KR20130021320A - Method for forming metal line - Google Patents

Abstract

PURPOSE: A method for forming a metal line is provided to minimize attack against a metal oxide layer. CONSTITUTION: A metal oxide layer is formed on a substrate. A copper metal layer is formed on the metal oxide layer. A photoresist material selectively remains on the copper metal layer. An upper copper metal layer is etched by using etching solution. The etching solution includes azole compound, hydrogen peroxide, organic peroxyacid, and water.

Description

[0001] METHOD FOR FORMING METAL LINE [0002]

The present invention relates to an etching solution composition of a copper-based metal film and a method of forming a wiring of a copper-based metal film using the etching solution composition.

The process of forming a metal wiring on a substrate in a liquid crystal display device is usually composed of a metal film forming process by sputtering or the like, a photoresist coating process, a photoresist forming process in an optional region by exposure and development, and a step by an etching process And a cleaning process before and after the individual unit process. This etching process refers to a process of leaving a metal film in a selective region using a photoresist as a mask. Typically, dry etching using plasma or wet etching using an etching composition is used.

Various wirings have been proposed according to the driving method and resolution to be implemented. A gate and a source / drain wiring using a lamination film of a molybdenum-based metal film and an aluminum-based metal film are most commonly used; a wiring using copper as the conductive film and a wiring using molybdenum or titanium as the barrier metal; and the like. In addition, in the FFS (Fringe Field Switching) mode and the partial transverse electric field system, the wiring for the multilayer film of copper and the metal oxide film is also used. However, in the case of the multilayer film, if the multilayer film is formed by etching only the upper copper film have. However, there is no development of etchant for this.

Korean Patent Publication No. 2005-0067934 discloses an etchant for collectively etching a copper metal layer containing nitric acid, hydrochloric acid, hydrogen peroxide and an azole compound and a transparent conductive layer. However, the above-mentioned patent has a problem that not only the upper copper film but also the indium oxide film as the lower film is etched.

KR 10-2005-0067934 A (2005.07.05)

It is an object of the present invention to minimize the attack of a metal oxide film when a multi-layered metal layer made of a metal oxide film and a copper-based metal film is wet-etched and to form a taper profile having an excellent direct- And the residue of the metal film is not left after the etching.

It is another object of the present invention to provide a method for forming a wiring of a copper-based metal film using the etchant composition.

The present invention relates to a composition comprising: A) from 5 to 25% by weight of hydrogen peroxide (H ₂ O ₂ ), from 0.1 to 5% by weight of an azole compound, C) from 1 to 5% by weight of organic and peroxyacid, and D) Of water. ≪ RTI ID = 0.0 > [10] < / RTI >

The present invention also relates to a method for manufacturing a semiconductor device, comprising: (I) forming a metal oxide film on a substrate; II) forming a copper-based metal film on the metal oxide film; III) selectively leaving a photoreactive material on the copper-based metal film; And (IV) etching the upper copper-based metal film using the etchant composition of the present invention.

The etchant composition of the present invention is excellent in etching uniformity and straightness without etching the underlying metal oxide film when etching the copper-based metal film on the upper one of the double films made of the metal oxide film and the copper-based metal film Taper profile, and does not generate residues, so that it does not cause problems such as electrical shorts, poor wiring, and reduced luminance.

Therefore, the etchant composition of the present invention can be very usefully used in manufacturing an array substrate for a liquid crystal display device in which a circuit of a large screen and a high luminance is realized.

1 is a SEM photograph of a profile section of a copper-based metal film etched with the etchant composition according to Example 4. FIG.

Hereinafter, the present invention will be described more specifically.

The present invention relates to a process for the preparation of a composition, comprising, in relation to the total weight of the composition, A) from 5 to 25% by weight of hydrogen peroxide (H ₂ O ₂ ), from 0.1 to 5% by weight of an azole compound, C) from 1 to 5% by weight of organic peroxyacid, Based metal film containing a residual amount of water.

In the present invention, the copper-based metal film includes copper as a constituent component of the film, and the copper-based metal film means pure copper, a nitride of copper, an oxide of copper, or an alloy of copper.

The copper alloy may be one selected from the group consisting of pure copper, a nitride of copper, and an oxide of copper, and at least one selected from the group consisting of aluminum (Al), magnesium (Mg), calcium (Ca), titanium (Ti) (Hf), tantalum (Ta), and tungsten (W), which is a group consisting of Cr, Cr, Mn, Fe, Zr, Nb, Mo, Pd, ≪ RTI ID = 0.0 > and / or < / RTI >

In the present invention, the etchant composition of the copper-based metal film refers to an etchant composition that etches only copper as the upper layer while minimizing the attack of the metal oxide film as a lower layer in the double-layered film made of the copper-based metal film and the metal oxide film.

In the present invention, the 'metal oxide film' generally has a composition of AxByCzO (where A, B and C are zinc, cadmium, gallium, indium, tin, hafnium, (Zr) and tantalum (Ta), and combinations of x, y, and z? 0, the oxide semiconductor layer being referred to as an oxide semiconductor layer Or a film constituting the oxide semiconductor layer.

The A) hydrogen peroxide contained in the etchant composition of the present invention is a main component for etching the copper-based metal film, and the content thereof is preferably 5 to 25 wt%, more preferably 15 to 23 wt% .

If the hydrogen peroxide is contained in an amount of less than 5% by weight based on the total weight of the composition, the etching rate is very slow. If the hydrogen peroxide is more than 25% by weight, the etching rate is accelerated.

The B) azole compound contained in the etchant composition of the present invention controls the etch rate of the copper-based metal and reduces the CD loss of the pattern, thereby enhancing the process margin. The content of the azole compound is preferably 0.1 to 5 wt%, more preferably 0.5 to 1.5 wt% based on the total weight of the composition. If the content of the azole compound is less than 0.1 wt%, the etch rate may become too high and the seed loss may be too large. If the content of the azole compound is more than 5 wt%, the etching rate of copper may become too slow, Can be.

Examples of the azole compound include aminotetrazole, benzotriazole, tolyltriazole, pyrazole, pyrrole, imidazole, 2-methylimidazole, One or two kinds selected from the group consisting of 2-ethylimidazole, 2-propylimidazole, 2-aminoimidazole, 4-methylimidazole, Or more may be used together, but the present invention is not limited thereto.

C) Organic Peroxyacid contained in the etchant composition of the present invention controls the etching rate of copper by increasing the activity of hydrogen peroxide by controlling the pH of the etching solution and at the same time serves as a supplementary oxidant for the copper film . In addition, the pH is lowered to inhibit the decomposition reaction of hydrogen peroxide by inhibiting the activity of Cu copper ions. The amount of the organic acid is preferably 1 to 5% by weight, more preferably 1 to 3% by weight based on the total amount of the composition. If the content of the organic peroxyacid is less than 1% by weight, the pH control effect is not so large, and Cu unetch phenomenon may occur. When the content is more than 5% by weight, Which makes process control difficult.

The organic peroxyacid may be peracetic acid, perbenzoic acid or a mixture thereof, but is not limited thereto.

The D) water contained in the etchant composition of the present invention is not particularly limited, but deionized water is preferred. More preferably, deionized water having a specific resistance value of water (that is, a degree of removal of ions in water) of 18 M OMEGA. Or more can be used. The water content is such that the total weight of the etchant composition of the present invention is 100% by weight.

In addition, the etchant composition may further comprise a surfactant. The surfactant serves to lower the surface tension and increase the uniformity of the etching. The surfactant is not particularly limited as long as it can withstand the etching composition of the present invention and is compatible with the surfactant. However, the surfactant may be an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant and a polyhydric alcohol surfactant , Or a combination thereof.

In addition to the above-described components, conventional additives may be further added. Examples of the additive include a metal ion blocking agent and a corrosion inhibitor.

(A) from 5 to 25% by weight of hydrogen peroxide (H ₂ O ₂ ), (B) from 0.1 to 5% by weight of an azole compound, (C) from 1 to 5% by weight of organic peroxyacid and The etching solution can be generally prepared by a known method, and preferably has a purity for semiconductor processing.

According to the present invention,

I) forming a metal oxide film on the substrate;

II) forming a copper-based metal film on the metal oxide film;

III) selectively leaving a photoreactive material on the copper-based metal film; And

IV) etching the copper-based metal film on the upper portion using the etchant composition of the present invention.

In the wiring forming method of the present invention, the photoreactive material is preferably a conventional photoresist material, and can be selectively left by a conventional exposure and development process.

In the present invention, the copper-based metal film includes copper as a constituent component of the film, and the copper means pure copper or an alloy of copper.

Wherein the copper-based metal film comprises one selected from the group consisting of pure copper, a nitride of copper, and an oxide of copper, or one selected from the group consisting of pure copper, a nitride of copper, and an oxide of copper, (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum Refers to an alloy of at least one metal selected from the group consisting of palladium (Pd), hafnium (Hf), tantalum (Ta), and tungsten (W).

The metal oxide film is usually made of a material selected from the group consisting of AxByCzO wherein A, B and C are zinc, cadmium, gallium, indium, tin, hafnium, zirconium, (Ta), and combinations of x, y, and z? 0, wherein the film is formed of an oxide semiconductor layer or an oxide semiconductor layer It can be a membrane to constitute.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Example  1 to 7 and Comparative Example  1 to 3: The etching composition  Produce

The etchant compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were prepared according to the compositions and contents shown in Table 1 below.

Unit: wt% Hydrogen peroxide (H ₂ O ₂ ) Aminotetrazole Peracetic Acid Deionized water Example 1 5 0.2 1.0 Balance Example 2 10 0.4 2.0 Balance Example 3 13 0.6 3.0 Balance Example 4 17 0.8 1.0 Balance Example 5 20 1.0 2.0 Balance Example 6 23 1.2 3.0 Balance Example 7 15 0.8 1.5 Balance Comparative Example 1 13 0.6 - Balance Comparative Example 2 13 0.6 0.5 Balance Comparative Example 3 13 0.6 7.0 Balance

Test Example : Etchant  Evaluation of composition characteristics

After depositing a metal oxide film on a glass substrate (100 mm x 100 mm) and depositing a copper film on the film, a photoresist having a predetermined pattern was formed on the substrate through a photolithography process, The copper-based metal films (Cu / ITO double films and Cu / IGZOx double films) were etched using the compositions of Comparative Examples 1 to 3, respectively. (ETCHER (TFT), manufactured by SEMES) was used as the etchant, and the temperature of the etchant composition was set at about 30 ° C. during the etching process. However, the optimum temperature was determined according to other process conditions and other factors can be changed. The etching time may vary depending on the etching temperature, but is usually about 100 seconds. The profile of the copper-based metal film etched in the etching process was inspected using a cross-sectional SEM (product of Hitachi, model name S-4700), and the results are shown in Table 2 below.

Etching profile Etching straightness Presence or absence of residue Metal oxide film
Attack Example 1 ○ ○ none None (ITO film) Example 2 ○ ○ none None (ITO film) Example 3 ○ ○ none None (ITO film) Example 4 ○ ○ none None (ITO film) Example 5 ○ ○ none None (ITO film) Example 6 ○ ○ none None (ITO film) Example 7 ○ ○ none None (IGZOx) Comparative Example 1 Cu Unetch Cu Unetch - - Comparative Example 2 △ X none None (ITO film) Comparative Example 3 X X none None (ITO film)

(?: Good,?: Normal, X: poor)

As can be seen from Table 2, the etching solutions of Examples 1 to 7 did not attack the lower ITO film and the IGZOx film of the copper layer. Also, as can be seen from FIG. 1, the copper-based metal film etched with the etchant composition according to Example 4 was excellent in profile and straightness, and no etching residue remained. On the other hand, in the case of the etchant of Comparative Example 1 in which there is no peracetic acid, etching of Cu was not possible due to Cu unetch phenomenon. On the other hand, as shown in Comparative Examples 2 and 3, when the content of organic peroxyacid is too low (peracetic acid, 0.5% by weight) or too high (peracetic acid, 7.0% by weight) Could not be used.

Claims (8)

I) forming a metal oxide film on the substrate;
II) forming a copper-based metal film on the metal oxide film;
III) selectively leaving a photoreactive material on the copper-based metal film; And
IV) etching the copper-based metal film on the upper portion using the etchant composition,
Wherein the etchant composition comprises A) from 5 to 25% by weight of hydrogen peroxide (H ₂ O ₂ ), B) from 0.1 to 5% by weight of an azole compound, C) from 1 to 5% by weight of an organic and an acid, and D) And forming a wiring pattern. The metal oxide film according to claim 1, wherein the metal oxide film is formed of a material selected from the group consisting of AxByCzO (where A, B and C are zinc, cadmium, gallium, indium, tin, hafnium, (Zr) and tantalum (Ta), and combinations of x, y, and z? 0). The copper-based metal film according to claim 1, wherein the copper-based metal film comprises one selected from the group consisting of pure copper, a nitride of copper, and an oxide of copper, or one selected from the group consisting of pure copper, a nitride of copper, (Al), magnesium, calcium, titanium, silver, chromium, manganese, iron, zirconium, niobium, molybdenum, Is an alloy of at least one metal selected from the group consisting of molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta) and tungsten (W). With respect to the total weight of the composition,
A) 5 to 25% by weight hydrogen peroxide (H ₂ O ₂ );
B) from 0.1 to 5% by weight of an azole compound;
C) 1 to 5% by weight of organic peroxyacid; And
D) water of the copper-based metal film. The method of claim 4, wherein the azole compound is selected from the group consisting of aminotetrazole, benzotriazole, tolyltriazole, pyrazole, pyrrole, imidazole, And at least one compound selected from the group consisting of aliphatic aldehyde, aldehyde, aldehyde, aldehyde, aldehyde, aldehyde, aldehyde, aldehyde, aldehyde, Wherein the copper-based metal film has an average particle size of not more than 100 nm. The etchant composition of a copper-based metal film according to claim 4, wherein the organic acid is one selected from the group consisting of peracetic acid and perbenzoic acid. 5. The etchant composition of claim 4, wherein the etchant composition further comprises a surfactant. [6] The method of claim 4, wherein the copper-based metal film comprises one selected from the group consisting of pure copper, a nitride of copper, and an oxide of copper, or one selected from the group consisting of pure copper, a nitride of copper, (Al), magnesium, calcium, titanium, silver, chromium, manganese, iron, zirconium, niobium, molybdenum, Is an alloy of at least one metal selected from the group consisting of molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta) and tungsten (W).

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