TWI636157B - Etching solution composition for silver layer and display substrate using the same - Google Patents
Etching solution composition for silver layer and display substrate using the same Download PDFInfo
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- TWI636157B TWI636157B TW105110057A TW105110057A TWI636157B TW I636157 B TWI636157 B TW I636157B TW 105110057 A TW105110057 A TW 105110057A TW 105110057 A TW105110057 A TW 105110057A TW I636157 B TWI636157 B TW I636157B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
Abstract
本發明涉及銀蝕刻液組合物，相對於組合物的總重量，其包含磷酸30~60重量%、硝酸0.5~10重量%、醋酸33~50重量%、唑系化合物0.01~10重量%、和餘量的脫離子水以使組合物的總重量成為100重量%。 The present invention relates to a silver etchant composition, which contains 30 to 60% by weight of phosphoric acid, 0.5 to 10% by weight of nitric acid, 33 to 50% by weight of acetic acid, 0.01 to 10% by weight of an azole compound, and The balance of the deionized water was such that the total weight of the composition became 100% by weight.
Description
本發明涉及銀蝕刻液組合物和使用了其的顯示基板，更詳細地說，涉及相對於組合物的總重量、包含磷酸30~60重量%、硝酸0.5~10重量%、醋酸33~50重量%、唑系化合物0.01~10重量%、和餘量的脫離子水以使組合物的總重量成為100重量%的銀蝕刻液組合物和使用了其的顯示基板。 The present invention relates to a silver etchant composition and a display substrate using the same. More specifically, it relates to 30 to 60% by weight of phosphoric acid, 0.5 to 10% by weight of nitric acid, and 33 to 50% by weight of the total weight of the composition. %, Azole-based compound 0.01 to 10% by weight, and a balance of deionized water so that the total weight of the composition becomes 100% by weight of the silver etching solution composition and a display substrate using the same.
隨著進入真正的資訊化時代，對大量的資訊進行處理和顯示的顯示器領域急速地發展，相應地開發了多種平板顯示器而受到關注。 With the entry into the real information age, the field of displays that process and display a large amount of information has developed rapidly, and a variety of flat panel displays have been developed and attracted attention.
作為這樣的平板顯示器裝置的例子，可列舉液晶顯示裝置(Liquid Crystal Display device：LCD)、等離子體顯示裝置(Plasma Display Panel device：PDP)、場致發射顯示裝置(Field Emission Display device：FED)、電致發光顯示裝置(Electroluminescence Display device：ELD)、有機發光顯示器(Organic Light Emitting Diodes：OLED) 等。另外，這樣的平板顯示裝置不僅在電視、視頻等的家電領域中，而且在筆記型電腦這樣的電腦和行動電話等多種用途中使用。這些平板顯示裝置由於薄型化、輕量化和低消耗電力化等優異的性能，已迅速地替代了以往使用的陰極射線管(Cathode Ray Tube：NIT)。 Examples of such a flat panel display device include a liquid crystal display device (LCD), a plasma display panel device (PDP), a field emission display device (FED), Electroluminescence display device (ELD), Organic Light Emitting Diodes (OLED) Wait. In addition, such a flat panel display device is used not only in the field of home appliances such as televisions and videos, but also in various applications such as computers such as notebook computers and mobile phones. These flat-panel display devices have rapidly replaced conventional cathode ray tubes (CITode Ray Tubes: NIT) due to their excellent performance such as thinness, weight reduction, and low power consumption.
特別地，OLED由於元件自身發光，即使以低電壓也能夠驅動，因此最近已在可攜式裝置等的小型顯示器市場中迅速地應用。另外，OLED的狀態為超越小型顯示器、目前已進行大型電視的商用化。 In particular, OLEDs can be driven even at low voltages because the elements emit light by themselves, so they have recently been rapidly applied in the small display market such as portable devices. In addition, the state of OLED is beyond the small display, and has been commercialized for large TVs.
另一方面，氧化錫銦(Indium Tin Oxide、ITO)和氧化鋅銦(Indium Zinc Oxide、IZO)這樣的導電性金屬對於光的透射率比較優異，具有導電性，因此在用於平板顯示裝置的濾色器的電極中已廣泛地使用。但是，這些金屬也具有高電阻，對於應答速度的改善引起的平板顯示裝置的大型化和高解析度的實現成為了障礙。 On the other hand, conductive metals such as Indium Tin Oxide (ITO) and Indium Zinc Oxide (IZO) have excellent light transmittance and conductivity, and are therefore used in flat panel display devices. Color filters have been widely used in electrodes. However, these metals also have high resistance, which has become an obstacle to the enlargement of the flat panel display device and the realization of high resolution due to the improvement in response speed.
另外，反射板的情況下，以往主要將鋁(Al)反射板用於製品。但是，為了實現亮度的提高引起的低電力消耗，其狀態是在摸索向反射率更高的金屬的材料變更。因此，將與在平板顯示裝置中應用的金屬相比具有低的比電阻和高的亮度的銀(Ag：比電阻約1.59μΩ cm)膜、銀合金、或者包含其的多層膜應用於濾色器的電極、LCD或OLED配線和反射板，為了實現平板顯示裝置的大型化和高解析度和低電力消耗等，要求開發用於適用該材料的蝕刻液。 In the case of a reflection plate, an aluminum (Al) reflection plate has been mainly used for products in the past. However, in order to achieve low power consumption due to improvement in brightness, the state is to change the material to a metal with a higher reflectance. Therefore, a silver (Ag: specific resistance of about 1.59 μΩ cm) film, a silver alloy, or a multilayer film including the same, which has a lower specific resistance and a higher brightness than a metal used in a flat panel display device, is used for color filtering. In order to realize the enlargement of the flat panel display device, the high-resolution, low power consumption, and the like of the electrode, LCD or OLED wiring and reflector of the device, it is required to develop an etching solution suitable for the material.
但是，銀(Ag)對於玻璃等的絕緣基板、或者由真正無定形矽、經摻雜的無定形矽等構成的半導體基板等的下部基板，黏接性(adhesion)極其不良，蒸鍍不容易，容易誘發配線的浮起(lifting)或剝離(Peeling)。另外，即使將銀(Ag)導電層蒸鍍於基板的情況下，為了將其圖案化，使用蝕刻液。作為這樣的蝕刻液，使用以往的蝕刻液的情況下，將銀(Ag)過度地蝕刻，不均勻地被蝕刻，發生配線的浮起或剝離現象，配線的側面輪廓變得不良。特別地，銀(Ag)是容易被還原的金屬，蝕刻速度快，在沒有誘發殘渣的情況下被蝕刻，但此時，蝕刻速度快，沒有產生上下部間的蝕刻速度之差，蝕刻後的錐角(taper angle)的形成難，靈活應用於配線具有眾多的限制。金屬膜沒有錐角而垂直地直立的情況下，後續程序中的絕緣膜或後續配線的形成時有時在銀(Ag)與絕緣膜或配線之間產生空隙，這樣的空隙的產生成為電短路等不良發生的原因。 However, silver (Ag) has extremely poor adhesion to an insulating substrate such as glass or a lower substrate such as a semiconductor substrate composed of truly amorphous silicon, doped amorphous silicon, or the like, and vapor deposition is not easy. It is easy to induce lifting or peeling of the wiring. Moreover, even when a silver (Ag) conductive layer is vapor-deposited on a substrate, an etching solution is used in order to pattern it. As such an etching solution, when a conventional etching solution is used, silver (Ag) is excessively etched, and is etched unevenly, so that floating or peeling of the wiring occurs, and the side profile of the wiring becomes poor. In particular, silver (Ag) is a metal that can be easily reduced. It has a fast etching speed and can be etched without inducing residues. However, at this time, the etching speed is fast without causing a difference in etching speed between the upper and lower portions. It is difficult to form a taper angle, and there are many restrictions on flexible application to wiring. When the metal film is standing upright without a taper angle, a gap may be generated between the silver (Ag) and the insulating film or wiring during the formation of the insulating film or subsequent wiring in the subsequent process, and the generation of such a gap becomes an electrical short. The cause of the bad.
另一方面，韓國註冊專利第10-0579421號中提出的銀蝕刻液在磷酸、硝酸、醋酸中作為添加劑使用了輔助氧化物溶解劑和含氟型碳系表面活性劑。但是，作為輔助氧化物溶解劑使用的SO4 2-化合物存在與銀(Ag)進行反應而以硫化銀(Ag2S)的形態在基板內作為殘渣殘留的缺點，ClO4 -化合物現在被規定為環境管制物質，在使用中存在困難。另外，使用所述組合物蝕刻包含銀的金屬膜的情況下，依然存在蝕刻後的錐角的形成難的問題。 On the other hand, the silver etching solution proposed in Korean Registered Patent No. 10-0579421 uses an auxiliary oxide dissolving agent and a fluorine-containing carbon-based surfactant as additives in phosphoric acid, nitric acid, and acetic acid. However, SO 4 2- compound oxide is used as an auxiliary dissolving agent disadvantage is reacted with silver (Ag) in the form of silver sulfide (Ag 2 S) as a residue in the substrate remaining, ClO 4 - is now specified compound As an environmentally controlled substance, there are difficulties in use. In addition, when the metal film containing silver is etched using the composition, there is still a problem that it is difficult to form a taper angle after the etching.
現有技術文獻 Prior art literature
專利文獻 Patent literature
專利文獻1：韓國註冊專利第10-0579421號 Patent Document 1: Korean Registered Patent No. 10-0579421
本發明的目的在於提供在包含銀的金屬膜的蝕刻後可以形成錐角(taper angle)的銀蝕刻液組合物。 An object of the present invention is to provide a silver etchant composition capable of forming a taper angle after etching a metal film containing silver.
另外，本發明的目的在於提供使用了所述銀蝕刻液組合物的顯示基板和配線。 Another object of the present invention is to provide a display substrate and wiring using the silver etching solution composition.
為了實現上述目的，本發明提供銀蝕刻液組合物，相對於組合物的總重量，其包含磷酸30~60重量%、硝酸0.5~10重量%、醋酸33~50重量%、唑系化合物0.01~10重量%、和餘量的脫離子水以使組合物的總重量成為100重量%。 In order to achieve the above object, the present invention provides a silver etchant composition, which contains 30 to 60% by weight of phosphoric acid, 0.5 to 10% by weight of nitric acid, 33 to 50% by weight of acetic acid, and 0.01 to azole based on the total weight of the composition. 10% by weight and the balance of deionized water so that the total weight of the composition became 100% by weight.
另外，本發明提供包含用所述銀蝕刻液組合物蝕刻的金屬膜的顯示基板。 The present invention also provides a display substrate including a metal film etched with the silver etchant composition.
進而，本發明提供用所述銀蝕刻液組合物蝕刻的配線。 Furthermore, this invention provides the wiring etched with the said silver etchant composition.
本發明的銀蝕刻液組合物在包含銀的金屬膜的蝕刻後可以形成錐角。由此，隨著後續程序的進行在形成後續的絕緣膜或配線時，具有沿四面緩和地形成錐角的效果。 The silver etching solution composition of the present invention may form a taper angle after etching of a metal film containing silver. Therefore, as the subsequent process proceeds, when a subsequent insulating film or wiring is formed, there is an effect of gently forming a taper angle along all four sides.
圖1為對於實施例1採用本申請的實施例的方法測定殘渣並評價的結果。 FIG. 1 is a result of measuring and evaluating the residue using the method of the example of the present application for Example 1. FIG.
圖2為對於比較例1採用本申請的實施例的方法測定殘渣並評價的結果。 FIG. 2 shows the results of measurement and evaluation of residues in Comparative Example 1 by the method of the example of the present application.
圖3為對於實施例1採用本申請的實施例的方法測定再吸附的有無並評價的結果。 FIG. 3 shows the results of measuring and evaluating the presence or absence of re-adsorption using the method of the example of the present application for Example 1. FIG.
圖4為對於比較例1採用本申請的實施例的方法測定再吸附的有無並評價的結果。 FIG. 4 shows the results of Comparative Example 1 in which the presence or absence of re-adsorption was measured and evaluated using the method of the example of the present application.
圖5為對於實施例1採用本申請的實施例的方法測定錐角並評價的結果。 FIG. 5 is a result of measuring and evaluating a cone angle using the method of the embodiment of the present application for Example 1. FIG.
圖6為對於比較例2採用本申請的實施例的方法測定錐角並評價的結果。 FIG. 6 shows the results of measuring and evaluating the taper angle for the comparative example 2 using the method of the embodiment of the present application.
圖7為蝕刻速度的測定時為了對於縱向蝕刻的理解所示的圖。 FIG. 7 is a diagram showing the understanding of vertical etching during the measurement of the etching rate.
以下對本發明更詳細地說明。 The present invention is explained in more detail below.
本發明涉及銀蝕刻液組合物，相對於銀蝕刻液組合物的總重量，其包含磷酸30~60重量%、硝酸0.5~10重量%、醋酸33~50重量%、唑系化合物0.01~10重量%、和餘量的脫離子水以使組合物的總重量成為100重量%。本發明人在實驗上確認了使用上述的蝕刻液組合物蝕刻包含銀的金屬膜的情況下可以形成蝕刻後的錐角(taper angle)。 The present invention relates to a silver etchant composition, which contains 30 to 60% by weight of phosphoric acid, 0.5 to 10% by weight of nitric acid, 33 to 50% by weight of acetic acid, and 0.01 to 10% by weight of an azole compound relative to the total weight of the silver etchant composition. % And the balance of deionized water so that the total weight of the composition becomes 100% by weight. The present inventors have experimentally confirmed that when the metal film containing silver is etched using the above-mentioned etchant composition, a taper angle after the etching can be formed.
本發明的銀蝕刻液組合物的特徵在於，能夠蝕刻由銀(Ag)或銀合金構成的單一膜、或者由所述單一膜和透明導電膜構成的多層膜，所述多層膜可以同時蝕刻。 The silver etching solution composition of the present invention is capable of etching a single film made of silver (Ag) or a silver alloy, or a multilayer film made of the single film and a transparent conductive film, and the multilayer films can be etched simultaneously.
所述銀合金可以為以銀作為主成分、包含In、P、Nd、Cu、Pd、Nb、Ni、Mo、Ni、Cr、Mg、W、和Ti等其他金屬的合金的形態、以及銀的氮化物、矽化物、碳化物、和氧化物的形態等多種形態，但並不限定於這些。 The silver alloy may be in the form of an alloy containing silver as a main component, and containing other metals such as In, P, Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W, and Ti, and silver. There are various forms of nitrides, silicides, carbides, and oxides, but they are not limited to these.
另外，所述透明導電膜一般如IZO和a-ITO那樣，具有在可見光區域中透射率為約90%以上、電阻率為1×10-4Ω cm以下的特性。由於透明導電膜為透明，一般傳導電子必須少，為了電導率變大，傳導電子必須多。在透明導電膜的情況下，必須滿足這樣相反的2個條件。在蒸鍍IZO和a-ITO的方法中，一般使用濺射(Sputtering)，其與CVD(Chemical Vapor Deposition)方法相比具有如下優點：容易調節蒸鍍條件，在使用大型的基板製造的情況下，容易實現薄膜的厚度和薄膜特性的均一化。在採用濺射方法製造的情況下，存在使用氧化物靶或合金靶(alloy target)的2種方法，在使用合金靶的情況下，具有如下優點：蒸鍍速度快，靶壽命也相當長，可以實現靶製造的容易性和再利用，但具有對程序變數顯示敏感的特性變化的缺點。如果使用氧化物靶，能夠具有再現性地控制薄膜的化學計量比，但與合金靶相比，蒸鍍速度慢，有時在蒸鍍中途在靶中產生物理的龜裂，存在在靶中產生電弧的缺點。在採用濺射蒸鍍銦-主成分系氧化物 的情況下，與O2反應，具有In2O3的形態，但為了提高電導率，作為摻雜劑，使用Ga、Ge、Si、Ti、Sb、Zr、Sn、和Zn等。本發明中，ITO意味著將In2O3和SnO2分別以適當比率混合而成的透明導電膜，但並不限定於此。例如，只使用作為摻雜劑使用的Ga和Zn製作的GZO的膜質等也可適用。進而，所述多層膜可以是由透明導電膜/銀、透明導電膜/銀合金、透明導電膜/銀/透明導電膜、或透明導電膜/銀合金/透明導電膜形成的多層膜，在使用本發明的銀蝕刻液組合物的情況下，能夠在不損傷下部膜的情況下顯示蝕刻均一性，可以在濕式蝕刻中有用地使用。 In addition, the transparent conductive film generally has characteristics such as IZO and a-ITO that have a transmittance of about 90% or more and a resistivity of 1 × 10 -4 Ω cm or less in the visible light region. Since the transparent conductive film is transparent, generally there must be few conductive electrons. In order to increase the conductivity, there must be more conductive electrons. In the case of a transparent conductive film, two opposite conditions must be satisfied. In the method of vapor-depositing IZO and a-ITO, sputtering is generally used, which has the following advantages compared with the CVD (Chemical Vapor Deposition) method: it is easy to adjust the vapor deposition conditions, and in the case of using a large substrate , It is easy to achieve the uniformity of the thickness of the film and the characteristics of the film. In the case of manufacturing by a sputtering method, there are two methods using an oxide target or an alloy target. When an alloy target is used, it has the following advantages: the vapor deposition rate is fast, and the target life is relatively long. The target can be easily manufactured and reused, but has the disadvantage of being sensitive to changes in the display of program variables. If an oxide target is used, the stoichiometry of the thin film can be controlled reproducibly. However, compared with an alloy target, the vapor deposition rate is slower, and sometimes physical cracks may occur in the target during the vapor deposition, which may occur in the target. Disadvantages of the arc. In the case of sputtering vapor deposition of indium-main component oxide, it reacts with O 2 and has the form of In 2 O 3. However, in order to improve the conductivity, Ga, Ge, Si, Ti, Sb, Zr, Sn, and Zn. In the present invention, ITO means a transparent conductive film obtained by mixing In 2 O 3 and SnO 2 at an appropriate ratio, but is not limited thereto. For example, the film quality of GZO made using only Ga and Zn used as a dopant is also applicable. Furthermore, the multilayer film may be a multilayer film formed of a transparent conductive film / silver, a transparent conductive film / silver alloy, a transparent conductive film / silver / transparent conductive film, or a transparent conductive film / silver alloy / transparent conductive film. In the case of the silver etching solution composition of the present invention, it is possible to show etching uniformity without damaging the lower film, and it can be usefully used in wet etching.
本發明的銀蝕刻液組合物中所含的磷酸(H3PO4)為主蝕刻劑，在蝕刻單一膜或多層膜時，與銀(Ag)或銀合金引起氧化還原反應，發揮使透明導電膜解離、進行濕式蝕刻的作用。 The phosphoric acid (H 3 PO 4 ) contained in the silver etchant composition of the present invention is a main etchant, and when a single film or a multilayer film is etched, it causes an oxidation-reduction reaction with silver (Ag) or a silver alloy to exert transparency and conductivity. The film dissociates and performs wet etching.
所述磷酸，相對於銀蝕刻液組合物的總重量，含有30~60重量%，優選含有40~50重量%。 The phosphoric acid contains 30 to 60% by weight, and preferably 40 to 50% by weight, based on the total weight of the silver etching solution composition.
如果以不到30重量%含有所述磷酸，有時蝕刻能力不足，無法進行充分的蝕刻。另外，在程序的進行中如果一定量以上的銀(Ag)溶解到銀蝕刻液組合物中，則出現銀(Ag)再吸附或銀(Ag)析出物，在後續程序中可發生電短路，可成為不良發生的原因。 If the phosphoric acid is contained in an amount of less than 30% by weight, the etching ability may be insufficient, and sufficient etching may not be performed. In addition, if more than a certain amount of silver (Ag) is dissolved in the silver etching solution composition during the process, silver (Ag) re-adsorption or silver (Ag) precipitates occur, and an electrical short circuit may occur in the subsequent process. Can be a cause of failure.
在所述磷酸超過60重量%的情況下，有時透明導電膜的蝕刻速度降低，銀或銀合金的蝕刻速度過度地加速而產生過蝕刻，由此有時產生無法發揮配線作用的蝕刻 量。另外，在將透明導電膜層疊於銀或銀合金而成的多層膜的情況下，有時產生銀或銀合金與透明導電膜的蝕刻速度之差引起的尖端(Tip)，在後續程序中產生問題。 When the phosphoric acid exceeds 60% by weight, the etching rate of the transparent conductive film may decrease, and the etching rate of silver or a silver alloy may be excessively accelerated to cause over-etching, which may cause etching to fail to perform the wiring function. the amount. In addition, in the case of a multilayer film in which a transparent conductive film is laminated on silver or a silver alloy, a tip (Tip) caused by a difference in the etching rate between the silver or silver alloy and the transparent conductive film may be generated in a subsequent procedure. problem.
本發明的銀蝕刻液組合物中所含的硝酸(HNO3)是發揮輔助蝕刻劑的作用的成分，單一膜或多層膜的蝕刻時發揮使銀(Ag)或銀合金與透明導電膜氧化而進行濕式蝕刻的作用。 The nitric acid (HNO 3 ) contained in the silver etchant composition of the present invention is a component that functions as an auxiliary etchant, and when a single film or a multilayer film is etched, it oxidizes silver (Ag) or a silver alloy and a transparent conductive film, The effect of wet etching is performed.
所述硝酸相對於銀蝕刻液組合物的總重量，含有0.5~10重量%，優選含有2~10重量%。 The nitric acid is contained in an amount of 0.5 to 10% by weight, and preferably 2 to 10% by weight, based on the total weight of the silver etching solution composition.
在所述硝酸的含量不到0.5重量%的情況下，有時出現銀或銀合金與透明導電膜的蝕刻速度的下降，由於銀殘渣，伴隨後續程序的進行而產生電短路和殘渣殘留的區域看起來暗的現象，即暗點不良。另外，在硝酸的含量超過10重量%的情況下，由於過度的蝕刻速度，程序上對蝕刻的調節困難，產生過蝕刻，無法發揮作為配線的作用。 When the content of the nitric acid is less than 0.5% by weight, the etching rate of silver or a silver alloy and the transparent conductive film may decrease. Due to the silver residue, an area where an electrical short circuit and residue remain due to the subsequent procedures may occur. The phenomenon that looks dark, that is, the dark spot is bad. In addition, when the content of nitric acid exceeds 10% by weight, due to the excessive etching speed, it is difficult to adjust the etching on the program, and over-etching occurs, and it cannot function as a wiring.
本發明的銀蝕刻液組合物中所含的醋酸(CH3COOH)為了調節反應速度等作為緩衝劑發揮作用，不僅如此，對於Ag單一或合金形成錐角起到非常重要的作用。 The acetic acid (CH 3 COOH) contained in the silver etching solution composition of the present invention functions as a buffer to adjust the reaction rate and the like, and not only that, but also plays a very important role in forming a cone angle of Ag or an alloy.
所述醋酸相對於銀蝕刻液組合物的總重量，含有33~50重量%。 The acetic acid contains 33 to 50% by weight based on the total weight of the silver etching solution composition.
如果所述醋酸的含量不到33重量%，則有時顯示基板，更詳細地說，TFT陣列基板的配線的蝕刻均一性降低，配線的直進性下降，配線電阻變大，或者在後續程 序中誘發不良，產生基板內的蝕刻速度變得不均一、在基板上產生斑點的問題。另外，發生銀表面的潤濕性的下降引起的光致抗蝕劑下端的浸透力降低所導致的錐角沒有形成的問題。 If the content of the acetic acid is less than 33% by weight, the display substrate may be displayed. More specifically, the etching uniformity of the wiring of the TFT array substrate is reduced, the straightness of the wiring is reduced, the wiring resistance is increased, or Defects are induced in the sequence, and the etching rate in the substrate becomes uneven, causing problems such as spots on the substrate. In addition, there was a problem that a taper angle was not formed due to a decrease in the penetrating force of the lower end of the photoresist due to a decrease in the wettability of the silver surface.
另外，如果所述醋酸的含量超過50重量%，成為揮發性非常強的組合物，程序適用時，由於組合物的揮發，在3小時以內發生組合物的含量變化，發生蝕刻速度隨著時間的經過而改變的問題。 In addition, if the content of the acetic acid exceeds 50% by weight, it becomes a highly volatile composition. When the procedure is applied, the content of the composition changes within 3 hours due to the volatilization of the composition, and the etching rate will change with time. Questions that change over time.
本發明的銀蝕刻液組合物中所含的唑系化合物是發揮起到減緩銀(Ag)或銀合金的蝕刻速度的作用的防腐蝕劑的作用的成分，在多層膜的蝕刻時能夠在相對地透明導電膜的速度不變慢的情況下控制透明導電膜的尖端(Tip)的產生，在程序上調節蝕刻時間。另外，能夠防止銀(Ag)的過蝕刻，形成窄的像素電極(Pixel)的配線，能夠作為添加劑在形成圖案微細的配線的蝕刻液組合物等中使用。 The azole-based compound contained in the silver etching solution composition of the present invention is a component that functions as an anti-corrosive agent that slows down the etching rate of silver (Ag) or a silver alloy. When the speed of the transparent conductive film is not slow, the generation of the tip of the transparent conductive film is controlled, and the etching time is adjusted in a program. In addition, it is possible to prevent over-etching of silver (Ag) and form narrow pixel electrode (Pixel) wirings, and it can be used as an additive in an etchant composition or the like for forming fine-patterned wirings.
另外，以往，如果用蝕刻液組合物蝕刻不具有透明導電膜等阻隔膜的銀或銀合金的單一膜，則產生了過蝕刻。為了防止這情況，在單一膜的上下部應用了阻隔膜，這成為了程序上費用增加的原因。 In addition, conventionally, when a single film of silver or a silver alloy without a barrier film such as a transparent conductive film is etched with an etchant composition, over-etching occurs. In order to prevent this, a barrier film is applied to the upper and lower portions of the single film, which becomes the reason for the increase in the cost of the procedure.
但是，本發明的銀蝕刻液組合物通過使用唑系化合物，可以預防過蝕刻，可不使用阻隔膜，由此，具有能夠實現減少程序時間和節省原材料、能夠減少生產費用的優點。 However, the silver etching solution composition of the present invention can prevent over-etching by using an azole-based compound, and can eliminate the need for a barrier film. This has the advantages of reducing process time, saving raw materials, and reducing production costs.
本發明的唑系化合物優選為四唑化合物，具體地，可以是選自四唑(Tetrazole、TZ)、甲基四唑(Methyltetrazole、MTZ)、和胺基四唑(Aminotetrazole、ATZ)中的1種以上。最優選地，可以為甲基四唑(Methyltetrazole、MTZ)。 The azole-based compound of the present invention is preferably a tetrazole compound, and specifically, may be selected from tetrazolium (Tetrazole, TZ), methyltetrazole (Methyltetrazole, MTZ), and aminotetrazole (Aminotetrazole, ATZ) More than that. Most preferably, it may be Methyltetrazole (MTZ).
所述唑系化合物相對於銀蝕刻液組合物的總重量，含有0.01~10重量%。如果所述唑系化合物的含量不到0.01重量%，則無法正經地發揮減緩蝕刻速度的作用，用於形成具有微細的圖案的配線時，有時產生過蝕刻引起的配線消失的不良。另外，如果超過10重量%，銀或銀合金的蝕刻速度顯著減小，沒有將不需要的部分完全地蝕刻，可發生電短路，成為不良發生的原因。進而，由於蝕刻速度的降低，殘留物殘留，有時在進行後續程序後、製品生產時誘發一部分區域看起來黑的暗點這樣的不良現象。 The azole-based compound is contained in an amount of 0.01 to 10% by weight based on the total weight of the silver etching solution composition. If the content of the azole-based compound is less than 0.01% by weight, the effect of slowing down the etching rate cannot be taken seriously, and when it is used to form a wiring having a fine pattern, there is a possibility that the wiring disappears due to over-etching. In addition, if it exceeds 10% by weight, the etching rate of silver or a silver alloy is significantly reduced, and unnecessary portions are not completely etched, and an electrical short circuit may occur, which may cause a failure. Further, due to the decrease in the etching rate, residues remain, and after the subsequent process, a defective phenomenon such that a part of the area appears dark during the production of the product may be induced.
本發明的銀蝕刻液組合物中所含的脫離子水使用半導體程序用脫離子水，優選使用18MΩ/cm以上的水。 As the deionized water contained in the silver etching solution composition of the present invention, deionized water for semiconductor processes is used, and water of 18 MΩ / cm or more is preferably used.
本發明的銀蝕刻液組合物除了以上提及的成分以外，可以進一步包含在該領域中通常使用的蝕刻調節劑和pH調節劑中的1種以上。 The silver etchant composition of the present invention may further include one or more of an etching regulator and a pH regulator generally used in this field in addition to the components mentioned above.
作為所述附加地含有的蝕刻調節劑，其為包含醋酸鉀或醋酸鈉中的1種醋酸鹽的化合物；作為附加地含有的pH調節劑，其為包含乙醇酸、谷胺酸、或甘胺酸中的1種有機酸的化合物。 The additional added etching regulator is a compound containing one acetate of potassium acetate or sodium acetate, and the additional added pH regulator is glycolic acid, glutamic acid, or glycine. A compound of one organic acid among acids.
本發明的銀蝕刻液組合物能夠作為在顯示器(OLED、LCD等)的TFT陣列基板、TSP Trace配線、和Flexible用納米線配線形成用中大量使用的透明導電膜、使用了銀、銀合金的單一膜、或者使用了2種以上的多層結構的蝕刻液使用。不僅如此，在所述明示的顯示器、TSP以外，也能夠在半導體等使用了所述金屬膜質的電子部件原料中使用。 The silver etchant composition of the present invention can be used as a transparent conductive film widely used in the formation of TFT array substrates for displays (OLEDs, LCDs, etc.), TSP Trace wiring, and flexible nanowire wiring, and using silver and silver alloys. A single film or an etching solution using two or more multilayer structures is used. In addition to this, in addition to the above-mentioned explicit display and TSP, it can also be used in electronic component raw materials using the metal film quality such as semiconductors.
另外，本發明能夠提供包含用本發明的銀蝕刻液組合物蝕刻的金屬膜的顯示基板。 In addition, the present invention can provide a display substrate including a metal film etched with the silver etchant composition of the present invention.
更詳細地說，所述顯示裝置可以為液晶顯示裝置(LCD)或有機發光元件(OLED)的薄膜電晶體(TFT)基板。 In more detail, the display device may be a thin film transistor (TFT) substrate of a liquid crystal display device (LCD) or an organic light emitting element (OLED).
另外，所述OLED能夠將金屬膜層疊於上部和下部，能夠用本發明的蝕刻液組合物蝕刻金屬膜。通過調節金屬膜的厚度、層疊於上部和下部，在OLED中，所述金屬膜能夠發揮反射膜和半透膜的作用。 In addition, in the OLED, a metal film can be laminated on the upper and lower portions, and the metal film can be etched with the etchant composition of the present invention. By adjusting the thickness of the metal film and stacking it on the upper and lower portions, in the OLED, the metal film can function as a reflective film and a semi-permeable film.
所述反射膜必須為幾乎不透光的厚度，所述半透膜必須為光幾乎全透過的厚度。因此，所述金屬膜的厚度優選為50~5000Å。 The reflective film must have a thickness that is almost opaque, and the semi-transmissive film must have a thickness that almost completely transmits light. Therefore, the thickness of the metal film is preferably 50 to 5000 Å.
所述金屬膜為由銀(Ag)或銀合金構成的單一膜、或者由所述單一膜和透明導電膜構成的多層膜。 The metal film is a single film made of silver (Ag) or a silver alloy, or a multilayer film made of the single film and a transparent conductive film.
所述銀合金可為以銀作為主成分、包含In、P、Nd、Cu、Pd、Nb、Ni、Mo、Ni、Cr、Mg、W、和Ti等其他金屬的合金的形態以及銀的氮化物、矽化物、碳化物、和氧化物的形態等多樣的形態，但並不限定於這些。 The silver alloy may be in the form of an alloy containing silver as a main component, and including other metals such as In, P, Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W, and Ti, and silver. Various forms such as a compound, a silicide, a carbide, and an oxide are not limited to these.
另外，所述透明導電膜一般如IZO和a-ITO那樣，具有在可見光區域中透射率為約90%以上、電阻率為1×10-4Ω cm以下的特性。由於透明導電膜為透明，一般傳導電子必須少，為了電導率變大，傳導電子必須多。在透明導電膜的情況下，必須滿足這樣相反的2個條件。在蒸鍍IZO和a-ITO的方法中，一般使用濺射(Sputtering)，其與CVD(Chemical Vapor Deposition)方法相比具有如下優點：容易調節蒸鍍條件，在使用大型的基板製造的情況下，容易實現薄膜的厚度和薄膜特性的均一化。在採用濺射方法製造的情況下，存在使用氧化物靶或合金靶(alloy target)的2種方法，在使用合金靶的情況下，具有如下優點：蒸鍍速度快，靶壽命也相當長，可以實現靶製造的容易性和再利用，但具有對程序變數顯示敏感的特性變化的缺點。如果使用氧化物靶，能夠具有再現性地控制薄膜的化學計量比，但與合金靶相比，蒸鍍速度慢，有時在蒸鍍中途在靶中產生物理的龜裂，存在在靶中產生電弧的缺點。在採用濺射蒸鍍銦-主成分系氧化物的情況下，與O2反應，具有In2O3的形態，但為了提高電導率，作為摻雜劑，使用Ga、Ge、Si、Ti、Sb、Zr、Sn、和Zn等。本發明中，ITO意味著將In2O3和SnO2分別以適當比率混合而成的透明導電膜，但並不限定於此。例如，只使用作為摻雜劑使用的Ga和Zn製作的GZO的膜質等也可適用。 In addition, the transparent conductive film generally has characteristics such as IZO and a-ITO that have a transmittance of about 90% or more and a resistivity of 1 × 10 -4 Ω cm or less in the visible light region. Since the transparent conductive film is transparent, generally there must be few conductive electrons. In order to increase the conductivity, there must be more conductive electrons. In the case of a transparent conductive film, two opposite conditions must be satisfied. In the method of vapor-depositing IZO and a-ITO, sputtering is generally used, which has the following advantages compared with the CVD (Chemical Vapor Deposition) method: it is easy to adjust the vapor deposition conditions, and in the case of using a large substrate , It is easy to achieve the uniformity of the thickness of the film and the characteristics of the film. In the case of manufacturing by a sputtering method, there are two methods using an oxide target or an alloy target. When an alloy target is used, it has the following advantages: the vapor deposition rate is fast, and the target life is relatively long. The target can be easily manufactured and reused, but has the disadvantage of being sensitive to changes in the display of program variables. If an oxide target is used, the stoichiometry of the thin film can be controlled reproducibly. However, compared with an alloy target, the vapor deposition rate is slower, and sometimes physical cracks may occur in the target during the vapor deposition, which may occur in the target. Disadvantages of the arc. In the case of sputtering vapor deposition of indium-main component oxide, it reacts with O 2 and has the form of In 2 O 3. However, in order to improve the conductivity, Ga, Ge, Si, Ti, Sb, Zr, Sn, and Zn. In the present invention, ITO means a transparent conductive film obtained by mixing In 2 O 3 and SnO 2 at an appropriate ratio, but is not limited thereto. For example, the film quality of GZO made using only Ga and Zn used as a dopant is also applicable.
進而，所述多層膜可以是由透明導電膜/銀、透明導 電膜/銀合金、透明導電膜/銀/透明導電膜、或透明導電膜/銀合金/透明導電膜形成的多層膜。 Further, the multilayer film may be made of transparent conductive film / silver, transparent conductive Multilayer film formed by electrical film / silver alloy, transparent conductive film / silver / transparent conductive film, or transparent conductive film / silver alloy / transparent conductive film.
另外，本發明能夠提供用本發明的銀蝕刻液組合物蝕刻的配線。 In addition, the present invention can provide a wiring etched with the silver etchant composition of the present invention.
更詳細地，該配線可以是觸控式螢幕面板(Touch screen panel、TSP)中主要讀取在X、Y座標感測的信號的示蹤(Trace)配線或柔性銀納米線配線。 In more detail, the wiring may be a trace wiring or a flexible silver nanowire wiring that mainly reads signals sensed at the X and Y coordinates in a touch screen panel (TSP).
另外，所述配線為由銀(Ag)或銀合金構成的單一膜、或者由所述單一膜和透明導電膜構成的多層膜。 The wiring is a single film made of silver (Ag) or a silver alloy, or a multilayer film made of the single film and a transparent conductive film.
所述銀合金可為以銀作為主成分、包含In、P、Nd、Cu、Pd、Nb、Ni、Mo、Ni、Cr、Mg、W和Ti等其他金屬的合金的形態以及銀的氮化物、矽化物、碳化物和氧化物的形態等多樣的形態，但並不限定於這些。 The silver alloy may be in the form of an alloy containing silver as a main component and containing other metals such as In, P, Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W, and Ti, and silver nitride , Silicide, carbide, and oxide, but are not limited to these.
另外，所述透明導電膜一般如IZO和a-ITO那樣，具有在可見光區域中透射率為約90%以上、電阻率為1×10-4Ω cm以下的特性。由於透明導電膜為透明，一般傳導電子必須少，為了電導率變大，傳導電子必須多。在透明導電膜的情況下，必須滿足這樣相反的2個條件。在蒸鍍IZO和a-ITO的方法中，一般使用濺射，其與CVD(Chemical Vapor Deposition)方法相比具有如下優點：容易調節蒸鍍條件，在使用大型的基板製造的情況下，容易實現薄膜的厚度和薄膜特性的均一化。在採用濺射方法製造的情況下，存在使用氧化物靶或合金靶(alloy target)的2種方法，在使用合金靶的情況下，具有 如下優點：蒸鍍速度快，靶壽命也相當長，可以實現靶製造的容易性和再利用，但具有對程序變數顯示敏感的特性變化的缺點。如果使用氧化物靶，能夠具有再現性地控制薄膜的化學計量比，但與合金靶相比，蒸鍍速度慢，有時在蒸鍍中途在靶中產生物理的龜裂，存在在靶中產生電弧的缺點。在採用濺射蒸鍍銦-主成分系氧化物的情況下，與O2反應，具有In2O3的形態，但為了提高電導率，作為摻雜劑，使用Ga、Ge、Si、Ti、Sb、Zr、Sn、和Zn等。本發明中，ITO意味著將In2O3和SnO2分別以適當比率混合而成的透明導電膜，但並不限定於此。例如，只使用作為摻雜劑使用的Ga和Zn製作的GZO的膜質等也可適用。 In addition, the transparent conductive film generally has characteristics such as IZO and a-ITO that have a transmittance of about 90% or more and a resistivity of 1 × 10 -4 Ω cm or less in the visible light region. Since the transparent conductive film is transparent, generally there must be few conductive electrons. In order to increase the conductivity, there must be more conductive electrons. In the case of a transparent conductive film, two opposite conditions must be satisfied. In the method of vapor-depositing IZO and a-ITO, sputtering is generally used, which has the following advantages compared with the CVD (Chemical Vapor Deposition) method: it is easy to adjust the vapor deposition conditions, and it is easy to realize when using a large substrate Uniformity of film thickness and film characteristics. In the case of manufacturing by a sputtering method, there are two methods using an oxide target or an alloy target. When an alloy target is used, it has the following advantages: the vapor deposition rate is fast, and the target life is relatively long. The target can be easily manufactured and reused, but has the disadvantage of being sensitive to changes in the display of program variables. If an oxide target is used, the stoichiometry of the thin film can be controlled reproducibly. However, compared with an alloy target, the vapor deposition rate is slower, and sometimes physical cracks may occur in the target during the vapor deposition, which may occur in the target. Disadvantages of the arc. In the case of sputtering vapor deposition of indium-main component oxide, it reacts with O 2 and has the form of In 2 O 3. However, in order to improve the conductivity, Ga, Ge, Si, Ti, Sb, Zr, Sn, and Zn. In the present invention, ITO means a transparent conductive film obtained by mixing In 2 O 3 and SnO 2 at an appropriate ratio, but it is not limited to this. For example, the film quality of GZO made using only Ga and Zn used as a dopant is also applicable.
進而，所述多層膜可以是由透明導電膜/銀、透明導電膜/銀合金、透明導電膜/銀/透明導電膜、或透明導電膜/銀合金/透明導電膜形成的多層膜。 Furthermore, the multilayer film may be a multilayer film formed of a transparent conductive film / silver, a transparent conductive film / silver alloy, a transparent conductive film / silver / transparent conductive film, or a transparent conductive film / silver alloy / transparent conductive film.
以下通過實施例更詳細地說明本發明。但是，下述的實施例用於對本發明更具體地說明，本發明的範圍並不由下述的實施例限定。下述的實施例在本發明的範圍內對於本領域技術人員而言可適當地修正、改變。 Hereinafter, the present invention will be described in more detail through examples. However, the following examples are used to explain the present invention more specifically, and the scope of the present invention is not limited by the following examples. The following embodiments can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
<銀蝕刻液組合物的製造> <Production of Silver Etching Solution Composition>
實施例1~11和比較例1~8 Examples 1 to 11 and Comparative Examples 1 to 8
將下述表1中記載的成分以該含量混合，製造銀蝕刻液組合物。(單位：重量%) The components described in Table 1 below were mixed at this content to produce a silver etchant composition. (unit weight%)
實驗例1.銀蝕刻液組合物的性能試驗 Experimental example 1. Performance test of silver etchant composition
在基板上蒸鍍有機絕緣膜，在其上蒸鍍Ag單一膜，使用金剛石刀具切斷為300 x 300mm，準備試驗片。 An organic insulating film was vapor-deposited on the substrate, and a single Ag film was vapor-deposited thereon, and cut to 300 x 300 mm with a diamond cutter to prepare a test piece.
使用上述實施例1~11和比較例1~8的銀蝕刻液組合物，進行了下述的性能試驗。 The following performance tests were performed using the silver etchant compositions of Examples 1 to 11 and Comparative Examples 1 to 8 described above.
1.配線(或反射膜)的單側蝕刻距離(S/E、Side Etch)的測定 1. Measurement of single-sided etching distance (S / E, Side Etch) of wiring (or reflective film)
在噴射式蝕刻方式的實驗裝備(型號名：ETCHER(TFT)、K.C.Tech社)內分別裝入上述實施例1~11和比較例1~8的銀蝕刻液組合物，將溫度設定為40℃、升溫後，在溫度到達了40±0.1℃時，進行了上述試驗片的蝕刻程序。將總蝕刻時間設為60秒而實施。 The experimental equipment (model name: ETCHER (TFT), KCTech) of the spray etching method was charged with the silver etching solution compositions of Examples 1 to 11 and Comparative Examples 1 to 8, respectively, and the temperature was set to 40 ° C. After the temperature was raised, when the temperature reached 40 ± 0.1 ° C, the etching procedure of the test piece was performed. The total etching time was set to 60 seconds.
放入基板開始噴射，成為60秒的蝕刻時間時取出， 用脫離子水清洗後，使用熱風乾燥裝置乾燥。清洗和乾燥後，將基板切斷，對斷面使用電子掃描顯微鏡(SEM；型號名：SU-8010、HITACHI社製造)測定。作為單側蝕刻距離的測定標準，測定從光致抗蝕劑的端部分將金屬蝕刻而進入到內側的寬度，用下述的標準評價，將結果示於下述表2中。 Put it into the substrate to start spraying, and take it out when it becomes an etching time of 60 seconds. After washing with deionized water, it was dried using a hot air dryer. After cleaning and drying, the substrate was cut, and the cross-section was measured using an electron scanning microscope (SEM; model name: SU-8010, manufactured by Hitachi). As a measurement standard for the one-sided etching distance, the width of the photoetched metal from the end portion of the photoresist to the inner side was measured, and the following criteria were evaluated. The results are shown in Table 2 below.
<單側蝕刻距離測定的評價標準> <Evaluation Criteria for Measuring Unilateral Etching Distance>
優秀：0.5μm以下 Excellent: below 0.5μm
良好：超過0.5μm~1.0μm以下 Good: more than 0.5μm ~ 1.0μm
不良：超過1.0μm Defect: more than 1.0 μm
2.殘渣的測定 2. Determination of residue
在噴射式蝕刻方式的實驗裝備(型號名：ETCHER(TFT)、K.C.Tech社)內分別裝入上述實施例1~11和比較例1~8的銀蝕刻液組合物，將溫度設定為40℃、加熱後，在溫度到達了40±0.1℃時，進行了上述試驗片的蝕刻程序。將總蝕刻時間設為60秒而實施。 The experimental equipment (model name: ETCHER (TFT), KCTech) of the spray etching method was charged with the silver etching solution compositions of Examples 1 to 11 and Comparative Examples 1 to 8, respectively, and the temperature was set to 40 ° C. After heating, when the temperature reached 40 ± 0.1 ° C, the above-mentioned test piece etching procedure was performed. The total etching time was set to 60 seconds.
放入基板開始噴射，成為60秒的蝕刻時間時取出，用脫離子水清洗後，使用熱風乾燥裝置乾燥，使用光致抗蝕劑剝離機(PR stripper)將光致抗蝕劑除去。清洗和乾燥後，使用電子掃描顯微鏡(SEM；型號名：SU-8010、HITACHI社製造)測定在沒有覆蓋光致抗蝕劑的部分沒有將銀(Ag)蝕刻而殘留的現象即殘渣，用下述的標準評價，將結果示於下述表2中。 The substrate was sprayed, and it was taken out at an etching time of 60 seconds. After washing with deionized water, it was dried with a hot air dryer and the photoresist was removed using a PR stripper. After washing and drying, a residue that does not etch silver (Ag) in a portion not covered with photoresist, that is, a residue, is measured using an electron scanning microscope (SEM; model name: SU-8010, manufactured by Hitachi). The results of the standard evaluation described above are shown in Table 2 below.
<殘渣測定的評價標準> <Evaluation criteria for residue measurement>
優秀：無殘渣(圖1) Excellent: no residue (Figure 1)
不良：產生殘渣(殘渣為蝕刻變得不完全的現象，在基板的全面以無定形存在。圖2) Defect: Residue is generated (residue is a phenomenon in which etching becomes incomplete, and it exists in an amorphous form throughout the substrate. Figure 2)
3.蝕刻速度的測定 3. Measurement of etching rate
在噴射式蝕刻方式的實驗裝備(型號名：ETCHER(TFT)、K.C.Tech社)內分別裝入上述實施例1~11和比較例1~8的銀蝕刻液組合物，將溫度設定為40℃、加熱後，在溫度到達了40±0.1℃時，進行了上述試驗片的蝕刻程序。將總蝕刻時間設為60秒而實施。 The experimental equipment (model name: ETCHER (TFT), KCTech) of the spray etching method was charged with the silver etching solution compositions of Examples 1 to 11 and Comparative Examples 1 to 8, respectively, and the temperature was set to 40 ° C. After heating, when the temperature reached 40 ± 0.1 ° C, the above-mentioned test piece etching procedure was performed. The total etching time was set to 60 seconds.
用肉眼進行終點檢測(End Point Detection、EPD)，得到了對應於時間的縱向蝕刻速度(E/R、Etch Rate)。將進行了蝕刻的金屬膜的厚度除以EPD，能夠求出每秒(時間)的Å(厚度)(Å/sec)的蝕刻速度，按照下述的標準評價，將結果示於下述表2中。 End point detection (EPD) was performed with the naked eye, and the vertical etching rate (E / R, Etch Rate) corresponding to time was obtained. By dividing the thickness of the etched metal film by EPD, the etch rate of Å (thickness) (Å / sec) per second (time) can be obtained, and evaluated according to the following criteria. The results are shown in Table 2 below. in.
<蝕刻速度的評價標準> <Evaluation Criteria for Etching Speed>
優秀：100Å/sec以下 Excellent: below 100Å / sec
良好：超過100Å/sec~200Å/sec以下 Good: more than 100Å / sec ~ 200Å / sec
不良：超過200Å/sec Bad: more than 200Å / sec
4.經時穩定性的測定 4. Determination of stability over time
使用上述實施例1~11和比較例1~8的銀蝕刻液組合物，進行參比蝕刻(reference etch)試驗，將剩餘的銀蝕刻液組合物在25℃下保管計畫的日期(1個月標準)。然後，使用經保管的銀蝕刻液組合物，在與上述蝕刻速度試驗相同的條件下再次進行蝕刻，與參比蝕刻試驗中的結果 比較。評價標準如下所述，將結果示於下述表2中。 Using the silver etchant compositions of Examples 1 to 11 and Comparative Examples 1 to 8 described above, a reference etch test was performed, and the remaining silver etchant composition was stored at 25 ° C for a planned date (one Monthly standard). Then, using the stored silver etching solution composition, etching was performed again under the same conditions as in the above-mentioned etching rate test, and the results in the reference etching test Compare. The evaluation criteria are as follows, and the results are shown in Table 2 below.
<經時穩定性的評價標準> <Evaluation Criteria for Stability Over Time>
優秀：進過1個月後的蝕刻輪廓優秀 Excellent: Excellent etching profile after 1 month
良好：經過1個月後的蝕刻輪廓良好 Good: Etching profile is good after 1 month
不良：未達到經過1個月後的蝕刻輪廓良好的水準 Bad: The level of the etching profile after one month has not reached a good level
5.再吸附的測定 5. Determination of re-adsorption
在噴射式蝕刻方式的實驗裝備(型號名：ETCHER(TFT)、K.C.Tech社)內分別裝入上述實施例1~11和比較例1~8的銀蝕刻液組合物，將溫度設定為40℃、加熱後，在溫度到達了40±0.1℃時，進行了上述試驗片的蝕刻程序。將總蝕刻時間設為60秒而實施。 The experimental equipment (model name: ETCHER (TFT), KCTech) of the spray etching method was charged with the silver etching solution compositions of Examples 1 to 11 and Comparative Examples 1 to 8, respectively, and the temperature was set to 40 ° C. After heating, when the temperature reached 40 ± 0.1 ° C, the above-mentioned test piece etching procedure was performed. The total etching time was set to 60 seconds.
放入基板開始噴射，成為60秒的蝕刻時間時取出，用脫離子水清洗後，使用熱風乾燥裝置乾燥，使用光致抗蝕劑剝離機(PR stripper)將光致抗蝕劑除去。清洗和乾燥後，使用電子掃描顯微鏡(SEM；型號名：SU-8010、HITACHI社製造)，在進行了蝕刻後對於主要在資料配線等的異種金屬露出的部分、由於彎曲現象可產生摩擦的特定部位被蝕刻的(Ag)吸附的現象，進行基於全面觀察的分析，按下述的標準評價，將結果示於下述表2。 The substrate was sprayed, and it was taken out at an etching time of 60 seconds. After washing with deionized water, it was dried with a hot air dryer and the photoresist was removed using a PR stripper. After cleaning and drying, using an electron scanning microscope (SEM; model name: SU-8010, manufactured by HITACHI), after etching, specific parts that are exposed to dissimilar metals such as data wiring and the like can be rubbed due to bending. The phenomenon of (Ag) adsorption on the etched portion was analyzed based on comprehensive observation, and evaluated according to the following criteria. The results are shown in Table 2 below.
<再吸附測定的評價標準> <Evaluation criteria for resorption measurement>
優秀：無再吸附(圖3) Excellent: No re-adsorption (Figure 3)
不良：再吸附發生(銀再吸附為還原導致的吸附，在上述特定部位觀察到球形。圖4) Defect: Re-adsorption occurs (Silver re-adsorption is the adsorption caused by reduction, and a spherical shape is observed in the specific part described above. Figure 4)
6.錐角(Taper angle)的測定 6. Measurement of Taper angle
在噴射式蝕刻方式的實驗裝備(型號名：ETCHER(TFT)、K.C.Tech社)內分別裝入上述實施例1~5和比較例1~5的銀蝕刻液組合物，將溫度設定為40℃、加熱後，在溫度到達了40±0.1℃時，進行了上述試驗片的蝕刻程序。將總蝕刻時間設為60秒而實施。 The experimental equipment (model name: ETCHER (TFT), KCTech) of the spray etching method was charged with the silver etchant composition of Examples 1 to 5 and Comparative Examples 1 to 5, respectively, and the temperature was set to 40 ° C. After heating, when the temperature reached 40 ± 0.1 ° C, the above-mentioned test piece etching procedure was performed. The total etching time was set to 60 seconds.
放入基板開始噴射，成為60秒的蝕刻時間時取出，用脫離子水清洗後，使用熱風乾燥裝置乾燥，使用光致抗蝕劑剝離機(PR stripper)將光致抗蝕劑除去。清洗和乾燥後，使用電子掃描顯微鏡(SEM；型號名：SU-8010、HITACHI社製造)，將進行了蝕刻的基板的要分析的配線垂直地切斷後，測定配線與下部絕緣膜所成的內側角度，進行分析，按照下述的標準評價，將結果示於下述表2中。 The substrate was sprayed, and it was taken out at an etching time of 60 seconds. After washing with deionized water, it was dried with a hot air dryer and the photoresist was removed using a PR stripper. After cleaning and drying, an electron scanning microscope (SEM; model name: SU-8010, manufactured by Hitachi) was used to vertically cut the wiring to be analyzed of the etched substrate, and then the inside of the wiring and the lower insulating film was measured The angle was analyzed and evaluated according to the following criteria. The results are shown in Table 2 below.
<錐角測定的評價標準> <Evaluation criteria for taper angle measurement>
優秀：錐角20°以上~60°以下(圖5) Excellent: Cone angle above 20 ° ~ 60 ° (Figure 5)
良好：錐角超過60°~80°以下 Good: Taper angle exceeds 60 ° ~ 80 °
不良：錐角不到20°或超過80° Bad: Taper angle is less than 20 ° or more than 80 °
通過上述實驗結果確認，本發明的蝕刻液組合物不僅在單側蝕刻距離、殘渣、蝕刻速度、經時穩定性和再吸附的有無的所有方面優異，而且在包含銀的金屬膜的蝕刻時具有形成蝕刻後的錐角的效果。 From the above experimental results, it was confirmed that the etching solution composition of the present invention is not only excellent in all aspects of one-sided etching distance, residue, etching speed, stability over time, and presence or absence of re-adsorption, but also has properties in etching a metal film containing silver. Effect of forming taper angle after etching.
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2015
- 2015-11-10 KR KR1020150157637A patent/KR102433385B1/en active IP Right Grant
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2016
- 2016-03-30 TW TW105110057A patent/TWI636157B/en active
- 2016-03-31 JP JP2016070480A patent/JP6669566B2/en active Active
- 2016-04-15 CN CN201610236340.3A patent/CN106676526A/en active Pending
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| US20030022518A1 (en) * | 2001-03-29 | 2003-01-30 | Sony Corporation; St Liquid Crystal Display Corporation; And Mitsubishi Chemical Corporation | Etching method and etching liquid |
| CN103000509A (en) * | 2011-09-09 | 2013-03-27 | 东友精细化工有限公司 | Method for manufacturing display device and etching solution composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6669566B2 (en) | 2020-03-18 |
| KR102433385B1 (en) | 2022-08-17 |
| KR20170054908A (en) | 2017-05-18 |
| CN106676526A (en) | 2017-05-17 |
| TW201716632A (en) | 2017-05-16 |
| JP2017092440A (en) | 2017-05-25 |
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