TWI662691B - Manufacturing method of an array substrate for liquid crystal display - Google Patents
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Abstract
一種製造用於液晶顯示器的陣列基板的方法，該方法包括：a)在基板上形成柵極佈線；b)在具有該柵極佈線的基板上形成柵極絕緣層；c)在該柵極絕緣層上形成半導體層；d)在該半導體層上形成源電極和漏電極；以及e)形成與該漏電極連接的圖元電極，其中，a)步驟或d)步驟包括：在該基板或該半導體層上形成Cu基金屬膜，以及利用蝕刻劑組合物通過蝕刻該Cu基金屬膜來形成該柵極佈線或該源電極和該漏電極，以及該蝕刻劑組合物為用於Cu基金屬膜的蝕刻劑組合物，包括過氧化氫(H2O2)、亞磷酸或多元鹼基化合物以及水。 A method of manufacturing an array substrate for a liquid crystal display, the method comprising: a) forming a gate wiring on a substrate; b) forming a gate insulating layer on a substrate having the gate wiring; c) insulating the gate Forming a semiconductor layer on the layer; d) forming a source electrode and a drain electrode on the semiconductor layer; and e) forming a primitive electrode connected to the drain electrode, wherein step a) or step d) includes: on the substrate or the Forming a Cu-based metal film on the semiconductor layer, and forming the gate wiring or the source electrode and the drain electrode by etching the Cu-based metal film using an etchant composition, and the etchant composition is for a Cu-based metal film The etchant composition includes hydrogen peroxide (H 2 O 2 ), phosphorous acid or a polybasic compound, and water.
Description
本申請主張2013年9月27日提交的韓國專利申請案KR 10-2013-0115037的權益和2013年10月18日提交的韓國專利申請案KR 10-2013-0124525的權益，在此將其全文藉由引用的方式併入本申請中。 This application claims the rights of the Korean patent application KR 10-2013-0115037 filed on September 27, 2013 and the rights of the Korean patent application KR 10-2013-0124525 filed on October 18, 2013, the entire text of which is hereby incorporated herein by reference. This application is incorporated by reference.
本發明係關於一種製造用於液晶顯示器的陣列基板的方法。 The present invention relates to a method for manufacturing an array substrate for a liquid crystal display.
在半導體裝置中，在基板上形成金屬佈線的工藝通常包括：利用濺射等形成金屬膜、塗覆光刻膠、進行曝光和顯影以便在選定的區域上形成光刻膠、以及進行蝕刻，其中，在每個單獨的工藝之前或之後進行清潔工藝。蝕刻工藝是使用光刻膠作為掩模來使得金屬膜能夠留在選定的區域的工藝，並且蝕刻工藝通常包括利用等離子體等的乾蝕刻或利用蝕刻劑組合物的濕蝕刻。 In a semiconductor device, a process for forming a metal wiring on a substrate generally includes forming a metal film by sputtering or the like, coating a photoresist, performing exposure and development to form a photoresist on a selected area, and performing etching, among which The cleaning process is performed before or after each individual process. The etching process is a process using a photoresist as a mask to enable a metal film to remain in a selected area, and the etching process generally includes dry etching using plasma or the like or wet etching using an etchant composition.
通常，對於用於柵極佈線和資料佈線的材料，使用包括銅的銅膜層或銅合金膜層，或金屬氧化物層，其中，銅具有良好的導電性並且電阻低，金屬氧化物層與銅膜層或 銅合金膜層具有良好的介面黏合性。 Generally, for materials used for gate wiring and data wiring, a copper film layer or a copper alloy film layer including copper, or a metal oxide layer is used. Among them, copper has good electrical conductivity and low resistance, and the metal oxide layer and Copper film or The copper alloy film has good interface adhesion.
就該點而言，韓國專利申請公開號10-2007-0055259公開了一種用於Cu基金屬膜的蝕刻劑組合物，包括過氧化氫、有機酸、磷酸鹽化合物等，其用於蝕刻銅-鉬合金膜層。 In this regard, Korean Patent Application Publication No. 10-2007-0055259 discloses an etchant composition for a Cu-based metal film, including hydrogen peroxide, an organic acid, a phosphate compound, etc., which is used to etch copper- Molybdenum alloy film.
然而，如果將蝕刻劑組合物應用至Cu基金屬膜的厚膜時，由於磷酸二氫鹽(phosphate monobasic)所導致的高錐角而可能在後續工藝中產生缺陷問題。 However, if the etchant composition is applied to a thick film of a Cu-based metal film, a defect problem may occur in a subsequent process due to a high taper angle caused by a phosphate monobasic salt.
[引用列表] [Quote list]
[專利文獻] [Patent Literature]
(專利文件1)韓國專利申請公開號10-2007-0055259A。 (Patent Document 1) Korean Patent Application Publication No. 10-2007-0055259A.
為了解決前述問題，本發明的一個目的是提供一種製造陣列基板的方法，該陣列基板用於液晶顯示器並且由Cu基金屬膜組成。 In order to solve the foregoing problems, an object of the present invention is to provide a method of manufacturing an array substrate, which is used for a liquid crystal display and is composed of a Cu-based metal film.
為了解決前述問題，本發明的另一目的是利用本發明的蝕刻劑組合物對Cu基金屬膜進行批量蝕刻，本發明的蝕刻劑組合物用於Cu基金屬膜並且包括亞磷酸(H3PO3)或多元鹼基化合物(polybasic compound)。 In order to solve the foregoing problem, another object of the present invention is to batch-etch a Cu-based metal film using the etchant composition of the present invention. The etchant composition of the present invention is used for a Cu-based metal film and includes phosphorous acid (H 3 PO 3 ) or polybasic compound.
為了實現上述目的，本發明提供了一種製造用於液晶顯示器的陣列基板的方法，該方法包括：a)在基板上形成柵極佈線；b)在具有該柵極佈線的該基板上形成柵極絕緣層； c)在該柵極絕緣層上形成半導體層；d)在該半導體層上形成源電極和漏電極；以及e)形成與該漏電極連接的圖元電極，其中，a)步驟或d)步驟包括：在該基板或該半導體層上形成Cu基金屬膜，以及利用蝕刻劑組合物通過蝕刻該Cu基金屬膜來形成該柵極佈線或該源電極和該漏電極，以及該蝕刻劑組合物是用於Cu基金屬膜的蝕刻劑組合物，包括：過氧化氫(H2O2)、亞磷酸或多元鹼基化合物、以及水。 In order to achieve the above object, the present invention provides a method of manufacturing an array substrate for a liquid crystal display, the method comprising: a) forming a gate wiring on the substrate; b) forming a gate on the substrate having the gate wiring An insulating layer; c) forming a semiconductor layer on the gate insulating layer; d) forming a source electrode and a drain electrode on the semiconductor layer; and e) forming a picture element electrode connected to the drain electrode, wherein a) step or d) a step including forming a Cu-based metal film on the substrate or the semiconductor layer, and forming the gate wiring or the source electrode and the drain electrode by etching the Cu-based metal film using an etchant composition, and the etching The agent composition is an etchant composition for a Cu-based metal film and includes: hydrogen peroxide (H 2 O 2 ), phosphorous acid or a polybasic compound, and water.
此外，本發明提供了一種用於Cu基金屬膜的蝕刻劑組合物，包括：過氧化氫(H2O2)、亞磷酸或多元鹼基化合物、以及水。 In addition, the present invention provides an etchant composition for a Cu-based metal film, including: hydrogen peroxide (H 2 O 2 ), phosphorous acid or a polybasic compound, and water.
此外，本發明提供了一種用於液晶顯示器的陣列基板，該陣列基板包括：選自柵極佈線、源電極和漏電極中的至少一種，該柵極佈線、該源電極和該漏電極經該用於Cu基金屬膜的蝕刻劑組合物蝕刻。 In addition, the present invention provides an array substrate for a liquid crystal display. The array substrate includes at least one selected from a gate wiring, a source electrode, and a drain electrode. The gate wiring, the source electrode, and the drain electrode pass through the Etchant composition etching for Cu-based metal films.
包括亞磷酸(H3PO3)或多元鹼基化合物的用於Cu基金屬膜的蝕刻劑組合物有利於提高蝕刻速率，並且它可以被應用至具有較厚厚度的厚膜。 The etchant composition for a Cu-based metal film including a phosphorous acid (H 3 PO 3 ) or a polybasic compound is advantageous for improving an etching rate, and it can be applied to a thick film having a thicker thickness.
另外，本發明的蝕刻劑組合物由於在蝕刻時錐角較低而可被應用至高解析度裝置。 In addition, the etchant composition of the present invention can be applied to a high-resolution device because the taper angle is low during etching.
結合下文的詳細描述和附圖，將更清楚地理解本發明的上述和其它目的、特徵和優點。 The above and other objects, features and advantages of the present invention will be more clearly understood in conjunction with the following detailed description and accompanying drawings.
圖1示出了在300ppm的銅的條件下，當使用實施例3的用於Cu基金屬膜的蝕刻劑組合物時，蝕刻剖面的掃描電子顯微鏡(SEM)圖像；圖2示出了在3000ppm的銅的條件下，當使用實施例3的用於Cu基金屬膜的蝕刻劑組合物時，蝕刻剖面的掃描電子顯微鏡(SEM)圖像；以及圖3示出了在6000ppm的銅的條件下，當使用實施例3的用於Cu基金屬膜的蝕刻劑組合物時，蝕刻剖面的掃描電子顯微鏡(SEM)圖像。 FIG. 1 shows a scanning electron microscope (SEM) image of an etching cross section when an etchant composition for a Cu-based metal film of Example 3 is used under conditions of 300 ppm copper; FIG. 2 shows Scanning electron microscope (SEM) image of the etching profile when using the etchant composition for a Cu-based metal film of Example 3 under the condition of 3000 ppm of copper; and FIG. 3 shows the condition of copper at 6000 ppm Next, when an etchant composition for a Cu-based metal film of Example 3 is used, a scanning electron microscope (SEM) image of an etching cross section.
在下文中，將詳細描述本發明。 Hereinafter, the present invention will be described in detail.
本發明涉及一種利用用於Cu基金屬膜的蝕刻劑組合物來製造用於液晶顯示器的陣列基板的方法，並且該製造方法如下。 The present invention relates to a method for manufacturing an array substrate for a liquid crystal display using an etchant composition for a Cu-based metal film, and the manufacturing method is as follows.
該製造方法包括：a)在基板上形成柵極佈線；b)在具有柵極佈線的基板上形成柵極絕緣層；c)在柵極絕緣層上形成半導體層；d)在半導體層上形成源電極和漏電極；以及e)形成與漏電極連接的圖元電極，其中，a)步驟或d)步驟包括：在基板或半導體層上形成Cu基金屬膜，並且利用蝕刻劑組合物通過蝕刻Cu基金屬膜來形成柵極佈線或源電極和漏電極。 The manufacturing method includes: a) forming a gate wiring on a substrate; b) forming a gate insulating layer on a substrate having a gate wiring; c) forming a semiconductor layer on the gate insulating layer; d) forming on the semiconductor layer A source electrode and a drain electrode; and e) forming a picture element electrode connected to the drain electrode, wherein step a) or step d) includes: forming a Cu-based metal film on a substrate or a semiconductor layer, and using an etchant composition to pass through etching A Cu-based metal film to form a gate wiring or a source electrode and a drain electrode.
蝕刻劑組合物是用於Cu基金屬膜的蝕刻劑組合物， 包括：過氧化氫(H2O2)、亞磷酸或多元鹼基化合物、以及水。 The etchant composition is an etchant composition for a Cu-based metal film and includes: hydrogen peroxide (H 2 O 2 ), phosphorous acid or a polybasic compound, and water.
特別地，該蝕刻劑組合物是用於Cu基金屬膜的蝕刻劑組合物，並且包括：基於組合物的總重量，15至25重量%的過氧化氫(H2O2)；0.3至5重量%的亞磷酸或0.1至5重量%的多元鹼基化合物；以及餘量的水，以使得組合物的總重量為100重量%。 In particular, the etchant composition is an etchant composition for a Cu-based metal film, and includes: 15 to 25% by weight of hydrogen peroxide (H 2 O 2 ) based on the total weight of the composition; 0.3 to 5 Wt% phosphorous acid or 0.1 to 5 wt% polybasic compound; and the balance of water such that the total weight of the composition is 100 wt%.
用於液晶顯示器的陣列基板是薄膜電晶體(TFT)基板。 An array substrate for a liquid crystal display is a thin film transistor (TFT) substrate.
另外，本發明涉及一種用於Cu基金屬膜的蝕刻劑組合物，包括：過氧化氫(H2O2)、亞磷酸或多元鹼基化合物，以及水。 In addition, the present invention relates to an etchant composition for a Cu-based metal film, including: hydrogen peroxide (H 2 O 2 ), phosphorous acid or a polybasic compound, and water.
最近，在顯示器，尤其在TV的情況下，為了顯示出較高的解析度，以狹窄的方式生產用於液晶顯示器的陣列基板的橫向的佈線寬度。然而，由於佈線寬度的變窄，產生電阻增大的問題。因而，為了防止這種問題的產生，在用於液晶顯示器的陣列基板中，使用這樣的厚膜，該厚膜具有通過增大軸向的佈線厚度所製備的金屬膜的較厚厚度。 Recently, in the case of a display, especially in the case of a TV, in order to display a higher resolution, a lateral wiring width of an array substrate for a liquid crystal display is produced in a narrow manner. However, as the wiring width becomes narrower, a problem arises in that the resistance increases. Therefore, in order to prevent such a problem, in the array substrate for a liquid crystal display, a thick film having a thicker thickness of a metal film prepared by increasing the wiring thickness in the axial direction is used.
在利用常規蝕刻劑組合物蝕刻厚膜的情況下，腐蝕速率緩慢並且處理時間增加，其中，常規蝕刻劑組合物不包括亞磷酸或多元鹼基化合物。因此，常規蝕刻劑組合物不可能被應用於蝕刻需要超過150Å/秒的腐蝕速率的厚膜。 In the case where a thick film is etched with a conventional etchant composition, the etching rate is slow and the processing time is increased, wherein the conventional etchant composition does not include phosphorous acid or a polybasic compound. Therefore, the conventional etchant composition cannot be applied to a thick film that requires an etching rate exceeding 150 Å / sec.
另外，由於在超過60°的錐角的情況下在後續工藝中可能會產生問題，所以必須降低錐角。然而，由於常規蝕刻 劑組合物的錐角過大，所以它不能被應用於蝕刻厚膜。 In addition, since a taper angle exceeding 60 ° may cause problems in subsequent processes, the taper angle must be reduced. However, due to conventional etching The taper angle of the agent composition is too large, so it cannot be used for etching thick films.
同時，根據本發明的用於Cu基金屬膜的蝕刻劑組合物解決了上述問題，因而它可以被應用於厚膜，其中，本發明的蝕刻劑組合物包括亞磷酸或多元鹼基化合物。較佳地，在Cu基金屬膜中，它可以被用於蝕刻厚度為5000Å或更大的銅膜或銅合金膜的厚膜。 Meanwhile, the etchant composition for a Cu-based metal film according to the present invention solves the above problems, and thus it can be applied to a thick film, wherein the etchant composition of the present invention includes phosphorous acid or a polybasic compound. Preferably, in a Cu-based metal film, it can be used to etch a thick film of a copper film or a copper alloy film having a thickness of 5000Å or more.
Cu基金屬膜包括銅作為組成物，並且包括銅或銅合金的單層膜；以及多層膜，該多層膜包括選自銅膜和銅合金膜中的至少一種以及選自鉬膜、鉬合金膜、鈦膜和鈦合金膜中的至少一種。合金膜包括氮化物或氧化物。 The Cu-based metal film includes copper as a composition and includes a single-layer film of copper or a copper alloy; and a multilayer film including at least one selected from a copper film and a copper alloy film, and selected from a molybdenum film, a molybdenum alloy film, At least one of a titanium film and a titanium alloy film. The alloy film includes a nitride or an oxide.
多層膜的實例包括雙層膜或三層膜，諸如銅/鉬膜、銅/鉬合金膜、銅合金/鉬合金膜、銅/鈦膜等。 Examples of the multilayer film include a double-layer film or a triple-layer film such as a copper / molybdenum film, a copper / molybdenum alloy film, a copper alloy / molybdenum alloy film, a copper / titanium film, and the like.
銅/鉬膜是指包括鉬膜和形成在鉬膜上的銅膜的一類膜；銅/鉬合金膜是指包括鉬合金膜和形成在鉬合金膜上的銅膜的一類膜；銅合金/鉬合金膜是指包括鉬合金膜和形成在鉬合金膜上的銅合金膜的一類膜；以及銅/鈦膜是指包括鈦膜和形成在鈦膜上的銅膜的一類膜。 The copper / molybdenum film refers to a type of film including a molybdenum film and a copper film formed on the molybdenum film; the copper / molybdenum alloy film refers to a type of film including a molybdenum alloy film and a copper film formed on the molybdenum alloy film; the copper alloy / The molybdenum alloy film refers to a type of film including a molybdenum alloy film and a copper alloy film formed on the molybdenum alloy film; and the copper / titanium film refers to a type of film including a titanium film and a copper film formed on the titanium film.
此外，鉬合金膜較佳由鉬(Mo)和選自鈦(Ti)、鉭(Ta)、鉻(Cr)、鎳(Ni)、釹(Nd)和鉬(In)中的至少一種金屬組成。 In addition, the molybdenum alloy film is preferably composed of molybdenum (Mo) and at least one metal selected from titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), and molybdenum (In) .
本發明的用於Cu基金屬膜的蝕刻劑組合物較佳可被應用於多層膜，該多層膜包括選自銅膜和銅合金膜中的至少一種，以及選自鉬膜和鉬合金膜中的至少一種。 The etchant composition for a Cu-based metal film of the present invention is preferably applicable to a multilayer film including at least one selected from a copper film and a copper alloy film, and a copper film selected from a molybdenum film and a molybdenum alloy film. At least one.
另外，在本發明的用於Cu基金屬膜的蝕刻劑組合物僅包括亞磷酸的情況下，該蝕刻劑組合物可額外地包含選 自下列物質中的至少一種：含氟化合物、唑類化合物、在分子中具有N原子和羧基的水溶性化合物、磷酸鹽化合物和多元醇類表面活性劑。 In addition, in the case where the etchant composition for a Cu-based metal film of the present invention includes only phosphorous acid, the etchant composition may additionally include an optional From at least one of the following: a fluorine-containing compound, an azole compound, a water-soluble compound having an N atom and a carboxyl group in a molecule, a phosphate compound, and a polyhydric alcohol surfactant.
另外，在本發明的用於Cu基金屬膜的蝕刻劑組合物包括多元鹼基化合物或者包括亞磷酸和多元鹼基化合物的情況下，該蝕刻劑組合物可額外地包含選自下列物質中的至少一種：含氟化合物、唑類化合物、在分子中具有N原子和羧基的水溶性化合物以及多元醇類表面活性劑。 In addition, in the case where the etchant composition for a Cu-based metal film of the present invention includes a polybasic compound or includes a phosphorous acid and a polybasic compound, the etchant composition may additionally include one selected from the following At least one kind: a fluorine-containing compound, an azole compound, a water-soluble compound having an N atom and a carboxyl group in a molecule, and a polyhydric alcohol surfactant.
在本發明的用於Cu基金屬膜的蝕刻劑組合物包括多元鹼基化合物的情況下，用於Cu基金屬膜的蝕刻劑組合物是酸性的，並且較佳pH為1.5至4。 In the case where the etchant composition for a Cu-based metal film of the present invention includes a polybasic compound, the etchant composition for a Cu-based metal film is acidic, and preferably has a pH of 1.5 to 4.
如果用於Cu基金屬膜的蝕刻劑組合物低於pH 1.5，那麼由於快速的腐蝕速率而可能出現過度蝕刻，而在高於pH 4的情況下，由於緩慢的腐蝕速率而可能無法進行蝕刻。 If the etchant composition for a Cu-based metal film is lower than pH 1.5, over-etching may occur due to a rapid etching rate, and above pH 4, etching may not be performed due to a slow etching rate.
以下，將詳細描述本發明的用於Cu基金屬膜的蝕刻劑組合物。 Hereinafter, the etchant composition for a Cu-based metal film of the present invention will be described in detail.
過氧化氫(H2O2) Hydrogen peroxide (H 2 O 2 )
在本發明的用於Cu基金屬膜的蝕刻劑組合物中所包含的過氧化氫(H2O2)是影響Cu基金屬膜的蝕刻的主氧化劑，其中Cu基金屬膜為包括鉬膜和形成在鉬膜上的銅膜的銅-鉬膜，或者包括鉬合金膜和形成在鉬合金膜上的銅膜的銅-鉬合金膜。 Hydrogen peroxide (H 2 O 2 ) contained in the etchant composition for a Cu-based metal film of the present invention is a main oxidant that affects the etching of a Cu-based metal film, wherein the Cu-based metal film includes a molybdenum film and A copper-molybdenum film of a copper film formed on a molybdenum film, or a copper-molybdenum alloy film including a molybdenum alloy film and a copper film formed on a molybdenum alloy film.
基於用於Cu基金屬膜的蝕刻劑組合物的總重量，過 氧化氫(H2O2)被設定為15至25重量%，較佳為18至23重量%。 Based on the total weight of the etchant composition for the Cu-based metal film, hydrogen peroxide (H 2 O 2 ) is set to 15 to 25% by weight, preferably 18 to 23% by weight.
在低於15重量%的上述量的範圍時，因缺乏對Cu基金屬膜的蝕刻能力而可能導致蝕刻不足。 In the range of less than 15 wt% of the above amount, insufficient etching may be caused due to lack of etching ability to the Cu-based metal film.
另外，在高於25重量%的上述量的範圍時，由於銅離子的升增加而使得熱穩定性高度地降低。 In addition, when the amount is in the range of more than 25% by weight, thermal stability is highly reduced due to an increase in the rise of copper ions.
亞磷酸(H3PO3) Phosphorous acid (H 3 PO 3 )
在本發明的用於Cu基金屬膜的蝕刻劑組合物中所包含的亞磷酸通過調節pH來增強蝕刻速率。如果本發明的用於Cu基金屬膜的蝕刻劑組合物中未包含亞磷酸，那麼蝕刻速率非常緩慢並且因此當蝕刻Cu基金屬膜的厚膜時，蝕刻剖面可能較差。 The phosphorous acid contained in the etchant composition for a Cu-based metal film of the present invention enhances the etching rate by adjusting the pH. If phosphorous acid is not included in the etchant composition for a Cu-based metal film of the present invention, the etching rate is very slow and therefore when etching a thick film of a Cu-based metal film, the etching profile may be poor.
基於用於Cu基金屬膜的蝕刻劑組合物的總重量，亞磷酸被設定為0.3至5.0重量%，較佳為0.5至3.0重量%。 The phosphorous acid is set to 0.3 to 5.0% by weight, preferably 0.5 to 3.0% by weight, based on the total weight of the etchant composition for the Cu-based metal film.
在低於0.3重量%的上述量的範圍時，蝕刻剖面可能較差。 In the range of less than 0.3% by weight of the above amount, the etching profile may be poor.
另外，在高於5重量%的上述量的範圍時，可能產生銅或銅合金膜的蝕刻速率過快或者鉬或鉬合金膜的蝕刻速率過慢的問題。 In addition, in the range of the above-mentioned amount of more than 5% by weight, there may be a problem that the etching rate of the copper or copper alloy film is too fast or the etching rate of the molybdenum or molybdenum alloy film is too slow.
多元鹼基化合物 Polybasic compound
在本發明的用於Cu基金屬膜的蝕刻劑組合物中所包含的多元鹼基化合物使得蝕刻剖面良好並且當蝕刻具有較厚厚度的Cu基金屬膜的厚膜時並不增加錐角。 The polybasic compound contained in the etchant composition for a Cu-based metal film of the present invention makes the etching profile good and does not increase the taper angle when etching a thick film of a Cu-based metal film having a thicker thickness.
如果用於Cu基金屬膜的蝕刻劑組合物僅包括磷酸二 氫鹽化合物而不包括亞磷酸和多元鹼基化合物，那麼該蝕刻劑組合物因待處理的片材數而使得錐角增加，從而不能被應用於Cu基金屬膜的厚膜。 If the etchant composition for a Cu-based metal film includes only phosphoric acid di The hydrogen salt compound does not include phosphorous acid and polybasic compounds, then the etchant composition increases the taper angle due to the number of sheets to be processed, and thus cannot be applied to a thick film of a Cu-based metal film.
因此，在多元鹼基化合物中，較佳為多元鹼基磷酸鹽化合物並且更佳為磷酸氫二鹽(dibasic phosphate compound)化合物。 Therefore, among polybasic compounds, polybasic phosphate compounds are preferred and dibasic phosphate compound compounds are more preferred.
磷酸氫二鹽並不特別受限，只要它選自兩個氫被鹼金屬或鹼土金屬取代的磷酸鹽，較佳選自磷酸氫二銨、磷酸氫二鈉和磷酸氫二鉀，更佳為磷酸氫二銨。 The dibasic hydrogen phosphate is not particularly limited as long as it is selected from the group consisting of two phosphates in which two hydrogens are replaced by an alkali metal or an alkaline earth metal, and is preferably selected from diammonium hydrogen phosphate, disodium hydrogen phosphate, and dipotassium hydrogen phosphate, more preferably Diammonium hydrogen phosphate.
基於用於Cu基金屬膜的蝕刻劑組合物的總重量，多元鹼基化合物被設定為0.1至5重量%，較佳為0.5至3重量%。 The polybasic compound is set to 0.1 to 5% by weight, preferably 0.5 to 3% by weight, based on the total weight of the etchant composition for the Cu-based metal film.
在低於0.1重量%的上述量的範圍時，因部分過度侵蝕而使得蝕刻剖面不好。另外，在高於5重量%的上述量的範圍時，可能發生銅或銅合金膜的腐蝕速率降低，並且鉬或鉬合金膜的蝕刻速率降低的問題。 In the range of less than 0.1% by weight, the etching profile is not good due to partial excessive erosion. In addition, in the range of the above-mentioned amount of more than 5% by weight, problems may occur in that the corrosion rate of the copper or copper alloy film is reduced and the etching rate of the molybdenum or molybdenum alloy film is reduced.
含氟化合物 Fluorinated compound
含氟化合物是指當水中解離時可產生氟離子的化合物。含氟化合物是影響鉬合金膜的蝕刻速率的輔助氧化劑，並且它調節鉬合金膜的蝕刻速率。 A fluorine-containing compound refers to a compound that can generate fluoride ions when dissociated in water. The fluorine-containing compound is an auxiliary oxidant that affects the etching rate of the molybdenum alloy film, and it regulates the etching rate of the molybdenum alloy film.
含氟化合物並不特別受限，只要它被用於相關領域，但是較佳為選自HF、NaF、NH4F、NH4BF4、NH4FHF、NH4F2、KF、KHF2、AlF3和HBF4中的至少一種，並且更佳為NH4F2。 The fluorine-containing compound is not particularly limited as long as it is used in the related field, but is preferably selected from HF, NaF, NH 4 F, NH 4 BF 4 , NH 4 FHF, NH 4 F 2 , KF, KHF 2 , At least one of AlF 3 and HBF 4 , and more preferably NH 4 F 2 .
基於用於Cu基金屬膜的蝕刻劑組合物的總重量，含氟化合物被設定為0.01至5.0重量%，較佳為0.1至3.0重量%。 The fluorine-containing compound is set to 0.01 to 5.0% by weight, preferably 0.1 to 3.0% by weight based on the total weight of the etchant composition for the Cu-based metal film.
在低於0.01重量%的上述量的範圍時，鉬合金膜的蝕刻速率變慢。 In the range of less than 0.01% by weight, the etching rate of the molybdenum alloy film becomes slow.
另外，在高於5.0重量%的上述量的範圍時，蝕刻剖面得到提高，然而總蝕刻速率也得到改善，並且從而使得下層(n+a-Si：H，a-Si：G)的底切或蝕刻所造成的損壞過大。 In addition, in the range above the amount of 5.0% by weight, the etching profile is improved, however, the total etching rate is also improved, and thus the undercut of the lower layer (n + a-Si: H, a-Si: G) is improved. Or the damage caused by etching is too large.
唑類化合物 Azoles
在本發明的用於Cu基金屬膜的蝕刻劑組合物中所包含的唑類化合物用於調節Cu基金屬膜的蝕刻速率、降低圖案的CD損失以及通過降低蝕刻剖面變化來增加工藝中的利潤。 The azole compound contained in the etchant composition for a Cu-based metal film of the present invention is used to adjust the etching rate of the Cu-based metal film, reduce the CD loss of the pattern, and increase the profit in the process by reducing the change in the etching profile. .
唑類化合物可包含，例如吡咯、吡唑、咪唑、***、四唑、五唑、惡唑(oxazole)、異惡唑(isoxazole)、噻唑、異噻唑等，並且它可單獨地進行使用或以兩種或更多種的組合進行使用。在唑類化合物中，較佳為***化合物或四唑化合物，並且更佳為3-胺基***、4-胺基***、5-甲基四唑和5-胺基四唑中的至少一種。 The azole compound may include, for example, pyrrole, pyrazole, imidazole, triazole, tetrazole, pentaazole, oxazole, isoxazole, thiazole, isothiazole, and the like, and it may be used alone or It is used in a combination of two or more. Among the azole compounds, a triazole compound or a tetrazole compound is preferred, and a 3-aminotriazole, a 4-aminotriazole, a 5-methyltetrazole, and a 5-aminotetrazole are more preferred. At least one.
在本發明中，可以混合使用3-胺基***、4-胺基***、5-甲基四唑和5-胺基四唑，並且在這種情況下，因為取決於化合物的調節蝕刻速率以及降低蝕刻剖面變化的能力隨著待處理的片材數的不同而不同，所以較佳根據工藝條件來進行計算和應用混合比。 In the present invention, 3-aminotriazole, 4-aminotriazole, 5-methyltetrazole, and 5-aminotetrazole may be used in combination, and in this case, since the etching is adjusted depending on the compound The rate and the ability to reduce the change in etching profile vary with the number of sheets to be processed, so it is better to calculate and apply the mixing ratio according to the process conditions.
基於用於Cu基金屬膜的蝕刻劑組合物的總重量，唑類化合物被設定為0.1至5.0重量%，較佳為0.5至1.5重量%。 The azole-based compound is set to 0.1 to 5.0% by weight, preferably 0.5 to 1.5% by weight, based on the total weight of the etchant composition used for the Cu-based metal film.
在低於0.1重量%的上述量的範圍時，由於高的蝕刻速率而使得可能產生巨大的CD損失。 In the range of less than 0.1% by weight of the above amount, a large CD loss may occur due to a high etching rate.
另外，在高於5.0重量%的上述量的範圍時，由於Cu基金屬膜的蝕刻速率太慢而使得處理時間增加，並且由於金屬氧化物層的蝕刻速率的相對加速而可能產生底切(undercut)。 In addition, in the range of more than 5.0% by weight, the processing time is increased due to the slow etching rate of the Cu-based metal film, and an undercut may occur due to the relative acceleration of the etching rate of the metal oxide layer. ).
在分子中具有N原子和羧基的水溶性化合物 Water-soluble compound with N atom and carboxyl group in the molecule
在本發明的用於Cu基金屬膜的蝕刻劑組合物中所包含在分子中具有N原子和羧基的水溶性化合物防止在蝕刻劑組合物的儲存期間可能發生的過氧化氫的自分解反應，並且也防止當蝕刻大量的基板時蝕刻特性的變化。 The water-soluble compound having an N atom and a carboxyl group in a molecule contained in the etchant composition for a Cu-based metal film of the present invention prevents a self-decomposition reaction of hydrogen peroxide that may occur during storage of the etchant composition, It also prevents changes in etching characteristics when a large number of substrates are etched.
通常地，在利用過氧化氫的蝕刻劑組合物的情況下，由於在儲存期間過氧化氫的自分解而使得儲存期不長，並且還具有容器可能***的危險因素。 Generally, in the case of an etchant composition using hydrogen peroxide, the storage period is not long due to the self-decomposition of hydrogen peroxide during storage, and there is also a risk factor that the container may explode.
然而，如果包含在分子中具有N原子和羧基的水溶性化合物，由於過氧化氫的分解率被降低了接近10倍而能夠確保較長儲存期和穩定性。 However, if a water-soluble compound having an N atom and a carboxyl group is included in the molecule, a long storage period and stability can be ensured because the decomposition rate of hydrogen peroxide is reduced by nearly 10 times.
具體地，在銅層的情況下，如果銅離子被大量保留在蝕刻劑組合物中，那麼形成鈍化並且因此在氧化變色(char)後可能不能進行進一步蝕刻。然而，可通過添加化合物來防止該情況。 Specifically, in the case of a copper layer, if copper ions are retained in the etchant composition in a large amount, passivation is formed and thus further etching may not be performed after oxidative discoloration (char). However, this can be prevented by adding compounds.
在分子中具有N原子和羧基的水溶性化合物可選自丙胺酸、胺基丁酸、谷胺酸、甘胺酸、亞胺基二乙酸、胺三乙酸和肌胺酸。在這些化合物中，較佳為亞胺基二乙酸。 The water-soluble compound having an N atom and a carboxyl group in the molecule may be selected from alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, aminetriacetic acid, and sarcosine. Among these compounds, iminodiacetic acid is preferred.
基於用於Cu基金屬膜的蝕刻劑組合物的總重量，在分子中具有N原子和羧基的水溶性化合物被設定為0.5至5.0重量%，較佳為1.0至3.0重量%。 The water-soluble compound having N atoms and carboxyl groups in the molecule is set to 0.5 to 5.0% by weight, preferably 1.0 to 3.0% by weight, based on the total weight of the etchant composition for the Cu-based metal film.
在低於0.5重量%的上述量的範圍時，由於在蝕刻大量的基板(約500張片材)之後鈍化而難以得到足夠的工藝利潤。 In the range of less than 0.5% by weight, it is difficult to obtain sufficient process profit due to passivation after etching a large number of substrates (about 500 sheets).
另外，在高於5.0重量%的上述量的範圍時，鉬膜或鉬合金膜的蝕刻速率變慢，並且因此在銅-鉬膜或銅-鉬合金膜的情況下，可能出現鉬或鉬合金膜的殘渣的問題。 In addition, in the range of the above amount above 5.0% by weight, the etching rate of the molybdenum film or molybdenum alloy film becomes slow, and therefore in the case of a copper-molybdenum film or a copper-molybdenum alloy film, molybdenum or molybdenum alloy may occur Problems with membrane residue.
磷酸鹽化合物 Phosphate compound
在本發明的用於Cu基金屬膜的蝕刻劑組合物中所包含的磷酸鹽化合物使得蝕刻剖面良好。如果本發明的用於Cu基金屬膜的蝕刻劑組合物未包含磷酸鹽化合物，那麼可能發生局部過度侵蝕。 The phosphate compound contained in the etchant composition for a Cu-based metal film of the present invention makes the etching profile good. If the etchant composition for a Cu-based metal film of the present invention does not contain a phosphate compound, local excessive erosion may occur.
磷酸鹽化合物並沒有特別受限，只要它選自一個或兩個氫被鹼金屬或鹼土金屬取代的磷酸鹽，較佳選自磷酸二氫銨、磷酸二氫鈉、磷酸二氫鉀、磷酸氫二銨、磷酸氫二鈉和磷酸氫二鉀，並且更佳為磷酸氫二銨。 The phosphate compound is not particularly limited as long as it is selected from phosphates in which one or two hydrogens are replaced by an alkali metal or an alkaline earth metal, and is preferably selected from ammonium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and hydrogen phosphate. Diammonium, disodium hydrogen phosphate and dipotassium hydrogen phosphate, and more preferably diammonium hydrogen phosphate.
在這些磷酸鹽化合物中，當用於Cu基金屬膜的蝕刻劑組合物不包括多元鹼基化合物且僅包括亞磷酸時，使用單鹽基化合物，諸如磷酸氫二銨、磷酸氫二鈉和磷酸氫二 鉀。 Among these phosphate compounds, when the etchant composition for a Cu-based metal film does not include a polybasic compound and includes only phosphorous acid, a monobasic compound such as diammonium hydrogen phosphate, disodium hydrogen phosphate, and phosphoric acid is used Hydrogen Di Potassium.
基於用於Cu基金屬膜的蝕刻劑組合物的總重量，磷酸鹽化合物被設定為0.1至5.0重量%，較佳為0.5至3.0重量%。 The phosphate compound is set to 0.1 to 5.0% by weight, preferably 0.5 to 3.0% by weight, based on the total weight of the etchant composition for the Cu-based metal film.
在低於0.1重量%的上述量的範圍時，由於部分過度侵蝕而可能使得蝕刻剖面不好。 In the range of less than 0.1% by weight, the etching profile may be poor due to partial excessive erosion.
另外，在高於5.0重量%的上述量的範圍時，可能出現銅或銅合金膜的腐蝕速率降低以及鉬或鉬合金膜的蝕刻速率降低的問題。 In addition, when the amount is in a range of more than 5.0% by weight, problems such as a decrease in the corrosion rate of the copper or copper alloy film and a decrease in the etching rate of the molybdenum or molybdenum alloy film may occur.
多元醇類表面活性劑 Polyol surfactants
在本發明的用於Cu基金屬膜的蝕刻劑組合物中可額外地包含的多元醇類表面活性劑用於通過降低表面張力來增加蝕刻的均勻性。 The polyol-based surfactant that may be additionally included in the etchant composition for a Cu-based metal film of the present invention is used to increase the uniformity of etching by reducing the surface tension.
另外，多元醇類表面活性劑通過包封在蝕刻Cu膜之後溶解在蝕刻劑組合物中的銅離子來抑制過氧化氫的分解反應，並且因而抑制銅離子的活性。 In addition, the polyol-based surfactant suppresses the decomposition reaction of hydrogen peroxide by encapsulating copper ions dissolved in the etchant composition after the Cu film is etched, and thus suppresses the activity of copper ions.
當如上抑制銅離子的活性時，能夠在使用蝕刻劑組合物期間穩定地進行該工藝。 When the activity of copper ions is suppressed as described above, the process can be stably performed during the use of the etchant composition.
對於多元醇類表面活性劑，可使用選自甘油、三甘醇和聚乙二醇中的至少一種。在這些化合物中，較佳為三甘醇。 For the polyol-based surfactant, at least one selected from the group consisting of glycerin, triethylene glycol, and polyethylene glycol can be used. Among these compounds, triethylene glycol is preferred.
基於用於Cu基金屬膜的蝕刻劑組合物的總重量，多元醇類表面活性劑被設定為0.001至5.0重量%，並且較佳為0.1至3.0重量%。 The polyol-based surfactant is set to 0.001 to 5.0% by weight, and preferably 0.1 to 3.0% by weight based on the total weight of the etchant composition for the Cu-based metal film.
在低於0.001重量%的上述量的範圍時，可能出現蝕刻均勻性降低和過氧化氫分解加速的問題。 In the range of less than 0.001% by weight of the above-mentioned amount, problems such as reduction in etching uniformity and accelerated decomposition of hydrogen peroxide may occur.
另外，在高於5.0重量%的上述量的範圍時，可能出現產生大量氣泡的缺點。 In addition, in the range of the above-mentioned amount of more than 5.0% by weight, a disadvantage that a large number of bubbles are generated may occur.
水 water
根據本發明的用於Cu基金屬膜的蝕刻劑組合物的水以餘量的方式進行使用，使得用於Cu基金屬膜的蝕刻劑組合物的總重量為100重量%。 The water of the etchant composition for a Cu-based metal film according to the present invention is used in a balance manner such that the total weight of the etchant composition for a Cu-based metal film is 100% by weight.
水並沒有特別受限，但較佳包含去離子水。特別有用的是電阻率(即，從水中除去離子的程度)為至少18MΩ．cm的去離子水。 Water is not particularly limited, but preferably contains deionized water. Particularly useful is a resistivity (ie, the extent to which ions are removed from water) of at least 18 MΩ. cm of deionized water.
除了上述成分以外，本發明的用於Cu基金屬膜的蝕刻劑組合物可包括添加劑，並且添加劑可包含金屬離子封閉劑(metal ion containment)、腐蝕抑制劑等。 In addition to the above components, the etchant composition for a Cu-based metal film of the present invention may include an additive, and the additive may include a metal ion containment, a corrosion inhibitor, and the like.
本發明中所使用的用於Cu基金屬膜的蝕刻劑組合物的組成可通過通常已知的方法進行製備，並且較佳用於Cu基金屬膜的蝕刻劑組合具有用於半導體工藝的純度。 The composition of the etchant composition for a Cu-based metal film used in the present invention can be prepared by a generally known method, and the etchant combination preferably used for the Cu-based metal film has purity for a semiconductor process.
另外，本發明提供了一種用於液晶顯示器的陣列基板，該陣列基板包括：柵極佈線，源電極和漏電極中的至少一種，其中，柵極佈線，源電極和漏電極經用於Cu基金屬膜的蝕刻劑組合物蝕刻。 In addition, the present invention provides an array substrate for a liquid crystal display. The array substrate includes at least one of a gate wiring, a source electrode, and a drain electrode. The gate wiring, the source electrode, and the drain electrode are used for a Cu-based substrate. The etchant composition of the metal film is etched.
以下，參照下面實施例將更詳細地描述本發明。然而，這些實施例用於解釋說明本發明，而並不用於限制本發明的範圍。本領域技術人員在本發明的範圍內可對這些實施 例進行適當的修改和改變。 Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are used to explain the present invention and are not intended to limit the scope of the present invention. Those skilled in the art can implement these on the scope of the present invention. Examples are modified and changed as appropriate.
用於Cu基金屬膜的蝕刻劑組合物的製備 Preparation of etchant composition for Cu-based metal film
實施例1至實施例4和比較例1至比較例2 Examples 1 to 4 and Comparative Examples 1 to 2
利用下面表1和表2中所示的組成來製備180kg的實施例1至實施例4以及比較例1至比較例2的用於Cu基金屬膜的蝕刻劑組合物。 Using the compositions shown in Tables 1 and 2 below, 180 kg of an etchant composition for a Cu-based metal film of Examples 1 to 4 and Comparative Examples 1 to 2 were prepared.
ABF：二氟化銨 ABF: ammonium difluoride
5-ATZ：5-胺基四唑 5-ATZ: 5-aminotetrazole
5-MTZ：5-甲基四唑 5-MTZ: 5-methyltetrazole
IDA：亞胺基二乙酸 IDA: iminodiacetic acid
APD：二鹽基磷酸銨 APD: Dibasic ammonium phosphate
TEG：三甘醇 TEG: triethylene glycol
GA：乙醇酸 GA: glycolic acid
NHP：磷酸二氫鈉 NHP: Sodium dihydrogen phosphate
測試例1：利用實施例1至實施例4的用於Cu基金屬膜的蝕刻劑組合物的蝕刻工藝 Test Example 1: Etching process using the etchant composition for a Cu-based metal film of Examples 1 to 4
利用實施例1至實施例4的各個用於Cu基金屬膜的蝕刻劑組合物來進行蝕刻工藝。使用噴霧型蝕刻機(ETCHER(TFT)，購自SEMES)，並且將蝕刻工藝中的用於Cu基金屬膜的蝕刻劑組合物的溫度設定為大約33℃。蝕刻的時間可隨著蝕刻的溫度不同而不同，並且LCD蝕刻工藝通常進行約30~80秒。使用SEM(S-4700，購自HITACHI)來觀察蝕刻工藝中蝕刻的Cu基金屬膜的切割側面和剖面。下面的表3中給出了該結果。 The etching process was performed using each of the etchant compositions for Cu-based metal films of Examples 1 to 4. A spray type etching machine (ETCHER (TFT), available from SEMES) was used, and the temperature of the etchant composition for the Cu-based metal film in the etching process was set to about 33 ° C. The etching time may vary with the temperature of the etching, and the LCD etching process usually takes about 30 to 80 seconds. A SEM (S-4700, available from HITACHI) was used to observe the cut sides and cross sections of the Cu-based metal film etched during the etching process. The results are given in Table 3 below.
將Cu/Mo-Nb 3000/300Å薄膜基板用作蝕刻工藝中的Cu基金屬膜。 A Cu / Mo-Nb 3000 / 300Å thin film substrate is used as a Cu-based metal film in the etching process.
(○：良好，△：普通，X：不好，Unetch：不能蝕刻) (○: Good, △: Normal, X: Not good, Unetch: Cannot be etched)
實施例1至實施例4中的用於Cu基金屬膜的蝕刻劑組合物具有良好的蝕刻特性。在這些實施例中，實施例3的用於Cu基金屬膜的蝕刻劑組合物具有良好的蝕刻剖面和平直度，並且不生產Mo、Ti殘渣。另外，待處理的片 材數的變化量(側蝕變化的量)滿足0.1μm的條件。 The etchant composition for a Cu-based metal film in Examples 1 to 4 has good etching characteristics. In these examples, the etchant composition for a Cu-based metal film of Example 3 has a good etching profile and flatness, and does not produce Mo and Ti residues. In addition, the pieces to be processed The amount of change in the number of materials (amount of side erosion change) satisfies the condition of 0.1 μm.
測試例2：利用實施例3和比較例1至比較例2的用於Cu基金屬膜的蝕刻劑組合物根據Cu濃度來評價蝕刻特性 Test Example 2: Etching characteristics were evaluated according to the Cu concentration using the etchant composition for a Cu-based metal film of Example 3 and Comparative Examples 1 to 2
利用實施例3和比較例1至比較例2的用於Cu基金屬膜的蝕刻劑組合物根據Cu濃度來評價蝕刻特性。 The etching characteristics for the Cu-based metal film of Example 3 and Comparative Examples 1 to 2 were evaluated based on the Cu concentration.
將Cu/Mo-Ti 6500/300Å厚膜基板用作蝕刻工藝中的Cu基金屬膜。 A Cu / Mo-Ti 6500 / 300Å thick film substrate was used as a Cu-based metal film in the etching process.
根據Cu濃度測量蝕刻速率、錐角、殘渣和側蝕變化的量(μm)。蝕刻速率是指每單位時間內所蝕刻的Cu的厚度，錐角是指Cu片材的斜度，側蝕是指光刻膠的端部和蝕刻後測量的下層金屬的端部之間的距離。 The amount (μm) of the etch rate, cone angle, residue, and side etching change was measured according to the Cu concentration. Etching rate refers to the thickness of Cu etched per unit time, cone angle refers to the slope of the Cu sheet, and side etching refers to the distance between the end of the photoresist and the end of the underlying metal measured after etching. .
當蝕刻速率過慢時，處理時間增加並且產量降低，因此高蝕刻速率是重要的。 When the etching rate is too slow, the processing time increases and the yield decreases, so a high etching rate is important.
另外，當錐角過高時，在去除後面的膜的時候由於不好的階梯覆蓋(Step Coverage)而引起裂紋，因而保持適當的錐角是重要的。 In addition, when the taper angle is too high, cracks are caused due to poor step coverage when the subsequent film is removed, so it is important to maintain a proper taper angle.
另外，如果側蝕的量變化，由於當驅動TFT時信號傳輸速率的變化而可能出現污點。因而，較佳最大限度地降低側蝕變化的量。 In addition, if the amount of side etching is changed, a stain may occur due to a change in a signal transmission rate when the TFT is driven. Therefore, it is preferred to minimize the amount of side etch changes.
在該評價中，評價被進行以建立能夠在蝕刻工藝中連續使用的蝕刻劑組合物，該蝕刻劑組合物具有高於150Å/秒的蝕刻速率、低於60°的錐角和±0.1μm的側蝕的變化量。 In this evaluation, evaluation was performed to establish an etchant composition capable of being continuously used in an etching process, the etchant composition having an etch rate higher than 150 Å / sec, a cone angle lower than 60 °, and a ± 0.1 μm The amount of change in side etch.
下面表4中給出該結果。 The results are given in Table 4 below.
比較例1的用於Cu基金屬膜的蝕刻劑組合物具有低的蝕刻速率，蝕刻速率根據待處理的片材數而降低，並且當洗脫4000ppm時產生熱量，因而不能應用比較例1的組合物。 The etchant composition for a Cu-based metal film of Comparative Example 1 has a low etching rate, the etching rate is reduced according to the number of sheets to be processed, and heat is generated when 4000 ppm is eluted, so the combination of Comparative Example 1 cannot be applied Thing.
在比較例2的用於Cu基金屬膜的蝕刻劑組合物的情況下，根據待處理的片材數的蝕刻速率的變化範圍和側蝕的變化範圍並不算太大，但蝕刻速率較慢並且錐角較高，因而比較例2的組合物不適合被應用於厚膜。 In the case of the etchant composition for a Cu-based metal film of Comparative Example 2, the variation range of the etching rate and the variation range of the side etching according to the number of sheets to be processed are not too large, but the etching rate is slow In addition, since the taper angle is high, the composition of Comparative Example 2 is not suitable for application to thick films.
因此，可以確認的是，比較例1和比較例2的用於Cu基金屬膜的蝕刻劑組合物不能蝕刻厚膜，其中，比較例1和比較例2的用於Cu基金屬膜的蝕刻劑組合物不包括亞磷酸或多元鹼基化合物。 Therefore, it can be confirmed that the etchant compositions for Cu-based metal films of Comparative Examples 1 and 2 cannot etch thick films, among which the etchant for Cu-based metal films of Comparative Examples 1 and 2 are not etchable. The composition does not include phosphorous acid or polybasic compounds.
然而，如上面表4和圖1至圖3中所示，在實施例3的用於Cu基金屬膜的蝕刻劑組合物(包括亞磷酸或多元鹼基化合物)的情況下，根據待處理的片材數保持高於180Å/ 秒的蝕刻速率，在開始時錐角為45°而在結束時錐角為53°，從而保持低於60°的錐角，並且側蝕變化的量滿足±0.1μm的條件，從而可以確認實施例3的組合物可以被使用直至洗脫6000ppm。 However, as shown in Table 4 above and FIGS. 1 to 3, in the case of the etchant composition (including phosphorous acid or polybasic base compound) for the Cu-based metal film of Example 3, according to the Sheet count stays above 180Å / The etching rate in seconds is 45 ° at the beginning and 53 ° at the end, so that the cone angle is kept below 60 °, and the amount of side etch changes meets the condition of ± 0.1 μm, so that the implementation can be confirmed The composition of Example 3 can be used until 6000 ppm is eluted.
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