KR20190033886A - Fluorine-free etching composition for multylayer metal film and method for etching of multylayer metal film using the composition - Google Patents

Abstract

The present invention relates to a fluorine-free etching solution composition for a multilayer metal film and a method for etching a multilayer metal film using the same. More specifically, the fluorine-free etching solution composition comprises: a) 15-30 wt% of hydrogen peroxide; b) 0.1-3 wt% of chelate agent; c) 0.1-3 wt% of auxiliary chelate agent; d) 0.01-5 wt% of corrosion inhibitor; e) 0.005-5 wt% of etching agent; f) 0.05-3 wt% of pH regulator; and g) 0.1-5 wt% of stabilizer and remaining water. The fluorine-free etching solution composition does not comprise a fluorine compound, and its pH is 1 to 4. According to the present invention, the fluorine-free etching solution composition for the multilayer metal film and the method for etching the multilayer metal film using the same are capable of having excellent stability and etching performance, suppressing the generation of molybdenum residue even without using a fluorine compound, and reducing IGZO damage, bias on one side, etc.

Description

FIELD OF THE INVENTION The present invention relates to a fluorine-free etching solution composition for a multilayered metal film, and a method for etching a multilayered metal film using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a fluorine-free etchant composition for a multilayered metal film, and a method for etching a multilayer metal film using the same, which is excellent in stability and etching performance, inhibits the generation of molybdenum residue without using a fluorine compound, The present invention relates to a fluorine-free etchant composition for a multi-layer metal film having an effect of reducing the side bias and the like, and a method for etching a multi-layer metal film using the same.

The microcircuit of the thin film transistor liquid crystal display (TFT-LCD) has a structure in which a photoresist is uniformly applied to an insulating film such as a conductive metal film such as Al, an Al alloy, an alloy including Cu and Cu or a silicon oxide film or a silicon nitride film formed on a substrate A photoresist of a desired pattern is formed through development, and a pattern is transferred to a metal film or an insulating film under the photoresist by dry or wet etching. Thereafter, Is removed through a stripping process.

The resistance of the metal film used at this time is a factor that causes electrical signal delay of the thin film transistor liquid crystal display device. Recently, the metal film has a low resistance value in order to reduce the electrical signal delay, (Cu) is spotlighted.

However, copper has a poor adhesion to the glass and silicon films, and various barrier metals are used to prevent the diffusion of Cu to the silicon layer. Of these barrier metals, Molybdenum or an alloy thereof. Concretely, in order to compensate for the disadvantages of the copper wiring described above, a metal film of a multilayer structure is used in which copper is formed of a main metal film and molybdenum or an alloy thereof is used as a buffer metal film as a barrier metal.

In order to effectively etch the multilayered metal film, the etchant is usually used. When the etchant is used, the lower the pH of the copper is, the better the etch rate of the molybdenum (or its alloy) . In addition, since the stability of hydrogen peroxide lowers in the high pH region, the pH of the hydrous etchant is generally set to 1 to 3, and if the fluorine compound is not used in such pH range, the residue of molybdenum (or its alloy) Residue is generated to cause defects in the panel manufacturing process. Therefore, a fluorine compound is used to prevent this.

However, the etching solution containing a fluorine compound causes etching of the glass substrate, thereby restricting the reuse of the glass substrate when a defect occurs in the panel manufacturing process. For this reason, a composition capable of efficiently etching a metal film having a multilayer structure is implemented There are many difficulties.

In the case of an oxide thin film transistor (oxide TFT), when an etching solution containing a fluorine compound is used, damage to the IGZO (Indium Gallium Zinc Oxide) film is caused in the same manner as the etching property of the glass substrate, The etchant used in the manufacture of the oxide thin film transistor needs to be preconditioned to have no IGZO damage at all.

In order to smoothly etch molybdenum (or an alloy thereof) without using a fluorine compound, the etching solution must have a condition capable of maintaining a high pH region. When the pH is high, the stability of hydrogen peroxide is significantly lowered, When copper and molybdenum, which are transition metals, are dissolved in the etchant during molybdenum etching, the decomposition stability of hydrogen peroxide is further lowered. Therefore, there is no process margin to such an extent that 1000 ppm of copper can not be used.

In addition, when the pH is low, most of the copper etching solution using hydrogen peroxide can not maintain the high pH because it can not prevent the IGZO film damage of the oxide thin film transistor.

Therefore, it is urgent to research and develop a multi-layered metal film etchant capable of reducing molybdenum residue and IGZO damage while having a low pH.

KR 10-0827575 B1

In order to solve the problems of the prior art as described above, it is an object of the present invention to provide a polyimide-based metal film which is excellent in stability and etching performance in etching a multilayered metal film including a copper-based metal film and a molybdenum- And a method of etching a metal film of a multilayer structure using the same, which is capable of suppressing the generation of residues and reducing the IGZO damage, bias on one side, and the like.

These and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention provides a process for the preparation of a composition comprising a) 15 to 30% by weight of hydrogen peroxide, b) 0.1 to 3% by weight of a chelating agent, c) 0.1 to 3% by weight of an auxiliary chelating agent, d) , e) 0.005 to 5 wt% of an etching agent, f) 0.05 to 3 wt% of a pH adjusting agent, g) 0.1 to 5 wt% of a stabilizer and a water balance, The present invention also provides a fluorine-free etching solution composition for a multi-layered metal film.

The present invention also provides a method for manufacturing a semiconductor device, which has an IGZO damage (35 ° C, 100 seconds etching) of 0.30 μm or less and a side bias (MoTi / Cu / MoTi; thickness 100 Å / 2,500 Å / 300 Å; overetched 30% The present invention also provides a fluorine-free etching solution composition for a multi-layered metal film.

The present invention also provides a method of manufacturing a semiconductor device, wherein the upper tip (MoTi / Cu / MoTi, thickness 100 Å / 2,500 Å / 300 Å, ppm or less of the fluorine-free etching solution composition of the present invention.

The present invention also provides a method of etching a multi-layered metal film using the fluorine-free etchant composition of the multi-layered metal film, wherein the multi-layered metal film including the copper-based metal film and the molybdenum-based metal film is etched.

INDUSTRIAL APPLICABILITY The fluorine-free etchant composition and the etching method using the fluorine-free etchant composition according to the present invention are excellent in stability and etching performance in etching a multilayered metal film including a copper-based metal film and a molybdenum-based metal film, It is possible to reuse the substrate due to no occurrence of a problem such as a short circuit or a wiring defect due to the suppression of the generation of the residue and the etching of the glass substrate does not occur and the substrate can be reused without causing the IGZO damage and greatly reducing the bias on one side Lt; / RTI >

1 is a scanning electron micrograph (side view) of a MoTi / Cu / MoTi triple layer etched using the etchant composition according to Example 1. FIG.
2 is a scanning electron micrograph (side view) of a MoTi / Cu / MoTi triple layer etched using the etchant composition according to the control example.

Hereinafter, the present invention will be described in detail.

The fluorine-free etchant composition of the multilayered metal film of the present invention comprises a) 15 to 30% by weight of hydrogen peroxide, b) 0.1 to 3% by weight of a chelating agent, c) 0.1 to 3% by weight of an auxiliary chelating agent, d) %, e) from 0.005 to 5% by weight of an etching agent, f) from 0.05 to 3% by weight of a pH adjusting agent, g) from 0.1 to 5% by weight of a stabilizer and the balance of water, .

As used herein, the term "fluorine-free" means that the fluorine compound is not intentionally added to the composition.

The etchant composition of the present invention suppresses the generation of molybdenum-based metal residues without using a fluorine compound, does not cause problems such as short-circuiting and wiring failure, and does not cause etching of the glass substrate, IGZO damage is also improved, which has the advantage of being applicable to an oxide TFT.

The etchant composition of the present invention may have a pH of 1 to 4, preferably 1 to 3, 1.5 to 2.5, or 1.8 to 2.3. Within this range, the etchant composition of the present invention is excellent in stability of the etching solution, The etching properties of both the film and the molybdenum-based metal film are excellent.

The etchant composition of the present invention may be, for example, a composition for etching a multi-layered metal film including a copper-based metal film and a molybdenum-based metal film, preferably a multi-layered metal film including a copper film and a molybdenum alloy film May be a composition for etching.

The molybdenum alloy film may be an alloy of molybdenum and at least one selected from the group consisting of titanium, tantalum, chromium, nickel, and neodymium. More preferably, the molybdenum alloy film is an alloy of molybdenum and titanium Lt; / RTI > In this case, the diffusion of Cu metal into the insulating film is suppressed and the device characteristics are excellent.

The metal film of the multi-layer structure may be a copper-based metal film / molybdenum-based metal film structure having a copper-based metal film as a lower film and a molybdenum-based metal film as an upper film, It may be a copper-based metal film structure. As another example, the metal film of the multi-layer structure may be a multi-layer structure of a triple layer or more in which a molybdenum-based metal film and a copper-based metal film are alternately stacked. As a preferable example, a molybdenum- And a ribbed metal film may be stacked in this order. In this case, the adhesion of Cu to the film disposed on the upper and lower surfaces of the metal film of the multilayer structure and the diffusion of Cu into the insulating film are improved, .

In the present invention, a) hydrogen peroxide is added as a main oxidizing agent for the multi-layered metal film, which may be contained in an amount of 15 to 30% by weight, more preferably 20 to 25% by weight based on 100% by weight of the total composition. When the composition of the present invention contains hydrogen peroxide within the above-mentioned range, it is possible to efficiently etch the metal film of a multilayered structure, thereby enabling effective etching, an appropriate etching rate, and easy control of the process. Efficiency and margin can be improved.

In the present invention, the chelating agent is used for the purpose of inhibiting the decomposition of hydrogen peroxide by inactivating the oxidized metal ion during the etching process to secure the stability of the etching solution composition.

The chelating agent may be contained in an amount of 0.1 to 3% by weight, more preferably 0.5 to 2.0% by weight, 0.5 to 1.5% by weight, 0.8 to 2.0% by weight or 0.8 to 1.5% by weight based on 100% %. In this case, the stability of the composition can be ensured while maintaining the etching efficiency high, and the number of accumulated treatments is high, which is economically advantageous.

The b) chelating agent may be, for example, an amino acid.

The amino acid may be at least one selected from the group consisting of alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid and sarcosine. In this case, decomposition of hydrogen peroxide is suppressed, Thereby providing an effect of improving stability.

As a more preferred example, the chelating agent b) may include iminodiacetic acid.

In the present invention, c) the auxiliary chelating agent can contribute to securing the stability of the etchant, and furthermore, it is possible to secure an excellent etching profile by controlling the etching speed between the metal components contained in the metal film of the multi-layer structure. Specifically, when the etching rate difference between the metals included in the multi-layered metal film is large, the etching of the specific metal film is relatively excessive and may cause an undercut phenomenon. If the undercut phenomenon is intensified, It is necessary to adjust the etching speed between the metal components.

In addition, when the etching process is repeatedly performed, the content of metal ions in the etching solution increases, and in this case, decomposition of hydrogen peroxide can be further promoted. When the combination of the chelating agent and the curing chelating agent is used, The stability of the etching solution can be maintained at a high level.

The c) auxiliary chelating agent is preferably contained in an amount of 0.1 to 3% by weight or 0.5 to 1.5% by weight based on 100% by weight of the total composition. Within this range, the stability of the composition is excellent and the etching rate is controlled There is an advantage that the etching profile is excellent.

The c) auxiliary chelating agent may be, for example, a polycarboxylic acid.

The multi-carboxylic acid may be, for example, tricarboxylic acid, preferably citric acid.

In the present invention, the corrosion inhibitor is added for the purpose of protecting the metal wiring by inhibiting corrosion by the etching composition in combination with the metal on the surface of the metal wiring.

The corrosion inhibitor may be included in an amount of 0.01 to 5% by weight, 0.05 to 3% by weight, 0.05 to 0.5% by weight, 0.1 to 0.5% by weight or 0.1 to 0.3% by weight based on 100% The corrosion of the wiring can be suppressed without deteriorating the etching efficiency.

The etching inhibitor may be an azole compound. In this case, even if the etching rate between the metal films is controlled to increase the cumulative number, the critical dimension bias (CD bias) of the metal wiring (pattern) Can be improved.

Wherein the azole compound is selected from the group consisting of 3-amino-1,2,3-triazole, 3-amino-1,2,4-triazole, , 4-triazole, 5-methyl tetrazole, 5-aminotetrazole, imidazole and pyrazole, more preferably 5-aminotetrazole. In this case, stability of the etchant And the etching efficiency.

In the present invention, e) etching agent is added to improve the etching rate by controlling the pH of the etching composition while being a component for etching the metal film of the multi-layer structure.

E) The etching agent may be included in an amount of 0.005 to 5% by weight, preferably 0.01 to 0.5% by weight or 0.01 to 0.1% by weight based on 100% by weight of the total composition. In the present invention, when the etching agent is included in the above-mentioned range, the etching rate is appropriate, and the etching efficiency is improved while the etching efficiency is improved.

The etchant may be at least one selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid, and pyrophosphoric acid, and preferably includes phosphoric acid or pyrophosphoric acid. In this case, And the like can be provided.

In another embodiment of the present invention, the e) etching agent may be added to the composition in combination with at least one salt selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid and pyrophosphoric acid. When the etching agent and the salt thereof are used in combination, the weight ratio of the etching agent and the salt thereof may be 1: 1 to 2: 1. In this case, the acid and the hydrogen-substituted salt thereof may be combined to control the pH more stably, The etching efficiency can be stably maintained even when the phosphorus is etched.

In the present invention, f) a pH adjusting agent is added in order to improve the etching property or speed while controlling the pH of the etching solution composition to a specific range to ensure stability of the composition, and f) the pH adjusting agent is added in an amount of 100% 0.05 to 3% by weight, preferably 0.1 to 2% by weight or 0.1 to 1% by weight. Within this range, the stability of the composition is ensured, the etching rate and the residue of the molybdenum-based metal film are improved, and the oxide film such as the glass substrate and the IGZO is etched and the etching profile is excellent.

The f) pH adjusting agent is not particularly limited as long as it is a substance containing a hydroxyl group as a functional group such as metal hydroxides and ammonium hydroxides, and may be appropriately selected, and preferable examples thereof include potassium hydroxide, sodium hydroxide, Ammonium, and more preferably, it may be potassium hydroxide. In this case, since the pH of the composition can be maintained at a stable level, the process efficiency is excellent and the etching profile is excellent.

G) Stabilizer in the present invention is a stabilizer which improves the stability of a composition by suppressing the decomposition of hydrogen peroxide by inhibiting the activity of the metal ions surrounded by the metal ions in the etching process while ensuring the uniformity of the etching by lowering the surface tension .

The g) stabilizer may be included in an amount of 0.1 to 5% by weight, preferably 0.5 to 3 or 1 to 2% by weight based on 100% by weight of the total composition. The composition of the present invention g) If the stabilizer is included in the above-mentioned range, uniformity and stability of etching are ensured and an etching profile is excellent.

The g) stabilizer may be, for example, a polyhydric alcohol having a weight average molecular weight of 200 g / mol or less or 50 to 200 g / mol. In this case, the uniformity and stability of the etching can be ensured without lowering the etching efficiency.

For example, the polyhydric alcohol may be at least one selected from the group consisting of glycerol, triethylene glycol, and polyethylene glycol, preferably triethylene glycol.

The fluorine-free etchant composition may contain water in addition to the above-mentioned components, and water may be included such that the total weight of the composition is 100% by weight.

The water is not particularly limited, but it may preferably be deionized water, and more preferably deionized water having a specific resistance value of 18 M OMEGA. Or more can be used.

The fluorine-free etchant composition is characterized in that the IGZO damage (35 ° C for 100 seconds etch) is 0.30 μm or less and the one side bias (MoTi / Cu / MoTi; thickness 100 Å / 2,500 Å / 300 Å; over etch 30% . ≪ / RTI >

In the present invention, for example, IGZO damage is measured by using a step difference measuring instrument (Veeco, Dektak 150) after etching an IGZO single film at 35 ° C for 100 seconds.

The fluorine-free etchant composition had an upper tip (MoTi / Cu / MoTi, thickness 100 Å / 2,500 Å / 300 Å, over etch 30% condition) of 0.02 ㎛ or less, permissible metal concentration (35 ° C., 24 hr) 3,000 ppm or less.

In describing the fluorine-free etchant composition of the present invention, additives and the like which are not explicitly described are not particularly limited when they are within the range usually practiced in the technical field of the present invention, and it is specified that the additives can be appropriately selected.

Hereinafter, a method of etching a multi-layered metal film using the fluorine-free etchant composition according to the present invention will be described.

The method for etching a multi-layered metal film of the present invention includes a step of etching a multi-layered metal film including a copper-based metal film and a molybdenum-based metal film, wherein the fluorine-free etching solution composition is used.

In a specific example, the method for etching the multi-layered metal film includes: forming a multi-layered metal film including a copper-based metal film and a molybdenum-based metal film on a glass substrate; Applying a photoreactive material on the multi-layered metal film; And etching the multi-layered metal film using the fluorine-free etchant composition.

When the etching process is performed using the fluorine-free etching solution composition of the present invention, the etchant is excellent in stability of the etchant and excellent in etching properties for the copper-based metal film and the molybdenum-based metal film, So that it can be reused, thereby providing an effect of improving the process margin.

In addition, when the etching process is performed using the fluorine-free etching solution composition of the present invention, damage due to etching of the oxide such as IGZO or the residue of the molybdenum-based metal film can be effectively suppressed. It is possible.

In describing the etching method of the multilayered metal film of the present invention, the etching conditions and the like which are not explicitly described are not particularly suggested when they are within the range usually practiced in the art, and can be appropriately selected and carried out.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

The etchant compositions of the examples, comparative examples and control examples were prepared by mixing the respective components as shown in the following Table 1, and the materials used were as follows.

* IDA: iminodiacetic acid

* CA: citric acid

* ATZ: 5-aminotetrazole

* AC: Ammonium acetate

* TEG: triethylene glycol

division Example Comparative Example Reference Example Control Example One 2 One 2 3 4 Oxidant H ₂ O ₂ 23 23 13 23 23 23 23 13 Chelating agent IDA One 2 5 One One One 0.5 5 Auxiliary chelating agent CA One One - One - One One - Corrosion inhibitor ATZ 0.1 0.3 0.3 0.2 0.3 0.3 0.3 0.3 Etchant Phosphoric acid 0.03 0.03 - 0.03 0.03 0.03 0.03 - Pyrophosphoric acid - - 3.0 - - - - 3.0 pH adjusting agent KOH 0.2 0.2 - 0.17 0.2 0.2 0.2 - AC - - 3.0 - - - - 3.0 stabilizator TEG One One - One One - One - Fluorine compound NH ₄ F - - 0.01 0.01 - - - -

(In Table 1, each composition contains a total amount of 100% by weight, including the remaining amount of water, and the content of each component is% by weight.)

[Experimental Example]

Experimental Example  One: Etching  Performance evaluation

An organic insulating film was deposited on a glass substrate, IGZO was deposited thereon, and MoTi / Cu / MoTi (thickness: 100 ANGSTROM / 2,500 ANGSTROM / 300 ANGSTROM) triple film was deposited as a source / drain electrode. The patterned glass was subjected to a photoresist process with a certain pattern thereon, and the glass was cut into 5 x 5 cm using a diamond knife to prepare a specimen.

8 kg of the etchant composition prepared as shown in Table 1 was placed in an experimental equipment (SEMES, model name: ETCHER) of a spray-type etching system, and etching was performed when the temperature reached 35 캜. The total etch time was based on the end point detection (EPD) and the over etch was 30%. In case of IGZO, etching was performed for 100 seconds.

After the etched substrate was cleaned, it was dried, and an etching profile was confirmed using a scanning electron microscope (Model: Hitachi, S-470). During the profile confirmation, the side etching was observed from the end of the photoresist to the portion where the triple film remained, and the degree of occurrence of the etching residue was observed in the profile of the degree of occurrence of the residue remaining on the lower film. In addition, to measure the occurrence of IGZO damage, the level difference of the etched specimens was measured using a step difference meter (Veeco, Dektak 150).

Experimental Example  2: Etchant  Stability evaluation

In the case of the hydrous etch solution, the decomposition reaction of hydrogen peroxide usually involves a sudden temperature rise. The stability of the etchant solution was determined by dissolving copper metal in each of the etchant compositions according to the examples, the comparative examples and the control examples so that the copper concentration was 3,000 ppm in one example, and then observing the temperature change for 24 hours. C, it can be judged as stable.

division Example Comparative Example Reference Example Control Example One 2 One 2 3 4 Composition pH 2.2 2.06 5.5 2.28 2.31 2.25 2.19 5.2 EPD Upper MoTi 33 43 35 33 32 34 28 41 Cu 65 55 58 52 70 60 55 51 Lower MoTi 35 39 32 31 32 31 26 34 Total 133 137 128 116 134 125 109 126 IGZO Damage [Å / sec] 0.20 0.31 0.42 0.51 0.21 0.23 0.28 0.21 One side bias [㎛] 0.43 0.53 0.49 0.55 0.38 0.4 0.47 0.51 Upper Tip [㎛] 0.02 0.07 0.03 0.03 0.02 0.02 0.01 0.05 Cumulative processing count
Allowable metal concentration [ppm] ~ 3,000 ~ 5,000 ~ 3,000 ~ 3,000 ~ 2,000 ~ 2,000 ~ 1,000 ~ 3,000

Referring to Table 2, the etchant composition according to the present invention has a significantly lower pH than the conventional hydrotreating solution and does not contain a fluorine compound for effectively etching the molybdenum-based metal film. In addition, the etchant composition of Comparative Example 1 and the etching solution The etching rate of the MoTi / Cu / MoTi triple layer is equivalent to that of the MoTi / Cu / MoTi triple layer, and both MoTi and Cu can be effectively etched.

1 and 2, the MoTi / Cu / MoTi triplet etched using the etchant composition according to Example 1 had a better etch profile due to less occurrence of MoTi residues compared to the etchant composition according to the control example Can be confirmed.

As a result of measuring the occurrence of IGZO damage, it is confirmed that the etching composition according to the present invention can be applied to an oxide thin film transistor from the result that the IGZO film has a considerable reduction in IGZO damage compared to Comparative Example 1, It was judged to be due to the reduction of the concentration of IDA used as a chelating agent.

Comparing Reference Example 1 and Example 2, the IGZO damage was different depending on the content of IDA, which is a chelating agent, in all of the other conditions being equal. As a result, the lower the content of IDA, (tip) and IGZO damage are reduced, but the number of Cu treatment increases.

As a result of evaluating the stability of the etchant composition, Examples 1 and 2 show that the maximum copper metal concentrations at which the temperature can be maintained at 35 DEG C for 24 hours are 3000 ppm and 5,000 ppm, respectively, It can be confirmed that it has a level stability.

On the other hand, when the content of IDA as the chelating agent is low (Reference Example 1), the chelating agent is not contained (Comparative Example 3), or the stabilizer TEG (Comparative Example 4), it is confirmed that the cumulative number of treatments is lower than that of the conventional etching process etchant.

In addition, when the etchant composition of the present invention is used, it can be confirmed that the one side bias and the upper MoTi tip are reduced compared to the conventional hydrotreating solution, while the stability is excellent, and the etching profile is excellent.

On the other hand, referring to the results of Comparative Example 2, even if the pH is controlled within the range of the present invention, it can be confirmed that the IGZO damage is considerable when the fluorine compound is included.

That is, the etchant composition according to the present invention can contribute to the reduction of production yield and cost by increasing the cumulative number of treatments without causing damage to the glass substrate or the oxide such as IGZO, It is possible to perform batch etching of the film, thereby contributing to improvement of quality and reduction of defect rate.

Claims (15)

a) from 15 to 30% by weight of hydrogen peroxide, b) from 0.1 to 3% by weight of a chelating agent, c) from 0.1 to 3% by weight of an auxiliary chelating agent, d) from 0.01 to 5% by weight of a corrosion inhibitor, e) f) 0.05 to 3% by weight of a pH adjusting agent, g) 0.1 to 5% by weight of a stabilizer and a residual water amount but not containing a fluorine compound and having a pH of 1 to 4
A fluorine-free etching solution composition for a multilayer metal film. The method according to claim 1,
The b) chelating agent is an amino acid.
A fluorine-free etching solution composition for a multilayer metal film. 3. The method of claim 2,
Wherein the amino acid is at least one selected from the group consisting of alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid and sarcosine
A fluorine-free etching solution composition for a multilayer metal film. The method according to claim 1,
Wherein the c) auxiliary chelating agent is a multi-carboxylic acid
A fluorine-free etching solution composition for a multilayer metal film. 5. The method of claim 4,
Wherein the polycarboxylic acid is a tricarboxylic acid.
A fluorine-free etching solution composition for a multilayer metal film. The method according to claim 1,
And d) the corrosion inhibitor is an azole compound.
A fluorine-free etching solution composition for a multilayer metal film. The method according to claim 6,
Wherein the azole compound is selected from the group consisting of 3-amino-1,2,3-triazole, 3-amino-1,2,4-triazole, , 4-triazole, 5-methyl tetrazole, 5-aminotetrazole, imidazole and pyrazole.
A fluorine-free etching solution composition for a multilayer metal film. The method according to claim 1,
And e) the etching agent is at least one selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid and pyrophosphoric acid.
A fluorine-free etching solution composition for a multilayer metal film. The method according to claim 1,
Wherein the f) pH adjusting agent is a metal hydroxide
A fluorine-free etching solution composition for a multilayer metal film. The method according to claim 1,
And g) the stabilizer is a polyhydric alcohol having a molecular weight of 200 g / mol or less
A fluorine-free etching solution composition for a multilayer metal film. 11. The method of claim 10,
Wherein the polyhydric alcohol is triethylene glycol.
A fluorine-free etching solution composition for a multilayer metal film. The method according to claim 1,
Wherein the multilayered metal film comprises a copper film and a molybdenum alloy film
A fluorine-free etching solution composition for a multilayer metal film. 13. The method according to any one of claims 1 to 12,
The fluorine-free etchant composition is characterized in that the IGZO damage (35 ° C for 100 seconds etch) is 0.30 μm or less and the one side bias (MoTi / Cu / MoTi; thickness 100 Å / 2,500 Å / 300 Å; over etch 30% Characterized by
A fluorine-free etching solution composition for a multilayer metal film. 13. The method according to any one of claims 1 to 12,
The fluorine-free etchant composition had an upper tip (MoTi / Cu / MoTi, thickness 100 Å / 2,500 Å / 300 Å, over etch 30% condition) of 0.02 ㎛ or less, permissible metal concentration (35 ° C., 24 hr) 3,000 ppm or less.
A fluorine-free etching solution composition for a multilayer metal film. A method for etching a multi-layered metal film comprising a copper-based metal film and a molybdenum-based metal film using the fluorine-free etchant composition according to any one of claims 1 to 12
Method of etching a multilayer metal film.

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