KR20200011394A - Etchant composition and method of manufacturing wiring substrate using the same - Google Patents

Abstract

The present invention relates to an etchant composition and a manufacturing method of a wiring substrate. The etchant composition comprises: peroxysulfate; a cyclic amine compound; a fluorine-containing compound; a chlorine-containing compound; inorganic acid; organic acid or an organic acid salt; a first amphoteric compound having a carboxyl group; and a second amphoteric compound different from the first amphoteric compound and having a sulfone group.

Description

Etching composition and manufacturing method of wiring board using same {ETCHANT COMPOSITION AND METHOD OF MANUFACTURING WIRING SUBSTRATE USING THE SAME}

The present invention relates to an etching solution composition and a method for producing a wiring board.

The importance of the display device is increasing with the development of multimedia. In response to this, various display devices, such as a liquid crystal display (LCD) and an organic light emitting diode display (OLED), have been developed.

The display device may implement image display and color display by including a plurality of pixels representing different colors. In order for each pixel of the display device to operate independently of each other, the display device may include a wiring board including a driving signal line, a thin film transistor, and the like for transmitting a driving signal.

The drive signal wiring of the wiring board requires low electrical resistance, high thermal stability, easy processability and excellent adhesion, and the like, in order to satisfy these characteristics, the driving signal wiring can be formed in a laminated structure of a plurality of layers of different materials. Can be.

The drive signal wiring of the wiring board is required to have an appropriate shape or profile as well as the physical properties of the material itself such as electrical resistance, thermal stability, processability and adhesion. For example, if the lateral inclination angle of the driving signal wiring is too large, the coverage difference may occur in the components stacked on the upper surface due to the sharp step formed by the wiring. Alternatively, when the side inclination angle of the drive signal wire is too small, the function as the drive signal wire cannot be performed completely.

On the other hand, when the drive signal wiring is formed in a laminated structure of a plurality of layers, the etching characteristics of each layer may be different, and thus the degree of etching may be different, and profile control of the drive signal wiring is more difficult.

The problem to be solved by the present invention is to provide an etchant composition that is easy to control the profile of the drive signal wiring.

Another problem to be solved by the present invention is to provide a method for manufacturing a wiring board including drive signal wiring having further improved processability and characteristics such as low electrical resistance and high thermal stability.

The objects of the present invention are not limited to the above-mentioned technical problems, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

Etch liquid composition according to an embodiment of the present invention for solving the above problems 1.0 wt% to 20 wt% peroxysulfate, 0.1 wt% to 5.0 wt% cyclic amine compound, 0.01 wt% to 2.0 wt% fluorine-containing compound %, 0.01% to 5.0% by weight of chlorine compound, 0.5% to 10.0% by weight of inorganic acid, 0.5% to 8% by weight of organic acid or organic acid salt, 0.5% to 1.5% by weight of first amphoteric compound having carboxyl group and And 0.5 wt% to 5.0 wt% of the second amphoteric compound having a sulfone group, which is different from the first amphoteric compound, wherein a weight ratio of the first amphoteric compound and the second amphoteric compound is 2 : 1 to 1: 5, and the weight ratio of the first amphoteric compound and the organic acid or organic acid salt in the above range is 2: 1 to 1: 8.

In addition, the content of the peroxide sulfate may be greater than the content of the first amphoteric compound.

The first amphoteric compound may include one or more of the compounds represented by the following Formula Ia to Formula Ie.

<Formula Ia>

<Formula Ib>

<Formula Ic>

<Formula Id>

<Formula Ie>

In addition, the second amphoteric compound may include one or more of the compounds represented by the following Chemical Formula IIa to the following Chemical Formula IIc.

<Formula IIa>

<Formula IIb>

<Formula IIc>

In addition, the peroxide sulfate is included in 1.0 wt% to 20.0 wt%, the cyclic amine compound is included in 0.1 wt% to 5.0 wt%, the first amphoteric compound is included in 0.01 wt% to 10.0 wt% The second amphoteric compound may be included in an amount of 0.1 wt% to 7.0 wt%.

The persulfate may include potassium persulfate (K ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ) or ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ).

The cyclic amine compound is 5-aminotetrazole, 1-methyl-5-aminotetrazole, 5-methyltetrazole, 1-ethyl -5-aminotetrazole, imidazole, indole, purine, pyrazole, pyridine, pyrimidine, pyrrole (pyrrole), pyrrolidine (pyrrolidine), and pyrroline (pyrroline) may include one or more.

The fluorine-containing compound may include one or more of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride and potassium bifluoride.

The chlorine-containing compound may include one or more of hydrochloric acid, sodium chloride, potassium chloride, ammonium chloride, iron (III) chloride, sodium perchlorate, potassium perchlorate, ethylsulfonyl chloride and methanesulfonyl chloride.

In addition, the inorganic acid may include nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ), phosphoric acid or phosphorous acid (H ₂ PO ₃ , H ₃ PO ₃ ).

The organic acid is acetic acid, formic acid, propenoic acid, butanoic acid, pentanic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, benzoic acid, succinic acid, phthalic acid, salicylic acid, lactic acid, glyceric acid, malic acid, tartaric acid, citric acid and isocitric acid. Including one or more, the organic acid salt may comprise a sodium salt, potassium salt or ammonium salt of the organic acid.

In addition, 0.01 wt% to 5.0 wt% may further include a copper salt.

In addition, the copper salt may include copper sulfate salt, copper chloride salt or copper nitrate salt.

According to another aspect of the present invention, there is provided a method of manufacturing a wiring board, the method including: forming a first wiring layer on a substrate, wherein the forming of the first wiring layer is performed. Forming a first metal layer on the substrate, forming a second metal layer different from the first metal layer on the first metal layer, and patterning the first metal layer and the second metal layer using an etchant composition. Including the step, wherein the etching liquid composition, peroxysulfate (peroxysulfate) 1.0 wt% to 20 wt%, cyclic amine compound 0.1 wt% to 5.0 wt%, fluorine-containing compound 0.01 wt% to 2.0 wt%, chlorine-containing compound 0.01 Wt% to 5.0 wt%, inorganic acid 0.5 wt% to 10.0 wt%, organic acid or organic acid salt 0.5 wt% to 8 wt%, 0.5 wt% to 1 amphoteric compound having carboxyl group .5 wt% and 0.5 wt% to 5.0 wt% of a second amphoteric compound having a sulfone group, which is different from the first amphoteric compound, and wherein the first amphoteric compound and the second amphoteric compound are within the range; The weight ratio of the compound is 2: 1 to 1: 5, and the weight ratio of the first amphoteric compound and the organic acid or organic acid salt within the range is 2: 1 to 1: 8.

The first metal layer may be a titanium layer or a titanium alloy layer, and the second metal layer may be a copper layer or a copper alloy layer.

The method may further include forming a second wiring layer on the substrate before the forming of the first wiring layer, wherein forming the first wiring layer on the second wiring layer to be insulated from the second wiring layer. It may be a step of forming the first wiring layer.

In addition, the second wiring layer may include a titanium or titanium alloy layer and a copper or copper alloy layer stacked on each other.

The side inclination angle of the second wiring layer may be smaller than the side inclination angle of the first wiring layer.

The inclination angle of the side surfaces of the first wiring layer may be 55 degrees to 80 degrees.

The patterning of the first metal layer and the second metal layer using the etchant composition may include forming a mask pattern on the first region and the second region of the first metal layer and the second metal layer. First etching the third region of the first metal layer and the second metal layer that does not overlap the mask pattern using an etchant composition, the mask pattern on the second region of the first metal layer and the second metal layer And removing second etching the second region of the first metal layer and the second metal layer using the etchant composition.

Details of other embodiments are included in the detailed description and drawings.

According to the etching solution composition and the method of manufacturing a wiring board according to an embodiment of the present invention, a wiring board including a driving signal wiring having an excellent profile, for example, an appropriate side inclination angle, may be manufactured.

Effects according to the embodiments of the present invention are not limited by the contents exemplified above, and more various effects are included in the present specification.

1 to 9 are cross-sectional views sequentially illustrating a method of manufacturing a wiring board according to an embodiment of the present invention.

Advantages and features of the present invention, and methods for achieving them will be apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, only the embodiments are to make the disclosure of the present invention complete, and those of ordinary skill in the art to which the present invention belongs. It is provided to fully inform the scope of the invention, and the invention is defined only by the scope of the claims.

When an element or layer is referred to as an 'on' of another element or layer, it includes any case where another element or layer is interposed over or in the middle of another element. On the other hand, when the device is referred to as 'directly on', it means that there is no intervening device or layer in between. Like reference numerals refer to like elements throughout. 'And / or' includes each and all combinations of one or more of the items mentioned.

The spatially relative terms 'below', 'beneath', 'lower', 'above', 'upper' and the like are shown in FIG. It can be used to easily describe the correlation of a device or components with other devices or components. Spatially relative terms are to be understood as terms that include different directions of the device in use in addition to the directions shown in the figures. For example, when the device shown in the figure is reversed, a device described as 'below or beneath' of another device may be placed 'above' of another device. Thus, the exemplary term 'below' may include both directions below and above.

Hereinafter, embodiments of the present invention will be described in detail.

The etchant composition according to the present embodiment may include a peroxysulfate, a cyclic amine compound, a first amphoteric compound having a carboxyl group, and a second amphoteric compound having a sulfone group. As used herein, the term "positive compound" refers to a compound which forms amphoteric ions in an aqueous solution, and which is electrically neutral with a positive and negative electrical property. The etchant composition according to the present embodiment may have excellent batch etching characteristics for copper (Cu) and titanium (Ti), but the present invention is not limited thereto.

The peroxide sulfate may be a staple angle component for a copper layer comprising a copper or a copper alloy comprising a copper component. Examples of the persulfate include potassium persulfate (K ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ) or ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ). The present invention is not limited thereto.

The content of sulfate peroxide may be included in about 1.0% to about 20.0% by weight relative to the total weight of the etching liquid composition. If the peroxide sulfate is included less than 1.0% by weight may not have sufficient etching characteristics for the copper component. For example, when the wiring includes a copper layer and a titanium layer, the titanium layer may be over-etched compared to the copper layer, resulting in poor wiring profile. In addition, when the peroxide sulfate is included in more than 20.0% by weight it may be difficult to control the etching process because the etching rate is excessively increased. For example, when the wiring includes a copper layer and a titanium layer, the copper layer may not be over-etched or a sufficient time for the titanium layer to be etched compared to the titanium layer.

The cyclic amine compound may be an auxiliary etching component that forms an excellent profile by controlling the etching rate with respect to the copper layer including the copper alloy including the copper or copper component and inducing uniform etching of the copper layer. In the present specification, the 'cyclic amine compound' means a cyclic compound having an amine group. For example, it may be an alicyclic heterocyclic compound having an amine group in the ring structure, or an aromatic heterocyclic compound. The ring structure may be a 4-membered hetero ring or a 5-membered hetero ring or a 6-membered hetero ring. The ring structure having the amine group may form a fused ring with another ring structure. The amine group may be a secondary amine (-NH-) or tertiary amine (= N-), but the present invention is not limited thereto.

The cyclic amine compound is 5-aminotetrazole, 1-methyl-5-aminotetrazole, 5-methyltetrazole, 1-ethyl Tetrazole compounds such as -5-amino-5-tetrazole, imidazole, indole, purine, pyrazole, pyridine, pyrimidine (pyrimidine), pyrrole (pyrrole), pyrrolidine (pyrrolidine), and pyrroline (pyrroline) may include one or more of the present invention is not limited thereto.

The content of the cyclic amine compound may be included in about 0.1% to about 5.0% by weight, or about 0.1% to about 2.0% by weight based on the total weight of the etchant composition. When the cyclic amine compound is included in less than 0.1% by weight it may not have the etching rate control characteristics of the copper component and the copper layer may be unevenly etched. For example, when the wiring includes a copper layer and a titanium layer, the copper layer may be over-etched compared to the titanium layer to form a uniform side profile. In addition, when the cyclic amine compound is included in more than 5.0% by weight may reduce the etching characteristics for the copper layer. In addition, the solubility of the cyclic amine compound in the etchant composition may be reduced, thereby decreasing processability.

The first amphoteric compound has a carboxyl group (-COOH) and may be electrically neutral in an aqueous solution. For example, the first amphoteric compound may be a compound having both a carboxyl group and an amine group and neutral in an aqueous solution state. Examples of the first amphoteric compound may include any one of the compounds represented by the following Chemical Formulas Ia to Ie, but the present invention is not limited thereto.

<Formula Ia>

<Formula Ib>

<Formula Ic>

<Formula Id>

<Formula Ie>

The first amphoteric compound may prevent a decrease in the side inclination angle of the copper layer including the copper component even when the number of etching of the etching target wiring using the etchant composition, that is, the wiring board is accumulated. In addition, it can contribute to the improvement of the profile of the titanium layer containing a titanium component.

The first amphoteric compound may be included in about 0.01% to about 10.0%, or about 0.1% to about 5.0% by weight relative to the total weight of the etchant composition. When the first amphoteric compound is included in an amount of 0.01% by weight or more, it may exhibit an effect of reducing the side slope angle of the copper layer and / or improving the profile of the titanium layer. In addition, when the first amphoteric compound is included in an amount of 5.0 wt% or less, a wiring having an improved profile may be formed without decreasing an etching rate with respect to the copper layer and the titanium layer.

The second amphoteric compound has a sulfone group (-SO ₃ H) and may be electrically substantially neutral in an aqueous solution. The second amphoteric compound is a compound different from the first amphoteric compound and may have different functions. For example, the second amphoteric compound may be a compound having both a sulfone group and an amine group and neutral in an aqueous solution state. Examples of the second amphoteric compound may include any one of compounds represented by the following Chemical Formulas IIa to IIc, but the present invention is not limited thereto.

<Formula IIa>

<Formula IIb>

<Formula IIc>

The second amphoteric compound may have a chelating action with metal ions such as copper ions or titanium ions, and may inhibit the metal ions from acting as impurities in the etchant composition. At the same time, it may be an auxiliary etching component for a copper layer comprising a copper or a copper alloy comprising a copper component. Through this, the number of wiring board treatment sheets of the etching liquid composition according to the present embodiment may be increased and processability may be improved.

The second amphoteric compound may be included in about 0.1% to about 7.0%, or about 0.2% to about 5.0% by weight relative to the total weight of the etchant composition. When the second amphoteric compound is included in an amount of 0.1 wt% or more, it exhibits sufficient chelating action and improves the etching rate of the copper layer. In addition, it is possible to exhibit the effect of increasing the number of wiring substrate treatment of the etching liquid composition according to the present embodiment. When the second amphoteric compound is included in an amount of 7.0 wt% or less, it is possible to prevent over-etching of the copper layer and to form a wiring including an improved copper layer.

In some embodiments, the contents of the first amphoteric compound and the second amphoteric compound described above may be in a particular relationship. For example, the weight ratio of the first amphoteric compound to the second amphoteric compound may range from about 2: 1 to about 1: 5. When the first amphoteric compound and the second amphoteric compound satisfy the content ratio within the above range, the etching rate of the etchant composition may be further improved, and further, the superior properties of the precipitation of the copper component and the deposition of the silicon component may be exhibited. . This will be described later in detail along with an experimental example.

In addition, the above-mentioned content of sulfate peroxide and the first amphoteric compound may have a specific relationship. In an exemplary embodiment, the content (eg, weight) of persulfate may be greater than or equal to the content (eg, weight) of the first amphoteric compound. When the content of the first amphoteric compound is larger than that of the peroxide sulfate, the copper etching property may be degraded by the first amphoteric compound, for example, a defect in which the copper component is not etched may occur. This will be described later in detail along with an experimental example.

In some embodiments, the etchant composition may further include a fluorine-containing compound, a chlorine-containing compound, an inorganic acid, an organic acid or an organic acid salt, and a residual amount of solvent.

The fluorine-containing compound may be a staple angle component for a titanium layer including a titanium alloy containing titanium or a titanium component. In addition, the fluorine-containing compound may improve the etching characteristics by removing residues that may occur in the etching process using the etching liquid composition. The fluorine-containing compound is not particularly limited as long as it can form fluorine ions or polyatomic fluorine ions in an aqueous solution, for example, ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride and potassium bifluoride. It may contain the above.

The content of the fluorine-containing compound may be included in about 0.01% to about 2.0% by weight, or about 0.05% to about 1.0% by weight based on the total weight of the etching liquid composition. If the fluorine-containing compound is contained in less than 0.01% by weight does not have sufficient etching characteristics for the titanium layer and the etching rate of the titanium layer may be lowered may cause residue. In addition, when the fluorine-containing compound is contained in an amount greater than 2.0% by weight, it may cause damage to the substrate forming the base of the wiring board including the wiring and / or the silicon-based insulating layer.

The chlorine-containing compound may improve the etching rate of the copper layer to improve the CDOS of the patterned wiring to improve the process margin. In addition, there is an effect that can improve the processability by suppressing the partial over-etching phenomenon of the wiring. The chlorine-containing compound is not particularly limited as long as it can form chlorine ions in an aqueous solution. One or more of the sulfonyls. Critical dimension loss (CD loss) is one of the pattern profile defects that occurs when the difference between the vertical and horizontal etching speeds is not large. The end of a mask pattern (eg, a photoresist pattern) for etching is used. And the horizontal distance between the ends of the etched pattern is shortened, which may mean a defect in which the wiring is not normally formed.

The content of the chlorine-containing compound may be included in about 0.01% to about 5.0% by weight, or about 0.1% to about 2.0% by weight based on the total weight of the etching liquid composition. When the chlorine-containing compound is included in less than 0.01% by weight does not show the effect of improving the etching rate and the side diroside, residues may occur in the etching process. In addition, when the chlorine-containing compound is included in more than 5.0% by weight, the etching rate of the copper layer may be too large, for example, when the lower layer of the wiring includes a titanium layer and the upper layer contains a copper layer, the overall CD-ROS of the wiring Can be too large.

The inorganic acid may serve as an auxiliary oxidant for the copper component and the titanium component. That is, the inorganic acid may assist the oxidation of the copper layer and the titanium layer. The inorganic acid may include one or more of nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ), phosphoric acid or phosphorous acid (H ₂ PO ₃ , H ₃ PO ₃ ).

The content of the inorganic acid may be included in about 0.5% to about 10.0% by weight based on the total weight of the etchant composition. When the inorganic acid is included in less than 0.5% by weight, the etching rate for the copper layer or titanium layer is lowered, which may cause an etching profile defect or a residue defect. In addition, when the inorganic acid is included in more than 10.0% by weight may over-etch the copper layer and titanium layer. In addition, damage to the organic mask pattern used in the etching process, for example, a photosensitive pattern including an organic material, may cause damage to the wiring short circuit.

The organic acid or organic acid salt may adjust the pH of the etchant composition. At the same time, the organic acid or the organic acid salt may maintain a constant etching rate of the copper layer including the copper component even when the number of treatments of the etching target wiring, that is, the wiring board using the etching solution composition is accumulated, to increase the impurity content in the etching solution composition. Can be. Examples of the organic acid include acetic acid (CH ₃ COOH), formic acid (HCOOH), propenoic acid (CH ₂ = CHCOOH), butanoic acid (CH ₃ (CH ₂ ) ₂ COOH), pentanic acid (CH ₃ (CH ₂ ) ₃ COOH ), Gluconic Acid (C ₆ H ₁₂ O ₇ ), Glycolic Acid (HOCH ₂ COOH), Malonic Acid (HOOCCH ₂ COOH), Oxalic Acid (HOOCCOOH), Benzoic Acid (C ₆ H ₅ COOH), Succinic Acid (HOOC (CH ₂ ) ₂ COOH), phthalic acid, salicylic acid (C ₇ H ₆ O ₃ ), lactic acid (CH ₃ CH (OH) COOH), glyceric acid (HOCH ₂ CH (OH) COOH), malic acid (C ₄ H ₆ O ₅ ), Tartaric acid (C ₄ H ₆ O ₆ ), citric acid (C ₆ H ₈ O ₇ ), and isocitric acid. In one non-limiting example, the organic acid may be a compound consisting of only carbon atoms, hydrogen atoms, and oxygen atoms. Alternatively, the organic acid may form an acidic ion in an aqueous solution, and may be an electrically negative compound. In addition, the organic acid salt may include a sodium salt, potassium salt or ammonium salt of the organic acid.

The content of the organic acid or organic acid salt may be included in about 1.0% to about 20.0% by weight, or about 1.5% to about 15.0% by weight relative to the total weight of the etchant composition. If the organic acid or organic acid salt is included in less than 1.0% by weight it is difficult to adjust the sufficient pH, the etching rate can be reduced. In addition, when an organic acid or an organic acid salt is included in an amount of more than 20.0 wt%, a wiring short circuit may occur due to overetching of the wiring.

In some embodiments, the content of the aforementioned first amphoteric compound and the organic acid or organic acid salt may be in a particular relationship. For example, the weight ratio of organic acid or organic acid salt and first amphoteric compound may range from about 15: 1 to about 1: 2. On the basis of the weight of the first amphoteric compound, when the content of the organic acid or the organic acid salt is larger than the above range, the over-etching failure of the copper component may occur, and when the content of the organic acid or the organic acid salt is less than the above range, poor taste may occur. have. This will be described later in detail along with an experimental example.

The solvent may be deionized water. In one non-limiting example, the solvent may be deionized water having a resistivity of at least 18 MΩ / cm. The solvent may be included in the remaining amount except for the solid content in the etching liquid composition.

In some embodiments, the etchant composition may further comprise a copper salt. The copper salt may suppress an initial hunting defect that may occur in the initial stage of the etching process as the number of etching of the etching target wiring using the etching solution composition, that is, the wiring board increases. The copper salt may include copper sulfate salt, copper chloride salt or copper nitrate salt. The copper salt may be included in an amount of about 0.01 wt% to about 5.0 wt% based on the total weight of the etchant composition.

Hereinafter, a method of manufacturing a wiring board according to the present invention will be described with reference to the accompanying drawings.

1 to 9 are cross-sectional views sequentially illustrating a method of manufacturing a wiring board according to an embodiment of the present invention.

First, referring to FIG. 1, a gate wiring layer 200 and an insulating layer 300 are formed on a substrate 100. In an exemplary embodiment, the gate wiring layer 200 may have a stacked structure of two or more layers including different materials. For example, the gate wiring layer 200 may include a gate lower metal pattern layer 210 and a gate upper metal pattern layer 220.

The gate lower metal pattern layer 210 may be directly disposed on the substrate 100 including a metal material having an excellent adhesion to the substrate 100. The gate lower metal pattern layer 210 may be a single layer including titanium or a titanium alloy. The titanium alloy may be an alloy of a refractory metal such as molybdenum (Mo), tantalum (Ta), chromium (Cr), nickel (Ni) or neodymium (Nd) and titanium. The thickness of the gate lower metal pattern layer 210 may be about 100 kPa to about 300 kPa, but the present invention is not limited thereto.

The gate upper metal pattern layer 220 may be directly disposed on the gate lower metal pattern layer 210. The gate upper metal pattern layer 220 may include a metal material having low electrical resistance and excellent electrical conductivity. For example, the gate upper metal pattern layer 220 may be a single layer including copper or a copper alloy. The thickness of the gate upper metal pattern layer 220 may be about 3,000 kPa to about 6,000 kPa, but the present invention is not limited thereto.

Although not shown in the drawings, the gate wiring layer 200 including the gate lower metal pattern layer 210 and the gate upper metal pattern layer 220 may include a gate wiring extending in one direction and a gate electrode protruding from the gate wiring. Can be.

The insulating layer 300 may include an insulating material to insulate the component on the top and the gate wiring layer 200 from each other. The insulating layer 300 may cover the top and side surfaces of the gate wiring layer 200. For example, the insulating layer 300 may be a gate insulating layer that insulates the gate wiring layer 200 and the source / drain wiring layer 500 to be described later. The insulating layer 300 may include an insulating inorganic material such as silicon nitride (SiNx), silicon oxide (SiOx), or silicon oxynitride.

1 and 2, a semiconductor material layer 400a is formed on the insulating layer 300. The semiconductor material layer 400a may include a silicon-based semiconductor material such as amorphous silicon, polycrystalline silicon, or single crystal silicon, or may include an oxide semiconductor. Although not illustrated, the method may further include doping the n-type impurity after the semiconductor material layer 400a is formed.

1 to 3, a source / drain lower metal layer 510a is formed on the semiconductor material layer 400a. The source / drain lower metal layer 510a may be a barrier layer that prevents metal ions in the source / drain upper metal layer 520a from being diffused into the semiconductor material layer 400a. The source / drain lower metal layer 510a may be a single layer including titanium or a titanium alloy. In some embodiments, the source / drain bottom metal layer 510a may include the same material as the gate bottom metal pattern layer 210 described above. The method of forming the source / drain lower metal layer 510a is not particularly limited, and may be formed through physical vapor deposition such as sputtering.

1 to 4, a source / drain upper metal layer 520a is formed on the source / drain lower metal layer 510a. The source / drain top metal layer 520a may include a metal material having low electrical resistance and excellent electrical conductivity compared to the source / drain lower metal layer 510a. For example, the source / drain top metal layer 520a may be a single layer comprising copper or a copper alloy. In some embodiments, the source / drain top metal layer 520a may include the same material as the gate top metal pattern layer 220 described above. The method of forming the source / drain top metal layer 520a is not particularly limited, and may be formed through physical vapor deposition such as sputtering. The thickness of the source / drain upper metal layer 520a may be greater than the thickness of the source / drain lower metal layer 510a.

The source / drain lower metal layer 510a and the source / drain upper metal layer 520a may be insulated from the gate wiring layer 200 by the insulating layer 300.

1 to 5, a first mask pattern 610 is formed on the source / drain upper metal layer 520a.

In an exemplary embodiment, the source / drain lower metal layer 510a and the source / drain upper metal layer 520a include a first region R1, a second region R2, and a third region R3. The mask pattern 610 may be formed in the first region R1 and the second region R2 and may not be disposed in the third region R3. That is, the first mask pattern 610 may be formed to expose the third region R3 of the source / drain lower metal layer 510a and the source / drain upper metal layer 520a.

The first mask pattern 610 may have a partly different thickness. In an exemplary embodiment, the thickness of the first mask pattern 610 in the first region R1 of the source / drain lower metal layer 510a and the source / drain upper metal layer 520a may be the first in the second region R2. It may be larger than the thickness of the mask pattern 610.

The first mask pattern 610 may include an organic material. For example, the first mask pattern 610 may include a photosensitive organic material. The photosensitive organic material may include a negative photosensitive organic material in which the exposed portion is partially cured, or a positive photosensitive organic material in which the exposed portion is partially decomposed. The first mask pattern 610 is coated with a photosensitive organic material and then partially cured by varying an exposure amount using a halftone mask or a slit mask or the like, so that the thickness in the first region R1 is the thickness in the second region R2. A larger first mask pattern 610 may be formed, but the present invention is not limited thereto.

1 to 6, the source / drain upper metal layer 520a and the source / drain lower metal layer 510a are first patterned using the etchant composition. That is, the source / drain upper metal pattern layer 520b and the source / drain lower metal pattern layer 510b are formed through a wet etching process using the etchant composition. The etchant composition may be an etchant composition according to an embodiment of the present invention described above bar overlapping description is omitted.

The third region R3 of the source / drain upper metal layer 520a and the source / drain lower metal layer 510a not covered by the first mask pattern 610 may be first etched and removed by the etchant composition. The source / drain top metal layer 520a and the source / drain bottom metal layer 510a may be collectively etched and removed together through one etching process.

On the other hand, the first region R1 and the second region R2 of the source / drain upper metal pattern layer 520b and the source / drain lower metal pattern layer 510b covered by the first mask pattern 610 are removed. It can be left unattended.

1 through 7, the source / drain top metal pattern layer 520b and the source / drain bottom metal pattern formed by partially removing the source / drain top metal layer 520a and the source / drain bottom metal layer 510a. The semiconductor material layer 400a that is not covered by the layer 510b is partially patterned. In an exemplary embodiment, the semiconductor material pattern layer 400 may be formed through a dry etching process.

1 to 8, the thickness of the first mask pattern 610 is reduced to form the second mask pattern 620. In an exemplary embodiment, reducing the thickness of the first mask pattern 610 may include forming the second mask pattern 620 through an ashing process or a dry etching process.

The second mask pattern 620 remains in the first region R1 of the source / drain lower metal pattern layer 510b and the source / drain upper metal pattern layer 520b, but does not remain in the second region R2. Can be. That is, the second mask pattern 620 may be formed to expose the second region R2 of the source / drain lower metal pattern layer 510b and the source / drain upper metal pattern layer 520b. This may be because the first mask pattern 610 has a partially different thickness, and the thickness of the first mask pattern 610 is reduced substantially uniformly through an ashing process or a dry etching process, but the present invention is not limited thereto. .

Subsequently, referring to FIGS. 1 to 9, the source / drain upper metal pattern layer 520b and the source / drain lower metal pattern layer 510b are secondly patterned using the etchant composition. That is, the source / drain upper metal pattern layer 520 and the source / drain lower metal pattern layer 510 are formed through a wet etching process using the etchant composition. The etchant composition used in the second patterning step may be the same as the etchant composition used in the first patterning step.

The second region R2 of the source / drain upper metal pattern layer 520b and the source / drain lower metal pattern layer 510b not covered by the second mask pattern 620 may be secondaryly etched and removed by the etchant composition. Can be. The source / drain upper metal pattern layer 520b and the source / drain lower metal pattern layer 510b may be collectively etched and removed together through one etching process.

On the other hand, the source / drain upper metal pattern layer 520b and the first region R1 of the source / drain lower metal pattern layer 510b covered by the second mask pattern 620 may remain unremoved. . As a result, the source / drain interconnection layer 500 including the source / drain lower metal pattern layer 510 and the source / drain upper metal pattern layer 520 spaced apart from each other may be formed on the semiconductor material pattern layer 400.

In some embodiments, the side inclination angle θ1 of the source / drain wiring layer 500 may be greater than the side inclination angle θ2 of the gate wiring layer 200. For example, the side inclination angle θ1 of the source / drain wiring layer 500 may be about 55 degrees to about 80 degrees. By forming the side inclination angle θ2 of the gate wiring layer 200 to be relatively small, the components stacked on the gate wiring layer 200, for example, the insulating layer 300, the semiconductor material pattern layer 400, and the source / drain wiring layer ( Coverage characteristics such as 500) can be improved.

The etchant composition according to the present exemplary embodiment has excellent batch etching characteristics for the source / drain wiring layer 500 including the source / drain lower metal pattern layer 510 and the source / drain upper metal pattern layer 520. Therefore, the source / drain wiring layer 500 having an excellent profile can be formed. For example, the side inclination angle θ1 of the source / drain wiring layer 500 may have an etching characteristic to have a range of about 55 degrees to 80 degrees, and thus, the components of the components stacked on the source / drain wiring layer 500 may be formed. The coverage characteristic can be improved.

Hereinafter, the present invention will be described in more detail with reference to Production Examples, Comparative Examples and Experimental Examples.

<Production example>

To prepare an etchant composition of Preparation Examples 1 to 14 using the composition shown in Table 1.

Comparative Example

To prepare an etchant composition of Comparative Examples 1 to 9 using the composition shown in Table 1.

SPS ABF ACl ATZ HNO ₃ AcOH Gly IDA SFA BSFA MSFA DIW Preparation Example 1 10.0 0.5 1.0 1.0 3.0 3.0 0.2 - 1.5 - - Remaining amount Preparation Example 2 10.0 0.5 1.0 1.0 3.0 3.0 0.5 - 1.5 - - Remaining amount Preparation Example 3 10.0 0.5 1.0 1.0 3.0 3.0 1.5 - 1.5 - - Remaining amount Preparation Example 4 10.0 0.5 1.0 1.0 3.0 3.0 4.0 - 1.5 - - Remaining amount Preparation Example 5 10.0 0.5 1.0 1.0 3.0 3.0 1.0 - 0.2 - - Remaining amount Preparation Example 6 10.0 0.5 1.0 1.0 3.0 3.0 1.0 - 0.5 - - Remaining amount Preparation Example 7 10.0 0.5 1.0 1.0 3.0 3.0 1.0 - 1.0 - - Remaining amount Preparation Example 8 10.0 0.5 1.0 1.0 3.0 3.0 1.0 - 3.0 - - Remaining amount Preparation Example 9 10.0 0.5 1.0 1.0 3.0 3.0 1.0 - 5.0 - - Remaining amount Preparation Example 10 10.0 0.5 1.0 1.0 3.0 3.0 1.0 - 6.0 - - Remaining amount Preparation Example 11 10.0 0.5 1.0 1.0 3.0 0.5 1.0 - 1.5 - - Remaining amount Preparation Example 12 10.0 0.5 1.0 1.0 3.0 4.0 1.0 - 1.5 - - Remaining amount Preparation Example 13 10.0 0.5 1.0 1.0 2.0 8,0 1.0 - 1.5 - - Remaining amount Preparation Example 14 10.0 0.5 1.0 1.0 2.0 13.0 1.0 - 1.5 - - Remaining amount Comparative Example 1 10.0 0.5 1.0 1.0 3.0 3.0 - - 1.5 - - Remaining amount Comparative Example 2 10.0 0.5 1.0 1.0 3.0 3.0 11.0 - 1.5 - - Remaining amount Comparative Example 3 10.0 0.5 1.0 1.0 3.0 3.0 1.0 - - - - Remaining amount Comparative Example 4 10.0 0.5 1.0 1.0 3.0 3.0 1.0 - 8.0 - - Remaining amount Comparative Example 5 10.0 0.5 1.0 1.0 3.0 - 1.0 - 1.5 - - Remaining amount Comparative Example 6 10.0 0.5 1.0 1.0 3.0 22.0 1.0 - 1.5 - - Remaining amount Comparative Example 7 10.0 0.5 1.0 1.0 3.0 3.0 - 1.5 1.5 - - Remaining amount Comparative Example 8 10.0 0.5 1.0 1.0 3.0 3.0 1.0 - - 2.0 - Remaining amount Comparative Example 9 10.0 0.5 1.0 1.0 3.0 3.0 1.0 - - - 2.0 Remaining amount

In Table 1, SPS means sodium persulfate, ABF means ammonium bifluoride, and ACl means ammonium chloride. ATZ means 5-aminotetrazole, HNO ₃ means nitric acid, and AcOH means acetic acid. In addition, Gly means glycine represented by the above-mentioned Formula (Ia), and IDA means imino diacetic acid. Iminodiacetic acid was used as a control of glycine to confirm the function of glycine. SFA means sulfamic acid represented by Formula IIa, BSFA means benzosulfonic acid, and MSFA means methanesulfonic acid. Benzosulfonic acid and methanesulfonic acid were used as controls for sulfamic acid to confirm the function of sulfamic acid. DIW means deionized water.

Experimental Example 1

A titanium alloy layer was deposited on a glass substrate having a size of 100 mm × 100 mm, and a copper layer was deposited on the titanium alloy layer. After forming a photosensitive material layer having a predetermined pattern on the copper layer, the copper layer and the titanium alloy layer were patterned by using the etching solution compositions according to Preparation Examples 1 to 14 and Comparative Examples 1 to 9.

Experimental equipment was ETCHER (TFT) (SEMES Co., Ltd.) of the spray etching method was used, the temperature of the etchant composition was maintained at about 28 ℃ during the etching process. The etching time was performed in the range of 50 seconds to 200 seconds in consideration of other process conditions and other factors. The profile of the patterned copper layer and the titanium alloy layer was measured using a cross section SEM S-4700 (HITACHI Co., Ltd.).

The etch rate (Å / sec) of the patterned copper layer and the titanium alloy layer and the profile of the patterned wiring were measured and shown in Table 2 below.

Experimental Example 2

After dissolving 3,000 ppm of copper in the etching solution composition according to Preparation Examples 1 to 14 and Comparative Examples 1 to 9 and stored at a low temperature at -8 ℃ to observe the presence of copper precipitates are shown in Table 2 below.

Experimental Example 3

After immersing the silicon in the etching solution composition according to Preparation Examples 1 to 14 and Comparative Examples 1 to 9 for 3 hours at 23 ° C., the precipitates were observed through filtration and drying, and the results are shown in Table 2 below.

Etch Rate (Å / sec) Copper component precipitate Silicon precipitate profile Preparation Example 1 ○ △ ○ Preparation Example 2 ○ ○ ○ Preparation Example 3 ○ ○ ○ Preparation Example 4 △ △ ○ Preparation Example 5 ○ △ ○ Preparation Example 6 ○ ○ ○ Preparation Example 7 ○ ○ ○ Preparation Example 8 ○ ○ ○ Preparation Example 9 ○ ○ ○ Preparation Example 10 △ ○ △ Preparation Example 11 ○ ○ ○ Preparation Example 12 ○ ○ ○ Preparation Example 13 ○ ○ ○ Preparation Example 14 ○ ○ ○ Comparative Example 1 ○ Х ○ Comparative Example 2 Х Х ○ Copper layer Comparative Example 3 ○ ○ △ Comparative Example 4 Х ○ △ Copper layer overetch Comparative Example 5 △ ○ ○ Copper layer non-uniform etching Comparative Example 6 Х ○ ○ Copper layer overetch Comparative Example 7 ○ Х ○ Comparative Example 8 ○ ○ Х Too much silicon precipitate Comparative Example 9 ○ ○ Х Too much silicon precipitate

In Table 2, when the etching rate is 200 Å / sec to 300 sec / sec is represented by '○', when the etch rate is less than 200 Å / sec or more than 300 Å / sec is represented by '△', poor taste or over-etching The case where a defect has occurred is shown as 'x'.

In addition, in Table 2, when the copper component precipitate does not occur for 90 days, it is represented by '○', and when the copper component precipitate occurs between 60 days and 90 days, it is represented by '△', and the copper precipitate is generated 60 days before. In the case indicated by 'x'. The shorter the period during which the copper component precipitate occurs, the less the solubility in the copper component, and the copper component acts as an impurity, which may cause a reduction in the number of sheets of the wiring board.

In addition, when the silicon component precipitate is less than 1.2g in Table 2, it is represented by '○', the silicon component precipitate is represented by '△' when 1.2g to 2.0g, and when the silicon component precipitate is more than 2.0g to '×' Indicated. The greater the amount of silicon component precipitates, the less the dissolution characteristics of the silicon component, and the silicon component may act as an impurity.

Referring to Table 2 above, Comparative Example 1, which does not include the first amphoteric compound (glycine), and Comparative Example 2, which contains 11.0% by weight of the first amphoteric compound, are vulnerable to precipitation of the copper component, particularly, the first In Comparative Example 2, where the content of the amphoteric compound is greater than the content of sulfate, the etching rate is very low, and it can be confirmed that poor taste occurs.

In addition, Comparative Example 3 containing no second amphoteric compound (sulfamic acid) and Comparative Example 4 containing 8.0% by weight of the second amphoteric compound are susceptible to precipitation of silicon components, and particularly in Comparative Example 4, etching rate. Not only is this very low, but it can be seen that overetching defects appear.

In addition, in Comparative Example 5 and the Comparative Example 6 containing 22.0% by weight of the organic acid containing no organic acid (acetic acid), the etching characteristics are poor, non-uniform etching or over-etching failure occurs, especially in the case of Comparative Example 6 You can see that it is very low.

It can be confirmed that the comparative example 7 including the imino diacetic acid which is electrically negative in aqueous solution instead of the first amphoteric compound (glycine) is susceptible to precipitation of copper components.

In addition, in the case of Comparative Example 8 containing benzene sulfonic acid and Comparative Example 9 including methane sulfonic acid instead of the second amphoteric compound (sulfamic acid), it can be confirmed that the silicon component is excessively precipitated.

Meanwhile, among the etching solution compositions according to Preparation Examples 1 to 14, in the case of the etching solution composition in which the weight ratio of the first amphoteric compound and the second amphoteric compound satisfies 2: 1 to 1: 5, compared to the etchant composition which is not It can be seen that the more stable etching characteristics. In addition, in the case of Comparative Example 6 containing an excessive amount of organic acid or organic acid salt based on the content of the first amphoteric compound that contributes to the stabilization of the profile, a poor etching occurs, and contains too little organic acid or organic acid salt. In the case of Comparative Example 2 can be confirmed that the poor taste. This may be because the first amphoteric compound and the organic acid or organic acid salt perform different functions from each other, but the present invention is not limited thereto.

Experimental Example 4

The copper layer and the titanium alloy layer were patterned under the same conditions as in Experimental Example 1 using the etchant compositions according to Preparation Examples 1 to 14 and Comparative Examples 1 to 9.

After recovering the etchant composition used for etching, the process of patterning the copper layer and the titanium alloy layer under the same conditions as in Experimental Example 1 was repeated.

At this time, the taper angle of the copper layer according to the number of repetitions was measured and shown in Table 3 below. In addition, the profile of the titanium alloy layer was measured and shown in Table 4 below. Specifically, the length of the protruding tail portion of the titanium alloy layer was measured and shown in Table 4. In addition, the side etching degree, specifically the etching depth of the copper layer was measured and shown in Table 5 below.

In Table 3, Table 4, and Table 5, '×' represents a case in which the taper side of the pattern collapses, and thus the profile measurement of the pattern is impossible.

In addition, in Table 3, Table 4 and Table 5 'ppm' means the concentration of copper ions in the etching liquid composition. That is, the concentration of copper ions in the etchant composition increases as the etchant composition is recovered and repeatedly used in an etching process. In other words, 0 ppm means an initial etchant composition having no history used in the etching process, and as the concentration (ppm) is increased, it means an etchant composition which is repeatedly used in the etching process to increase the impurity content.

0 ppm 1,000 ppm 2,000 ppm 3,000 ppm 4,000 ppm 5,000 ppm 6,000 ppm Preparation Example 1 65 degrees 63 degrees 66 degrees 66 degrees 67 degrees 69 degrees Х Preparation Example 2 63 degrees 63 degrees 63 degrees 64 degrees 65 degrees 67 degrees Х Preparation Example 3 59 degrees 59 degrees 59 degrees 59 degrees 59 degrees 59 degrees Х Preparation Example 4 54 degrees 54 degrees 54 degrees 54 degrees 54 degrees 54 degrees Х Preparation Example 5 57 degrees 54 degrees 54 degrees 54 degrees 54 degrees 54 degrees Х Preparation Example 6 57 degrees 54 degrees 54 degrees 54 degrees 54 degrees 54 degrees Х Preparation Example 7 58 degrees 58 degrees 58 degrees 58 degrees 58 degrees 59 degrees Х Preparation Example 8 59 degrees 59 degrees 59 degrees 59 degrees 59 degrees 59 degrees 62 degrees Preparation Example 9 60 degrees 60 degrees 61 degrees 61 degrees 61 degrees 61 degrees Х Preparation Example 10 60 degrees 60 degrees 61 degrees 62 degrees 63 degrees 63 degrees Х Preparation Example 11 57 degrees 54 degrees 54 degrees 54 degrees 54 degrees 54 degrees Х Preparation Example 12 57 degrees 54 degrees 54 degrees 54 degrees 54 degrees 54 degrees Х Preparation Example 13 58 degrees 58 degrees 58 degrees 58 degrees 58 degrees 59 degrees Х Preparation Example 14 60 degrees 60 degrees 60 degrees 60 degrees 60 degrees 60 degrees Х Comparative Example 1 66 degrees 67 degrees 69 degrees 76 degrees 81 degrees 79 degrees Х Comparative Example 2 Gastronomy Gastronomy Gastronomy Gastronomy Gastronomy Gastronomy Gastronomy Comparative Example 3 58 degrees 58 degrees 58 degrees 58 degrees Х Х Х Comparative Example 4 Overetching Overetching Overetching Overetching Overetching Overetching Overetching Comparative Example 7 60 degrees 62 degrees 63 degrees 66 degrees 71 degrees 72 degrees Х Comparative Example 8 60 degrees 60 degrees 60 degrees 61 degrees Х Х Х Comparative Example 9 71 degrees 71 degrees 72 degrees 73 degrees 77 degrees 82 degrees Х

In Table 3, the smaller the difference between the taper angle of the pattern using the etching liquid composition (that is, 0 ppm) of the initial state and the pattern taper angle of the pattern using the etching liquid composition having a higher concentration of copper ions, the higher the number of sheets to be processed and excellent etching characteristics. It means having

Referring to Table 3, in the etching solution composition according to Preparation Examples 1 to 14 and Comparative Examples, it can be seen that the taper angle of the pattern increases as the copper ion concentration increases.

First, in the case of the etching solution compositions according to Preparation Examples 1 to 14 including both the first amphoteric compound (glycine) and the second amphoteric compound (sulfame acid), an etching process is performed using the etching solution composition in an initial state. It can be seen that there is no significant difference between the taper angle of the pattern and the taper angle of the pattern subjected to the etching process by using the etching liquid composition containing the copper ion of 5,000 ppm concentration.

On the other hand, Comparative Example 2 comprising 11.0 wt% of the first amphoteric compound and Comparative Example 4 comprising 8.0 wt% of the second amphoteric compound, respectively, indicate that a defect occurs in which the copper layer is not etched or overetched. You can check.

In addition, in the case of the etchant composition of Comparative Examples 1 and 7 which do not contain the first amphoteric compound and the etchant composition of Comparative Example 9 which does not contain the second amphoteric compound, the taper angle of the pattern using the etchant composition in the initial state It can be seen that there is a defect that the taper angle of the pattern using the etching liquid composition containing the copper ion of 5,000 ppm concentration is increased by about 10 degrees or more.

In addition, in the case of Comparative Example 3 and Comparative Example 8, which does not include the second amphoteric compound, the number of treatments on the wiring board increased, specifically, when the concentration of copper ions was 4,000 ppm or more, the tapered slope fell and measurement was impossible.

That is, in the case of the etchant composition according to the preparation example including both the first amphoteric compound and the second amphoteric compound, the etchant composition according to the comparative example which does not include any one of the first amphoteric compound or the second content is too large It can be seen that the number of treatable substrates can be improved compared to the etchant composition according to the comparative example including the amphoteric compound, and an excellent taper angle can be formed.

0 ppm 1,000 ppm 2,000 ppm 3,000 ppm 4,000 ppm 5,000 ppm 6,000 ppm Preparation Example 1 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.12 μm 0.13 μm Х Preparation Example 2 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.12 μm Х Preparation Example 3 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm Х Preparation Example 4 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm Х Preparation Example 5 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm Х Preparation Example 6 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm Х Preparation Example 7 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm Х Preparation Example 8 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.13 μm Preparation Example 9 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm Х Preparation Example 10 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm Х Preparation Example 11 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm Х Preparation Example 12 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm Х Preparation Example 13 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm Х Preparation Example 14 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm 0.11 μm Х Comparative Example 1 0.11 μm 0.11 μm 0.12 μm 0.13 μm 0.16 μm 0.21 μm Х Comparative Example 2 Gastronomy Gastronomy Gastronomy Gastronomy Gastronomy Gastronomy Gastronomy Comparative Example 7 0.11 μm 0.11 μm 0.12 μm 0.13 μm 0.16 μm 0.22㎛ Х

Referring to Table 4, in the case of the etching liquid composition according to Preparation Examples 1 to 14 containing 0.01 wt% to 10.0 wt% of the first amphoteric compound (glycine), it was confirmed that the profile of the titanium alloy layer was good. have.

On the other hand, in the case of Comparative Example 2 containing 11.0% by weight of the first amphoteric compound, it can be seen that a defect occurs in which the copper layer is not etched.

In addition, in the etching solution compositions of Comparative Example 1 and Comparative Example 7, which do not contain the first amphoteric compound, it is confirmed that the profile of the titanium alloy layer rapidly deteriorates as the number of processed substrates increases.

That is, in the case of the etchant composition according to the preparation example including about 0.01 wt% to 10.0 wt% of the first amphoteric compound, it can be seen that the profile of the titanium alloy layer can be improved compared to the etchant composition that is not.

0 ppm 1,000 ppm 2,000 ppm 3,000 ppm 4,000 ppm 5,000 ppm 6,000 ppm Preparation Example 1 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.68 μm Preparation Example 2 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.68 μm Preparation Example 3 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.68 μm Preparation Example 4 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.74 μm 0.69㎛ Preparation Example 5 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.68 μm Preparation Example 6 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.68 μm Preparation Example 7 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.68 μm Preparation Example 8 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.68 μm Preparation Example 9 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.68 μm Preparation Example 10 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.70 μm Preparation Example 11 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.68 μm Preparation Example 12 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.68 μm Preparation Example 13 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.74 μm 0.69㎛ Preparation Example 14 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm 0.75 μm Comparative Example 5 0.75 μm 0.75 μm 0.77 μm 0.79 μm 0.83 μm 0.86 μm 0.75 μm

Referring to Table 5, in the case of the etching liquid composition according to Preparation Examples 1 to 14 containing 1.0% to 20.0% by weight of an organic acid (acetic acid) it can be confirmed that the etching profile of the copper layer is good.

On the other hand, in Comparative Example 5, which does not include an organic acid, it can be seen that the etching profile of the copper layer is rapidly deteriorated as the number of processed substrates increases.

That is, in the case of the etching liquid composition according to the preparation example containing about 1.0% by weight to 20.0% by weight of the organic acid, it can be seen that the profile of the copper layer can be improved compared to the etching liquid composition that is not.

Although described above with reference to the embodiments of the present invention, which is merely an example and not limiting the present invention, those skilled in the art to which the present invention pertains without departing from the essential characteristics of the embodiments of the present invention. It will be appreciated that various modifications and applications are not possible. For example, each component specifically shown in the embodiment of the present invention may be modified. And differences relating to such modifications and applications will have to be construed as being included in the scope of the invention defined in the appended claims.

100: substrate
200: gate wiring layer
300: insulation layer
400: semiconductor material pattern layer
500: source / drain wiring layer

Claims (16)

1.0 wt% to 20 wt% peroxysulfate;
0.1% to 5.0% by weight of the cyclic amine compound;
0.01 wt% to 2.0 wt% of a fluorine-containing compound;
0.01 wt% to 5.0 wt% chlorine-containing compound;
Inorganic acid 0.5% to 10.0% by weight;
0.5% to 8% by weight of organic acid or organic acid salt;
0.5 wt% to 1.5 wt% of the first amphoteric compound having a carboxyl group; And
Different from the first amphoteric compound and comprises 0.5 wt% to 5.0 wt% of a second amphoteric compound having a sulfone group,
Within this range, the weight ratio of the first amphoteric compound and the second amphoteric compound is 2: 1 to 1: 5,
Within the range, the weight ratio of the first amphoteric compound and the organic acid or organic acid salt is from 2: 1 to 1: 8. According to claim 1,
The content of the sulfate peroxide is greater than the content of the first amphoteric compound. The method of claim 2,
The first amphoteric compound is an etchant comprising at least one of the compounds represented by the formula (Ia) to formula (Ie).
<Formula Ia>

<Formula Ib>

<Formula Ic>

<Formula Id>

<Formula Ie>

The method of claim 2,
The second amphoteric compound is an etching solution composition comprising one or more of the compounds represented by the following formula (IIa) to formula (IIc).
<Formula IIa>

<Formula IIb>

<Formula IIc>

The method of claim 1,
The sulfate persulfate is an etching solution composition comprising potassium persulfate (K ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ) or ammonium bisulfate ((NH ₄ ) ₂ S ₂ O ₈ ). The method of claim 1,
The cyclic amine compound is 5-aminotetrazole, 1-methyl-5-aminotetrazole, 5-methyltetrazole, 1-ethyl -5-aminotetrazole, imidazole, indole, purine, pyrazole, pyridine, pyrimidine, pyrrole An etchant composition comprising at least one of (pyrrole), pyrrolidine, and pyrroline. The method of claim 1,
The fluorine-containing compound is an etching solution composition comprising one or more of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride and potassium bifluoride. The method of claim 1,
The chlorine-containing compound is an etching solution composition comprising one or more of hydrochloric acid, sodium chloride, potassium chloride, ammonium chloride, iron (III) chloride, sodium perchlorate, potassium perchlorate, ethylsulfonyl chloride and methanesulfonyl chloride. The method of claim 1,
The inorganic acid comprises nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ), phosphoric acid or phosphorous acid (H ₂ PO ₃ , H ₃ PO ₃ ). The method of claim 1,
The organic acid is acetic acid, formic acid, propenoic acid, butanoic acid, pentanic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, benzoic acid, succinic acid, phthalic acid, salicylic acid, lactic acid, glyceric acid, malic acid, tartaric acid, citric acid and isocitric acid. Contains one or more,
The organic acid salt is an etchant composition comprising sodium salt, potassium salt or ammonium salt of the organic acid. The method of claim 1,
Further comprising 0.01 wt% to 5.0 wt% copper salt,
The copper salt is an etching solution composition containing copper sulfate, copper chloride salt or copper nitrate salt. A method of manufacturing a wiring board comprising the step of forming a first wiring layer on a substrate,
Forming the first wiring layer,
Forming a first metal layer on the substrate;
Forming a second metal layer different from the first metal layer on the first metal layer; And
Patterning the first metal layer and the second metal layer using an etchant composition,
The etchant composition,
1.0 wt% to 20 wt% peroxysulfate;
0.1% to 5.0% by weight of the cyclic amine compound;
0.01 wt% to 2.0 wt% of a fluorine-containing compound;
0.01 wt% to 5.0 wt% chlorine-containing compound;
Inorganic acid 0.5% to 10.0% by weight;
0.5% to 8% by weight of organic acid or organic acid salt;
0.5 wt% to 1.5 wt% of the first amphoteric compound having a carboxyl group; And
Different from the first amphoteric compound and comprises 0.5 wt% to 5.0 wt% of a second amphoteric compound having a sulfone group,
Within this range, the weight ratio of the first amphoteric compound and the second amphoteric compound is 2: 1 to 1: 5,
A weight ratio of the first amphoteric compound and the organic acid or organic acid salt within the above range is 2: 1 to 1: 8 manufacturing method of a wiring board. The method of claim 12,
And the first metal layer is a titanium layer or a titanium alloy layer, and the second metal layer is a copper layer or a copper alloy layer. The method of claim 13,
Before forming the first wiring layer, further comprising the step of forming a second wiring layer on the substrate,
The forming of the first wiring layer is a step of forming the first wiring layer on the second wiring layer to be insulated from the second wiring layer,
The second wiring layer is a method of manufacturing a wiring board comprising a titanium or titanium alloy layer, and a copper or copper alloy layer stacked on each other. The method of claim 14,
The side inclination angle of the second wiring layer is smaller than the side inclination angle of the first wiring layer,
The side inclination angle of the first wiring layer is a manufacturing method of the wiring board 55 to 80 degrees. The method of claim 12,
The patterning of the first metal layer and the second metal layer using the etchant composition may include:
Forming a mask pattern on the first and second regions of the first metal layer and the second metal layer;
First etching the third region of the first metal layer and the second metal layer which do not overlap the mask pattern using the etchant composition,
Removing the mask pattern on the second region of the first metal layer and the second metal layer, and
And etching the second region of the first metal layer and the second metal layer by using the etchant composition.

Images