201204875 六、發明說明： 【發明所屬之技術領域】 本發明係有關—種含銅及鈦之 物，及其係用於半導體裝置及平板顯_ 晶體_之閘極、源極/沒極布線，及電極。猶電 ⑽本案請求韓國專利申請㈣職10-0040568號申往 |案。1〇年4月30日之權益，該案全文係以制方式併二 【先前技術】 於半導體裝置及平极顧干哭φ . 線之f裎並刑^ & 3，在基板上形成金屬布 传用i h 使用賤鑛而形成金屬層、施加光阻、 此外而在—選定區上形成光阻、及進行飯刻。 此外’在各項個別處理步驟之前或之後進行料 理運用光阻作為遮罩，使得金屬層留在選定^ 刻。d地包括錢賴之乾_或制_液之濕兹 源搞/針對半導體裝置及平板顯示^，制^ ΤΗ，閘極及 屬層ΓΓ陣Γ布線係由0包括具有低電阻之链製導電層的金 中:开;旦紹層有問題’原因在於由於在隨後處理步驟 化物層二=與因另二電1Γ短路’及因接觸氧 ㈣风、，e· m此’揭不含缺鈦之雙層 之閘極、源極/汲極陣列布線、及電極。 ‘、’、 =了钱刻含銅及鈦之雙層，針對個別層應使用不同 成物。更明確言之，用以颠刻含銅之金屬層的姓 二G之=主要包括基於過氧化氫之蝕刻液組成物或基 、片乳之侧液組成物。以基於過氧化氫之敍刻液組成物 3/13 201204875 … 蝕刻液組成物可能分解而儲存期短 姓刻液組成物為例，㈣ f存』短以基於臭氧之 過變不穩定。 、率緩慢且組成物隨著時間之經 【發明内容】 其允供-_液組成物’ ㈣。 之金屬層_ ’特別銅/鈦雙層之總满 又人本!x月，第—目的係提供—種朗液組成物，其甚矣 1乳化氫及/或臭氧而針對銅具有快速姓刻速率7 仆射丨Ϊ明之第二目的係提供—觀舰組成物，其可簡 化蝕刻處理步驟且改進生產力。 本發明之第四目的係提供一種姓刻液組成物，其可達 成快速蝕刻速率及一致的蝕刻。 本發明之第五目的係提供一種姓刻液組成物，其不會 損壞設備且蝕刻時無需使用昂貴的設備。 八 本發明之第六目的係提供一種敍刻液組成物，其可有 利地％用至大尺寸顯示面板，如此產生經濟效益。 本發明之第七目的係提供一種姓刻液組成:，盆除了 含銅及鈦之金屬層外，可姓刻用於像素電極之ιζ〇 a-ITO。 本發明之-態樣係提供-種含銅及鈦之金屬層用姓刻 液組成物，以該組成物總重為基準，包括5至2G研％過硫 酸鹽’ 0.01至2 wt%說化合物，1至10 wt%選自無機酸二 無機酸鹽、及其混合物中之-者或多者，Q 3至5糾％環狀 胺化合物，0.1至5 wt%氯化合物，0.1至5 wt%對曱笨續酸， 及剩餘為水。 4/13201204875 VI. Description of the Invention: [Technical Field] The present invention relates to a copper-and-titanium-containing material, and a gate, source/polar wiring for a semiconductor device and a flat panel , and electrodes. Judian (10) The case requested the Korean patent application (4) to apply for the case of No. 10-0040568. The rights and interests of the case on April 30, 1st, the full text of the case is based on the system and the second [previous technology] in the semiconductor device and the flat pole cough φ. The line f裎 and the punishment ^ & 3, the formation of metal on the substrate The cloth is conveyed by using ih to form a metal layer, applying a photoresist, and forming a photoresist on the selected area, and performing a meal. In addition, the use of photoresist as a mask before or after each individual processing step leaves the metal layer at a selected time. d includes Qian Lai's dry _ or system _ liquid wet source / for semiconductor devices and flat panel display ^, system ^, gate and genus layer ΓΓ array wiring system consists of 0 with low resistance chain The gold of the conductive layer: open; there is a problem in the layer of the layer. The reason is that due to the subsequent processing step, the second layer = short circuit with the other two wires, and the contact with oxygen (four) wind, e·m Titanium double layer gate, source/drain array wiring, and electrodes. ‘,’, = money is engraved with double layers of copper and titanium, and different products should be used for individual layers. More specifically, the surname of the metal layer for indenting the copper-containing metal layer mainly includes the composition of the etching solution based on hydrogen peroxide or the side liquid composition of the base and the milk. Composition based on hydrogen peroxide-based engraving solution 3/13 201204875 ... The composition of the etching solution may be decomposed and the storage period is short. For example, the engraved composition is short, and (4) f is short to be unstable based on ozone. The rate is slow and the composition is over time. [Summary of the Invention] It is allowed to supply - liquid composition ' (4). The metal layer _ 'Special copper / titanium double layer is full and human! x month, the first - the purpose is to provide a kind of lang liquid composition, which is 1 emulsified hydrogen and / or ozone and has a fast surname for copper The second objective of the rate 7 servant is to provide a ship-watching composition that simplifies the etching process steps and improves productivity. A fourth object of the present invention is to provide a surname composition which achieves a fast etch rate and uniform etching. A fifth object of the present invention is to provide a surname engraving composition which does not damage the apparatus and which does not require the use of expensive equipment when etching. The sixth object of the present invention is to provide a stencil composition which can be advantageously used for a large-sized display panel, which is economical. A seventh object of the present invention is to provide a surname engraving composition which, in addition to a metal layer containing copper and titanium, can be used for the ιζ〇 a-ITO of the pixel electrode. The invention provides a metal layer containing copper and titanium with a surname engraving composition, based on the total weight of the composition, including 5 to 2G % persulfate '0.01 to 2 wt% said compound , 1 to 10 wt% selected from the group consisting of inorganic acid dibasic acid salts, and mixtures thereof, Q 3 to 5 % by weight of cyclic amine compounds, 0.1 to 5 wt % of chlorine compounds, 0.1 to 5 wt % It is sour and sour, and the rest is water. 4/13
S 201204875 ^日狀$ —紐係H種製辭導體裝置或平板 ”、、’、器之方法包括使用该餘刻液組成物餘刻含銅及鈦之 金屬層之步驟。 本I月之又另—態樣係提供—種使用該磁彳液組成物 所製造的半導體裝置或平板顯示器。 【實施方式】 後文中將針對本發明作詳細說明。 .依據本發明之含銅及鈇之金屬層用㈣液組成物包 $.過硫酸鹽；敗化合物；選自無機酸、無機酸鹽、及其 混合物中之-者❹者；環狀胺化合物；氯化合物；對甲 本石黃酸；及水。 包含於依據本發明之姓刻液組成物中之過硫酸鹽為含 鋼層侧用之主要氧化劑，且該組成物總重絲準，其用 ^為5%至20 wt%，及較佳7%至18過。當此種成分之含 ®落入於前述範圍内時，含銅層係以適量⑽，且钱刻輪 廓情況變優異。 當過硫酸鹽之含量係低於5 wt%時，⑽速率減低，及 如此無法充分地進行㈣。又復，當其含量係大於2〇 wt% 钱刻速率增高過速’使得_控制⑽速率，結果欽 薄膜及銅薄膜可能被過蝕。 過硫酸鹽可選自於由過硫酸銨(Aps)、過硫酸鈉(sps)、 及過硫酸鉀(PPS)所組成之群組。 ^包含於依據本發明之餘刻液組成物中之氟化合物主要 係用來酬含鈦、izo、4a_IT〇之—層，且以組成物總重 為基準，係以〇.01%至2 wt%及較佳〇 〇5%至！ 之數量 添加。當此種成分之含量係落入於前述範圍内時，含鈦層 5/13 201204875 係以適里敍刻，且姓刻輪廓情況變優里。 量係低於前述下限_，人 ”田此種成分之含 能產蝴殘i f刻速率可能減低，且可 上限時，魏料朗及切mm係超過前述 合物❹料氣離子之化 她、及氟化 酸、+之選自於無機 含銅;物中之一者或多者可氧化細 s且了虱化含鈦層。以組成物總重 •無機酸鹽、及其混合物令之-者或多者可： 川哪及較佳2%至7 wt%之數量使用。當此種者成 係落入於㈣翻時，含銅層及含鈦層細適量 2 ^刻輪雜況變優異。當此種成分之含量係低於前述下限 所’钱刻速率減低’飯刻輪摩非期望地降級且產生兹刻殘 貝。相反地，當此種成分之含量係超過前述上限時，則可 能，生過姓，光阻可能裂開而形成裂縫，因而钱刻液可滲 入裂縫’造成導線非期望地短路。 無機酸係選自於由硝酸、硫酸、填酸、及過氣酸所组 成之群組。 ^ 無機酸鹽係選自於由瑣酸、硫酸、罐酸、及過氣酸之 卸鹽、鈉鹽及銨鹽所組成之群組。 一包含於依據本發明之蝕刻液組成物中之環狀胺化合物 當侧含銅層時可形成一輪廓。以組成物總重為基準:環 狀胺化合物係以0.3%至5 wt%及較佳〇 5%至3 wt%之數量 使用▲此種成刀之含量係落入於前述範圍時，可形成適 201204875 當銅姓刻速率及錐角’且可有效地控她刻程度。 之射上合物之含量係低於0.3 wt%時二^ 之银刻連率增㊣，及如此含銅金制可能被祕。又更备 ==Γ%時’含銅金屬層之餘刻速率減低，及: 此3銅金屬層無法被適當地蝕刻。 …環狀胺化合物係選自於由5_胺基时、甲苯基三峻、 苯并三唑、及甲基三唑所組成之群組。 土 含Γ依據本發明之蝕刻液組成物之氯化合物為用以 U 3銅層之助氧化劑，且以組成物總重為基準，以〇以。 較佳0.5%至3 wt%之數量使用。當氣化合物之 3置為2.1/。至5wt%時’可更有效_成錐角。 當氯化合物之含量係低於〇J wt%時，錐角過低，使得 ，形斜面，，因崎賴後製程上的問題。又復當其含 ，係大於5 Wt%時，錐角變過高，使得隨後製程中的^級覆 蓋率變差。 氯j物為可解離成為氣離子之化合物，且可以是選 自於由氫氣酸、氯化鈉、氯化鉀、及氣化銨(顺仰所組成 之群組中之至少一者。 匕s於依據本發明之钱刻液組成物之對甲苯石备酸係用 來防止似m㈣練關本身的老化造成朗劑組成的 改變而被修改，以及絲使得_劑可儲存長時間。以植 成物總重為基準，對曱苯顧之含量為Gl%h心，較 佳為0.5%至3 wt%。當對f苯魏之含量係低於Q」威 時’難=止因_劑本身的老化造餘刻劑組成的改 文。又復含量係、大於5 wt%時’能夠防止因㈣劑本身 的老化造成蝕刻劑組成的改變’但出現過蝕，因而無法獲 7/13 201204875 得優異的輪廓。 匕δ於依據本發明之蝕刻液組成物 水’其係制於半導體製程處理，及其;子 之電阻倾。敗祕總重絲準， "18跡咖 得_液組成物總重變成卿wt%。、、水作為剩餘’使 除了前述成分外，依據本發明之蝕刻液組 刻控制劑、界面活性劑、整合劑及防钕劑匕 本發明之蝕刻液組成物係有效地用於蝕刻含銅及鈦之 金屬層，特別為具有銅/鈦結構之雙膜(增亮片）。又復此種 飯刻液喊物係纽刻於㈣IZ0薄贱a_lT〇薄膜。 列舉下列實施例及測試例來舉例說明本發明，但非解 譯為限制本發明，而可提供更明白瞭解本發明。 實施例1及比較例1:蝕刻液組成物之製備 使用如下表1顯示之成分之數量，製備18〇公斤的蝕 刻液組成物。 【表1】 APS ABF hno3 ATZ NaCl PTA 水 (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) 實施例1 10 0.5 3 1 1 2 剩餘 赛例1 10 0.5 3 1 1 0 剩餘 IPS :過硫酸銨 ABF :氟化氫銨 ATZ : 5-胺基四唑 PTA :對曱苯磺酸 8/13S 201204875 ^The shape of the H-type vocabulary conductor device or plate", the method of the device includes the step of using the metal layer containing the copper and titanium in the composition of the residual liquid. The other aspect provides a semiconductor device or a flat panel display manufactured using the composition of the magnetic enthalpy. [Embodiment] Hereinafter, the present invention will be described in detail. A metal layer containing copper and bismuth according to the present invention. Using (iv) a liquid composition comprising: persulfate; a sacrificial compound; selected from the group consisting of inorganic acids, inorganic acid salts, and mixtures thereof; cyclic amine compounds; chlorine compounds; p-halofic acid; The persulfate contained in the composition of the surname according to the present invention is the main oxidant for the side of the steel containing layer, and the total weight of the composition is 5% to 20 wt%, and 7% to 18%. When the content of this component falls within the above range, the copper-containing layer is in an appropriate amount (10), and the contour of the money is excellent. When the persulfate content is less than 5 wt% At the time, (10) the rate is reduced, and so can not be fully carried out (4). Again, when its content is More than 2〇wt%, the rate of increase in the rate of excess, so that the rate of _ control (10), the film and copper film may be over-etched. Persulfate may be selected from ammonium persulfate (Aps), sodium persulfate (sps) And a group consisting of potassium persulfate (PPS). The fluorine compound contained in the composition of the residual liquid according to the present invention is mainly used for the layer of titanium, izo, 4a_IT, and the composition. The total weight is based on the amount of 〇.01% to 2 wt% and preferably 〇〇5% to !. When the content of this component falls within the above range, the titanium-containing layer 5/13 201204875 It is based on the syllabus, and the name of the surname is better. The quantity is lower than the lower limit _, and the rate of the enrichment of this component of the human body may be reduced, and the upper limit may be The cut mm system is more than one of the above-mentioned compound gas ions, and the fluorinated acid, and + is selected from the inorganic copper-containing one; or one of them may oxidize the fine s and deuterate the titanium-containing layer. The total weight of the composition • the inorganic acid salt, and the mixture thereof may be used in the amount of: Kawasaki and preferably 2% to 7 wt%. When such a system falls into (4), the copper-containing layer and the titanium-containing layer have an excellent amount of 2 ^ engraving. When the content of such a component is lower than the aforementioned lower limit, the rate of deceleration is undesirably degraded and the residue is produced. On the contrary, when the content of such a component exceeds the aforementioned upper limit, it is possible that the surname is generated, the photoresist may be cracked to form a crack, and thus the money engraving may penetrate into the crack, causing the wire to be undesirably short-circuited. The inorganic acid is selected from the group consisting of nitric acid, sulfuric acid, acid-filled acid, and peroxyacid. ^ The inorganic acid salt is selected from the group consisting of tribasic acid, sulfuric acid, can acid, and unsalted salt, sodium salt and ammonium salt of peroxyacid. A cyclic amine compound contained in the composition of the etching solution according to the present invention forms a profile when the copper layer is contained on the side. Based on the total weight of the composition: the cyclic amine compound is used in an amount of 0.3% to 5% by weight and preferably 5% to 3% by weight. ▲ When the content of the knives falls within the foregoing range, it can be formed. Suitable for 201204875 when the copper name engraved rate and cone angle 'and can effectively control her degree. When the content of the shot compound is less than 0.3 wt%, the silver engraving rate of the two is increased, and thus the copper-containing gold system may be secret. Further, when == Γ%, the residual rate of the copper-containing metal layer is reduced, and: the 3 copper metal layer cannot be properly etched. The cyclic amine compound is selected from the group consisting of 5-amino, tolyltris, benzotriazole, and methyltriazole. The chlorine compound according to the etching liquid composition of the present invention is a co-oxidizing agent for the U 3 copper layer, and is based on the total weight of the composition. It is preferably used in an amount of from 0.5% to 3% by weight. When the gas compound 3 is set to 2.1/. When it is 5 wt%, it can be more effective _ into a taper angle. When the content of the chlorine compound is lower than 〇J wt%, the taper angle is too low, so that the bevel is formed, and the problem is caused by the post-slag process. When the content is more than 5 Wt%, the cone angle becomes too high, which makes the coverage of the subsequent process worse. The chlorine substance is a compound which can be dissociated into a gas ion, and may be selected from at least one selected from the group consisting of hydrogen acid, sodium chloride, potassium chloride, and ammonium sulfate. The p-toluene acid preparation for the composition of the money engraving according to the present invention is used to prevent the change of the composition of the aging agent caused by the aging of the m (4) process itself, and the wire allows the agent to be stored for a long time. The total weight of the material is the benchmark, and the content of the phthalic acid is Gl%h, preferably 0.5% to 3 wt%. When the content of the f benzene is lower than the Q wei, the difficulty is the cause of the agent. The composition of the aging remnant engraving agent. When the content is more than 5 wt%, it can prevent the change of the composition of the etchant due to the aging of the (4) agent itself. However, it can not get 7/13 201204875 Excellent profile. 匕δ in the etchant composition according to the present invention, the water is 'manufactured in the semiconductor process, and its sub-resistance is tilted. The total weight is fine, "18 traces _ liquid composition The total weight is changed to clear wt%., water as the remaining 'in addition to the aforementioned components, the etching solution according to the present invention The etching agent, the surfactant, the integrator and the anti-caries agent are effective for etching a metal layer containing copper and titanium, in particular, a double film (brightening film) having a copper/titanium structure. The above-mentioned examples and test examples are exemplified to illustrate the invention, but are not to be construed as limiting the invention, but may provide a clearer understanding of the present invention. Invention Example 1 and Comparative Example 1: Preparation of Etching Liquid Composition An 18 〇 kg etching liquid composition was prepared using the amounts of the components shown in Table 1 below. [Table 1] APS ABF hno3 ATZ NaCl PTA Water (wt% (wt%) (wt%) (wt%) (wt%) (wt%) Example 1 10 0.5 3 1 1 2 Remaining Case 1 10 0.5 3 1 1 0 Remaining IPS: Ammonium Persulfate ABF: Ammonium Bifluoride ATZ : 5-Aminotetrazole PTA : p-Toluenesulfonic acid 8/13
S 201204875 測试例.钱刻液組成物性質之評估 SlNx層沈積在破璃上，銅層形成在SiNx層上，而鈦層 形成在銅層上。光阻係以預定圖案施加在鈦層上，所形成 的基板使用鑽石刀切割成55〇毫米χ 65〇毫米，如此製作成 試樣。 C蝕刻性質之評估> 實施例1及比較例1各自之蝕刻液組成物導入喷灑型 蝕刻裝置内（蝕刻器（ETCHER)(；TFT)，得自西姆斯公司 :SEMES)) ’然後溫熱至25〇c溫度。隨後讓溫度達到3〇土〇1 c接著進行蝕刻。總蝕刻時間係基於40% EPD設定。試 樣放置A j置内及i灑以該組成物。射彳完成後，試樣以 去離子水π U使用熱風乾㈣錢，其後絲(pR)係使 =光阻剝離劑去除。清潔與乾燥後，使崎描電子顯微鏡 f田XS_-4· ’得自日立公司(HITACm))評估侧性質。 〈儲存特性之評估> 實麵i及比㈣〗钱舰域㈣ 减刻液組成物進行參相刻。參考㈣ 儲存預定曰數(此處為5曰)，然後於罐 係與果刻。其結果 【表2】S 201204875 Test Example. Evaluation of the properties of the money engraving composition The SlNx layer was deposited on the glass, the copper layer was formed on the SiNx layer, and the titanium layer was formed on the copper layer. The photoresist was applied to the titanium layer in a predetermined pattern, and the formed substrate was cut into 55 mm mm χ 65 mm using a diamond knife, thus preparing a sample. Evaluation of C Etching Properties> The etching liquid compositions of each of Example 1 and Comparative Example 1 were introduced into a spray type etching apparatus (etcher (ETCHER) (TFT), available from Sims: SEMES)) Warm to 25 ° C temperature. The temperature is then brought to 3 〇 1 接着 and then etched. The total etch time is based on a 40% EPD setting. The sample was placed in A j and sprinkled with the composition. After the shot is completed, the sample is dried with hot air (4) in deionized water π U, and the wire (pR) is used to remove the photoresist stripper. After cleaning and drying, the Sakae electron microscope f field XS_-4·' was obtained from Hitachi (HITACm) to evaluate the side properties. <Evaluation of storage characteristics> Solid surface i and ratio (4) 〗 〖Qian Shipu domain (4) Reduce the composition of the engraving liquid to carry out the phase contrast. Refer to (4) Store the predetermined number of turns (here 5 曰), then in the can and the fruit. The result [Table 2]
飯刻特性 儲存特性 實施例1 ◎ I ◎ 比較例1 ◎ X 9/13 201204875 度） ◎•極為優異(CD扭斜：u微米，錐角：4〇度至6〇 ◦’優異(CD扭斜：乱5微米，錐角：3〇度至度） △良好(CD扭斜：2微米，錐角：3〇度至6〇度） X .不佳(金屬層受損及殘餘浮渣形成） <儲存特性> ◎•極為優異(五日後，蝕刻輪廓優異） X .不佳(五曰後，姓刻輪廓不佳） 考上表2’可確林發明實施例1之#刻液組成物的 二寺性及儲存特性優異，而比較们之*含μ笨續酸 之蝕刻液組成物的儲存特性不佳。 文所述’本發明提供一種用於含銅及鈦之金屬層 蝕相組。_本㈣，侧賴 =金屬層’及更明確言之，峨雙層，如此 且及改良生彦力。又依據本發明’钱刻液版成物 速率且允許形成均—_，如此提供優· 刻㈣液組成物不會損壞設備且钱 夺：…汉備’可有利地施用至大型顯示面板 經濟效益。又依據本發明，除了含銅及欽之金 ，刻液組成物可㈣祕像素電極之ί20或a4T〇。^於 3銅及狀金屬層驗源/汲電極而120紅ιτ去 電極之情盯’依縣發日仅__絲可=素 2極及像素電極。域縣㈣，_成H 3過氣化纽/或臭氧仍可達成針對鋼之快速 未 雖然已經為了例示說明目的而揭示本發明:多:能樣Example of cooking characteristics storage characteristics Example 1 ◎ I ◎ Comparative Example 1 ◎ X 9/13 201204875 degrees) ◎•Excellent (CD skew: u micron, taper angle: 4 至 to 6 〇◦ 'excellent (CD skew) : chaos 5 microns, cone angle: 3 degrees to degrees) △ good (CD skew: 2 microns, cone angle: 3 to 6 degrees) X. Poor (damage of metal layer and residual scum formation) <Storage characteristics> ◎•Excellent (excellent after five days, excellent etching profile) X. Poor (after five ,, the surname is not well-characterized) Tested in Table 2' can be confirmed by the invention of Example 1 The second temple property and storage characteristics of the object are excellent, and the storage characteristics of the etchant composition containing the μ acid acid are not good. The present invention provides a metal layer etching phase for copper and titanium. Group. _ Ben (four), side depends on the metal layer 'and more specifically, 峨 double layer, and thus improve the health of the Yan Li. According to the invention, the rate of money engraving is allowed to form a uniform - _, so Providing excellent (4) liquid composition will not damage the equipment and the money will be: ... Hanbei' can be advantageously applied to large display panels economic benefits. Invented, in addition to containing copper and Chinzhi gold, the engraved composition can be (4) the pixel electrode of the ί20 or a4T〇. ^ in the 3 copper and metal layer test source / 汲 electrode and 120 red ιτ to the electrode of the situation stare 'Yi County The date is only __ silk can be 2 poles and pixel electrodes. Domain County (four), _ into H 3 over gasification New Zealand / or ozone can still achieve rapid for steel, although the invention has been disclosed for illustrative purposes: : can sample
S 201204875 及具體例，但熟諳技藝人士瞭解可未悖離如隨附之申請專 利範圍揭示之本發明之範圍及精髓而可能做出多項修改、 添加、及取代。 【圖式簡單說明】 【主要元件符號說明】 無0 11/13S 201204875 and specific examples, but those skilled in the art will appreciate that many modifications, additions, and substitutions may be made without departing from the scope and spirit of the invention as disclosed in the appended claims. [Simple diagram description] [Main component symbol description] No 0 11/13