201224211 ^、發明說明： 【發明所屬之技術領域】 本發明係有關於-種用於餘刻鋼基 溶液組成及使用其製造液晶顯示器之陣二 、姓刻銅基金屬層的方法及液晶顯示器的_基板。 【先前技術】 在液晶顯示器的基板上形成金屬接 包括利用濺射形成金屬層、塗覆光刻膠、、的方法通爷 影以便在選擇區域上形錢卿以及進行^ 述每個製程之前或之後進行清潔製程。進㈣刻製程， 為掩膜’將金屬層留在所述選擇區域 程可包括利用電黎進行乾式名虫刻或者利 用姓刻洛液組成進行濕式蝕刻。 的„晶顯示器近來所關注的重點在於金屬接線 it電阻電容（rc)信號延遲的問題對增加 。卢廷沪：寸和獲得高解析度至關重要，其中所述RC作 ==由電阻造成的。因此，為了減少該Ret j、u曰’十減乂 Rc#號延遲對增大TFT_LCD的尺寸來 。兄疋必需的），有必要開發低電阻材料。 )、相為I通常使用鉻（Cr，電阻率：12 7他8Qm :2.65 xJd S’—、紹(A1，電阻率 電阻，故Γ 其合金。但是，這些金屬具有高 極接線和用於大尺寸的TFT_LCD的開 枓接線。因此，低電阻金屬層，例如銅層和 4/20 201224211 二:之類_?銅基金屬層，以及1虫刻溶液組成受到關注 二=疋，目前已知的蝕刻銅基金屬的蝕刻溶液組成不能 卜用戶需求，並且需要研究與開發以改善其性能。 包含有過氧化氫的傳統钱刻溶液能夠 刻包括銅或銅合金和钥或麵合金的金屬多層結構。作是 金屬層時’其中之金屬離子且特別是銅離子會 谷解的現象，導致過氧化氫的分解率可能增大，進 產生過熱並且明顯地使餘刻溶液的穩定性變差。 此外，在金屬多層的情況下，由於電效應以及用過 =絲刻銅層的速率和用氣化合物钱刻銷合金層的 間的差值（該差值與所溶解的金屬離子的漢度的 =比例)’所以兩個相互結合的金屬層之間的介面 17月b s發生變形，進而導致蝕刻性能差。 【發明内容】 因此’本發明謹記相關技術中存在的上述問題，並 明的目的在於提供一種用於钱刻銅基金屬層的 二液組成’藉此，當濕式_包括銅或鋼合金和翻 或銷&金的金屬多層結構時，無論金屬離子的量為多少 ，都可形成具有優良線性的錐形輪廓，且可抑制因過 後==高而產生的過熱’此外，刻金屬層之 金屬在於提供一種用於触刻銅基 、ρ二，成’該溶液組成能夠成批蝕刻閘極 間極接線、源/汲極和數據接線，所述閘 線、源敁極和資料接線構成了 5/20 201224211 (TFT)。 本發明的又一目的在於提供一種利用上述蝕刻溶 、、、’成I虫亥J銅基金屬層的方法和一種製造液晶顯示器 的陣列基板的方法。 為了貝現上述目的，本發明提供一種用於钱刻銅基 孟層的钱刻溶液組A，基於該組成 溶液組成包括a)5〜25w_氧化氫（H202)、B)= ;·〇 wt%含氟化合物、c) 〇1〜5 吡咯基化合物、 )人0.1〜则wt%選自磷酸衍生物及其鹽的一個或多個 °物E ) 〇·1〜5 wt%磷酸鹽化合物以及F )餘量的 +赞明另提供 1王成〜則岙贫屬層的方法，包括： ，基板上形仙基金層；n)摘基 光反應材料；以及丨I丨）利用根攄本發明的If xj/谷液組成蝕刻銅基金屬層。 本：a月又提供一種製造液晶顯示器的陣列基板的 極接繞3)在基板上形成間極接線；b)在包括間 )开Q、“ 成源極和汲極；以及e 接汲㈣像素電極，其中a)包括在基板 以及利用根據本發明侧溶液組成/ 導體層上形成㈣金屬層，並括在半 溶液組成制誠w彻根據本發明的钱刻 攻钱刻銅基金屬層，從而形成源極和汲極。 括選本㈣提供—種液晶顯示1^陣縣板，包 U利用根據本發_⑽溶液組絲刻 匕 201224211 線和源/沒極中的一個或多個。 【實施方式】 下文將具體描述本發明。 本發明涉及一種用於蝕刻銅基金屬層的蝕刻溶液 組成’包括A) 5〜25 wt%過氧化氫（h2〇2) ; B) 0.01〜 1.0 wt%含氟化合物；c) 〇1〜5加％吡咯基化合物；d )0.1〜10.0 wt%選自磷酸衍生物及其鹽的一個或多個 化合物；E) 0‘1〜5 wt%磷酸鹽化合物；以及F)餘量 的水。 、，隹本务明中，銅基金屬層包含作為該層的組分的銅 ’亚且具有單層的形式和包括雙層#多層的形式。例如 ’使用銅或銅合金的單層，以及包括銅紹層、銅麵合金 層的多層結構等。其巾，所述_目層的結構包括有一鉬 層和-形成在層上的銅層，另外，所述銅鉬合金層的 結構包括有一翻合金層和—形成在鉬合金層上的銅層 。所仙合金層係由紳選自以下物f構成的組中的一 個或多個的合金做成··鈦（Ti)、组㈤、鉻（ 鎳（Ni)、斂（刚）和銦（& )。 本發明祕刻溶液叙成中，A)過氧化氮（ 的於侧銅基金騎，其量為該組成總重量 的5〜25wt%。如果Α)過氧化氫的含量小於5wt%， 則^能刻銅基金屬，或者糊速率變得非常低。反之 率二：過乳化氫的含量超過25 wt%，則整個兹刻速 率可犯會增大，導致難以控制該製程。 在根據本發__溶液组心，3)含氟化合物 7/20 201224211 表不在水中離解而產生氟離子的化合物。 氟化合物具有去除殘餘物的作用，該殘餘物是由同: 刻銅層和鉬層的溶液不可避免地產生的。B)人:人 物的量為該組成總重量的0.01〜1.0 Wt%。若】）八Γ 化合物的含量小於〇·〇】wt% ’則可能生成蝕3:。 氣化合物的含量超過〗.°wt%，卿璃 基板的逮率可能會大幅增加。 ’ 作為B)含氟化合物，可使用本技術領域中的任何 特別限制’只要該材料能夠在溶液中離解 出氣離子或夕原子I離子即可。該含㈣合物可包括撰 自氟化銨（nh4f)、氟化鈉（NaF)、氟化鉀 、： 八物 構成的組中的任何一個、或兩個或多個的混201224211 ^, invention description: [Technical field of the invention] The present invention relates to a method for preparing a steel-based solution composition and a method for manufacturing a liquid crystal display, a method for producing a copper-based metal layer, and a liquid crystal display _ substrate. [Prior Art] Forming a metal bond on a substrate of a liquid crystal display includes forming a metal layer by sputtering, coating a photoresist, and varnishing the film to form a money on the selected area and before performing each process or Then proceed to the cleaning process. Into the (four) engraving process, as a mask, leaving the metal layer in the selected region may include performing a dry-type insect engraving using electric liters or wet etching using a surname enclave composition. The focus of „crystal displays has recently been on the metal wiring. The resistance of the resistors and capacitors (rc) has a problem with the delay. It is important for Lu Tinghu: to achieve high resolution, where the RC is == caused by resistance. In order to reduce the Ret j, u曰 '10 minus 乂 Rc# delay to increase the size of the TFT_LCD. Brothers must be), it is necessary to develop low-resistance materials.), phase I usually use chromium (Cr, resistor Rate: 12 7 he 8Qm: 2.65 xJd S'-, Shao (A1, resistivity resistor, Γ alloy. However, these metals have high-pole wiring and open-circuit wiring for large-size TFT_LCD. Therefore, low resistance Metal layers, such as copper layers and 4/20 201224211 2: _? copper-based metal layers, and 1 insect solution composition are concerned about two = 疋, the currently known etching solution of copper-based metal etching solution can not meet user needs And need research and development to improve its performance. The traditional money engraving solution containing hydrogen peroxide can engrave a metal multilayer structure including copper or copper alloy and key or face alloy. When it is a metal layer, it is a metal ion and special The phenomenon that copper ions will decompose, resulting in a possible increase in the decomposition rate of hydrogen peroxide, which causes overheating and significantly deteriorates the stability of the solution. In addition, in the case of metal multilayers, due to electrical effects and use = the difference between the rate of the copper layer engraved and the alloy layer engraved with the gas compound (the difference is the ratio of the difference between the dissolved metal ions), so between the two bonded metal layers The interface bs is deformed in the 17th month, which results in poor etching performance. [Invention] Therefore, the present invention keeps in mind the above problems in the related art, and aims to provide a two-liquid composition for a copper-based metal layer. 'But this, when the wet type includes a copper or steel alloy and a metal multilayer structure of a turn or pin & gold, regardless of the amount of metal ions, a tapered profile with excellent linearity can be formed, and the after-effect can be suppressed. ==High and generated overheating' In addition, the metal of the engraved metal layer is provided for the purpose of inducing copper base, ρ2, into the composition of the solution capable of batch etching the inter-gate wiring, source/drain and data The line, the gate line, the source drain and the data wiring constitute 5/20 201224211 (TFT). It is still another object of the present invention to provide a copper-based metal layer which is etched by using the above etching solution. The method and a method for manufacturing an array substrate of a liquid crystal display. In order to achieve the above object, the present invention provides a money engraving solution group A for a copper engraved layer, based on the composition of the composition comprising a) 5~25w_oxidation Hydrogen (H202), B)=;·〇wt% fluorine-containing compound, c) 〇1~5 pyrrolyl compound, ) human 0.1~ then wt% is selected from one or more of the phosphoric acid derivatives and their salts 〇·1~5 wt% phosphate compound and F) balance + praise provides another method of Wang Cheng ~ then 岙 岙 属 layer, including:, the substrate on the foundation layer; n) radiant photoreaction The material; and 丨I丨) etches the copper-based metal layer using the If xj/valley solution of the present invention. Ben: A month provides a pole connection for manufacturing an array substrate of a liquid crystal display 3) forming a terminal wiring on the substrate; b) opening Q, "source and drain", and e-connecting (four) pixels in between An electrode, wherein a) comprises forming a (four) metal layer on the substrate and using the side solution composition/conductor layer according to the present invention, and enclosing the copper-based metal layer according to the invention Forming the source and the drain. The selection (4) provides a liquid crystal display 1 ^ array plate, the package U is used according to the hair _ (10) solution group to engrave one or more of the 201224211 line and the source / immersion. BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The present invention relates to an etching solution composition for etching a copper-based metal layer 'including A) 5 to 25 wt% hydrogen peroxide (h2〇2); B) 0.01 to 1.0 wt% Fluorine-containing compound; c) 〇1~5 plus % pyrrolyl compound; d) 0.1~10.0 wt% one or more compounds selected from the group consisting of phosphoric acid derivatives and salts thereof; E) 0'1~5 wt% phosphate compound And F) the balance of water. In, 隹本务明, the copper-based metal layer is included as the layer The copper of the component is sub- and has a single layer form and a form including a double layer # multilayer. For example, 'a single layer using copper or a copper alloy, and a multilayer structure including a copper layer, a copper alloy layer, etc. The structure of the _ mesh layer comprises a molybdenum layer and a copper layer formed on the layer. In addition, the structure of the copper-molybdenum alloy layer comprises a layer of overturned alloy and a copper layer formed on the layer of the molybdenum alloy. The alloy layer is made of an alloy of one or more selected from the group consisting of titanium (Ti), group (five), chromium (nickel (Ni), condensed (instant), and indium (& In the secret solution of the present invention, A) nitrogen peroxide (in the side copper fund ride, the amount is 5 to 25 wt% of the total weight of the composition. If the hydrazine) content of hydrogen peroxide is less than 5 wt%, then ^ Can be engraved with copper-based metal, or the paste rate becomes very low. Conversely, the rate of over-emulsified hydrogen exceeds 25 wt%, the entire rate can be increased, making it difficult to control the process. _ Solution group, 3) Fluorine-containing compound 7/20 201224211 The compound which does not dissociate in water to produce fluoride ion. The compound has the effect of removing residues which are inevitably produced by the same solution of the copper layer and the molybdenum layer. B) Person: The amount of the character is 0.01 to 1.0 Wt% of the total weight of the composition. ) The content of the compound of the gossip is less than 〇·〇] wt% 'There may be etch 3: The content of the gas compound exceeds 〖.°wt%, and the catch rate of the glazing substrate may increase significantly. 'As B) fluorochemical Any particular limitation in the art can be used as long as the material is capable of dissociating a gas ion or a cation I ion in solution. The tetra-containing compound may include ammonium fluoride (nh4f), sodium fluoride ( NaF), potassium fluoride,: any one of the groups consisting of eight substances, or a mixture of two or more
在根據本發明的姓刻溶液組成中，C)料美化A 物用於調整蝕刻銅基金屬的速率並減少^案二 CD(Cm丨ca丨Dimension，關鍵尺寸）損失，進而增大製程 範圍（process職_)。〇吡咯基化合物的量為該組 成總重量的0」〜5 wt%。如果c)吡咯基化合物的含量 =於〇.1Wt%，則可能會增加關速率而造成過多的⑶ 損失相反地，如果α比略基化合物的含量超過$ wt〇/〇， 則钱刻銅的速率可能會減低，侧I目或鉬合金的速率可 能會增加，可能會過度蝕刻鉬或鉬合金而產生下挖（ under-cut)的現象。 C)吡咯基化合物的實例可包括氨基四唑（ amin〇tetrazo丨e)、笨並***（benz〇tHaz〇ie)、甲苯*** 8/20 201224211 (t〇_azo】e)、吡唑"比咯、咪唑、2呀基味唾、2_ =唑、2-丙基咪唑、2_氨基咪唑、4_甲基咪。坐、心 個二、:坐，4_丙基咪唑等’這些可單獨使用或者以兩 们或夕個的混合物的形式使用。 在根據本發日__溶液組成巾，d)選自碑酸衍 =及其鹽的一個或多個化合物用於螯合在钱刻銅層 日禮解在I虫刻溶液中的銅離子，進而抑制銅離子的活性 、、’藉此防止過氧化氫分解。當以所述方式降低銅離子的 :舌性時’㈣溶液可穩定地進行該製程。D)選自礙酸 :生物及其鹽的-個或多個化合物的量為該組成總重 量的0.1〜10.0 wt%。如果D)選自鱗酸衍生物及其鹽 的-個或多個化合物的含量小於〇1 wt%，則蝕刻均勻 性可能會下降，過氧化氫的分解可能會加速。反之，如 果其含量超過lG.Gwt%’則仙速率可能會過度增加。 在選自磷酸衍生物及其鹽的一個或多個化合物中 ’磷酸衍生物的典型實例為卜羥基乙叉_u_二磷酸（ HEDP)，磷酸衍生物鹽的典型實例為卜羥基乙叉山 一碌酸的納鹽或卸鹽。 在根據本發明的蝕刻'溶液組成中，E)磷酸鹽化合 物使得錐形輪廓良好，並且可減低電效應以及銅層和鉬 合金層之間的蝕刻速率的差值，該差值與金屬離子的濃 度的增加成比例。藉此，即使存在有過量的金屬離子， 也可防止兩個相互結合的金屬層之間的介面變形，進而 獲得良好的I虫刻輪廓。 E)磷酸鹽化合物的量為該組成總重量的〜5 wt%。如果E)磷酸鹽化合物的含量小於〇1 wt%，則 9/20 201224211 在具有高濃度金屬離子的情況下獲得良好的錐形 輪廢。反之，如果其含量超過5，則钱刻翻合金層 的速率可能會明顯降低而增加殘餘物。 作為E) _鹽化合物，可❹本技術領域中的任 :可材料，而沒有特別限制，只要該材料能夠在溶液中離 解出碟酸鹽離子即可。該碟酸鹽化合物可包括選自鱗酸 :風銨、磷酸二氫納、磷酸二氫鈣、磷酸二氫鉀、磷酸 氣―銨、碟酸氤二鈉、碟酸氫妈（calciuraph〇_ate 1 aS1C)以及磷酸氫二鉀構成的組中的-個或多個。 ，本發明的蝕刻溶液組成t，不特別限制用作 的F)水’但是該水可包括去離子水。更特別有 去離子水的電阻率（從水t去除的離子的度 婁人）為]8 ΜΏ/cm或更大c ，樣地’本發日㈣|±刻溶液㈣射包括表面活性 =该活性劑用於減少表面張力，以增純刻均勾性。 ^把縣面活性劑並沒⑽職制，只要該表面活性 二了^根據本發明的_溶液組成並具有相容性即 可0舌亥表面活性劑可^j 土堅 子表面活性劑、兩性表面活性劑、非離::::生:離 ^型表面活性劑構成的組中一個、’兩:: 多個的混合物。 U次兩個或 成還二分，根據本發明的卿液，组 合劑、祕劑;f這些添加劑的實例可包括髮 ，其= =明:使用的_溶液 乳化風（H2〇2)、B)含氟化合物、c) 10/20 201224211 比咯基化口物、D)選自磷酸衍生^ ^ =二·鹽化合物以及F)餘量二= s亥浴液的純度可適合於半導體技術。 金屬溶液組成可用於成批#刻銅基 至少ί:以ί:明提供一種钱刻銅基金屬層的方法，其 )利用根據本發明==反應材料;以及m 9蝕"]/合液組成蝕刻銅基金屬層。 的光的侧方法中，光反應材料可為典型 選=二光刻膠可通過典型的曝光和顯影製程而被 此外’本發明提供一種贺 的方法，苴至小勺扛 衣心液日日蝻不态的陣列基板 線.b) / it 下步驟a)在基板上形成間極接 ）在”有閘極接線的基板上形成閛絕管屛Ή 間絕緣層上形成半導體層；0在半導在 可包括在基板上形成銅基金屬層據=:) 蝕刻溶液組成蝕刻銅基金屬居 / 只月的 )可包純半導體層上形^基 Ο ' ^ 而形=源極和汲極 列基=顯示器的陣列基板可為_電晶體（TFT)陣 下面提出的實施例是用於闡述而非限制本發明，這 11/20 201224211 些實例可幫助更好地理解本發明。 實施例 蝕刻溶液組成的製備 利用下面表1所示的組分製備實例1到6的㈣溶液組 成。 表1 (單位：wt%) H202 nh4f 氨基四唾 HEDP 磷酸鹽 去離子水 實施例1 5 0.3 0.2 3.0 0.2 餘量 貫施例2 10 0.2 0.5 4.0 0.5 餘量 實施例3 15 0.1 0.8 5.0 0.8 餘量 實施例4 18 0.08 1.0 7.0 1.0 餘量 實施例5 22 0.05 1.5 9.0 1.5 餘量 實施例6 25 0.03 3.0 10.0 1 3.0 餘量 *HEDP: 1-羥基乙又_1，〗_二磷酸 銅基金屬層的蝕刻 翻-欽（Μο·Τί)層沉積在玻璃基板（〗〇〇 mrnxl〇〇 mm )上，銅層沉積在M〇_Ti層上，然後進行光刻，從而在 基板上形成具有預定圖案的光刻膠，之後，利用實例 1-6的每種蝕刻溶液組成蝕刻銅基金屬層（Cu單層和 Cu/Mo-Ti 雙層）。In the surname solution composition according to the present invention, C) material beautification A is used to adjust the rate of etching the copper-based metal and reduce the loss of the CD (Cm丨ca丨Dimension, critical dimension), thereby increasing the process range ( Process job _). The amount of the pyrrole group compound is from 0" to 5 wt% of the total weight of the composition. If the content of c) pyrrolyl compound = 〇.1Wt%, it may increase the shutdown rate and cause excessive (3) loss. Conversely, if the content of α is slightly more than $wt〇/〇, then the copper is engraved. The rate may be reduced, the rate of the side I or molybdenum alloy may increase, and the molybdenum or molybdenum alloy may be over-etched to cause an under-cut phenomenon. C) Examples of the pyrrolyl compound may include aminotetrazole (amin〇tetrazo丨e), benza triazole (benz〇tHaz〇ie), tolutriazole 8/20 201224211 (t〇_azo) e), pyrazole "Biloxime, imidazole, 2 yoghurt saliva, 2_ = oxazole, 2-propylimidazole, 2-aminoimidazole, 4-methylimidazole. Sitting, heart two, sitting, 4_propyl imidazole, etc. These can be used alone or in the form of a mixture of two or a mixture. In the composition according to the present day, the composition of the towel, d) one or more compounds selected from the group consisting of the acid and its salts are used to chelate the copper ions in the solution of the copper in the engraved solution. Further, the activity of the copper ions is suppressed, thereby preventing decomposition of hydrogen peroxide. When the copper ion: tongue is lowered in the manner described, the '(iv) solution can be stably carried out. D) is selected from the group consisting of acid-inducing compounds: the amount of one or more compounds of the organism and its salt is 0.1 to 10.0% by weight based on the total weight of the composition. If D) the content of one or more compounds selected from the group consisting of squaraine derivatives and salts thereof is less than 〇1 wt%, the etching uniformity may be lowered, and the decomposition of hydrogen peroxide may be accelerated. On the other hand, if the content exceeds lG.Gwt%', the rate of sensation may increase excessively. A typical example of a 'phosphoric acid derivative' in one or more compounds selected from the group consisting of phosphoric acid derivatives and salts thereof is hydroxyethylidene-u-diphosphate (HEDP), and a typical example of a phosphate derivative salt is hydroxyethylidene The sodium salt of the acid or the salt is removed. In the etching 'solution composition according to the present invention, E) the phosphate compound makes the tapered profile good, and can reduce the electrical effect and the difference in etching rate between the copper layer and the molybdenum alloy layer, the difference with the metal ion The increase in concentration is proportional. Thereby, even if there is an excessive amount of metal ions, the interface between the two mutually bonded metal layers can be prevented from being deformed, thereby obtaining a good I-worm contour. E) The amount of the phosphate compound is 〜5 wt% of the total weight of the composition. If the content of the phosphate compound is less than 〇1 wt%, then 9/20 201224211 obtains a good cone wheel waste with a high concentration of metal ions. On the other hand, if the content exceeds 5, the rate at which the alloy layer is etched may be significantly lowered to increase the residue. As the E) salt compound, any material can be used without particular limitation as long as the material can dissociate the discate ions in the solution. The disc acid salt compound may include a selected from the group consisting of scaly acid: phosgene: ammonium sulphate, dihydrogen phosphate, calcium dihydrogen phosphate, potassium dihydrogen phosphate, phosphoric acid-ammonium, disodium bisulphate, and hydrogen hydride (calciuraph〇_ate). One or more of the groups consisting of 1 aS1C) and dipotassium hydrogen phosphate. The etching solution composition t of the present invention is not particularly limited to the water used as F) but the water may include deionized water. More specifically, the resistivity of deionized water (the degree of ions removed from water t) is 8 ΜΏ/cm or more c, and the plot 'this day (four)|±etched solution (four) shot includes surface activity = the The active agent is used to reduce the surface tension to enhance the homogenization. ^The county active agent is not (10), as long as the surface activity is two. According to the composition of the present invention and has compatibility, the 0 surfactant can be used as a surfactant, amphoteric surfactant Agent, non-off:::: raw: one of the group consisting of ^ type surfactant, 'two:: a mixture of multiple. U times two or two minutes, the clear liquid, the combination agent, the secret agent according to the present invention; f Examples of these additives may include hair, which = = Ming: used _ solution emulsified wind (H2 〇 2), B) Fluorine-containing compound, c) 10/20 201224211 specific group, D) selected from the group consisting of phosphoric acid-derived ^^=di-salt compounds, and F) balance 2 = s-hai bath can be suitable for semiconductor technology. The composition of the metal solution can be used for batching a copper base at least: a method for providing a copper-based metal layer, using a ==reactive material according to the invention; and m 9 etch " Forming an etched copper-based metal layer. In the side method of light, the photoreactive material can be a typical selective=two photoresist which can be further provided by the present invention by a typical exposure and development process, and the method of the invention provides a method of congratulation to the small spoon. Non-state array substrate line.b) / it Next step a) Forming a junction on the substrate) Forming a semiconductor layer on the insulating layer of the gate with a gate wiring; 0 in the semiconductor Forming a copper-based metal layer on the substrate can be included: =) etching solution composition etching copper-based metal / monthly) can be wrapped on a pure semiconductor layer on the surface of the ^ ^ shape = source and drain column The array substrate of the display may be a transistor (TFT) array. The following examples are presented to illustrate and not to limit the invention. These examples can help to better understand the present invention. Preparation The composition of (4) solutions of Examples 1 to 6 was prepared using the components shown in Table 1 below. Table 1 (unit: wt%) H202 nh4f Aminotetrahydro HEDP Phosphate Deionized Water Example 1 5 0.3 0.2 3.0 0.2 Example 2 10 0.2 0.5 4.0 0.5 Balance Example 3 15 0.1 0 .8 5.0 0.8 Balance Example 4 18 0.08 1.0 7.0 1.0 Balance Example 5 22 0.05 1.5 9.0 1.5 Balance Example 6 25 0.03 3.0 10.0 1 3.0 Balance *HEDP: 1-Hydroxyethyl _1, _ The etching of the copper diphosphate metal layer is deposited on a glass substrate (〗 〖Mrnxl〇〇mm), and a copper layer is deposited on the M〇_Ti layer, and then photolithography is performed, thereby A photoresist having a predetermined pattern was formed on the substrate, and thereafter, a copper-based metal layer (Cu single layer and Cu/Mo-Ti double layer) was etched using each of the etching solutions of Examples 1-6.
利用喷射型蝕刻機（ETCHER ( TFT )，從SEMES 可購買到）進行蝕刻製程，在該蝕刻製程中，蝕刻溶液 組成的溫度設為大約30。(：，其中該溫度可根據其他製 程的條件和因素的要求而適當地變化。雖然钱刻時間係 12/20 201224211 根據㈣溫度而變化，但是钱刻時間設為大約3〇_18〇 秒。 餘刻溶液組成的性能評估 使用SEM ( S-4700，從日立公司（Hhachi)可購買 )觀察上述蝕刻製程中被蝕刻的銅基金屬層的橫截面 圖。結果顯示在下面的表2中。 同才水’為了在金屬離子（尤其是銅離子）存在的情 下，通過過氧化氫的鏈分解評估過熱的程度，在實施 为―1到6的蝕刻溶液中洗脫3〇⑻卯mCu粉末，之後， ，餘刻溶液停留預定㈣間段，並且測量其溫度。結 *'員示在下面的表2中。An etching process was performed using a jet type etching machine (ETCHER (TFT), commercially available from SEMES) in which the temperature of the composition of the etching solution was set to about 30. (:, where the temperature can be appropriately changed according to the requirements of other process conditions and factors. Although the time of the money is 12/20 201224211 according to (4) temperature, the time is set to be about 3〇_18〇 seconds. Performance Evaluation of Residual Solution Composition A cross-sectional view of the etched copper-based metal layer in the above etching process was observed using SEM (S-4700, available from Hitachi, Hhachi). The results are shown in Table 2 below. In order to evaluate the degree of superheat by chain decomposition of hydrogen peroxide in the presence of metal ions (especially copper ions), 3 〇(8) 卯mCu powder is eluted in an etching solution of “1 to 6”, Thereafter, the remaining solution is left in the predetermined (four) interval, and its temperature is measured. The knots are shown in Table 2 below.
13/20 201224211 均表現出良好的餘匕 的_組成㈣二基出:用實施例】 輪廓。同樣，如圖2和；層乂現出良好的錐形 刻溶液組成㈣鋼基金屬層利=施例4㈣ ，並且不留下蝕列终 n/ 又得優良的線性 使用實施例！到6^1 外，從表2可明顯看出， ，、、西/、虫刻浴液時，即使洗脫3〇〇〇ppmCu 性:度也僅僅升高到⑽，這就大幅改善了過:穩Ϊ 和實施例4:祕聽独成評估若干處 R 2下面表3所示的比較實施例1的_溶液組成 (其為傳絲刻溶液組成）和根據本發明的實施例A的 银刻溶液組成，在不_以濃度下測量最大溫度 '殘 餘物的產生以及㈣輪廓。這樣，由於過氧化氫的鍵分 解與銅濃度的增加成比例，糾最大溫度表示關溶液 溫度變化的最大值。 處理片的編 號（Cu_) C.Ex.l (比較實施例1) Ex_4 (實施例4) H202/丙 咪嗤/N 二酸/^1*12?〇4/亞氨基二乙酸/ H4F (25/2/1/0.5/1/0.1 ) Wt% H202/NH4F/氨基四唑/HEDP/KH2p〇4 ( 18/0.08/1.0/7.0/1,0) wt% 最大溫 度GO 殘餘物 的產生 姓刻輪廊 最大溫度 (°C) 殘餘物的 產生 飯刻輪廓 Cu單層 Cu/Mo-Ti Cu單層 Cu/Mo-Ti 0 20.6 No 0 0 20.0 No 0 0 ___100 23.0 -——— No 0 0 20.2 No 0 〇 ^_5〇〇^ 24.3 No 0 0 20.8 No 0 〇 表3 14/20 20122421113/20 201224211 Both show good embers _ composition (four) two base out: use the example] contour. Similarly, as shown in Fig. 2 and; the layer 乂 shows a good conical engraving solution composition (4) steel-based metal layer profit = example 4 (four), and does not leave the etched end n / again excellent linearity using the embodiment! From 6^1, it can be clearly seen from Table 2 that, when,, and when the bath is engraved, even if the elution is 3〇〇〇ppmCu, the degree is only increased to (10), which greatly improves the : Stabilization and Example 4: secret evaluation of several places R 2 _ solution composition of Comparative Example 1 shown in Table 3 below (which is a wire-forming solution composition) and silver according to Example A of the present invention The composition of the solution was measured, and the maximum temperature 'residue generation and (iv) profile were measured at a concentration not. Thus, since the bond decomposition of hydrogen peroxide is proportional to the increase in copper concentration, the maximum correction temperature represents the maximum value of the temperature change of the shut-off solution. Handling sheet number (Cu_) C.Ex.l (Comparative Example 1) Ex_4 (Example 4) H202/Protonium/N diacid/^1*12?〇4/iminodiacetic acid/H4F (25 /2/1/0.5/1/0.1 ) Wt% H202/NH4F/Aminotetrazole/HEDP/KH2p〇4 (18/0.08/1.0/7.0/1,0) wt% Maximum temperature GO Residue generation Maximum temperature of the gallery (°C) Residue generation of rice contour Cu single layer Cu/Mo-Ti Cu single layer Cu/Mo-Ti 0 20.6 No 0 0 20.0 No 0 0 ___100 23.0 -———— No 0 0 20.2 No 0 〇^_5〇〇^ 24.3 No 0 0 20.8 No 0 〇表3 14/20 201224211
—鱗雜細雜都差_ 從表3、圖4和圖5可明顯看出，當洗脫至少‘ PP^Cu時，比較實施例]的傳統蝕刻溶液組成的溫度 升南到99.2〇C ’不合期望地且明顯地使穩定性變差，並 且由於電效應以及用過氧化氫姓刻銅層的速率和=氟 化合物㈣鉬合金層的速率之_差值，造成介面變形 、’=而導致姓刻輪廓差。但是，使用實施例4的姓刻溶 液4 ’如表3、圖6和圖7所示，即使洗脫_Q Cu 也不發生過熱，並且沒有殘餘物，而且獲得了良好的 =刻輪廓。因此’可使用根據本發明的實施例4的 溶液組成，直到洗脫6〇〇〇 ppm Cu。 如上所述’本發明提供—種製造液晶顯示器的陣列 :板的方法。當蝕刻包括銅或銅合金和鉬或鉬合金的金 方夕層時，根據本發明的餘刻溶液組成能夠進行成批餘 』並進行構圖。此外，即使金屬離子的濃度增大，也可 防止祕刻溶液過熱，從而保持其穩定性，並且由於電 效應以及金屬層之間⑽速率的差值，介面不變形。而 15/20 201224211 二:獲iT?良的錐形輪琢，並且_也不留下 、=差在短路 的餅溶液组 極和杳祖姐力…战彳蝕刻閘極、閘極接線、源/汲 因此可簡化飯刻製程並最大化製程良率。 幕和:嗔列基板，從而獲得大尺寸的營 γ丨雖f為了鬧述的目的，已經公開本發明的優選實施 歹I’但疋本技術領域的技術人員應瞭解在不違背所附權 ’要求所公開的本發明的範圍和精神的情況下，可進 各種更改、添加和替換。 【圖式簡單說明】 結合附圖，從下面的具體描述中很容易理解本發明 的上述和其他目的、特徵和進一步的優勢，其中：χ 圖1顯不了銅基金屬層的橫戴面的掃描電子顯微鏡（ SEM)圖像，其中，該銅基金屬層被根據本發明的蝕刻 溶液組成（實施例1 )蝕刻； 圖2和圖3分別顯示了利用根據本發明的蝕刻溶液組成 (實施例4)蝕刻銅基金屬層之後，銅接線周圍的整個 名虫刻輪廓和表面的SEM圖像； 圖4和圖5分別顯示了利用比較實施例1的蝕刻溶液組 成以4,000 ppm Cu蝕刻Cu/Mo-Ti玻璃之後，所钱刻的 橫戴面和整個蝕刻輪廓的SEM圖像；以及 16/20 201224211 圖6和圖7分別顯示了利用實施例4的㈣溶液 6,〇〇〇 ppm Cu蝕刻Cu/M〇_Ti破璃之後’所蝕刻的 面和整個蝕刻輪廓的SEM圖像。 〜哉 Γ主要元件符號說明】 無 17/20- scaly impurities are poor _ From Table 3, Figure 4 and Figure 5, it is apparent that when eluting at least 'PP^Cu, the temperature of the conventional etching solution of Comparative Example] rises to 99.2 〇C ' Undesirably and significantly deteriorates stability, and due to electrical effects and the difference between the rate of hydrogen peroxide surnamed copper layer and the rate of =fluorochemical (tetra) molybdenum alloy layer, causing interface deformation, '= The surname is poorly contoured. However, using the surname solution 4' of Example 4 as shown in Table 3, Fig. 6, and Fig. 7, even if elution _Q Cu did not overheat, and there was no residue, and a good = engraved profile was obtained. Thus, the composition of the solution according to Example 4 of the present invention can be used until 6 〇〇〇 ppm Cu is eluted. As described above, the present invention provides a method of manufacturing an array of liquid crystal displays: a board. When etching a gold layer comprising copper or a copper alloy and a molybdenum or molybdenum alloy, the composition of the residual solution according to the present invention can be batched and patterned. Further, even if the concentration of the metal ions is increased, the solution of the secret solution can be prevented from being overheated, thereby maintaining its stability, and the interface is not deformed due to the electrical effect and the difference in the rate between the metal layers (10). And 15/20 201224211 2: get the iT? good cone rim, and _ does not leave, = the short circuit of the pie solution group and the ancestral scorpion force... 彳 彳 etch gate, gate wiring, source /汲This simplifies the cooking process and maximizes process yield. Curtain and: arranging the substrate to obtain a large-sized camp γ 丨 Although the preferred embodiment of the present invention has been disclosed for the purpose of narration, it should be understood by those skilled in the art that the right is not violated. Various changes, additions and substitutions are possible in the case of the scope and spirit of the invention disclosed. BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and further advantages of the present invention will be readily understood from the following description in conjunction with the accompanying drawings in which: Figure 1 Figure 1 shows a scanning of the cross-face of a copper-based metal layer An electron microscope (SEM) image in which the copper-based metal layer is etched by the etching solution composition according to the present invention (Example 1); FIGS. 2 and 3 respectively show the composition of the etching solution according to the present invention (Example 4) After etching the copper-based metal layer, the entire worm image and the SEM image of the surface around the copper wiring; FIG. 4 and FIG. 5 respectively show the etching of Cu/Mo- at 4,000 ppm Cu using the etching solution composition of Comparative Example 1. SEM image of the cross-face and the entire etched profile after the Ti glass; and 16/20 201224211 Figures 6 and 7 respectively show the etching of Cu/ using (ppm Cu using the solution (4) of Example 4 SEM image of the etched face and the entire etched profile after M〇_Ti is broken. ~哉 ΓMain component symbol description] None 17/20