銅金屬層之主成分的前述過硫酸銨，抑制其分解而可保障前述蝕刻液之穩定性。前述磺酸化合物可含有例如苯磺酸(benzenesulfonic acid)、對－甲苯磺酸(para－toluenesulfonic acid)、甲磺酸(methanesulfonic acid)、胺磺酸(amidosulfonic acid)等。The etching solution may further contain a sulfonic acid compound containing a sulfonic acid. In the etching solution of the present invention, the fluoride-based compound is contained in an amount of from 0.01% to 10% by weight based on the total etching solution. The sulfonic acid compound can stabilize the etching liquid by inhibiting the decomposition of the ammonium persulfate containing the main component of the copper metal layer. The sulfonic acid compound may contain, for example, a benzenesulfonic acid, a para-toluenesulfonic acid, a methanesulfonic acid, an amidosulfonic acid or the like.

前述蝕刻液可更含有螯合劑。在本發明之蝕刻液中，前述螯合劑係以全體蝕刻液作為重量比佔有0.0001%至5%。前述螯合劑係結合前述蝕刻液與含有前述銅金屬層蝕刻時所發生之銅離子，使前述銅離子不影響前述蝕刻液之蝕刻速度。前述螯合劑係例如可有膦酸鹽系(phosphonic series)、磺磺酸鹽系(sulfonic series)、乙酸鹽系(acetate series) 等之物質。The etching solution may further contain a chelating agent. In the etching solution of the present invention, the chelating agent accounts for 0.0001% to 5% by weight of the entire etching solution. The chelating agent combines the etching liquid and the copper ions generated when the copper metal layer is etched, so that the copper ions do not affect the etching rate of the etching liquid. The chelating agent may be, for example, a phosphonic series, a sulfonic series, or an acetate series. Etc.

本發明所揭示之蝕刻液或蝕刻液組成物之範圍中，當然包含前述所示重量比之範圍內的蝕刻液，例如組成在於該重量比範圍的數值之外，或雖於前述作為例示顯示之部分成分所取代而其變化之構成，在該領域中具有通常知識的人士，認為與前述蝕刻液組成實質上均等者，此種構成亦包含在內。In the range of the etching liquid or the etching liquid composition disclosed in the present invention, it is a matter of course that the etching liquid in the range of the weight ratio shown above is contained, for example, the composition is outside the numerical value range of the weight ratio range, or is shown as an example. A configuration in which a part of the components is substituted and whose composition is changed, and those having ordinary knowledge in the field are considered to be substantially equal to the composition of the etching liquid, and such a configuration is also included.

以下，本發明舉述實施例更進一步說明。以下之實施例中所示之構成係為帮助徹底地理解本發明，故在此表明於任何情形下，對於本發明的技術性範圍未對於以實施例所提示之實施態樣而加以限制。Hereinafter, the present invention will be further described by way of examples. The composition shown in the following examples is intended to facilitate a thorough understanding of the present invention, and thus it is intended that the technical scope of the present invention is not limited to the embodiment presented by the embodiments.

蝕刻液組成物之實施例Example of etching liquid composition

根據本發明之蝕刻液組成物之實施例1至4之蝕刻液根據下述第1表製造。實施例1至4之組成顯示於第1表，全體之%值係重量比。The etching liquids of Examples 1 to 4 according to the etching liquid composition of the present invention were produced in accordance with Table 1 below. The compositions of Examples 1 to 4 are shown in Table 1, and the overall % value is a weight ratio.

參照第1表，根據本發明實施例1之蝕刻液，含有2重量%之過硫酸銨、0.7重量%之吡咯系化合物及1重量%之第1化合物。Referring to Table 1, the etching solution according to Example 1 of the present invention contains 2% by weight of ammonium persulfate, 0.7% by weight of a pyrrole compound, and 1% by weight of the first compound.

根據本發明實施例2之蝕刻液，含有3重量%之過硫酸銨、0.1重量%之吡咯系化合物及0.5重量%之第2化合物。The etching solution according to Example 2 of the present invention contains 3% by weight of ammonium persulfate, 0.1% by weight of a pyrrole compound, and 0.5% by weight of a second compound.

根據本發明實施例3之蝕刻液，含有3重量%之過硫酸銨、0.1重量%之吡咯系化合物及0.5重量%之第3化合物。The etching solution according to Example 3 of the present invention contains 3% by weight of ammonium persulfate, 0.1% by weight of a pyrrole compound, and 0.5% by weight of a third compound.

根據本發明實施例4之蝕刻液，含有3重量%之過硫酸銨及0.5重量%之第4化合物。The etching solution according to Example 4 of the present invention contains 3 wt% of ammonium persulfate and 0.5 wt% of the fourth compound.

參照第2表，根據本發明實施例5之蝕刻液，含有5重量%之過硫酸銨、0.5重量%之吡咯系化合物、0.2重量%之氟化物系化合物、1重量%之第1化合物、1重量%之第4化合 物、0.2重量%之磺酸系化合物及0.001重量%之螯合劑。Referring to Table 2, the etching solution according to Example 5 of the present invention contains 5% by weight of ammonium persulfate, 0.5% by weight of a pyrrole compound, 0.2% by weight of a fluoride compound, and 1% by weight of a first compound, 1 4th percent by weight A 0.2% by weight sulfonic acid compound and 0.001% by weight of a chelating agent.

根據本發明實施例6之蝕刻液，含有5重量%之過硫酸銨、0.5重量%之吡咯系化合物、0.5重量%之氟化物系化合物、1重量%之第1化合物、1重量%之第4化合物、0.2重量%之磺酸系化合物及0.001重量%之螯合劑。The etching solution according to Example 6 of the present invention contains 5% by weight of ammonium persulfate, 0.5% by weight of a pyrrole compound, 0.5% by weight of a fluoride compound, 1% by weight of a first compound, and 1% by weight of the fourth compound. A compound, 0.2% by weight of a sulfonic acid compound, and 0.001% by weight of a chelating agent.

根據本發明實施例7之蝕刻液，含有5重量%之過硫酸銨、0.5重量%之吡咯系化合物、0.7重量%之氟化物系化合物、1重量%之第1化合物、1重量%之第4化合物、0.2重量%之磺酸系化合物及0.001重量%之螯合劑。The etching solution according to Example 7 of the present invention contains 5% by weight of ammonium persulfate, 0.5% by weight of a pyrrole compound, 0.7% by weight of a fluoride compound, 1% by weight of a first compound, and 1% by weight of the fourth compound. A compound, 0.2% by weight of a sulfonic acid compound, and 0.001% by weight of a chelating agent.

根據本發明實施例8之蝕刻液，含有5重量%之過硫酸銨、0.5重量%之吡咯系化合物、0.2重量%之氟化物系化合物、1重量%之第1化合物、1重量%之第4化合物、0.2重量%之磺酸系化合物及0.001重量%之螯合劑。The etching solution according to Example 8 of the present invention contains 5% by weight of ammonium persulfate, 0.5% by weight of a pyrrole compound, 0.2% by weight of a fluoride compound, 1% by weight of a first compound, and 1% by weight of the fourth compound. A compound, 0.2% by weight of a sulfonic acid compound, and 0.001% by weight of a chelating agent.

根據本發明實施例9之蝕刻液，含有5重量%之過硫酸銨、0.5重量%之吡咯系化合物、0.2重量%之氟化物系化合物、1重量%之第1化合物、0.5重量%之磺酸系化合物及0.001重量%之螯合劑。The etching solution according to Example 9 of the present invention contains 5% by weight of ammonium persulfate, 0.5% by weight of a pyrrole compound, 0.2% by weight of a fluoride compound, 1% by weight of a first compound, and 0.5% by weight of a sulfonic acid. A compound and 0.001% by weight of a chelating agent.

根據本發明實施例10之蝕刻液，含有5重量%之過硫酸銨、0.5重量%之吡咯系化合物、0.2重量%之氟化物系化合物、1重量%之第1化合物、0.2重量%之磺酸系化合物及0.001重量%之螯合劑。The etching solution according to Embodiment 10 of the present invention contains 5% by weight of ammonium persulfate, 0.5% by weight of a pyrrole compound, 0.2% by weight of a fluoride compound, 1% by weight of a first compound, and 0.2% by weight of a sulfonic acid. A compound and 0.001% by weight of a chelating agent.

根據本發明實施例11之蝕刻液，含有5重量%之過硫酸銨、0.5重量%之吡咯系化合物、0.2重量%之氟化物系化合物、1重量%之第2化合物、0.2重量%之磺酸系化合物及0.001 重量%之螯合劑。The etching solution according to Example 11 of the present invention contains 5% by weight of ammonium persulfate, 0.5% by weight of a pyrrole compound, 0.2% by weight of a fluoride compound, 1% by weight of a second compound, and 0.2% by weight of a sulfonic acid. Compounds and 0.001 9% by weight of chelating agent.

根據本發明實施例12之蝕刻液，含有5重量%之過硫酸銨、0.5重量%之吡咯系化合物、0.2重量%之氟化物系化合物、1重量%之第3化合物、0.2重量%之磺酸系化合物及0.001重量%之螯合劑。The etching solution according to Example 12 of the present invention contains 5% by weight of ammonium persulfate, 0.5% by weight of a pyrrole compound, 0.2% by weight of a fluoride compound, 1% by weight of a third compound, and 0.2% by weight of a sulfonic acid. A compound and 0.001% by weight of a chelating agent.

根據本發明實施例13之蝕刻液，含有5重量%之過硫酸銨、0.5重量%之吡咯系化合物、0.2重量%之氟化物系化合物、1重量%之第4化合物、0.2重量%之磺酸系化合物及0.001重量%之螯合劑。The etching solution according to Example 13 of the present invention contains 5% by weight of ammonium persulfate, 0.5% by weight of a pyrrole compound, 0.2% by weight of a fluoride compound, 1% by weight of a fourth compound, and 0.2% by weight of a sulfonic acid. A compound and 0.001% by weight of a chelating agent.

蝕刻液組成物之實驗例－蝕刻液組成物之蝕刻能力評價Experimental Example of Etching Liquid Composition - Evaluation of Etching Ability of Etching Liquid Composition

具體而言，在銅單一膜之時間基準中超過30%蝕刻之過浸蝕(overetching)之實驗，評價實施例1至4之蝕刻液之蝕刻速度、切斷尺寸偏斜(cut dimension skew)及錐形角。又，以顯微鏡照相觀察蝕刻過之銅層的橫斷面。其結果顯示於第3表及第1圖至第4圖。Specifically, the etching rate, the cut dimension skew, and the cone of the etching solutions of Examples 1 to 4 were evaluated in an experiment of overetching of more than 30% etching in the time base of the copper single film. Shaped angle. Further, the cross section of the etched copper layer was observed by a microscope. The results are shown in Table 3 and Figures 1 to 4.

蝕刻之終點係藉由蝕刻液蝕刻銅單一膜完成後，玻璃基板的玻璃露出之狀態稱之。蝕刻終點之值愈小表示旺盛之蝕刻能力。切斷尺寸偏斜係表示光阻劑(photoresist)末端 與銅末端間之距離，為要具有無段差且均勻之錐形角，該距離須在適當的範圍內。錐形角係由蝕刻過之金屬膜的側面所觀察之傾斜，且約以45∘至60∘為適當之值。參照第3表，則本發明之蝕刻液組成物顯示優良蝕刻速度及切斷尺寸偏斜，藉由可將錐形輪廓調整為30∘至70∘而可暸解。如顯示於第1至第4圖，在模式之直進性具有良好之優良穩定性，雖對多數之銅金屬膜蝕刻，仍具有維持於與初期同樣之性能的長處。The end point of the etching is performed by etching a single copper film by an etching solution, and the glass of the glass substrate is exposed. The smaller the value of the end point of the etch, the stronger the etching ability. Cut-off dimension skew indicates the end of the photoresist The distance from the end of the copper is such that there is a stepless and uniform taper angle which is within the appropriate range. The taper angle is inclined as viewed from the side of the etched metal film, and is about 45 ∘ to 60 ∘ is an appropriate value. Referring to Table 3, the etching liquid composition of the present invention exhibits an excellent etching rate and a cut size deflection, which can be understood by adjusting the taper profile to 30 ∘ to 70 。. As shown in the first to fourth figures, the straightness of the mode has excellent excellent stability, and the etching of a large number of copper metal films has the advantage of maintaining the same performance as the initial stage.

銅膜及與含有前述銅膜接觸形成之鈦膜的多層膜，實施在時間基準中過超過30%蝕刻之過浸蝕(overetching)之實驗，根據實施例5至13之蝕刻液的蝕刻速度、切斷尺寸偏斜及錐形角予以評價。其結果顯示於第4表。The copper film and the multilayer film formed by contacting the copper film in contact with the copper film were subjected to an overetching process of over 30% etching in a time reference, and the etching rate of the etching liquid according to Examples 5 to 13 was cut. The size deviation and the cone angle were evaluated. The results are shown in Table 4.

參照第4表，則本發明之蝕刻液組成物顯示優良蝕刻速度及切斷尺寸偏斜，可暸解錐形輪廓可調整為30∘至70∘。Referring to Table 4, the etching liquid composition of the present invention exhibits an excellent etching speed and a cut size deflection, and it can be understood that the tapered profile can be adjusted to 30 ∘ to 70 。.

以上，雖參照實施例說明，熟練於該技術領域之業者，在於不脫離申請專利所記載的本發明之思想及領域的範圍內，對於可將本發明多樣地修正及變更，當然可予以理解。It is to be understood that the present invention can be variously modified and changed without departing from the scope of the invention and the scope of the invention.

第1圖係顯示以本發明實施例1之蝕刻液組成物，蝕刻銅單一膜之30%過浸蝕實驗中，所蝕刻之銅層側面的顯微鏡照相。Fig. 1 is a photomicrograph showing the side of the etched copper layer in a 30% overetching experiment of etching a copper single film by the etching liquid composition of Example 1 of the present invention.

第2圖係顯示以本發明之實施例2之蝕刻液組成物，蝕刻銅單一膜之30%過浸蝕實驗中，所蝕刻之銅層側面的顯微鏡照相。Fig. 2 is a photomicrograph showing the side of the etched copper layer in the 30% overetching experiment of etching a copper single film by the etching liquid composition of Example 2 of the present invention.

第3圖係顯示以本發明之實施例3之蝕刻液組成物，蝕刻銅單一膜之30%過浸蝕實驗中，所蝕刻之銅層側面的顯微鏡照相。Fig. 3 is a photomicrograph showing the side of the etched copper layer in the 30% overetching experiment of etching a copper single film by the etching liquid composition of Example 3 of the present invention.

第4圖係顯示以本發明之實施例4之蝕刻液組成物，蝕刻銅單一膜之30%過浸蝕實驗中，所蝕刻之銅層側面的顯微鏡照相。Fig. 4 is a photomicrograph showing the side of the etched copper layer in the 30% overetching experiment of etching a copper single film by the etching liquid composition of Example 4 of the present invention.

Claims (11)

一種銅蝕刻液組成物，含有：(a)過硫酸銨【(NH4 )2 S2 O8 ；ammonium persulfate】0.1重量%至50重量%；(b)選自於由胺基四唑(aminotetrazole)、咪唑(imidazole)及吡唑(pyrazole)所構成之群之吡咯(azole)系化合物0.01重量%至5重量%；(c)選自於由氫氟酸(hydrofluoric acid)、氟化銨(ammonium fluoride)、二氟化銨(ammonium bifluoride)、氟化鉀(potassium fluoride)及氟化鈉(sodium fluoride)所構成之群之氟化物系化合物0.01重量%至10重量%；(d)選自於由含有超過0重量%、10重量%以下之硝酸或硝酸鹽之第1化合物；含有超過0重量%、10重量%以下之硫酸或硫酸鹽之第2化合物；含有超過0重量%、10重量%以下之磷酸或磷酸鹽之第3化合物；及含有超過0重量%、10重量%以下之乙酸或乙酸鹽之第4化合物所構成之群之至少一個化合物；及(e)餘量的水。A copper etching solution composition comprising: (a) ammonium persulfate [(NH 4 ) 2 S 2 O 8 ; ammonium persulfate] 0.1% by weight to 50% by weight; (b) selected from aminotetrazole And an azole compound of the group consisting of imidazole and pyrazole is 0.01% by weight to 5% by weight; (c) is selected from the group consisting of hydrofluoric acid and ammonium fluoride ( a fluoride-based compound of a group consisting of ammonium fluoride, ammonium bifluoride, potassium fluoride, and sodium fluoride; 0.01% by weight to 10% by weight; (d) selected from a first compound containing more than 0% by weight and 10% by weight or less of nitric acid or nitrate; a second compound containing more than 0% by weight and 10% by weight or less of sulfuric acid or a sulfate; containing more than 0% by weight and 10% by weight a third compound of phosphoric acid or phosphate of less than %; and at least one compound of the group consisting of a fourth compound containing more than 0% by weight and 10% by weight of acetic acid or acetate; and (e) the balance of water. 如申請專利範圍第1項之蝕刻液組成物，其中前述第1化合物含有選自於由硝酸、硝酸鐵(III)【Fe(NO3 )3 】、硝酸鉀、硝酸銨及硝酸鋰所構成之群之至少一個以上的物質。The etchant composition of claim 1, wherein the first compound comprises a compound selected from the group consisting of nitric acid, iron (III) nitrate [Fe(NO 3 ) 3 ], potassium nitrate, ammonium nitrate, and lithium nitrate. At least one or more substances in the group. 如申請專利範圍第1項之蝕刻液組成物，其中前述第2化合物含有選自於由硫酸、硫酸氫銨(NH4 HSO4 )、硫酸氫 鉀(KHSO4 )及硫酸鉀(K2 SO4 )所構成之群之至少一個以上的物質。The etchant composition of claim 1, wherein the second compound is selected from the group consisting of sulfuric acid, ammonium hydrogen sulfate (NH 4 HSO 4 ), potassium hydrogen sulfate (KHSO 4 ), and potassium sulfate (K 2 SO 4 ). At least one or more substances of the group formed. 如申請專利範圍第1項之蝕刻液組成物，其中前述第3化合物含有選自於由磷酸、磷酸銨【(NH4 )3 PO4 】、磷酸氫銨【(NH4 )2 HPO4 】、磷酸二氫銨(NH4 H2 PO4 )、磷酸鉀(K3 PO4 )、磷酸氫鉀(K2 HPO4 )、磷酸二氫鉀(KH2 PO4 )、磷酸鈉(Na3 PO4 )、磷酸氫鈉(Na2 HPO4 )及磷酸二氫鈉(NaH2 PO4 )所構成之群之至少一個以上的物質。The etchant composition of claim 1, wherein the third compound is selected from the group consisting of phosphoric acid, ammonium phosphate [(NH 4 ) 3 PO 4 ], ammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ], Ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), potassium phosphate (K 3 PO 4 ), potassium hydrogen phosphate (K 2 HPO 4 ), potassium dihydrogen phosphate (KH 2 PO 4 ), sodium phosphate (Na 3 PO 4 ) And at least one or more of the group consisting of sodium hydrogen phosphate (Na 2 HPO 4 ) and sodium dihydrogen phosphate (NaH 2 PO 4 ). 如申請專利範圍第1項之蝕刻液組成物，其中前述第4化合物含有選自於由乙酸、乙酸銨、乙酸鉀、乙酸鈉及亞胺二乙酸【HN(CH2 COOH)2 ；iminodiacetic acid；IDA】所構成之群之至少一個以上的物質。The etchant composition of claim 1, wherein the fourth compound is selected from the group consisting of acetic acid, ammonium acetate, potassium acetate, sodium acetate and imine diacetic acid [HN(CH 2 COOH) 2 ; iminodiacetic acid; IDA] At least one or more substances of the group formed. 如申請專利範圍第1項之蝕刻液組成物，更含有含磺酸之磺酸系化合物。 The etchant composition of claim 1 further contains a sulfonic acid-containing sulfonic acid compound. 如申請專利範圍第6項之蝕刻液組成物，其中前述磺酸系化合物含有0.001重量%至10重量%。 The etching liquid composition of claim 6, wherein the sulfonic acid-based compound contains 0.001% by weight to 10% by weight. 如申請專利範圍第7項之蝕刻液組成物，其中前述磺酸系化合物含有選自於由苯磺酸(benzenesulfonic acid)、對-甲苯磺酸(para-toluenesulfonic acid)、甲磺酸(methanesulfonic acid)及胺磺酸(amidosulfonic acid)所構成之群之至少一個以上的物質。 The etchant composition of claim 7, wherein the sulfonic acid compound is selected from the group consisting of benzenesulfonic acid, para-toluenesulfonic acid, and methanesulfonic acid. And at least one or more substances of the group consisting of amidosulfonic acid. 如申請專利範圍第6項之蝕刻液組成物，更含有螯合劑。 The etchant composition of claim 6 of the patent application further contains a chelating agent. 如申請專利範圍第9項之蝕刻液組成物，其中前述螯合劑含有0.0001重量%至5重量%。 The etching liquid composition of claim 9, wherein the chelating agent contains 0.0001% by weight to 5% by weight. 如申請專利範圍第10項之蝕刻液組成物，其中前述螯合劑含有選自於由膦酸鹽系(phosphonic series)、磺酸鹽系(sulfonic series)及乙酸鹽系(acetate series)所構成之群之化合物至少一個以上。 The etchant composition of claim 10, wherein the chelating agent comprises a phosphonic series, a sulfonic series, and an acetate series selected from the group consisting of a phosphonic series, a sulfonic series, and an acetate series. Group of compounds at least one or more.
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