TWI613329B - Method for manufacturing display device and an etching solution composition for metal layer containing copper/metal oxide layer - Google Patents

Abstract

Disclosed are a method for manufacturing a display device and an etching solution composition for a copper metal layer / metal oxide layer used in the above method. This etching solution composition for a copper metal layer / metal oxide layer is used to simultaneously etch a data metal layer including a copper metal layer and an oxide semiconductor layer including a metal oxide layer, which in turn performs its patterning so that A semiconductor pattern and a source pattern including a data line, a source, and a drain are formed. Therefore, the progressive composition is effectively applied to a method for manufacturing a display device, and the productivity and reliability of the thin film transistor and the display device are improved.

Description

Method for manufacturing display device and etchant composition for metal layer containing copper / metal oxide layer

Related applications

This application claims the priority of Korean Patent Application No. 10-2011-0091917 filed with the Korean Intellectual Property Office on September 9, 2011, the entire disclosure of which is incorporated herein by reference.

The present invention relates to a method for manufacturing a display device using an etching solution composition for simultaneously etching a copper-based metal layer ("copper metal layer") and an oxide semiconductor layer. The oxide semiconductor layer is made of a metal oxide layer. Composition, and an etching solution composition for a copper metal layer / metal oxide layer of the display device.

A representative electronic circuit that drives any kind of semiconductor device and flat display device is a thin film transistor (TFT). Typically, a metal thin film as a wiring material for gates and data is formed on a substrate, a photoresist is prepared on a selected region on the metal thin film, and the metal thin film is etched with the photoresist as a mask to typically etch the metal thin film. Provide traditional manufacturing process for TFT.

Although a single mask with a desired pattern is routinely used to etch a metal layer, in order to minimize the use of relatively expensive masks while simplifying the process, it is often only recently used Use a mask to etch at least two or more metal layers. However, even if a single mask is used, if the mask is applied to a metal layer to be etched having different characteristics, the layers are subjected to different etching modes for the metal layer, thus causing substantial difficulties in reducing the number of processes. .

The circuit materials used for gates and data are typically metal films containing only copper or copper alloys and additional metal oxide layers with excellent interface adsorption to them, where copper has suitable electrical conductivity and low resistance. In this regard, due to the different properties of the two metal layers, it is difficult for these metal layers to be sufficiently etched by using a single etching process.

Therefore, an object of the present invention is to provide a method for manufacturing a display device, which ensures improved productivity and reliability in a manufacturing process.

Another object of the present invention is to provide an etching solution composition for a copper metal layer / metal oxide layer used in a method for manufacturing a display device as described above.

To achieve the above object, the present invention provides the following.

(1) A method for manufacturing a display device, comprising: forming a gate pattern including a gate line and a gate on a substrate; and providing an oxide on the substrate having the gate pattern formed thereon Material semiconductor layer, wherein the semiconductor layer includes a metal oxide layer; a data metal layer is provided on the oxide semiconductor layer, wherein the data metal layer includes a copper metal layer; an etching solution composition is used, and The data metal layer and the oxide semiconductor layer are completely etched to pattern the data metal layer and the oxide semiconductor layer to form a source including a semiconductor pattern, a data line, a source, and a drain. A pattern; and a pixel electrode electrically connected to the drain, wherein the etching solution composition includes: 0.5 to 20% by weight of persulfate, 0.01 to 2% by weight of a monofluoro compound, and 1 to 10% by weight of Inorganic acids, 0.5 to 5% by weight of cyclic amine compounds, 0.001 to 5% by weight of chlorine compounds, 0.1 to 10% by weight of organic acids, salts or mixtures thereof, and water forming the remaining components of the composition .

(2) The composition according to the above item (1), the copper metal layer is a single copper layer, and the single copper layer includes a group selected from the group consisting of copper, its nitrides, and oxides to One of them; a copper alloy layer comprising a group selected from the group consisting of aluminum, magnesium, calcium, titanium, silver, chromium, manganese, iron, zirconium, niobium, molybdenum, palladium, hafnium, tantalum, and tungsten At least one of the group and at least one selected from the group consisting of copper, its nitride and oxide; or a thin plate thereof.

(3) The composition according to the above item (2), wherein the copper alloy layer is a thin film containing copper and manganese.

(4) The composition according to the above item (1), wherein the metal oxide layer comprises a material selected from the group consisting of zinc, tin, cadmium, gallium, aluminum, beryllium, magnesium, calcium, strontium, barium, radium, thallium, thallium, At least two of the group consisting of indium, yttrium, lanthanum, hafnium, titanium, zirconium, hafnium, tantalum, and furnace.

(5) The composition according to the above item (4), wherein the metal oxide layer is a three-component thin film, and the three-component thin film includes a material selected from , Strontium, barium, radium, thallium, thorium, yttrium, lanthanum, thorium, titanium, zirconium, hafnium, tantalum, and furnaces, and indium and zinc.

(6) The composition according to the above item (1), the data metal layer comprises a copper alloy layer and a single copper layer provided on the copper alloy layer.

(7) The composition according to the above item (1), the data metal layer includes a copper alloy layer, a single copper layer provided on the copper alloy layer, and another copper layer provided on the single copper layer. A copper alloy layer.

(8) An etching solution composition for a copper metal layer / metal oxide layer, comprising: 0.5 to 20% by weight of persulfate; 0.01 to 2% by weight of a monofluoro compound; 1 to 10% by weight of an inorganic acid 0.5 to 5% by weight of a monocyclic amine compound; 0.001 to 5% by weight of a monochloride compound; 0.1 to 10% by weight of an organic acid, a salt or mixture thereof; and water forming the remaining ingredients of the composition.

(9) The composition according to the above item (8), wherein the persulfate is at least one selected from the group consisting of ammonium persulfate, sodium persulfate, and potassium persulfate.

(10) The composition according to the above item (8), wherein the fluorine compound is selected Free fluoric acid, ammonium fluoride, ammonium difluoride, ammonium fluoborate, potassium fluoride, potassium difluoride, potassium fluoborate, sodium fluoride, sodium difluoride, aluminum fluoride, fluoboric acid, lithium fluoride, and At least one of the groups consisting of calcium fluoride.

(11) The composition according to the above item (8), wherein the inorganic acid is at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, and perchloric acid.

(12) The composition according to the above item (8), wherein the cyclic amine compound is selected from the group consisting of 5-aminotetrazole, tolyltriazole, benzotriazole, and methylbenzotriazole At least one of the group consisting of an imidazole compound, an indole compound, a purine compound, a pyrazole compound, a pyridine compound, a pyrimidine compound, a pyrrole compound, a pyrrolidine compound, and a pyrroline compound.

(13) The composition according to the above item (8), wherein the chlorine compound is at least one selected from the group consisting of chloric acid, sodium chloride, potassium chloride, and ammonium chloride.

(14) The composition according to the above item (8), wherein the organic acid is selected from the group consisting of acetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, butyric acid, citric acid, isocitric acid, formic acid, and gluconic acid. , Glycolic acid, malonic acid, oxalic acid, valeric acid, sulfobenzoic acid, succinic acid, sulfosuccinic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid, and acrylic acid At least one of them.

(15) The composition according to the above item (8), wherein the salt is a potassium salt, a sodium salt, or an ammonium salt.

(16) The composition according to the above item (8), further comprising 0.05 to 3% by weight of a copper salt.

(17) The composition according to the above item (16), wherein the copper salt is at least one selected from the group consisting of copper nitrate, copper sulfate, and copper ammonium phosphate.

(18) The composition according to the above item (8), wherein the copper metal layer is a single copper layer, and the single copper layer includes at least one selected from the group consisting of copper, a nitride, and an oxide thereof. A copper alloy layer, the copper alloy layer comprising a member selected from the group consisting of aluminum, magnesium, calcium, titanium, silver, At least one of the group consisting of chromium, manganese, iron, zirconium, niobium, molybdenum, palladium, hafnium, tantalum and tungsten, and at least one selected from the group consisting of copper, its nitrides and oxides; Or one of its sheets.

(19) The composition according to the above item (8), wherein the metal oxide layer contains a material selected from the group consisting of zinc, tin, cadmium, gallium, aluminum, beryllium, magnesium, calcium, strontium, barium, radium, thallium, thallium, At least two of the group consisting of indium, yttrium, lanthanum, hafnium, titanium, zirconium, hafnium, tantalum, and furnace.

(20) The composition according to the above item (8), the metal oxide layer is a three-component thin film, and the three-component thin film includes a material selected from the group consisting of tin, cadmium, gallium, aluminum, beryllium, magnesium, and calcium , Strontium, barium, radium, thallium, thorium, yttrium, lanthanum, thorium, titanium, zirconium, hafnium, tantalum, and furnaces, and indium and zinc.

According to the method for manufacturing a display device of the present invention, a data metal layer having a copper metal layer and an oxide semiconductor layer having a metal oxide layer can be simultaneously patterned, thereby simplifying the manufacturing process. In addition, it is possible to prevent the oxide semiconductor layer from being overcut. Therefore, the productivity and reliability of the thin film transistor and the display device during the manufacturing process can be improved.

DE‧‧‧ Drain

DL‧‧‧Data Line

ES‧‧‧ Etch barrier

GE‧‧‧Gate

GL‧‧‧Gate line

SE‧‧‧Source

SW‧‧‧ Thin Film Transistor

10‧‧‧Source area

20‧‧‧ Drain area

30‧‧‧Source line area

40‧‧‧passage area

100‧‧‧ display device

110‧‧‧ substrate

120‧‧‧Gate insulation

130‧‧‧oxide semiconductor layer

132‧‧‧Semiconductor pattern

140‧‧‧ data metal layer

152‧‧‧Photoresist pattern

160‧‧‧ passivation layer

170‧‧‧pixel electrode

The above and other objects, features, and advantages of the present invention will be more clearly understood from the following detailed description combined with the accompanying drawings, wherein: FIG. 1 is a plan view of an example display device; and FIG. 2 is taken along A cross-sectional view of a line II ′ shown in FIG. 1 and FIGS. 3 to 5 are cross-sectional views explaining a method of manufacturing a display device according to an example of the present invention.

The invention provides a method for manufacturing a display device having a copper metal layer / metal oxide layer, and further, an etching solution composition for the copper metal layer / metal oxide layer, the etching solution composition is Application to the method of manufacturing a display device as described above.

Hereinafter, the present invention will be described in more detail.

Etching solution composition

The etching solution composition of the present invention is used to simultaneously etch a copper metal layer and a metal oxide layer.

The etching solution composition of the present invention may include: persulfate; fluorine compounds; inorganic acids; cyclic amine compounds; chlorine compounds; organic acids, salts or mixtures thereof; and water.

More specifically, the progressive composition may include 0.5 to 20% by weight of persulfate; 0.01 to 2% by weight of a fluoro compound; 1 to 10% by weight of an inorganic acid; and 0.5 to 5% by weight of a cyclic amine Compounds; 0.001 to 5% by weight of chlorine compounds; 0.1 to 10% by weight of organic acids, salts or mixtures thereof; and water in the remainder of the total weight of the composition.

Persulfate is the main component used to etch the copper metal layer. Specific examples thereof may include ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ), potassium persulfate (K ₂ S ₂ O ₈ ), or the like, which may be Used alone or in combination with two or more of them.

The persulfate may be included in an amount of 0.5 to 20% by weight in a total of 100% by weight of the etching solution composition. If the content of persulfate is less than 5% by weight, the copper metal layer is sometimes not etched or may have a low etching rate. When the content is more than 20% by weight, the overall etching is performed very quickly (that is, the etching rate is high), which in turn causes difficulty in controlling the etching process.

The fluorine compound is a compound that may be dissociated by fluorine ions or polyatomic fluorine ions in the composition of the etching solution, and is a main component for removing residues generated during the etching and increasing the etching rate of the copper metal layer. The type of fluorine compound is not particularly limited, but may include, for example: fluoric acid (HF), ammonium fluoride (NH ₄ F), ammonium difluoride (NH ₄ HF ₂ ), ammonium fluoborate (NH ₄ BF ₄ ) , Potassium fluoride (KF), potassium difluoride (KHF ₂ ), potassium fluoride borate (KBF ₄ ), sodium fluoride (NaF), sodium difluoride (NaHF ₂ ), aluminum fluoride (AlF ₃ ), fluorine Boric acid (HBF ₄ ), lithium fluoride (LiF), calcium fluoride (CaF ₂ ), or the like may be used alone or as a mixture of two or more thereof.

The fluorine compound may be included in an amount of 0.01 to 2% by weight in a total of 100% by weight of the etching solution composition. If the content of the fluorine compound is less than 0.01% by weight, the metal oxide layer Has a reduced etch rate to cause residue generation. When the content exceeds 2% by weight, the metal oxide layer is over-etched to cause the oxide semiconductor layer to "peel off" from the substrate.

Inorganic acid is an oxidation aid to etch copper metal layers and metal oxide layers. Specific examples thereof may include nitric acid, sulfuric acid, phosphoric acid, perchloric acid, and the like, which are used alone or as a mixture of two or more thereof.

The inorganic acid may be included in an amount of 1 to 10% by weight in a total of 100% by weight of the etching solution composition. If the content of the inorganic acid is less than 1% by weight, the etching rate of the copper metal layer or the metal oxide layer is reduced to cause a poor etching profile, and a residue may remain. When the content exceeds 10% by weight, excessive etching occurs, the photoresist includes a crack, and the etching solution composition penetrates into the crack, resulting in a short circuit of the line.

The cyclic amine compound is a component for controlling the etching rate and suppressing over-etching during the etching of the copper metal layer, thereby reducing the etching loss (critical dimension, CD). Specific examples thereof may include 5-aminotetrazole, tolyltriazole, benzotriazole, methylbenzotriazole, imidazole compound, indole compound, purine compound, pyrazole compound, pyridine Compounds, pyrimidine compounds, pyrrole compounds, pyrrolidine compounds, pyrroline compounds, and the like are used alone or as a mixture of two or more thereof.

The cyclic amine compound may be included in an amount of 0.5 to 5% by weight, preferably 0.5 to 3% by weight, in a total of 100% by weight of the etching solution composition. Within such a content range, a desired copper etching rate and taper angle can be provided, and side etching can be controlled. If the content is less than 0.5% by weight, it is difficult to properly control the etching rate of the copper metal layer, resulting in excessive etching. When the content exceeds 5% by weight, the etching rate of the copper metal layer is reduced, and the etching time of the process is prolonged, thereby reducing productivity.

Chlorine compound is a compound that may dissociate into chloride ions in the composition of the etching solution. It is an oxidation aid to etch the copper metal layer and is also used to compete with persulfate for the etching of the copper metal layer. The etching rate and the composition of the cone angle are controlled so that the persulfate is locally overly corroded to the copper metal layer. Specific examples thereof may include hydrochloric acid (HCl), sodium chloride (NaCl), potassium chloride (KCl), ammonium chloride (NH ₄ Cl), and the like, which are used alone or as two or more of them. Use as a mixture.

The chlorine compound may be included in an amount of 0.001 to 5% by weight in a total of 100% by weight of the etching solution composition. If the content of the chlorine compound is less than 0.001% by weight, the etching solution may cause local excessive corrosion of the copper metal layer, thereby resulting in deterioration of its quality. When the content exceeds 5% by weight, the number of sheets to be processed is reduced by etching at a desired content, and the etching rate is so fast that a poor etching profile is caused.

Organic acids, their salts, or mixtures are ingredients that ensure a fixed etching profile over time by etching the number of pieces to be processed, so that the cone angle and etching rate of the copper metal layer are controlled, so it provides an idea Etching to the side. In addition, the above components can prevent the chimeric reaction with the etched metal ions from being affected by the composition of the etching solution, and therefore can increase the number of pieces to be processed at a fixed content. Specific examples of organic acids, salts or mixtures thereof may include acetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, butyric acid, citric acid, isocitric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid , Valeric acid, sulfobenzoic acid, succinic acid, sulfosuccinic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid, acrylic acid or the like, alone or as their Two or more mixtures are used. In addition, the salts of organic acids may include, for example, potassium salts, sodium salts, ammonium salts, and the like of the above-mentioned organic acids, which are used alone or as a mixture of two or more thereof.

The organic acid, a salt thereof, or a mixture thereof may be included in an amount of 0.1 to 10% by weight in a total of 100% by weight of the etching solution composition. If the content of the organic acid is less than 0.1% by weight, it is difficult to maintain a constant etching profile with respect to the number of sheets to be processed, and the effect on increasing the number of sheets to be processed is small. When the content is more than 10% by weight, excessive etching occurs and side etching is increased, and further effects of increasing the number of sheets to be processed cannot be expected, and therefore bear economic disadvantages.

The etching solution composition may further include a copper salt.

Copper salts control CD variation (skew). Specific examples may include copper nitrate, Copper sulfate, copper ammonium phosphate, and the like are used alone or as a mixture of two or more thereof.

The copper salt may be included in an amount of less than 3% by weight, preferably 0.05 to 3% by weight, in a total of 100% by weight of the etching solution composition. If the content of the copper salt exceeds 3% by weight, the oxidation efficiency of the main oxidant is reduced and the number of sheets to be treated is reduced.

Water is a solvent, and its type is not particularly limited, however, it may include deionized distilled water, and more particularly, deionized distilled water for semiconductor processes, and its specific resistance may be 18 MΩ / cm or higher.

The water may include the remainder of the etching solution composition as a total of 100% by weight.

The etching solution composition of the present invention may further include at least one additive, such as an etching modifier, a surfactant, a metal ion release agent (or a chelating agent), a corrosion inhibitor, a pH adjuster, and the like, and the above-mentioned components.

The etching solution composition having the technical configuration as described above is particularly useful for uniformly and simultaneously etching a copper metal layer and a metal oxide layer. Therefore, it is possible to simplify the etching process while improving productivity. In addition, penetration into the bottom of the oxide semiconductor layer is reduced, and the penetration does not cause overcutting in the bottom of the oxide semiconductor layer, thereby preventing peeling of the semiconductor pattern.

The “copper metal layer / metal oxide layer” of the present invention may include, for example, a double thin film including a copper metal layer / metal oxide layer made of a thin plate in this order, and a metal oxide containing metal oxide made of a thin plate in this order. Layer / copper metal layer. In addition, it may include a multilayer metal film including a copper metal layer and a metal oxide layer alternately made into three or more thin plates, for example, a triple film including a copper metal layer / metal oxide layer / copper metal layer, and a metal oxide. Triple film of physical layer / copper metal layer / metal oxide layer, multi-layer film including copper metal layer / metal oxide layer / copper metal layer / metal oxide layer / copper metal layer, or the like. Herein, the thickness of each copper metal layer and the metal oxide layer is not particularly limited.

Similarly, the "copper metal layer" of the present invention is a thin film containing copper in the composition of the thin film, and in particular, may include a single copper layer including a material selected from the group consisting of pure copper and its At least one of the group consisting of a nitride or an oxide. In addition, the copper metal layer may be a copper alloy layer made of a copper alloy, the copper alloy including at least one selected from the group consisting of pure copper, its nitrides, and oxides, and selected from the group consisting of aluminum (Al), Magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), At least one of the group consisting of palladium (Pd), hafnium (Hf), tantalum (Ta), and tungsten (W). In addition, the copper metal layer may be a thin plate including a single copper layer and a copper alloy layer. Hereinafter, the copper metal layer is represented by Cu-X.

As used herein, a "metal oxide layer" is a thin film containing at least two component oxides, such as two to four component oxides, which can be expressed. Herein, A, B, C, and D are different from each other, and each may be zinc (Zn), tin (Sn), cadmium (Cd), gallium (Ga), aluminum (Al), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), thorium (Tl), thallium (Sc), indium (In), yttrium (Y), lanthanum (La), thorium (Ac), titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta) or furnace (Rf), and each of a, b, c, and d is at least 0, provided that at least one of them Both are numbers other than 0. Preferably, the metal oxide layer may include a two-component metal oxide layer. The two-component metal oxide layer contains gallium, which is represented by Ga _a B _b C ₀ D ₀ O, or a three-component metal oxide layer. A metal oxide layer. The three-component metal oxide contains indium and zinc, and is represented by A _a In _b Zn _c D ₀ O. Specific examples thereof may include gallium oxide-zinc oxide (Ga ₂ O ₃ -ZnO, GZO), gallium oxide-indium oxide-zinc oxide (Ga ₂ O ₃ -In ₂ O ₃ -ZnO, GIZO), hafnium oxide- Indium oxide-zinc oxide (HfO ₂ -In ₂ O ₃ -ZnO, HIZO) and the like. The thickness of the metal oxide layer may range from 300 to 500.

Manufacturing of display devices

The present invention can provide a method for manufacturing a display device using the etching solution composition as described above.

FIG. 1 is a plan view of a display device of Example 1, and FIG. 2 is a cross-sectional view taken along a line I-I 'shown in FIG.

The display device 100 may include a gate line GL, a data line DL, and a thin film transistor SW. And the pixel electrode 170, and, in addition, the gate insulating layer 120 and the passivation layer 160.

A method of manufacturing a display device may include: forming a gate pattern including a gate line and a gate on a substrate; and providing an oxide semiconductor layer on the substrate having the gate pattern formed thereon, wherein the semiconductor layer includes a metal An oxide layer; providing a data metal layer on the oxide semiconductor layer, wherein the data metal layer includes a copper metal layer; and using the etching solution composition of the present invention, the data metal layer and the oxide are simultaneously and completely etched A semiconductor layer to pattern the data metal layer and the oxide semiconductor layer so as to form a source pattern including a semiconductor pattern, a data line, a source, and a drain; and a pixel electrode electrically connected to the drain.

3 to 5 are sectional views explaining a method of manufacturing a display device according to an example of the present invention, respectively.

First, as shown in FIG. 3, a gate pattern having a gate line GL and a gate GE is formed on a substrate 110, and a gate insulating layer is provided on the substrate 110 having the gate pattern formed thereon. 120.

The gate pattern may be formed by providing a gate metal layer on the substrate 110 and patterning the gate metal layer by etching. That is, the gate metal layer may contain copper.

Then, as shown in FIG. 4, the oxide semiconductor layer 130 and the data metal layer 140 provided in the metal oxide layer are sequentially provided on the substrate 110 including the gate insulating layer 120.

The oxide semiconductor layer 130 may include a metal oxide layer including a material selected from the group consisting of zinc, tin, cadmium, gallium, aluminum, beryllium, magnesium, calcium, strontium, barium, radium, scandium, thallium, indium, yttrium, At least two of the group consisting of lanthanum, hafnium, titanium, zirconium, hafnium, tantalum, and furnace. For example, the metal oxide may include gallium oxide-indium oxide-zinc oxide (Ga ₂ O ₃ -In ₂ O ₃ -ZnO, GIZO), hafnium oxide-indium oxide-zinc oxide (HfO ₂ -In ₂ O ₃ -ZnO) , HIZO) and so on. The thickness of the oxide semiconductor layer 130 may range from 300 to 500.

An etch stop layer ES may be provided between the oxide semiconductor layer 130 and the data metal layer 140 so as to overlap with the gate electrode GE.

The etch stop layer ES may be formed by providing an insulating layer on the oxide semiconductor layer 130 and then patterning the insulating layer through etching. The insulating layer may be made of silicon dioxide or silicon nitride, and the etch stop layer ES may be formed by removing all parts except a part overlapping with a part where the gate electrode GE is formed.

The data metal layer 140 may include a copper metal layer, in particular, an alloy containing copper and manganese and a copper alloy layer stably provided on the oxide semiconductor layer 130 because it has excellent interfacial adsorption. The data metal layer 140 may be substantially a single thin film composed of a copper alloy layer, and includes the copper alloy layer and a single copper layer formed thereon. Alternatively, it may include a copper alloy layer, a single copper layer provided on the copper alloy layer, and another copper alloy layer provided on the single copper layer. The thickness of the data metal layer 140 may range from 2,000 to 4,000.

Next, as shown in FIG. 5, a photoresist pattern 152 is formed on the data metal layer 140. The photoresist pattern 152 may be formed on the source region 10, the drain region 20 and the source line region 30, and the data metal layer 140 is exposed from other regions including the channel region 40.

The photoresist pattern 152 is used as an etching prevention film and a progressive etching solution composition, and the data metal layer 140 and the oxide semiconductor layer 130 can be etched simultaneously and completely.

Through the simultaneous and complete etching of the data metal layer 140 and the oxide semiconductor layer 130, a source SE and a drain DE are provided on the source region 10 and the drain region 20, respectively. Similarly, the data line DL is provided to the source line region 30. When the source pattern is formed as described above, the semiconductor pattern 132 is formed. The data metal layer 140 in the channel region 40 is exposed by the photoresist pattern 152 and is removed by the etching solution composition. At the same time, due to the etch stop layer ES, the semiconductor pattern 132 in the channel region 40 may remain without being removed.

By removing the photoresist pattern 152 using a removal composition, a thin film transistor SW including a gate electrode GE, a semiconductor pattern 132, an etch stop layer ES, a source electrode SE, and a drain electrode DE can be provided on the substrate 110.

After that, a passivation layer 160 is provided on the substrate 110 prepared as described above, and then the passivation layer 160 is patterned to form a contact hole, through which the drain electrode DE is exposed. The end. Subsequently, a transparent electrode layer is provided on the substrate 110 having the contact hole formed thereon, and then the transparent electrode layer is patterned to form a pixel electrode 170 electrically connected to the drain electrode DE via the contact hole. .

According to the above method, the display device 100 shown in FIG. 1 can be manufactured. In particular, the etching solution composition of the present invention can be used to simultaneously and completely etch the data metal layer 140 having a copper metal layer and an oxide semiconductor layer 130 composed of a metal oxide layer, thereby simplifying the etching process and improving productivity. .

Hereinafter, preferred embodiments will be described to more specifically understand the present invention with reference to examples and comparative examples. However, those skilled in the art will appreciate that such specific embodiments are provided for illustrative purposes only and are not limited to the subject matter to be protected as disclosed in the detailed description and the examples of accompanying patent applications. Therefore, it will be apparent to those skilled in the art that, within the scope and spirit of the present invention, various alternatives and modifications of the specific embodiments are possible, and are fully included in the scope of the accompanying patent application. In the range.

example

Example 1

10% by weight of sodium persulfate (SPS), 1% by weight of ammonium difluoride (ABF), 4% by weight of nitric acid (HNO ₃ ), 1.5% by weight of 5-aminotetrazole (ATZ), 1 Sodium chloride (NaCl) by weight, 3% by weight acetic acid, and water in the remaining portion of the total 100% by weight mixture were mixed together to prepare 180 kg of an etching solution composition.

Comparative Examples 1 to 4

The same procedure described in Example 1 was repeated, except that the individual ingredients and contents listed in Table 1 below were used. Herein, the content is expressed in% by weight.

Table 1

Experiment example

<Evaluation of Etching Properties>

By providing an oxide semiconductor layer (the oxide semiconductor layer sequentially includes a metal oxide layer containing hafnium oxide-indium oxide-zinc oxide (HfO ₂ -In ₂ O ₃ -ZnO, HIZO), and copper containing copper and manganese An alloy layer is then formed on the copper alloy layer in a desired form to prepare a substrate. The substrate is prepared by cutting a sample with a diamond knife, and each sample has a size of 550 mm × 650 mm.

The prepared etching solution composition was placed in a tester (ETCHER (TFT), SEMES company) in an injection etching mode, and heated to a preset temperature of 30 ° C. Then, after the temperature reaches 30 ± 0.1 ° C, an etching process is performed. During the total etch time with reference to the EPD (Endpoint Detector) time, 200% over-etching was performed. Each sample was introduced into the test instrument, and injection was started. After the etching is completed, the processed sample is removed from the instrument, rinsed with deionized water, dried using a hot hair dryer, and the photoresist is removed from the dried sample using a photoresist remover. After rinsing and drying, a scanning electron microscope (SEM) (S-4700, Hitachi) evaluated the etching properties of the sample, including side etch loss (critical dimension (CD)), cone angle, metal film damage, etc.

<Evaluation criteria>

◎ -Excellent (CD skew 1 μm, cone angle: 40 to 60 °).

○ -Excellent (1 μm <CD deviation 1.5 μm, cone angle: 30 to 60 °).

Δ-Good (1.5 µm <CD deviation 2 µm, cone angle: 30 to 60 °).

× -failure (loss of metal film or appearance of residue).

As shown in Table 2, it was confirmed that, compared with the etching solution composition according to Comparative Examples 1 to 4, the etching solution composition prepared in Example 1 of the present invention (which contains: persulfate; fluorine compounds; Inorganic acids; cyclic amine compounds; chlorine compounds; organic acids, their salts or mixtures; and the rest of the water in its optimal content) can be excellent when the copper metal layer and metal oxide layer are completely etched Etching properties.

DE‧‧‧ Drain

DL‧‧‧Data Line

ES‧‧‧ Etch barrier

GE‧‧‧Gate

GL‧‧‧Gate line

SE‧‧‧Source

SW‧‧‧ Thin Film Transistor

10‧‧‧Source area

20‧‧‧ Drain area

30‧‧‧Source line area

40‧‧‧passage area

110‧‧‧ substrate

120‧‧‧Gate insulation

132‧‧‧Semiconductor pattern

152‧‧‧Photoresist pattern

Claims (19)

A method for manufacturing a display device includes: forming a gate pattern including a gate line and a gate on a substrate; and providing an oxide semiconductor layer on the substrate having the gate pattern formed thereon Wherein the semiconductor layer includes a metal oxide layer; a data metal layer is provided on the oxide semiconductor layer, wherein the data metal layer includes a copper metal layer; and an etching solution composition is used to simultaneously and completely etch The data metal layer and the oxide semiconductor layer to pattern the data metal layer and the oxide semiconductor layer to form a source pattern including a semiconductor pattern, a data line, a source, and a drain; and A pixel electrode electrically connected to the drain is provided, wherein the etching solution composition comprises: 0.5 to 20% by weight of a persulfate; and 0.01 to 2% by weight of a monofluoro compound based on the total weight of the etching solution composition. ; 1 to 10% by weight of an inorganic acid; 0.5 to 5% by weight of a monocyclic amine compound; 0.001 to 5% by weight of a monochloride compound; 0.1 to 10% by weight of an organic acid, a salt thereof or a mixture thereof A copper salt; 0.05 to 3% by weight; and water that forms the remaining ingredients of the composition. The method of claim 1, wherein the copper metal layer is a single copper layer, a copper alloy layer, or a thin plate of the single copper layer and the copper alloy layer, and the single copper layer includes a layer selected from copper. At least one of the group consisting of its nitrides and oxides, the copper alloy layer comprises a material selected from the group consisting of aluminum, magnesium, calcium, titanium, silver, chromium, manganese, iron, zirconium, niobium, molybdenum, palladium, hafnium, At least one of the group consisting of tantalum and tungsten and at least one selected from the group consisting of copper, its nitride and oxide. The method of claim 2, wherein the copper alloy layer is a thin film containing copper and manganese. The method of claim 1, wherein the metal oxide layer comprises a material selected from the group consisting of zinc, tin, cadmium, gallium, aluminum, beryllium, magnesium, calcium, strontium, barium, radium, thallium, thallium, indium, and yttrium. , Lanthanum, hafnium, titanium, zirconium, hafnium, tantalum, and furnaces. The method of claim 4, wherein the metal oxide layer is a three-component thin film, and the three-component thin film includes a material selected from the group consisting of tin, cadmium, gallium, aluminum, beryllium, magnesium, calcium, strontium, At least one of the group consisting of barium, radium, thallium, thorium, yttrium, lanthanum, osmium, titanium, zirconium, hafnium, tantalum, and furnace, and indium and zinc. The method of claim 1, wherein the data metal layer comprises a copper alloy layer and a single copper layer provided on the copper alloy layer. The method of claim 1, wherein the data metal layer includes a copper alloy layer, a single copper layer provided on the copper alloy layer, and another copper alloy provided on the single copper layer. Floor. An etching solution composition for a copper metal layer / metal oxide layer. Based on the total weight of the etching solution composition, the etching solution composition includes: 0.5 to 20% by weight of persulfate; 0.01 to 2% by weight of Monofluoro compound; 1 to 10% by weight of inorganic acid; 0.5 to 5% by weight of monocyclic amine compound; 0.001 to 5% by weight of monochloride; 0.1 to 10% by weight of organic acid, a salt or a mixture thereof; 0.05 to 3% by weight of a copper salt; and water forming the remainder of the composition. The composition according to item 8 of the scope of patent application, wherein the persulfate is at least one selected from the group consisting of ammonium persulfate, sodium persulfate, and potassium persulfate. The composition according to item 8 of the scope of patent application, wherein the fluorine compound is selected from the group consisting of fluoric acid, ammonium fluoride, ammonium difluoride, ammonium fluoroborate, potassium fluoride, potassium difluoride, potassium fluoroborate, fluorine At least one of the group consisting of sodium chloride, sodium difluoride, aluminum fluoride, fluoboric acid, lithium fluoride, and calcium fluoride. The composition according to item 8 of the scope of patent application, wherein the inorganic acid is at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, and perchloric acid. The composition according to item 8 of the scope of patent application, wherein the cyclic amine compound is selected from the group consisting of 5-aminotetrazole, tolyltriazole, benzotriazole, methylbenzotriazole, imidazole At least one of the group consisting of a compound, an indole compound, a purine compound, a pyrazole compound, a pyridine compound, a pyrimidine compound, a pyrrole compound, and a pyrroline compound. The composition according to item 8 of the scope of patent application, wherein the chloride is at least one selected from the group consisting of chloric acid, sodium chloride, potassium chloride, and ammonium chloride. The composition according to item 8 of the scope of the patent application, wherein the organic acid is selected from the group consisting of acetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, butyric acid, citric acid, isocitric acid, formic acid, gluconic acid, and ethanol Acid, malonic acid, oxalic acid, valeric acid, sulfobenzoic acid, succinic acid, sulfosuccinic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid, and acrylic acid At least one of them. The composition according to item 8 of the scope of patent application, wherein the salt is a potassium salt, a sodium salt, or an ammonium salt. The composition according to item 8 of the scope of patent application, wherein the copper salt is selected from the group consisting of copper nitrate, sulfuric acid At least one of the group consisting of copper and copper ammonium phosphate. The composition according to item 8 of the scope of patent application, wherein the copper metal layer is a single copper layer, a copper alloy layer, or a thin plate of the single copper layer and the copper alloy layer, and the single copper layer comprises a material selected from At least one of the group consisting of copper, its nitrides, and oxides, and the copper alloy layer comprises a member selected from the group consisting of aluminum, magnesium, calcium, titanium, silver, chromium, manganese, iron, zirconium, niobium, molybdenum, palladium, hafnium At least one of the group consisting of tantalum, tantalum, and tungsten, and at least one selected from the group consisting of copper, its nitrides, and oxides. The composition according to item 8 of the patent application scope, wherein the metal oxide layer comprises a material selected from the group consisting of zinc, tin, cadmium, gallium, aluminum, beryllium, magnesium, calcium, strontium, barium, radium, thallium, thallium, indium, At least two of the group consisting of yttrium, lanthanum, hafnium, titanium, zirconium, hafnium, tantalum, and furnace. The composition according to item 8 of the scope of patent application, wherein the metal oxide layer is a three-component thin film, and the three-component thin film includes a material selected from the group consisting of tin, cadmium, gallium, aluminum, beryllium, magnesium, calcium, and strontium. , Barium, radium, thallium, thallium, yttrium, lanthanum, hafnium, titanium, zirconium, hafnium, tantalum, and furnace, and indium and zinc.