200844215 九、發明說明： 發明領域 本發明係有關用於薄膜電晶體液晶顯示裝置之蝕刻液 5 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 5 TFT-LCD device)的製造步驟中所用之蝕刻液組成物。 【先前技術1 發明背景200844215 IX. Description of the Invention: Field of the Invention The present invention relates to an etchant 5 composition for a thin film transistor liquid crystal display device, and more particularly to a thin film transistor-liquid crystal display device (thin film transistor-liquid crystal display device) 5 Etching liquid composition used in the manufacturing steps of the TFT-LCD device). [Prior Art 1 Background of the Invention]
10 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 私子回路的代表者，非薄膜電晶體(thin film transist沉，TFT) 15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(s〇urce/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蚀性之氣體或溶液敍 刻’以貫現期望之電氣回路的線路之钮刻（滅㈣)製程。 TFT基板上由於置有許多之薄膜、薄層，在該等之間， 扣為防止發生電力的短路，在已姓刻基板之橫切面側面，即， 蝕刻輪廓(Pr〇file)呈均等地傾斜成之下方寬過上方，以呈顯 緩緩的錐形(_)形狀為佳。餘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。閑極金 屬之_模式紐_以且精料，會發生肌咖映 5 200844215 像，解像度降低且色彩不正確之問題。姓刻方法中雖有利 用孔體之乾式餘刻及利用餘刻液之濕式侧 ，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 #、對於則環境不需維持之於高真㈣態，對於遮蔽及 5基板均具有優良的钱刻選擇性之長處，因此對於濕式姓 刻液之需要仍持續存在。 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M旦回路之小型化、積層化愈進步回線愈細， 產生私阻相對地增加愈大之問題點。由於電阻係引起信 10號延遲之主要因子。特別於丁!^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 低值疋成為面板大小之增大及解像度之實現的關鍵。因 此’為要貫現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 15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。 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 對裱境更為親和之長處。但，由於銅對於氧化劑之抵抗性 2〇高於鋁或鉻，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(Η"2)及高鐵【Fe(III)】等廣被使 用。 具體而言，過氧化氫時，在下述專利文獻丨對於作為銅 膜之姓刻溶液，揭示有過氧化氫與無機酸或中性鹽之混合 6 200844215 下述專利文獻2揭示有過氧化氫、銅反應抑制劑、水八 ^定化^、氟化離子之組成物；下述專利文獻3揭示有在 過乳化風中添加含有氟化合物、有機分子等5種添加劑 成。 尚鐵氧化劑日寸’下述專利文獻4揭示有氯化鐵(HI%水合 物及氟化氫酸之混合物。一方面，作為含銅多層膜之颠刻 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。 但是，該蝕刻液引起銅膜與其他的金屬層積層形成之 半$體基板之蝕刻速度過快，引起被蝕刻的金屬膜之錐形 輪磨超過9〇度等不良餘刻之問題點。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 (山Spr〇P〇rtionation)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 15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。 【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2〇〇5_〇〇〇682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2〇〇〇_〇32999號 【專利文獻5】大韓民國公開專利第1999_〇17836號 【專利文獻6】美國登錄專利第414〇772號 【發明内容】 發明揭示 7 200844215 發明所要解決之課題 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蝴， 本發明係藉由提供不使用過氧化氫之姓刻液，以解決製程 5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^ 廓。 解決課題之方法 根據本發明之蝕刻液組成物，含有過硫酸銨 10 【（姻4)2心〇8 ; ammonium persulfate】及咄咯(az〇le)系化人 物。 鈾述過硫酸銨係含有姓刻液之重量對比〇1%至知％。 前述吡咯系化合物係含有餘刻液之重量對比〇 〇1%至5%。 前述蝕刻液組成物，可更含有氟化物系化合物。 15 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。 别述I虫刻液組成物，可更含有績酸系化合物。 20 前述蝕刻液組成物，可更含有螯合劑。 發明效果 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 200844215 蝕刻之長處。以本發明之蝕刻液組成物形成鋼配線時，確 保蝕刻液之穩定性且可長期維持蝕刻液之性能，具有充八 保障餘刻製程上之範圍而降低費用之效果。 刀 C實施方式j 5實施發明之最佳形態 本發明係提供由過硫酸銨【（NH4)2s,n · ^ ammonium perSUlfate】比略（az〇le)系化合㉗，及相當於殘餘部分之 水所構成之蝕刻液。 刀 本發明中之水，雖未明確地提及，相對於全體之_ 10液中，佔有除水外之其他成分的重量％合計為1〇〇%之殘餘 部分。在本發明關液中所使用之水，以使用半導體用等 級之水或超純水(ultrapure water)為佳。 蝕刻液組成物 本發明之過硫酸錢係氧化劑，且係餘刻含銅金屬層之 Μ主要成分。過硫酸銨以使用具有半導體工程用之純度二為 佳。本發明之餘刻液中，過硫酸銨係餘刻液之重量對比佔 有 0.1°/。至 50%。 本發明之t各系化合物，係含有以氮作為元素之至少工 個以上的非碳原子，具備於環巾之5隸環稱之。雖無特別 2〇限制，在本發明之料系化合物，可舉例如苯并三唾 (benzotriazo丨e)、胺基四唑（amin〇tetraz〇ie)、咪唑 (imidazole)、t坐(Py_le)等。本發明之蝕刻液中吡咯 系化合物係以全體㈣液作為重量比佔有〇 〇1%〜5%。吡咯 系化合物於前述含銅金屬層中抑制銅之侧，且於含有前 9 200844215 述鋼之金屬層的上部及/或下部 多層膜中， ，銅及其他的金屬層形成之10 Liquid crystal display device (LCD device) provides excellent image resolution by excellent resolution, and has the characteristics of thinness of display screen due to low power consumption, and is the most popular among flat panel display devices. Attention. Recently, as a representative of a private sub-circuit for driving such a liquid crystal display device, a thin film transist (TFT) 15 circuit is a circuit. In the manufacture of a TFT-LCD, first, a gate layer and a source/drain (s〇urce/drain) are used as electrode wiring materials on a glass substrate, and a metal layer is laminated, and then the metal layer is corroded. The gas or solution is characterized by a button engraving (extinguishing (four)) process that traverses the desired electrical circuit. Since a plurality of thin films and thin layers are disposed on the TFT substrate, between them, the short circuit is prevented from being generated, and the side surface of the cross-section of the substrate has been slanted, that is, the etching profile (Pr〇file) is uniformly inclined. The width is lower than the top, and the shape of the tapered (_) is preferred. The contour of the engraving is such that it becomes a tapered shape in order to reduce the step difference between the formed plurality of film layers. Idle mode metal _ mode _ _ and fine material, will occur muscle 映 5 200844215 image, the resolution is reduced and the color is not correct. In the method of surname engraving, although the dry remnant of the hole body and the wet side of the remnant liquid are used, the disadvantages of the wet etching are not limited, because the equipment investment cost for the process is required, Maintaining in the high-true (four) state, it has excellent advantages in terms of shielding and 5 substrates, so the need for wet-type engraving still persists. The miniaturization and stratification of the circuit has always been the trend of the electronics industry. Although there is no exception in the TFT circuit, the miniaturization of the M-tanner circuit and the gradual progress of the stratification become finer, and the problem that the private resistance increases relatively increases. Due to the resistance, the main factor of the delay of the signal is caused. Especially in Ding!^, the trend of the industry tends to be more important as the size of the panel increases and the resolution increases, and whether the resistance can be maintained at a low value becomes the key to the increase of the panel size and the realization of the resolution. Therefore, in order to reduce the delay of the rC signal, which is required to increase the size of the TFT_LCD, it is necessary to develop a material having a low resistance. However, in the past, the material of the return line 15 is mainly chromium, molybdenum, aluminum, and the like. , its resistance value is large, so it is not suitable for future large TFT-LCD electrode wiring. On the other hand, a copper-based metal having excellent conductivity and a large amount of storage has a resistance which is remarkably lower than that of an aluminum film or a chromium film when the copper film is used for TFT wiring, 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 (Η"2) and high-iron [Fe(III)]. Specifically, in the case of hydrogen peroxide, in the following patent document, a mixture of hydrogen peroxide and a mineral acid or a neutral salt is disclosed for a solution of a copper film as a surname solution. 200844215 The following Patent Document 2 discloses hydrogen peroxide, The composition of the copper reaction inhibitor, the water, and the fluoride ion; the following Patent Document 3 discloses that five kinds of additives such as a fluorine compound and an organic molecule are added to the emulsified air. The following Patent Document 4 discloses a mixture of ferric chloride (HI% hydrate and hydrogen fluoride). On the other hand, as an indentation solution of a copper-containing multilayer film, the following Patent Document 5 also discloses the use of phosphoric acid. The composition of a general-purpose etching solution of nitric acid and acetic acid. However, the etching liquid causes the etching speed of the half-body substrate formed by the copper film and other metal layers to be too fast, causing the bevel wheel grinding of the etched metal film to exceed 9 The problem of poor residuals such as enthalpy, especially the widely used hydrogen peroxide, especially due to the inhomogeneity (Mountain Spr〇P〇rtionation) in the presence of copper and iron ions, which is decomposed into water and oxygen ( Referring to the following Patent Document 6), there is a change in composition due to heat generation and intense composition. Therefore, many problems occur in the process range and stability. In order to solve such a problem, the addition of a hydrate stabilizer is expensive because of the high price. [Patent Document 1] Korean Patent Publication No. 2000_079355 [Patent Document 2] Korean Republic Patent Publication No. 2〇〇5_〇〇〇682 [Patent Document 3] Korean Patent Publication No. 2006-064881 [Patent Document 4] Korean Republic Patent Publication No. 2 〇 999 32999 [Patent Document 5] Korean Republic Patent Publication No. 1999_〇17836 [Patent Document 6] US Patent Registration No. 414 〇772号 [Summary of the Invention] Disclosure of the Invention 7 200844215 Problem to be Solved by the Invention An object of the present invention is to provide an excellent etching liquid, which can ensure high stability and a range of processes, and a copper-containing metal layer can be made into an equal conical butterfly. The invention provides a problem of solving the problem of the range and stability of the process 5, adding a hydrate stabilizer, etc. by providing a surname without using hydrogen peroxide, and selectively adding an inorganic salt oxidation regulator to ensure Excellent etching method. Method for solving the problem According to the etching liquid composition of the present invention, ammonium persulfate 10 is contained, and ammonium persulfate and az〇le are used to characterize the uranium. The ammonium persulfate system contains a weight ratio of 姓1% to 5% by weight. The pyrrole compound contains a weight ratio of 余1% to 5% of the residual liquid. Further, the etchant composition may further comprise one selected from the group consisting of a first compound containing nitric acid or nitrate, a second compound containing sulfuric acid or a sulfate, and containing phosphoric acid or phosphate. The third compound and the compound of the group consisting of the fourth compound containing acetic acid or acetate. The composition of the insect immersion liquid may further contain an acid-based compound. 20 The etching liquid composition may further contain a chelate compound. Mixing effect. 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, and there is no need to add an expensive stabilizing agent, and copper can be used. Good speed forms the strength of the cone 200844215 etch. When the steel 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 of reducing the range in the process of the etching process and reducing the cost is obtained. Knife C Embodiment j 5 BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides an aqueous solution of ammonium persulfate [(NH 4 ) 2 s, n · ^ ammonium perSUlfate], and a water equivalent to the remainder The etchant formed. Knife The water in the present invention, although not explicitly mentioned, accounts for a total of 1% by weight of the total weight of the components other than water, relative to the entire liquid. The water used in the liquid of the present invention is preferably water or ultrapure water of a semiconductor grade. Etching liquid composition The persulfate money oxidizing agent of the present invention is the main component of the copper-containing metal layer remaining. Ammonium persulfate is preferably used in the purity of semiconductor engineering. In the remnant of the present invention, the weight ratio of the ammonium persulfate-based residual solution is 0.1 ° /. Up to 50%. Each of the compounds of the present invention contains at least one or more non-carbon atoms containing nitrogen as an element, and is represented by a ring of 5 rings. Although not particularly limited, in the compound of the present invention, for example, benzotriazo丨e, amin〇tetraz〇ie, imidazole, and t(Py_le) may be mentioned. Wait. In the etching solution of the present invention, the pyrrole compound is contained in an amount of 〇 1% to 5% by weight based on the total (iv) liquid. The pyrrole compound inhibits the side of the copper in the copper-containing metal layer, and is formed in the upper and/or lower multilayer film of the metal layer of the steel of the above-mentioned 9 200844215, copper and other metal layers.
loss)，將金屬配線作為閘極及數據配線使用。咄咯系化合 任務。前述銅及其他金屬層例如可含鈦 物係藉由減少金屬配線之切斷尺寸損 $，不但無法調節對銅之蝕刻速 配線之直進性亦降低，在量產製 物不添加本發明之蝕刻液時， 度’切斷尺寸損失增大，配_ 程適用時可引起嚴重問題。 前述触刻液可更含有含氟之氟化物系化合物。本發明 H)之姓刻液中，前述氟化物系化合物係以全體姓刻液作為重 量比佔有0.01%〜10%。前述氟化物系化合物係作為前述银 刻液之氧化輔助劑，可提高前述含銅金屬層之触刻速度。 又’前述氟化物系化合物可餘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 15 acid)、氣化敍（ammoniun flU0ride)、二氟化铵㈣m〇niun bifluoride)、氟化鉀（p〇tassiun fluoride)、氣化納（s〇diun fluoride)等。 本發明更於前述過硫酸銨及吼略系化合物中，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 20 部未被使用’包括全部使用時在内，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 或石粦酸鹽之第3化合物、及含有乙酸或乙酸鹽之第4化合物。 本發明之前述第1化合物，係於|虫刻液内釋出硝酸離子 200844215 (no3 )之物質。本發明之⑽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^化合物 例如可含有硝酸鐵(III)【Fe(N〇3)3】、硝酸鉀、硝酸銨:硝 酸鋰等。 5 本發明之前述第2化合物，係於餘刻液内釋出硫酸離子 (SO/-)或硫酸氫離子(HSO，）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 H) (30。至60。），一方面，不但使後製程時膜之被覆⑼卬 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， 排除别述弟2化合物時雖亦可進行銅之|虫刻，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 15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(NH4HS04)、硫酸氫钟(KHS〇4)、 硫酸鉀(K2S04)等。 本發明中前述第3化合物，係於蝕刻液内放出磷酸離子 (ρ〇Λ)、磷酸氫離子(hpo42_ )、磷酸二氫離子(η2Ρ〇Λ )之 20 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【（ΝΗ4)3Ρ04】、磷酸氫銨 【（ΝΗ4)2ΗΡ〇4】、磷酸二氫銨【（ΝΗ4)2Η2Ρ〇4】、磷酸鉀 (Κ3Ρ〇4)、磷酸氫鉀(Κ2ΗΡ04)、磷酸二氫鉀(ΚΗ2Ρ〇4)、磷酸 11 200844215 納(Ν々ρ〇4)、磷酸氫鈉(Na2HP〇4)及磷酸二氫鈉⑽灿α > 等。含有適當的前述第3化合物之蝕刻液，可使含銅金2屬層 形成均等之錐形蝕刻。 曰 本發明中前述第4化合物，係於蝕刻液内放出乙酸離子 (CHsCocr)之物質。本發明之選擇性構成成分之前述第4化 合物以重量比佔有〇%至10%。前述第4化合物例如可含 酸 乙酸錢、乙酸钟、乙酸鈉、亞 乙酸 10 力。 【HN(CH2CO〇H)2 ; iminodiacetic acid ; IDA】等。前述— 化合物可提高蝕刻液之第丨化合物之安全性，維持蝕列& 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 有鈾述銅金屬層之主成分的前述過硫酸銨，抑制其分解而 15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-甲苯石f酸 (para_t〇hieneSUlf〇nic add)、甲磺酸(methanesulf〇nic add)、 胺磺酸(amidosulfonic acid)等。 前述蝕刻液可更含有螯合劑。在本發明之蝕刻液中， 20前述螯合劑係以全體蝕刻液作為重量比佔有〇.〇〇〇1%至 5%。别述螯合劑係結合前述姓刻液與含有前述銅金屬層餘 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（ph〇sph〇nic series)、磺磺酸鹽系（sulfonic series)、乙酸鹽系（acetate series) 12 200844215 等之物質。 本發明所揭示之餘刻液或姓刻液組成物之範圍中，每 所示重量比之範圍内的_液，例如組成在: =魏_的數值之外，或雖於前述作為例示顯示之部 取代而其變化之構成，在該領射具有通常知識 ，、入，_與料㈣m組成實質上均等者，此種構成 亦包含在内。 以下，本發明舉述實施例更進一步說明。以下之實施 例中所不之構成係為帮助徹底地理解本發明，故在此表明 w於^可情形下，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。 成物之f施你丨 根據本發明之蝕刻液組成物之實施例丨至4之蝕刻液根 康下述第1表製造。實施例1至4之組成顯示於第1表，全體 15之％值係重量比。Loss), using metal wiring as a gate and data wiring.咄 系 化 化 。 。. The copper and other metal layers may contain, for example, a titanium material, and the cut size of the metal wiring may be reduced by $, and the straightness of the copper etched wiring may not be adjusted, and the etching of the present invention may not be added to the mass production article. When the liquid is used, the degree 'cutting size loss is increased, and the matching process can cause serious problems. The aforementioned etchant may further contain a fluorine-containing fluoride-based compound. In the surname engraving of H) of the present invention, the fluoride-based compound is contained in an amount of 0.01% to 10% by weight of the entire surname. The fluoride compound is an oxidation auxiliary agent for the silver etching solution, and the etch rate of the copper-containing metal layer can be improved. Further, the above-mentioned fluoride-based compound may optionally contain the metal layer of the titanium described above. The fluoride-based compound may, for example, contain hydrofluoric 15 acid, ammoniun flU0ride, ammonium difluoride (m)niun bifluoride, potassium fluoride (p〇tassiun fluoride), gasified sodium ( S〇diun fluoride) and so on. The present invention further contains four types of oxidation regulators in the above-mentioned ammonium persulfate and a compound of the sulphate. All of the four types of oxidation modifiers are not used, including all possible combinations, all of which are possible. The four types of oxidation regulators are respectively 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 phosphite, and the first containing acetic acid or acetate. 4 compounds. The first compound of the present invention is a substance which releases nitrate ions 200844215 (no3) in a worm liquid. In the liquid of the (10) liquid of the present invention, the first compound described above is contained in a weight ratio of 0% to 10%. The above compound may contain, for example, iron (III) nitrate [Fe(N〇3)3], potassium nitrate, ammonium nitrate: lithium nitrate or the like. The second compound of the present invention is a compound which releases a sulfate ion (SO/-) or a hydrogen sulfate ion (HSO,) in the residual liquid. The second compound of the selective constituent of the present invention contains 0% to 10% by weight of the entire etching liquid. In the metal wiring etching solution of the present invention, the second compound is formed in an etching solution containing a copper metal layer to form a suitable taper angle H) (30 to 60), on the one hand, not only in the post process The coating of the film (9) is good to contribute to the improvement of the yield, and at the same time, the etching speed of the copper is increased to help improve the productivity of the etching process. In the etching solution of the present invention, when the compound of the second embodiment is excluded, the copper can be etched, but when the second compound is used, the taper angle can be maintained at an appropriate level to prevent the coating of the subsequent film 15. Reduce the phenomenon to prevent the occurrence of bad. The second compound may, for example, contain sulfuric acid, ammonium hydrogen sulfate (NH4HS04), hydrogen sulfate clock (KHS〇4), potassium sulfate (K2S04) or the like. In the present invention, the third compound is a compound in which phosphoric acid ions (ρ〇Λ), hydrogen phosphate ions (hpo42_), and dihydrogen phosphate ions (η2Ρ〇Λ) are released in the etching solution. The third compound of the selective constituent 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 [(ΝΗ4)3Ρ04], ammonium hydrogen phosphate [(ΝΗ4)2ΗΡ〇4], ammonium dihydrogen phosphate [(ΝΗ4)2Η2Ρ〇4], potassium phosphate (Κ3Ρ〇4). Potassium hydrogen phosphate (Κ2ΗΡ04), potassium dihydrogen phosphate (ΚΗ2Ρ〇4), phosphoric acid 11 200844215 nano (Ν々ρ〇4), sodium hydrogen phosphate (Na2HP〇4) and sodium dihydrogen phosphate (10)can α > The etchant containing the appropriate third compound can form a uniform cone-shaped etching of the copper-containing gold 2 layer. In the present invention, the fourth compound is a substance which releases acetic acid ions (CHsCocr) in an etching solution. The above-mentioned fourth compound of the selective constituent of the present invention accounts for 〇% to 10% by weight. The above fourth compound may contain, for example, acid acetic acid, acetic acid clock, sodium acetate, and acetic acid. [HN(CH2CO〇H)2; iminodiacetic acid; IDA] and the like. The foregoing - the compound enhances the safety of the ruthenium compound of the etching solution, and maintains the etch & the etchant may further contain a sulfonic acid-containing sulfonic acid compound. 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 uranium-bearing copper metal layer. The sulfonic acid compound may contain, for example, benzenesulfonic acid, p-toluene f acid (para-t〇hieneSUlf〇nic add), methanesulfuric acid added, amidosulfonic acid or the like. The etching solution may further contain a chelating agent. In the etching solution of the present invention, 20 of the above-mentioned chelating agent accounts for 1% to 5% by weight of the entire etching liquid. The chelating agent is a combination of the above-mentioned surname and the copper ions which are generated when the copper metal layer is contained, so that the copper ions do not affect the etching rate of the etching liquid. The chelating agent may be, for example, a phosphonate-based series, a sulfonic acid series, or an acetate series 12 200844215. In the range of the remnant or surname composition disclosed in the present invention, the liquid in the range of the indicated weight ratio, for example, the composition is outside the value of: = Wei, or although the foregoing is shown as an example The composition of the change is replaced by the general knowledge, and the composition of the _ and the material (4) m is substantially equal, and such a composition is also included. Hereinafter, the present invention will be further described by way of examples. The following description of the embodiments is provided to facilitate a thorough understanding of the present invention, and thus it is indicated that the technical scope of the present invention is not limited to the embodiment presented by the embodiments. . The etch root of the etchant composition according to the present invention is manufactured in Table 1 below. The compositions of Examples 1 to 4 are shown in Table 1, and the % value of the whole 15 is a weight ratio.
13 200844215 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。 根據本發明實施例2之蝕刻液，含有3重量％之過硫酸 5 銨、0.1重量％之吡咯系化合物及0.5重量％之第2化合物。 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％之吼咯系化合物及0.5重量％之第3化合物。 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。 10 第2表 餘刻液 組成 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 實施例11 實施例12 實施例13 過石ίΐ酸錢 5% 5% 5% 5% 5% 5% 5% 5% 5% 吼口各系 化合物 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% 氟化物系 化合物 0.2% 0.5% 0.7% 0.2% 0.2% 0.2% 0.2% 0.2% 0.2% 第1化合物 1% 1% 1% 1% 1% 1% - - - 第2化合物 1% 第3化合物 1% 第4化合物 1% 1% 1% 1% 1% 續酸系 化合物 0.2% 0.2% 0.2% 0.2% 0.5% 0.2% 0.2% 0.2% 0.2% 螯合劑 0.001% 0.001% 0.001% 0.001% 0.001% 0.001% 0.001% 0.001% 0.001% 水 添加到100重量％為止 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 14 200844215 物、0.2重量％之磺酸系化合物及0.001重量％之螯合劑。 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％ 5 之石黃酸系化合物及0.001重量％之螯合劑。 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％之吼咯系化合物、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％ 之石黃酸系化合物及0.001重量％之螯合劑。 10 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％之咄咯系化合物、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％ 之石黃酸系化合物及0.001重量％之螯合劑。 根據本發明實施例9之蝕刻液，含有5重量％之過硫酸 15 銨、0.5重量％之吼咯系化合物、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。 根據本發明實施例10之蝕刻液，含有5重量％之過硫酸 鏔、0.5重量％之吼洛系化合物、0.2重量％之氟化物系化合 20 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。 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％之吼洛系化合物、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 15 200844215 重量％之螯合劑。 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、〇·2重量％之氟化物系化合 物、1重量％之第3化合物、0.2重量％之磺酸系化合物及〇〇〇1 5 重量％之螯合劑。 根據本發明實施例13之#刻液，含有5重量％之過硫酸 銨、0.5重量％之吡咯系化合物、〇·2重量％之氟化物系化合 物、1重量❹/。之第4化合物、0.2重量％之磺酸系化合物及〇〇〇1 重量％之螯合劑。13 200844215 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. The etching solution according to Example 2 of the present invention contains 3% by weight of 5 ammonium persulfate, 0.1% by weight of a pyrrole compound, and 0.5% by weight of a second compound. The etching solution according to Example 3 of the present invention contains 3 wt% of ammonium persulfate, 0.1 wt% of a ruthenium compound, and 0.5 wt% of a third compound. The etching solution according to Example 4 of the present invention contains 3% by weight of ammonium persulfate and 0.5% by weight of the fourth compound. 10 Table 2 Remnant Composition Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Permeable 5% 5% 5% 5% 5% 5% 5% 5% 5% Sakaguchi compound 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% 0.5% Fluoride compound 0.2% 0.5% 0.7% 0.2% 0.2% 0.2% 0.2% 0.2 % 0.2% First compound 1% 1% 1% 1% 1% 1% - - - Second compound 1% Third compound 1% Fourth compound 1% 1% 1% 1% 1% Continued acid compound 0.2% 0.2% 0.2% 0.2% 0.5% 0.2% 0.2% 0.2% 0.2% Chelating agent 0.001% 0.001% 0.001% 0.001% 0.001% 0.001% 0.001% 0.001% 0.001% Water is added to 100% by weight, refer to Table 2, according to this The etching solution of Inventive Example 5 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 a fourth compound 14 200844215, 0.2% by weight of a sulfonic acid compound and 0.001% by weight of a chelating agent. 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. Compound, 0.2% by weight of 5 rhein compound and 0.001% by weight of a chelating agent. The etching solution according to Example 7 of the present invention contains 5% by weight of ammonium persulfate, 0.5% by weight of a ruthenium compound, 0.7% by weight of a fluoride compound, 1% by weight of a first compound, and 1% by weight. 4 compound, 0.2% by weight of a crude acid compound and 0.001% by weight of a chelating agent. The etching solution according to Example 8 of the present invention, comprising 5% by weight of ammonium persulfate, 0.5% by weight of a ruthenium compound, 0.2% by weight of a fluoride compound, 1% by weight of a first compound, and 1% by weight The fourth compound, 0.2% by weight of the rhein compound, and 0.001% by weight of a chelating agent. The etching solution according to Example 9 of the present invention contains 5% by weight of 15 ammonium persulfate, 0.5% by weight of a ruthenium compound, 0.2% by weight of a fluoride compound, 1% by weight of a first compound, and 0.5% by weight. A sulfonic acid compound and a 0.001% by weight chelating agent. The etching solution according to Example 10 of the present invention contains 5% by weight of barium persulfate, 0.5% by weight of a quinone compound, 0.2% by weight of a fluorinated compound 20, 1% by weight of a first compound, and 0.2% by weight. The sulfonic acid compound and 0.001% by weight of a chelating agent. The etching solution according to Example 11 of the present invention contains 5% by weight of ammonium persulfate, 0.5% by weight of a ruthenium compound, 0.2% by weight of a fluorinated compound, 1% by weight of a second compound, and 0.2% by weight of sulfonate. Acid compound and 0.001 15 200844215% by weight of a chelating agent. 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, 2% by weight of a fluoride compound, 1% by weight of a third compound, and 0.2% by weight. A sulfonic acid compound and a chelating agent of 15% by weight of hydrazine. The #刻液 according to Example 13 of the present invention contains 5 wt% of ammonium persulfate, 0.5 wt% of a pyrrole compound, 2 wt% of a fluoride compound, and 1 wt%. The fourth compound, 0.2% by weight of the sulfonic acid compound, and 1% by weight of a chelating agent.
具體而言，在銅單一膜之時間基準中超過3〇%蝕刻之 過浸蝕（overetching)之實驗，評價實施例丨至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 15第3表及第1圖至第4圖。 第3表 蝕刻終點(秒） 切斷尺寸偏斜(μη) 錐形角（°) 實施例1 25 0.2 47 實施例2 35 0.2 42 實施例3 40 0.2 40 實施例4 45 ^ 0.3 50 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 20之姓刻此力切斷尺寸偏斜係表示光阻劑(photoresist)末端 16 200844215 與銅末端間之距離，為要具有無段差且均句之錐形角，該 距離須在適當的範圍内。錐形角係由餘刻過之金屬膜的側 面所觀察之傾斜，且約以45。至6()。為適當之值。參照第3 表，則本發明之餘刻液組成物顯示優良敍刻速度及切斷尺 寸偏斜藉由可將錐形輪廓調整為3〇。至7〇。而可瞭解。如 頁丁於第1至第4圖，在模狀直她具有良好之優良穩定 性，雖對多數之銅金屬膜姓刻，仍具有維持於與初期同樣 之性能的長處。 銅膜及與含有所述銅膜接觸形成之欽膜的多層膜，實 10施在時間基準中過超過3 _刻之過浸似〇爾tching)之 實驗’根據實施例5至13之_液的軸彳速度、切斷尺寸偏 斜及錐形角予以評價。其結果顯示於第4表。 蝕刻終點(秒） 實施例5 ' 35 實施例6 實施例7 實施例8 ^0- 實施例9 ' 28 實施例10 S- 實施例lT~ 實施例1厂 40 實施例ιΓ~ ' ^- —----Specifically, the etching rate of the etching solution of Examples 丨 to 4, the cut dimension skew and the cut dimension skew of the etching solutions of Examples 丨 to 4 were evaluated in an overetching of more than 3% by etching in the time base of the copper single film. Cone angle. Further, the cross section of the etched copper layer was observed by a microscope. The results are shown in Tables 15 and 1 and 4 of Figure 15. Table 3 Etching End Point (sec) Cut Size Deviation (μη) Cone Angle (°) Example 1 25 0.2 47 Example 2 35 0.2 42 Example 3 40 0.2 40 Example 4 45 ^ 0.3 50 End of Etch After the copper single film is etched by the etching solution, the glass of the glass substrate is exposed. The smaller the value of the end point of the etch, the more the name of the sturdy 20 is to cut the size. The skew is the distance between the end of the photoresist 16 200844215 and the end of the copper, in order to have a stepless angle and a cone angle of the sentence. This distance must be within the appropriate range. The taper angle is inclined by the side of the metal film which has been left over, and is about 45. To 6 (). Is the appropriate value. Referring to Table 3, the remnant composition of the present invention exhibits excellent scribe speed and cut-off dimension deflection by adjusting the taper profile to 3 〇. To 7 〇. And you can understand. As shown in the first to fourth figures, she has good stability and stability in the form of a mold. Although most of the copper metal films are surnamed, they still have the same advantages as the initial performance. The copper film and the multilayer film formed by contacting the copper film in contact with the copper film are subjected to an experiment of over 3 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The shaft speed, the cut size deflection, and the taper angle were evaluated. The results are shown in Table 4. Etching End Point (sec) Example 5 '35 Example 6 Example 7 Example 8 ^0- Example 9 '28 Example 10 S- Example lT~ Example 1 Plant 40 Example ιΓ~ ' ^- —- ---
錐形角(°) 蒼妝第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3()。至7〇。。 17 15 200844215 以上，雖參照實施例說明，熟練於該技術領域之業者， 於不脫離申請專利所記載的本發明之思想及領域的範圍 内，對认 ;可將本發明多樣地修正及變更，當然可予以理解。 I场式簡單說明】 第1圖係顯示以本發明實施例丨之蝕刻液組成物，蝕刻 祺之30%過浸蝕實驗中，所蝕刻之銅層側面的顯微 鏡照相。 夯第2圖係顯不以本發明之實施例2之蝕刻液組成物，蝕 二鋼單膜之30%過浸蝕實驗中，所蝕刻之銅層側面的顯 域鏡照相。 第3圖係顯示以本發明之實施例3之㈣液組成物，姑 ^單-狀30%過韻實財，所關之銅層侧面的顯 喊鏡照相。 第4圖係顯示以本發明之實施例4之_液組成物勉 刻鋼單-膜之30%過紐實驗中，職刻之銅層側面的顯 微鏡照相。 【主要元件符號說明】 (無） 18Cone angle (°) Bess makeup No. 4 shows that 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 3 (). To 7 〇. . 17 15 200844215 The above description of the present invention is made without departing from the spirit and scope of the invention as described in Of course it can be understood. BRIEF DESCRIPTION OF THE FOUR FIELDS Fig. 1 shows a microscopic photograph of the side of the etched copper layer in the 30% overetching experiment of the etched etchant composition of the embodiment of the present invention. Fig. 2 is a perspective photomicrograph showing the side of the etched copper layer in the 30% overetch test of the etched steel single film in the etchant composition of Example 2 of the present invention. Fig. 3 is a view showing the liquid composition of the liquid material of the fourth embodiment of the present invention, which is 30% of the rhyme, and the photographing of the side of the copper layer which is closed. Fig. 4 is a view showing the microscopic photograph of the side of the copper layer of the etched steel single-film of the liquid-liquid composition of Example 4 of the present invention. [Main component symbol description] (none) 18