KR102353679B1 - Etchant composition and method of manufacturing wiring substrate using the same - Google Patents

Abstract

An etchant composition and a method of manufacturing a wiring board are provided. The etchant composition is different from peroxysulfate, a cyclic amine compound, a fluorine-containing compound, a chlorine-containing compound, an inorganic acid, an organic acid or an organic acid salt, a first amphoteric compound having a carboxyl group, and the first amphoteric compound, and a second amphoteric compound having a sulfone group.

Description

Etchant composition and method for manufacturing a wiring board using the same

The present invention relates to an etchant composition and a method for manufacturing a wiring board.

The importance of the display device is gradually 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 expressing different colors. In order for each pixel of the display device to operate independently of each other, the display device may include a driving signal line for transmitting a driving signal and a wiring board including a thin film transistor.

The driving signal wiring of the wiring board requires low electrical resistance, high thermal stability, easy processability, and excellent adhesion. can

The driving signal wiring of the wiring board is required to have an appropriate shape or profile as well as physical properties of the material itself such as electrical resistance, thermal stability, workability and adhesion. For example, when the side inclination angle of the driving signal wiring is too large, coverage defects may occur in components stacked thereon due to a sudden step difference formed by the wiring. Alternatively, if the side inclination angle of the driving signal wiring is too small, the function as the driving signal wiring may not be fully performed.

On the other hand, when the driving signal wiring is formed in a stacked structure of a plurality of layers, the etching characteristics of each layer are different, so the degree of etching may be different, and it is more difficult to control the profile of the driving signal wiring.

Accordingly, the problem to be solved by the present invention is to provide an etchant composition in which the profile control of the driving signal wiring is easy.

Another object of the present invention is to provide a method of manufacturing a wiring board including a driving signal line having characteristics such as improved processability and low electrical resistance and high thermal stability.

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

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

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

The first amphoteric compound may include at least one of compounds represented by the following Chemical Formulas Ia to Ie.

<Formula Ia>

<Formula Ib>

<Formula Ic>

<Formula Id>

<Formula Ie>

In addition, the second amphoteric compound may include at least one of compounds represented by the following Chemical Formulas IIa to IIc.

<Formula IIa>

<Formula IIb>

<Formula IIc>

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

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

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

The fluorinated compound may include at least one of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, and potassium bifluoride.

The chlorine-containing compound may include at least one 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 selected from among acetic acid, formic acid, propenoic acid, butanoic acid, pentanoic 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. It contains one or more, and the organic acid salt may include a sodium salt, a potassium salt, or an ammonium salt of the organic acid.

In addition, 0.01 wt% to 5.0 wt% of a copper salt may be further included.

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

A method of manufacturing a wiring board according to an embodiment of the present invention for solving the above other object is a method of manufacturing a wiring board comprising forming a first wiring layer on the substrate, wherein the forming of the first wiring layer includes: , 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 comprising: 1.0 wt% to 20 wt% of peroxysulfate, 0.1 wt% to 5.0 wt% of a cyclic amine compound, 0.01 wt% to 2.0 wt% of a fluorine-containing compound, 0.01 wt% of a chlorine-containing compound 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 1.5 wt% of a first amphoteric compound having a carboxyl group and the first amphoteric compound and 0.5 wt% to 5.0 wt% of a second amphoteric compound having a sulfone group, wherein the weight ratio of the first amphoteric compound to the second amphoteric compound is 2:1 to 1:5 within the above range. and the weight ratio of the first amphoteric compound to the organic acid or organic acid salt within the above 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, before forming the first wiring layer, forming a second wiring layer on the substrate, wherein the forming of the first wiring layer is 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 with each other.

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

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

In addition, the patterning of the first metal layer and the second metal layer by using the etchant composition includes forming a mask pattern on the first and second regions of the first metal layer and the second metal layer, the First etching the third region of the first metal layer and the second metal layer that do 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 removing the etchant, and performing secondary etching of 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 etchant composition and the method for manufacturing a wiring board according to an embodiment of the present invention, a wiring board including a driving signal line 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 exemplary embodiment of the present invention.

Advantages and features of the present invention and methods of achieving them will become 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 will be implemented in various different forms, and only the embodiments allow the disclosure of the present invention to be complete, and those of ordinary skill in the art to which the present invention pertains. It is provided to fully inform the person of the scope of the invention, and the present invention is only defined by the scope of the claims.

Reference to an element or layer 'on' of another element or layer includes any intervening layer or other element directly on or in the middle of the other element or layer. On the other hand, when an element is referred to as 'directly on', it indicates that no other element or layer is interposed therebetween. Like reference numerals refer to like elements throughout. 'and/or' includes each and every combination of one or more of the recited items.

Spatially relative terms 'below', 'beneath', 'lower', 'above', 'upper', etc. It can be used to easily describe the correlation between an element or components and other elements or components. Spatially relative terms should be understood as terms including different orientations of the device when used in addition to the orientations shown in the drawings. For example, when an element shown in the drawing is turned over, an element described as 'below or beneath' of another element may be placed 'above' of the other element. Accordingly, the exemplary term 'down' may include both the direction of the bottom and the top.

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

The etchant composition according to the present embodiment may include 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 'amphoteric compound' refers to a compound that forms a zwitterion in an aqueous solution state and is electrically positive and negative and is substantially neutral. The etchant composition according to the present embodiment may have excellent batch etching properties for copper (Cu) and titanium (Ti), but the present invention is not limited thereto.

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

The content of peroxysulfate may be included in an amount of about 1.0 wt% to about 20.0 wt% based on the total weight of the etchant composition. When peroxysulfate is included in an amount of less than 1.0 wt%, it may not have sufficient etching properties 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 a poor wiring profile. In addition, when peroxysulfate is included in an amount of more than 20.0 wt %, the etching rate may be excessively increased, and thus it may be difficult to control the etching process. 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, or sufficient time for the titanium layer to be etched may not be secured.

The cyclic amine compound may be an auxiliary etching component that controls the etching rate of the copper layer including copper or a copper alloy including a copper component and induces uniform etching of the copper layer to form an excellent profile. As used herein, the term 'cyclic amine compound' refers to 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 a tertiary amine (=N-), but the present invention is not limited thereto.

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

The content of the cyclic amine compound may be included in an amount of about 0.1 wt% to about 5.0 wt%, or about 0.1 wt% to about 2.0 wt%, based on the total weight of the etchant composition. When the cyclic amine compound is included in an amount of less than 0.1 wt %, the copper layer may be etched non-uniformly without having the etch rate controlling property of the copper component. For example, when the wiring includes a copper layer and a titanium layer, the copper layer is over-etched compared to the titanium layer, so that a uniform side profile cannot be formed. In addition, when the cyclic amine compound is included in an amount of more than 5.0 wt %, the etching properties of the copper layer may be deteriorated. In addition, the solubility of the cyclic amine compound in the etchant composition may decrease, thereby reducing fairness.

The first amphoteric compound may have a carboxyl group (-COOH) and may be electrically neutral in an aqueous solution state. For example, the first amphoteric compound may have both a carboxyl group and an amine group, and may be a neutral compound in an aqueous solution state. Examples of the first amphoteric compound include any one of 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 can prevent a decrease in the side inclination angle of the copper layer including the copper component even when the number of lines to be etched using the etchant composition, that is, the number of processing of the wiring board is accumulated. In addition, it may contribute to improving the profile of the titanium layer including the titanium component.

The first amphoteric compound may be included in an amount of about 0.01 wt% to about 10.0 wt%, or about 0.1 wt% to about 5.0 wt%, based on the total weight of the etchant composition. When the first amphoteric compound is included in an amount of 0.01 wt % or more, an effect of preventing a decrease in the side inclination angle of the copper layer and/or an effect of improving the profile of the titanium layer may be exhibited. 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 lowering the etching rates for the copper layer and the titanium layer.

The second amphoteric compound may have a sulfone group (—SO ₃ H) and be substantially electrically neutral in an aqueous solution state. The second amphoteric compound is a different compound from the first amphoteric compound and may have a different function. For example, the second amphoteric compound may have both a sulfone group and an amine group, and may be a neutral compound in an aqueous solution state. Examples of the second amphoteric compound 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 including copper or a copper alloy including a copper component. Through this, it is possible to increase the number of wiring board treatments of the etchant composition according to the present embodiment and improve processability.

The second amphoteric compound may be included in an amount of about 0.1 wt% to about 7.0 wt%, or about 0.2 wt% to about 5.0 wt%, based on the total weight of the etchant composition. When the second amphoteric compound is included in an amount of 0.1 wt % or more, a sufficient chelating action may be exhibited and the etching rate of the copper layer may be improved. In addition, the etchant composition according to the present embodiment may exhibit an effect of increasing the number of wiring boards processed. When the second amphoteric compound is included in an amount of 7.0 wt % or less, over-etching of the copper layer may be prevented and a wiring including the copper layer having an improved profile may be formed.

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

In addition, the content of the above-described peroxysulfate and the first amphoteric compound may have a specific relationship. In an exemplary embodiment, the content (eg, weight) of peroxysulfate 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 greater than that of the peroxysulfate, copper etching properties may be deteriorated by the first amphoteric compound, and for example, a defect in which the copper component is not etched may occur. This will be described later in detail along with experimental examples.

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 the remaining amount of the solvent.

The fluorine-containing compound may be a stock component for a titanium layer including titanium or a titanium alloy containing a titanium component. In addition, the fluorine-containing compound can improve etching properties by removing residues that may be generated in the etching process using the etching solution composition. The fluorine-containing compound is not particularly limited as long as it can form fluorine ions or polyatomic fluorine ions in aqueous solution, but for example, one of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride and potassium bifluoride may include more than one.

The content of the fluorine-containing compound may be included in an amount of about 0.01 wt% to about 2.0 wt%, or about 0.05 wt% to about 1.0 wt%, based on the total weight of the etchant composition. When the fluorine-containing compound is included in an amount of less than 0.01 wt %, it may not have sufficient etching properties for the titanium layer, and the etching rate of the titanium layer may be lowered, and residues may be generated. In addition, when the fluorine-containing compound is included in an amount of more than 2.0 wt%, it may cause damage to the substrate constituting the base of the wiring substrate including wiring, and/or to the silicon-based insulating layer.

The chlorine-containing compound may improve the etching rate of the copper layer to improve the CD loss of the patterned wiring, thereby improving the margin on the process. In addition, there is an effect of improving the processability by suppressing a 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, but for example, hydrochloric acid, sodium chloride, potassium chloride, ammonium chloride, iron (III) chloride, sodium perchlorate, potassium perchlorate, ethylsulfonyl chloride and methane chloride and one or more of sulfonyl. The critical dimension loss (CD loss) is one of pattern profile defects that occurs when the difference between the etching rate in the vertical direction and the etching rate in the horizontal direction is not large. The horizontal distance between the etched pattern and the end of the etched pattern is shortened, which may mean a defect in which wiring is not normally formed.

The content of the chlorine-containing compound may be included in an amount of about 0.01 wt% to about 5.0 wt%, or about 0.1 wt% to about 2.0 wt%, based on the total weight of the etchant composition. When the chlorine-containing compound is included in an amount of less than 0.01 wt%, the etching rate improvement effect and the cydiros improvement effect cannot be exhibited, and residues may be generated in the etching process. In addition, if the chlorine-containing compound is contained in an amount of more than 5.0 wt%, the etching rate of the copper layer may become excessively large. For example, when the lower layer of the wiring includes a titanium layer and the upper layer includes a copper layer, the overall CD loss of the wiring may become too large.

The inorganic acid may serve as an auxiliary oxidizing agent 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 at least one 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 an amount of about 0.5 wt% to about 10.0 wt% based on the total weight of the etchant composition. When the inorganic acid is included in an amount of less than 0.5 wt %, the etching rate for the copper layer or the titanium layer is lowered, and thus an etching profile defect or a residue defect may occur. In addition, when the inorganic acid is included in an amount greater than 10.0 wt %, over-etching of the copper layer and the titanium layer may occur. Also, an organic mask pattern used in an etching process, for example, a photosensitive pattern including an organic material may be damaged, thereby causing a 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 maintains the etching rate of the copper layer containing the copper component constant even when the amount of impurities in the etchant composition increases due to the accumulation of the number of lines to be etched, that is, the wiring board using the etchant composition. can 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), pentanoic 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. As a non-limiting example, the organic acid may be a compound composed of only carbon atoms, hydrogen atoms, and oxygen atoms. Alternatively, the organic acid may be an electrically negative compound that forms acidic ions in an aqueous solution state. 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 an amount of about 1.0 wt% to about 20.0 wt%, or about 1.5 wt% to about 15.0 wt%, based on the total weight of the etchant composition. When the organic acid or organic acid salt is included in an amount of less than 1.0 wt %, it is difficult to sufficiently control the pH, and thus the etching rate may decrease. In addition, when the organic acid or organic acid salt is included in an amount of more than 20.0 wt %, over-etching of the wiring may be caused and a wiring short circuit defect may occur.

In some embodiments, the content of the above-described first amphoteric compound and an organic acid or an organic acid salt may have a specific relationship. For example, the weight ratio of the organic acid or organic acid salt to the first amphoteric compound may be in the range of about 15:1 to about 1:2. Based on the weight of the first amphoteric compound, when the content of the organic acid or organic acid salt is greater than the above range, overetching defects of the copper component may occur, and when the content of the organic acid or organic acid salt is less than the above range, poor etching may occur. have. This will be described later in detail along with experimental examples.

The solvent may be deionized water. In a non-limiting example, the solvent may be deionized water having a resistivity of 18 MΩ/cm or more. The solvent may be included in the remaining amount excluding the solid content in the etchant composition.

In some embodiments, the etchant composition may further include 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 lines to be etched using the etchant composition, ie, the number of processing of the wiring board increases. The copper salt may include copper sulfate, copper chloride, or copper nitrate. The content of 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 exemplary 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 an upper gate metal pattern layer 220 .

The lower gate metal pattern layer 210 may include a metal material having excellent adhesion to the substrate 100 and may be directly disposed on the substrate 100 . The lower gate metal pattern layer 210 may be a single layer including titanium or a titanium alloy. The titanium alloy may be an alloy of titanium and a refractory metal such as molybdenum (Mo), tantalum (Ta), chromium (Cr), nickel (Ni), or neodymium (Nd). The thickness of the lower gate metal pattern layer 210 may be about 100 Å to about 300 Å, 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 upper gate metal pattern layer 220 may include a metal material having a low resistivity 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 Å to about 6,000 Å, 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 wire extending in one direction and a gate electrode protruding from the gate wire. can

The insulating layer 300 may include an insulating material to insulate an upper component and the gate wiring layer 200 from each other. The insulating layer 300 may cover an upper surface and a side surface 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.

Next, referring to FIGS. 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 an oxide semiconductor. Although not shown in the drawings, the method may further include doping an n-type impurity after forming the semiconductor material layer 400a.

Next, referring to FIGS. 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 diffusing into the semiconductor material layer 400a, which will be described later. The source/drain lower metal layer 510a may be a single layer including titanium or a titanium alloy. In some embodiments, the source/drain lower metal layer 510a may include the same material as the gate lower metal pattern layer 210 described above. A 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.

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

Next, referring to FIGS. 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 , wherein the first The mask pattern 610 may be formed in the first region R1 and the second region R2 , but 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 partially 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 is the first in the second region R2 . It may be greater 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 cured using a halftone mask or a slit mask after applying a photosensitive organic material with different exposure doses, so that the thickness in the first region R1 is increased to the thickness in the second region R2 . A larger first mask pattern 610 may be formed, but the present invention is not limited thereto.

Next, referring to FIGS. 1 to 6 , the source/drain upper metal layer 520a and the source/drain lower metal layer 510a are first patterned using an 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 the etchant composition according to an embodiment of the present invention described above, and overlapping descriptions will be omitted.

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

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. can remain untouched.

Next, referring to FIGS. 1 to 7 , the source/drain upper metal pattern layer 520b and the source/drain lower metal pattern formed by partially removing the source/drain upper metal layer 520a and the source/drain lower metal layer 510a. The exposed semiconductor material layer 400a 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.

Next, referring to FIGS. 1 to 8 , a second mask pattern 620 is formed by reducing the thickness of the first mask pattern 610 . 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 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 approximately uniformly reduced through an ashing process or a dry etching process, but the present invention is not limited thereto. .

Next, referring to FIGS. 1 to 9 , the source/drain upper metal pattern layer 520b and the source/drain lower metal pattern layer 510b are secondary patterned using an 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 an 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 that are not covered by the second mask pattern 620 is removed by secondary etching with an 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 through a single etching process and removed together.

On the other hand, the first region R1 of the source/drain upper metal pattern layer 520b and the source/drain lower metal pattern layer 510b covered by the second mask pattern 620 may remain in a non-removed state. . Through this, the source/drain wiring 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 interconnection layer 500 may be about 55 degrees to about 80 degrees. Components stacked on the gate wiring layer 200 by forming the side inclination angle θ2 of the gate wiring layer 200 to be relatively small, such as the insulating layer 300, the semiconductor material pattern layer 400, and the source/drain wiring layer ( 500) and the like can be improved.

The etchant composition according to the present 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 . Accordingly, the source/drain wiring layer 500 having an excellent profile may be formed. For example, the source/drain wiring layer 500 may have an etching characteristic such that the side inclination angle θ1 is in the range of about 55 degrees to 80 degrees, and through this, the components stacked on the source/drain wiring layer 500 are Coverage characteristics can be improved.

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

<Production Example>

Etching liquid compositions of Preparation Examples 1 to 14 were prepared using the compositions shown in Table 1 below.

<Comparative example>

Etching solution compositions of Comparative Examples 1 to 9 were prepared using the compositions shown in Table 1 below.

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 2 10.0 0.5 1.0 1.0 3.0 3.0 0.5 -- 1.5 -- -- remaining amount Preparation 3 10.0 0.5 1.0 1.0 3.0 3.0 1.5 -- 1.5 -- -- remaining amount Preparation 4 10.0 0.5 1.0 1.0 3.0 3.0 4.0 -- 1.5 -- -- remaining amount Preparation 5 10.0 0.5 1.0 1.0 3.0 3.0 1.0 -- 0.2 -- -- remaining amount Preparation 6 10.0 0.5 1.0 1.0 3.0 3.0 1.0 -- 0.5 -- -- remaining amount Preparation 7 10.0 0.5 1.0 1.0 3.0 3.0 1.0 -- 1.0 -- -- remaining amount Preparation 8 10.0 0.5 1.0 1.0 3.0 3.0 1.0 -- 3.0 -- -- remaining amount Preparation 9 10.0 0.5 1.0 1.0 3.0 3.0 1.0 -- 5.0 -- -- remaining amount Preparation 10 10.0 0.5 1.0 1.0 3.0 3.0 1.0 -- 6.0 -- -- remaining amount Preparation 11 10.0 0.5 1.0 1.0 3.0 0.5 1.0 -- 1.5 -- -- remaining amount Preparation 12 10.0 0.5 1.0 1.0 3.0 4.0 1.0 -- 1.5 -- -- remaining amount Preparation 13 10.0 0.5 1.0 1.0 2.0 8,0 1.0 -- 1.5 -- -- remaining amount Preparation 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 peroxide disulfate, ABF means ammonium bifluoride, and ACl means ammonium chloride. In addition, ATZ means 5-aminotetrazole, HNO ₃ means nitric acid, AcOH means acetic acid. In addition, Gly means glycine represented by Formula Ia, and IDA means iminodiacetic acid. Iminodiacetic acid was used as a control for glycine to confirm the function of glycine. SFA means sulfamic acid represented by the aforementioned 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 stands for 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 using the etchant compositions according to Preparation Examples 1 to 14 and Comparative Examples 1 to 9.

As the experimental equipment, ETCHER (TFT) (SEMES) of the spray etching method was used, and the temperature of the etchant composition was maintained at about 28° C. 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. Profiles of the patterned copper layer and titanium alloy layer were measured using a cross-section SEM S-4700 (HITACHI).

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

<Experimental Example 2>

After dissolving 3,000 ppm of copper in the etchant compositions according to Preparation Examples 1 to 14 and Comparative Examples 1 to 9, and storing it at a low temperature at -8°C, the occurrence of copper precipitates was observed and shown in Table 2 below.

<Experimental Example 3>

After immersing silicon in the etchant composition according to Preparation Examples 1 to 14 and Comparative Examples 1 to 9 at 23° C. for 3 hours, the degree of precipitate generation was observed through filtration and drying, and is shown in Table 2 below.

Etching rate (Å/sec) Copper Component Precipitation silicon component precipitate profile Preparation Example 1 ○ △ ○ Preparation 2 ○ ○ ○ Preparation 3 ○ ○ ○ Preparation 4 △ △ ○ Preparation 5 ○ △ ○ Preparation 6 ○ ○ ○ Preparation 7 ○ ○ ○ Preparation 8 ○ ○ ○ Preparation 9 ○ ○ ○ Preparation 10 △ ○ △ Preparation 11 ○ ○ ○ Preparation 12 ○ ○ ○ Preparation 13 ○ ○ ○ Preparation 14 ○ ○ ○ Comparative Example 1 ○ Х ○ Comparative Example 2 Х Х ○ copper layer gourmet 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 Excessive silicon deposits Comparative Example 9 ○ ○ Х Excessive silicon deposits

In Table 2, when the etch rate is 200 Å/sec to 300 Å/sec, it is indicated by '○', and when the etch rate is less than 200 Å/sec or exceeds 300 Å/sec, it is indicated by 'Δ', and poor etching occurs or over-etched. A case in which a defect occurred is indicated by 'X'.

In addition, in Table 2, if the copper component precipitate did not occur for 90 days, it is indicated by '○', if the copper component precipitate occurred between 60 days and 90 days, it is indicated by 'Δ', and the copper precipitate occurred before 60 days case is indicated by 'x'. The shorter the period during which the copper component precipitates occur, the more insufficient the solubility of the copper component is, and the copper component acts as an impurity, which may cause a decrease in the number of processed wiring boards.

In addition, in Table 2, when the silicon component precipitate is less than 1.2 g, it is represented by '○', when the silicon component precipitate is 1.2 g to 2.0 g, it is represented by 'Δ', and when the silicon component precipitate is more than 2.0 g, it is represented by '×'. indicated. The greater the amount of silicon component precipitates generated, the more insufficient dissolution properties for the silicon component are, and the silicon component may act as an impurity.

Referring to Table 2, Comparative Example 1 not including the first amphoteric compound (glycine) and Comparative Example 2 including 11.0 wt% of the first amphoteric compound are vulnerable to copper component precipitation, and in particular, In Comparative Example 2, in which the content of the amphoteric compound is greater than the content of peroxysulfate, it can be seen that the etch rate is very low and poor etching occurs.

In addition, Comparative Example 3 not including the second amphoteric compound (sulfamic acid) and Comparative Example 4 including 8.0 wt% of the second amphoteric compound were vulnerable to silicon component precipitation, and in particular, the etching rate in Comparative Example 4 It can be seen that not only this is very low, but also the over-etching defect appears.

In addition, in Comparative Example 5 that does not contain an organic acid (acetic acid) and Comparative Example 6 containing 22.0 wt% of an organic acid, the etching characteristics are poor, resulting in uneven etching or over-etching failure. In particular, in Comparative Example 6, the etch rate is It can be seen that it is very low.

It can be seen that Comparative Example 7 containing iminodiacetic acid, which is electrically negative in an aqueous solution state instead of the first amphoteric compound (glycine), is vulnerable to copper component precipitation.

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

On the other hand, among the etchant compositions according to Preparation Examples 1 to 14, in the case of the etchant composition in which the weight ratio of the first amphoteric compound to the second amphoteric compound satisfies 2:1 to 1:5, compared to the etchant composition that does not It can be seen that a more stable etching characteristic is exhibited. In addition, based on the content of the first amphoteric compound contributing to profile stabilization, in the case of Comparative Example 6 including an excessive amount of an organic acid or an organic acid salt, an overetching defect occurred, and too little amount of an organic acid or organic acid salt was included In the case of Comparative Example 2, it can be confirmed that non-etching defects occur. This may be because the first amphoteric compound and the organic acid or the organic acid salt perform different functions, 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.

And 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 degree of side etching of the copper layer, specifically, the etching depth was measured and shown in Table 5 below.

In Tables 3, 4, and 5, 'x' indicates a case in which the profile measurement of the pattern is impossible because the tapered side of the pattern is collapsed.

In addition, in Tables 3, 4, and 5, 'ppm' means the concentration of copper ions in the etchant composition. That is, it refers to the concentration of copper ions in the etchant composition that is increased as the etchant composition is recovered and repeatedly used in the etching process. In other words, 0 ppm means an initial etchant composition that has no history used in the etching process, and as the concentration (ppm) increases, it is repeatedly used in the etching process to mean an etchant composition with an increased 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 2 63 degrees 63 degrees 63 degrees 64 degrees 65 degrees 67 degrees Х Preparation 3 59 degrees 59 degrees 59 degrees 59 degrees 59 degrees 59 degrees Х Preparation 4 54 degrees 54 degrees 54 degrees 54 degrees 54 degrees 54 degrees Х Preparation 5 57 degrees 54 degrees 54 degrees 54 degrees 54 degrees 54 degrees Х Preparation 6 57 degrees 54 degrees 54 degrees 54 degrees 54 degrees 54 degrees Х Preparation 7 58 degrees 58 degrees 58 degrees 58 degrees 58 degrees 59 degrees Х Preparation 8 59 degrees 59 degrees 59 degrees 59 degrees 59 degrees 59 degrees 62 degrees Preparation 9 60 degrees 60 degrees 61 degrees 61 degrees 61 degrees 61 degrees Х Preparation 10 60 degrees 60 degrees 61 degrees 62 degrees 63 degrees 63 degrees Х Preparation 11 57 degrees 54 degrees 54 degrees 54 degrees 54 degrees 54 degrees Х Preparation 12 57 degrees 54 degrees 54 degrees 54 degrees 54 degrees 54 degrees Х Preparation 13 58 degrees 58 degrees 58 degrees 58 degrees 58 degrees 59 degrees Х Preparation 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 gastronomic gastronomic gastronomic gastronomic gastronomic gastronomic gastronomic Comparative Example 3 58 degrees 58 degrees 58 degrees 58 degrees Х Х Х Comparative Example 4 over-etched over-etched over-etched over-etched over-etched over-etched over-etched 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 etchant composition in the initial state (that is, 0 ppm) and the taper angle of the pattern using the etchant composition having a high copper ion concentration, the higher the number of sheets to be processed and excellent etching properties means to have

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

First, in the case of the etchant composition according to Preparation Examples 1 to 14 containing both the first amphoteric compound (glycine) and the second amphoteric compound (sulfamic acid), the etching process is performed using the etchant composition in an initial state. It can be seen that there is no significant difference between the taper angle of one pattern and the taper angle of a pattern in which an etching process is performed using an etchant composition including copper ions at a concentration of 5,000 ppm.

On the other hand, in the case of Comparative Example 2 containing 11.0 wt% of the first amphoteric compound and Comparative Example 4 including 8.0 wt% of the second amphoteric compound, the copper layer was not etched or over-etched. can be checked

In addition, in the etchant composition of Comparative Example 1 and Comparative Example 7 not including the first amphoteric compound and the etchant composition of Comparative Example 9 not including 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 in that the taper angle of the pattern using the etchant composition containing copper ions at a concentration of 5,000 ppm is increased by about 10 degrees or more compared to the above.

In addition, in Comparative Examples 3 and 8, which do not include the second amphoteric compound, as the number of wiring boards processed increases, specifically, when the copper ion concentration is 4,000 ppm or more, the tapered slope collapses, making it impossible to measure.

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 that does not contain any one and an excessively large content of the first amphoteric compound or the second amphoteric compound It can be seen that the number of processable 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㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.12㎛ 0.13㎛ Х Preparation 2 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.12㎛ Х Preparation 3 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ Х Preparation 4 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ Х Preparation 5 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ Х Preparation 6 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ Х Preparation 7 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ Х Preparation 8 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.13㎛ Preparation 9 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ Х Preparation 10 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ Х Preparation 11 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ Х Preparation 12 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ Х Preparation 13 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ Х Preparation 14 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ 0.11㎛ Х Comparative Example 1 0.11㎛ 0.11㎛ 0.12㎛ 0.13㎛ 0.16㎛ 0.21㎛ Х Comparative Example 2 gastronomic gastronomic gastronomic gastronomic gastronomic gastronomic gastronomic Comparative Example 7 0.11㎛ 0.11㎛ 0.12㎛ 0.13㎛ 0.16㎛ 0.22㎛ Х

Referring to Table 4, in the case of the etchant composition according to Preparation Examples 1 to 14 containing 0.01% to 10.0% by weight of the first amphoteric compound (glycine), it can be seen that the profile of the titanium alloy layer is good. have.

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

In addition, in the case of the etchant compositions of Comparative Examples 1 and 7 that do not include the first amphoteric compound, it can be seen that the profile of the titanium alloy layer rapidly deteriorates as the number of substrates processed increases.

That is, in the case of the etchant composition according to Preparation Example including about 0.01% to 10.0% by weight of the first amphoteric compound, it can be seen that the profile of the titanium alloy layer can be improved compared to that of the etchant composition that does 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㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.68㎛ Preparation 2 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.68㎛ Preparation 3 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.68㎛ Preparation 4 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.74㎛ 0.69㎛ Preparation 5 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.68㎛ Preparation 6 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.68㎛ Preparation 7 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.68㎛ Preparation 8 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.68㎛ Preparation 9 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.68㎛ Preparation 10 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.70㎛ Preparation 11 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.68㎛ Preparation 12 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.68㎛ Preparation 13 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.74㎛ 0.69㎛ Preparation 14 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ 0.75㎛ Comparative Example 5 0.75㎛ 0.75㎛ 0.77㎛ 0.79㎛ 0.83㎛ 0.86㎛ 0.75㎛

Referring to Table 5, in the case of the etchant compositions according to Preparation Examples 1 to 14 containing 1.0 wt% to 20.0 wt% of an organic acid (acetic acid), it can be seen that the etching profile of the copper layer is good.

On the other hand, in the case of 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 substrates to be processed increases.

That is, it can be seen that in the case of the etchant composition according to Preparation Example including about 1.0 wt% to 20.0 wt% of the organic acid, the profile of the copper layer can be improved compared to that of the etchant composition that does not.

In the above, the embodiment of the present invention has been mainly described, but this is only an example and does not limit the present invention. It will be appreciated that various modifications and applications not exemplified above are possible. For example, each component specifically shown in the embodiment of the present invention may be implemented by modification. And differences related to such modifications and applications should be construed as being included in the scope of the present invention defined in the appended claims.

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

Claims (16)

In the etchant composition of a double film made of copper or a copper alloy and titanium or a titanium alloy,
1.0% to 20% by weight of peroxysulfate;
0.1 wt% to 5.0 wt% of a cyclic amine compound;
0.01 wt% to 2.0 wt% of a fluorinated compound;
0.01 wt% to 5.0 wt% of a chlorine-containing compound;
0.5% to 10.0% by weight of inorganic acid;
0.5% to 8% by weight of an organic acid or an organic acid salt;
0.5 wt% to 1.5 wt% of a first amphoteric compound having a carboxyl group; and
and 0.5 wt% to 5.0 wt% of a second amphoteric compound different from the first amphoteric compound and having a sulfone group;
Within the above range, the weight ratio of the first amphoteric compound to the second amphoteric compound is 2:1 to 1:5,
In the above range, the weight ratio of the first amphoteric compound and the organic acid or organic acid salt is 2:1 to 1:8 of the etchant composition. According to claim 1,
The content of the peroxysulfate is greater than the content of the first amphoteric compound etchant composition. 3. The method of claim 2,
The first amphoteric compound is an etchant composition comprising at least one of the compounds represented by the following Chemical Formulas Ia to Ie.
<Formula Ia>

<Formula Ib>

<Formula Ic>

<Formula Id>

<Formula Ie>

3. The method of claim 2,
The second amphoteric compound is an etchant composition comprising at least one of the compounds represented by the following Chemical Formulas IIa to IIc.
<Formula IIa>

<Formula IIb>

<Formula IIc>

According to claim 1,
The peroxide sulfate is potassium peroxide disulfate (K ₂ S ₂ O ₈ ), sodium peroxide disulfate (Na ₂ S ₂ O ₈ ), or ammonium peroxide disulfate ((NH ₄ ) ₂ S ₂ O ₈ ) Etching solution composition comprising. According to claim 1,
The cyclic amine compound is 5-aminotetrazole (5-aminotetrazole), 1-methyl-5-aminotetrazole (1-methyl-5-aminotetrazole), 5-methyltetrazole (5-methyltetrazole), 1-ethyl -5-aminotetrazole (1-ethyl-5-aminotetrazole), imidazole (imidazole), indole (indole), purine (purine), pyrazole (pyrazole), pyridine (pyridine), pyrimidine (pyrimidine), pyrrole (pyrrole), pyrrolidine (pyrrolidine), and an etchant composition comprising at least one of pyrroline (pyrroline). According to claim 1,
The fluorinated compound is an etchant composition comprising at least one of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride and potassium bifluoride. According to claim 1,
The chlorine-containing compound is an etchant composition comprising at least one of hydrochloric acid, sodium chloride, potassium chloride, ammonium chloride, iron (III) chloride, sodium perchlorate, potassium perchlorate, ethylsulfonyl chloride and methanesulfonyl chloride. According to claim 1,
The inorganic acid is nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ), phosphoric acid or phosphorous acid (H ₂ PO ₃ , H ₃ PO ₃ ) Etch solution composition comprising a. According to claim 1,
The organic acid is selected from among acetic acid, formic acid, propenoic acid, butanoic acid, pentanoic 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 a sodium salt, potassium salt or ammonium salt of the organic acid. According to claim 1,
Further comprising 0.01% to 5.0% by weight of a copper salt,
The copper salt is an etchant composition comprising a copper sulfate salt, a copper chloride salt or a copper nitrate salt. A method of manufacturing a wiring board comprising forming a first wiring layer on the substrate, the method comprising:
Forming the first wiring layer comprises:
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
Using an etchant composition comprising the step of patterning the first metal layer and the second metal layer,
The etchant composition is an etchant composition of a double layer made of copper or a copper alloy and titanium or a titanium alloy,
1.0% to 20% by weight of peroxysulfate;
0.1 wt% to 5.0 wt% of a cyclic amine compound;
0.01 wt% to 2.0 wt% of a fluorinated compound;
0.01 wt% to 5.0 wt% of a chlorine-containing compound;
0.5% to 10.0% by weight of inorganic acid;
0.5% to 8% by weight of an organic acid or an organic acid salt;
0.5 wt% to 1.5 wt% of a first amphoteric compound having a carboxyl group; and
and 0.5 wt% to 5.0 wt% of a second amphoteric compound different from the first amphoteric compound and having a sulfone group;
Within the above range, the weight ratio of the first amphoteric compound to the second amphoteric compound is 2:1 to 1:5,
Within the above range, the weight ratio of the first amphoteric compound to the organic acid or organic acid salt is 2:1 to 1:8. 13. The method of claim 12,
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. 14. 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 method of manufacturing a wiring board, wherein the second wiring layer includes a titanium or titanium alloy layer and a copper or copper alloy layer stacked on each other. 15. The method of claim 14,
a side inclination angle of the second wiring layer is smaller than a side inclination angle of the first wiring layer;
A side inclination angle of the first wiring layer is 55 degrees to 80 degrees. 13. The method of claim 12,
The step of patterning the first metal layer and the second metal layer using the etchant composition,
forming a mask pattern on the first and second regions of the first metal layer and the second metal layer;
first etching a third region of the first metal layer and the second metal layer that 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 performing secondary etching of the second region of the first metal layer and the second metal layer using the etchant composition.

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