KR20160001294A - Etching solution composition for metal layer and manufacturing method of an array substrate for Liquid crystal display using the same - Google Patents

Abstract

The present invention provides an etching solution composition and a method for manufacturing an array substrate for a liquid crystal display using the composition. The etching solution composition comprises: a metal film oxidizing agent; a compound of a chemical formula 1; and water.

Description

TECHNICAL FIELD The present invention relates to an etching solution composition for a metal film and an array substrate for a liquid crystal display using the same,

The present invention relates to an etching liquid composition for a metal film and a method of manufacturing an array substrate for a liquid crystal display using the same.

In the case of flat panel displays such as LCDs, PDPs and OLEDs, in particular, in the case of TFT-LCDs, a single film of copper or copper alloy, or copper or copper alloy, in order to reduce the wiring resistance and increase the adhesion with the silicon insulating film, An alloy / other metal, an intermetallic alloy or a metal oxide has been widely studied. For example, a copper / molybdenum film, a copper / titanium film or a copper / molybdenum-titanium film can form a source / drain wiring constituting a gate wiring and a data line of the TFT-LCD, . Therefore, it is required to develop a composition having excellent etching properties capable of etching a metal film including the copper-based film.

Such etching compositions are typically known as etching solutions based on hydrogen peroxide and amino acids, etching solutions based on hydrogen peroxide and phosphoric acid, etching solutions based on hydrogen peroxide and polyethylene glycol, and the like.

For example, Korean Patent Laid-Open No. 10-2011-0031796 discloses an etching solution comprising A) a hydrogen peroxide (H ₂ O ₂ ) B) and a sulfate, C) a water-soluble compound having a carboxyl group and an amine group, and water.

Korean Patent Laid-Open No. 10-2012-0044630 discloses a copper-containing metal film etchant containing hydrogen peroxide, phosphoric acid, cyclic amine compound, sulfate, boron fluoride acid and water.

Korean Patent Publication No. 10-2012-0081764 discloses an etching solution comprising A) ammonium hydroxide, B) hydrogen peroxide, C) fluorine compound, D) polyhydric alcohol and E) water.

However, such etchants do not sufficiently satisfy the conditions required in this field in terms of CD loss, taper, pattern straightness, metal residue, storage stability, number of treatments, etc. with respect to a metal film containing a copper-based film have.

Korean Patent Publication No. 10-2011-0031796 Korean Patent Publication No. 10-2012-0044630 Korean Patent Publication No. 10-2012-0081764

Disclosure of Invention Technical Problem [8] The present invention has been made to solve the above-mentioned problems of the prior art, and it is an object of the present invention to provide an etchant composition for a metal film and a liquid crystal display device using the same, having excellent workability, excellent etching speed and storage stability, And an object of the present invention is to provide a method of manufacturing an array substrate.

According to the present invention,

Metal film oxidizer; A compound represented by Formula 1 below; And water. ≪ RTI ID = 0.0 >

[Chemical Formula 1]

In this formula,

R ₁ is hydrogen, an aliphatic hydrocarbon having 1 to 5 carbon atoms, an aliphatic hydrocarbon having 1 to 5 carbon atoms containing an amino group, an aliphatic hydrocarbon having 2 to 4 carbon atoms containing an amino group substituted with a hydrocarbon having 6 to 13 carbon atoms including an aromatic ring , Or an aliphatic hydrocarbon having 2 to 6 carbon atoms containing a carboxyl group;

R ₂ is hydrogen, an aliphatic hydrocarbon of 1 to 5 carbon atoms, an aliphatic hydrocarbon of 1 to 5 carbon atoms containing an amino group, or a hydrocarbon of 6 to 13 carbon atoms containing an aromatic ring, and when two R ₂ are present, R ₂ may combine with each other to form a ring;

m is 1 to 3;

n is a natural number from 1 to 20.

In addition,

a) forming a gate electrode on a substrate;

b) forming a gate insulating layer on the substrate including the gate electrode;

c) forming a semiconductor layer on the gate insulating layer;

d) forming a source / drain electrode on the semiconductor layer; And

e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:

Wherein the steps a), d), or e) comprise forming a metal film and etching the metal film with the etchant composition of the present invention to form an electrode. to provide.

The metal film etchant composition of the present invention provides an effect of treating a large amount of substrates by including aminopolyethylene glycol (Chemical Formula 1).

In addition, the etching composition of the metal film including the copper-based film, which is an embodiment of the present invention, includes a low content of hydrogen peroxide, thereby providing excellent work safety and economical disposal of the etchant, Respectively. In addition, it is excellent in storage stability and contains a large amount of substrate processing ability by including aminopolyethylene glycol (Chemical Formula 1).

The method for manufacturing an array substrate for a liquid crystal display device using the etching liquid composition of the present invention is characterized in that an electrode having an excellent etching profile is formed on an array substrate for a liquid crystal display device to manufacture an array substrate for a liquid crystal display .

According to the present invention,

Metal film oxidizer; A compound represented by Formula 1 below; And water. ≪ RTI ID = 0.0 > [0002] < / RTI >

[Chemical Formula 1]

In this formula,

R ₁ is hydrogen, an aliphatic hydrocarbon having 1 to 5 carbon atoms, an aliphatic hydrocarbon having 1 to 5 carbon atoms containing an amino group, an aliphatic hydrocarbon having 2 to 4 carbon atoms containing an amino group substituted with a hydrocarbon having 6 to 13 carbon atoms including an aromatic ring , Or an aliphatic hydrocarbon having 2 to 6 carbon atoms containing a carboxyl group;

R ₂ is hydrogen, an aliphatic hydrocarbon of 1 to 5 carbon atoms, an aliphatic hydrocarbon of 1 to 5 carbon atoms containing an amino group, or a hydrocarbon of 6 to 13 carbon atoms containing an aromatic ring, and when two R ₂ are present, R ₂ may combine with each other to form a ring;

m is 1 to 3;

n is a natural number from 1 to 20.

In the above-mentioned "aliphatic hydrocarbon having 2 to 4 carbon atoms including an amino group substituted with a hydrocarbon having 6 to 13 carbon atoms and including an aromatic ring ", the aromatic ring is a concept including an aromatic heterocycle, Pyridine, pyrimidine, pyrrole, imidazole, and the like.

In the above, m is 1 or 3, and n is more preferably 1 to 5.

As concrete compounds, the compounds of formulas (2) to (9), wherein m is 1, and the compounds of formulas (10) to (11) wherein m is 3 are shown below:

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

The metal film oxidizing agent is not particularly limited and may be typically at least one selected from the group consisting of hydrogen peroxide, peracetic acid, metal oxide, nitric acid, persulfate, halogen acid, halide acid salt and the like.

The metal oxide means an oxidized metal, for example, Fe ^{3 +} , Cu ^{2 +} or the like. The metal oxide also includes a compound dissociated into Fe ^{3 +} , Cu ^{2 +} or the like in a solution state, Sulfates include ammonium persulfate, persulfate alkali metal salts, oxone, and halide salts include chlorate, perchlorate, bromate, perbromate, and the like.

In the present invention, the compound of Chemical Formula 1 functions to increase the number of processed substrates by chelating metal ions such as copper ions present in the etching solution at the time of etching.

The etchant composition comprises 1 to 40% by weight of a metal film oxidizing agent, 1 to 10% by weight of a compound of the formula (1), And water balance.

The content of the metal film oxidizing agent may be appropriately controlled depending on the type and characteristics of the oxidizing agent.

It is more preferable that the compound of Formula 1 is contained in an amount of 2 to 5% by weight. When the amount of the compound of formula (1) is less than 1% by weight, it is difficult to expect an increase in the number of substrates to be treated. When the amount exceeds 10% by weight, the effect is not expected to increase any more. Which is undesirable because it causes a decrease in etching rate.

The etchant composition of the present invention can be used regardless of the film quality to be etched, but can be more preferably used for etching a copper-based metal film, a molybdenum-based metal film, a titanium-based metal film, or a multilayer film made of the same.

The copper-based metal film means a copper film or a copper alloy film, and the molybdenum-based metal film means a molybdenum film or a molybdenum alloy film, and the titanium-based metal film means a titanium film or a titanium alloy film.

The multilayered film may be a multilayer film of a molybdenum-based metal / copper-based metal film having a copper-based metal film as a lower film and a molybdenum-based metal film as an upper film; A double layered film of a copper-based metal film / molybdenum-based metal film having a molybdenum-based metal film as a lower film and a copper-based metal film as an upper film, a molybdenum metal film / a copper metal film / a molybdenum metal film, Or a multi-layered film including a copper-based metal film / a molybdenum-based metal film / a copper-based metal film alternately laminated with a copper-based metal film and a molybdenum-based metal film alternately.

The multi-layered film may be a double-layered film of a titanium-based metal film / copper-film-based metal film having a copper-based metal film as a lower film and a titanium-based metal film as an upper film, a titanium-based metal film as a lower film, And a titanium-based metal film / a copper-based metal film / a titanium-based metal film or a copper-based metal film / a titanium-based metal film / a copper- And a multi-layered film of three or more layers alternately laminated with a metal film.

The interlayer coupling structure can be determined by taking into account the composition of the film disposed on the upper part of the multilayer film or the material constituting the film disposed on the lower part of the multilayer film or adhesion with the films.

The term "copper, molybdenum or titanium alloy film" as used herein refers to a metal film made of copper, molybdenum or titanium as a main component and made of an alloy using another metal, depending on the characteristics of the film. For example, the molybdenum alloy film is made of molybdenum as a main component and at least one selected from among titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd) And the like.

The etchant composition of the present invention may further comprise at least one member selected from the group consisting of a nitrogen atom-containing compound, a fluorine compound, an acid containing a sulfur (S) atom or phosphorus (P) atom and the like.

The nitrogen atom-containing compound contained in the etchant composition of the present invention has a role of improving the etching rate and the number of treatments of the etching solution. As the nitrogen atom-containing compound, any compound known in the art may be used without limitation, and typically a compound containing an amino group and a carboxylic acid group in the molecule may be used,

Examples of the compound containing an amino group and a carboxylic acid group in the molecule include an alpha amino acid including one carbon atom between a carboxylic acid and an amino group. Representative examples of the compound include a monovalent amino acid such as glycine, glutamic acid, glutamine, isoleucine proline, tyrosine, arginine, , Iminodiacetic acid, nitrilodriacetic acid, and ethylene glycol tetraacetic acid. These nitrogen atom-containing compounds may be used alone or in combination of two or more.

The nitrogen atom-containing compound may be contained in an amount of 0.1 to 10% by weight, more preferably 1 to 5% by weight based on the total weight of the composition. When the amino acid is included in the above-mentioned range, the etching rate and the number of treatments of the etching solution can be improved.

The fluorine compound contained in the etching solution composition of the present invention serves to remove the etching residue and to etch the titanium-based metal film.

The fluorinated compound may be contained in an amount of 0.1 to 5% by weight, more preferably 0.1 to 2% by weight based on the total weight of the composition. When the above-mentioned range is satisfied, it is preferable to prevent etching residues and not to etch the glass substrate or the lower silicon film. However, deviating from the above-described range may cause unevenness in the substrate due to non-uniform etching characteristics, excessive etching may damage the underlying film, and etching rate control may be difficult during processing.

The fluorinated compound is preferably a compound capable of dissociating into a fluorine ion or a polyatomic fluorine ion. The compound capable of dissociating into fluorine ion or polyatomic fluorine ion may be one or more selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, sodium bisulfite, and potassium bisulfate.

The acid containing the sulfur (S) atom or phosphorus (P) atom may be contained in an amount of 0.01 to 10% by weight, more preferably 0.01 to 1% by weight based on the total weight of the composition. When the acid satisfies the above-mentioned range, it is possible to avoid the excessive etching of the metal film and the corrosion of the lower film due to the acid, and the acid content is too low to lower the etching rate of the metal film. Function can be performed.

As the acid containing the sulfur (S) atom or phosphorus (P) atom, sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid and the like can be used without limitation, and phosphoric acid can be preferably used . The phosphoric acid promotes copper etching of hydrogen peroxide by providing hydrogen ions to the etching solution. In addition, it forms a phosphate by binding with oxidized copper ions, thereby increasing solubility in water and eliminating residues of the metal film after etching.

The water used in the present invention means deionized water and is used for semiconductor processing, preferably water of 18 M / cm or more.

The etchant composition of the present invention may further comprise at least one of an etching control agent, a surfactant, a sequestering agent, a corrosion inhibitor and a pH adjuster in addition to the above-mentioned components.

The etchant composition of the present invention is a specific example,

Hydrogen peroxide may be used as the metal film oxidizing agent, and it may further comprise a nitrogen atom-containing compound together with the crown ether compound represented by the formula (1) and water.

It may further contain at least one selected from the group consisting of fluorine compounds and acids containing sulfur (S) atoms and phosphorus (P) atoms.

The etchant composition is preferably used particularly for etching a copper-based metal film or a copper-based metal film / molybdenum metal film or a copper-based metal film / titanium-based metal film. However, the use of the composition is not limited to the film quality.

The hydrogen peroxide is the main component that oxidizes copper, molybdenum, and titanium. The hydrogen peroxide is preferably contained in an amount of 1 to 25% by weight, preferably 1 to 10% by weight, more preferably 1 to 5% by weight based on the total weight of the composition. When the above-mentioned range is satisfied, deterioration of the etching rate of copper, molybdenum, and titanium is prevented, an appropriate amount of etching can be realized, and an excellent etching profile can be obtained. However, if the range is out of the above range, the film to be etched may not be etched, or an excessive angle may be generated, and pattern loss and function as a metal wiring may be lost.

The components constituting the etchant composition of the present invention preferably have purity for semiconductor processing.

The present invention also relates to

a) forming a gate electrode on a substrate;

b) forming a gate insulating layer on the substrate including the gate electrode;

c) forming a semiconductor layer on the gate insulating layer;

d) forming a source / drain electrode on the semiconductor layer; And

e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:

Wherein the steps a), d), or e) comprise forming a metal film and etching the metal film with the etchant composition of the present invention to form an electrode. to provide.

The array substrate for a liquid crystal display manufactured by the above method has excellent driving characteristics because it includes an electrode having an excellent etching profile.

The array substrate for a liquid crystal display may be a thin film transistor (TFT) array substrate.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Example  1 to 10 and Comparative Example 1 ~ 3: Etchant  Preparation of composition

The components listed in Table 1 below were mixed in the respective amounts to prepare an etchant composition.

division Metal film oxidizing agent Polyamino ether compound Ammonium fluoride Glycine Phosphoric acid Triethylene glycol Deionized water Example 1 nitric acid 10 Formula 11 5 One Balance Example 2 Ammonium persulfate 10 Formula 11 5 One Balance Example 3 Hydrogen peroxide 10 Formula 11 5 One Balance Example 4 Hydrogen peroxide 10 Formula 11 5 One One Balance Example 5 Hydrogen peroxide 5 Formula 11 5 One One 0.1 Balance Example 6 Hydrogen peroxide 5 (2) 5 One One 0.1 Balance Example 7 Hydrogen peroxide 5 (3) 5 One One 0.1 Balance Example 8 Hydrogen peroxide 5 6 5 One One 0.1 Balance Example 9 Hydrogen peroxide 5 Formula 7 5 One One 0.1 Balance Example 10 Hydrogen peroxide 5 8 5 One One 0.1 Balance Comparative Example 1 Hydrogen peroxide 5 One Balance Comparative Example 2 Hydrogen peroxide 5 One One Balance Comparative Example 3 Hydrogen peroxide 5 One One 0.1 5 Balance

(Unit: wt%)

week)

(2)

(3)

[Chemical Formula 6]

(7)

[Chemical Formula 8]

(11)

Test Example  One: Etchant  Of the composition Etch characteristics  evaluation

(One) Cu Single membrane Etching

Etching of the Cu single layer was performed using the etchant compositions of Examples 1 to 3 and Comparative Example 1. During the etching process, the etchant composition was etched at a temperature of about 30 캜 for 100 seconds. EPD (End Point Detection) was measured with the naked eye to obtain the etching rate with time. The profile sections of the etched Cu single films were inspected using SEM (product of Hitachi, model name S-4700) and the results are shown in Table 2 below.

(2) Cu / Mo - Ti Bilayer Etching

Etching of Cu / Mo-Ti bilayers was performed using the etchant compositions of Examples 4 to 10 and Comparative Examples 2 to 3. During the etching process, the etchant composition was etched at a temperature of about 30 캜 for 100 seconds. EPD (End Point Detection) was measured with the naked eye to obtain the etching rate with time. The profile sections of the etched Cu / Mo-Ti bilayers were examined using an SEM (product of Hitachi, Model S-4700), and the results are shown in Table 2 below.

Test Example  2: Evaluation of the number of processing

Reference etch tests were performed on the etchant compositions of Examples 1 to 10 and Comparative Examples 1 to 3, and 4,000 ppm of copper powder was added to the reference test etchant to completely dissolve them. Thereafter, etching was again carried out to carry out the reference etching test, and the etching rate was evaluated by the lowering rate of the etching rate.

<Evaluation Criteria>

Good: Excellent (lowering rate of etching rate is less than 10%)

?: Good (etching rate lowering rate: 10% to 20%)

×: poor (etching rate lowering rate exceeding 20%)

division Etching rate
(Å / sec) Number of processing Example 1 147 ○ Example 2 162 ○ Example 3 123 ○ Example 4 125 ○ Example 5 142 ○ Example 6 145 ○ Example 7 139 ○ Example 8 147 ○ Example 9 144 ○ Example 10 149 ○ Comparative Example 1 127 × Comparative Example 2 122 × Comparative Example 3 144 △

Claims (9)

Metal film oxidizer; A compound represented by Formula 1 below; And water. &Lt; RTI ID = 0.0 &gt;
[Chemical Formula 1]

In this formula,
R ₁ is hydrogen, an aliphatic hydrocarbon having 1 to 5 carbon atoms, an aliphatic hydrocarbon having 1 to 5 carbon atoms containing an amino group, an aliphatic hydrocarbon having 2 to 4 carbon atoms containing an amino group substituted with a hydrocarbon having 6 to 13 carbon atoms including an aromatic ring , Or an aliphatic hydrocarbon having 2 to 6 carbon atoms containing a carboxyl group;
R ₂ is hydrogen, an aliphatic hydrocarbon of 1 to 5 carbon atoms, an aliphatic hydrocarbon of 1 to 5 carbon atoms containing an amino group, or a hydrocarbon of 6 to 13 carbon atoms containing an aromatic ring, and when two R ₂ are present, R ₂ may combine with each other to form a ring;
m is 1 to 3;
n is a natural number from 1 to 20. The method according to claim 1,
In Formula 1, m is 1 or 3,
n is from 1 to 5. &lt; RTI ID = 0.0 &gt; 8. &lt; / RTI &gt; The method according to claim 1,
Wherein the metal film oxidizing agent is at least one selected from the group consisting of hydrogen peroxide, peracetic acid, metal oxide, nitric acid, persulfate, halogen acid, and halide acid salt. The method according to claim 1,
1 to 40% by weight, based on the total weight of the composition, of a metal film oxidizing agent; 1 to 10% by weight of the compound of Formula 1; And an amount of water remaining. The method of claim 4,
0.1 to 10% by weight of a nitrogen atom-containing compound, 0.1 to 5% by weight of a fluorine compound and 0.01 to 10% by weight of an acid containing a sulfur (S) atom or phosphorus (P) atom &Lt; / RTI &gt; The method of claim 5,
Hydrogen peroxide as the metal film oxidizing agent is contained in an amount of 1 to 25% by weight; Wherein the nitrogen atom-containing compound is an amino acid, and the acid containing a sulfur (S) atom or phosphorus (P) atom is a phosphoric acid. The method according to claim 1,
Wherein the etchant composition is used for etching a copper-based metal film, a molybdenum-based metal film, a titanium-based metal film, or a multilayer film made of the same. The method of claim 7,
Wherein the multilayered film is a copper-based metal film / molybdenum metal film, or a copper-based metal film / titanium-based metal film. a) forming a gate electrode on a substrate;
b) forming a gate insulating layer on the substrate including the gate electrode;
c) forming a semiconductor layer on the gate insulating layer;
d) forming a source / drain electrode on the semiconductor layer; And
e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:
Wherein the step a), the step d) or the step e) includes the step of forming a metal film and etching the metal film with the etching liquid composition according to any one of claims 1 to 6 to form an electrode. / RTI &gt;