KR102570307B1 - etching composition - Google Patents

Abstract

The present invention is to provide an etching composition and an etching method using the same, the etching composition of the present invention is hydrogen peroxide; an auxiliary oxidizing agent which is an organic or inorganic compound containing one or more ions selected from silver, iron, copper, nickel, manganese, and cerium; corrosion inhibitor; and an aliphatic cyclic ketone compound, a lactone compound, or a water stabilizer that is a mixture thereof.

Description

Etching composition {etching composition}

The present invention relates to an etching composition, and more particularly, to an etching composition used for etching a metal wiring film used as an electrode of a TFT-LCD display.

A single film of a molybdenum alloy film and an indium oxide film or a multi-film of a molybdenum alloy film and an indium oxide film is used for a pixel electrode of a semiconductor device and a liquid crystal display device such as a TFT-LCD.

Pixel electrodes are generally stacked on a substrate through sputtering, etc., and photoresist is uniformly applied thereon, then light is irradiated through a mask with a pattern engraved thereon, and then photoresist with a desired pattern is formed through development. Then, the pattern is transferred to the metal film under the photoresist by dry or wet etching, and then unnecessary photoresist is removed by a peeling process, which is completed through a series of lithography processes.

If the molybdenum alloy film and the indium oxide film are etched with the same etchant, the manufacturing process can be simplified, but in general, the molybdenum alloy film has excellent chemical resistance and is not easy to wet etch. In addition, to etch the indium oxide film There is a problem in that the molybdenum alloy film cannot be etched with an oxalic acid-based etchant for this purpose.

To solve this problem, Korean Patent Publication No. 2016-0041873 includes hydrogen peroxide as a main oxidizing agent, and silver (Ag), iron (Fe), copper (Cu), nickel (Ni), manganese (Mn) and cerium as auxiliary oxidizing agents. An etchant composition for a metal wiring film comprising at least one ion selected from (Ce) or an organic or inorganic compound containing these ions is disclosed. However, when a transition metal is used as an auxiliary oxidizing agent in the above composition, or when the etching material is a transition metal, the hydrogen peroxide is decomposed by the fenton reaction between hydrogen peroxide and the metal or the etching composition itself is decomposed. there is

Korean Patent Publication No. 2010-0040352 discloses a hydrogen peroxide-based etching composition including hydrogen peroxide, phosphoric acid, a phosphate salt, a chelating agent, and a cyclic amine compound.

However, it still causes a disproportionation reaction, which causes the etching composition itself to decompose and is unstable. In particular, the cyclic amine compound combines with copper ions generated during copper film etching. In this case, when chlorine ions are present in the etching composition, When the binding material reacts, it has problems such as the generation of poorly soluble precipitates.

Korean Patent Publication No. 2016-0041873 Korean Patent Publication No. 2010-0040352

The present invention provides an etching composition comprising a transition metal auxiliary oxidizing agent and a hydrolysis stabilizer.

The present invention provides an etching composition having excellent stability and improved etching characteristics by including an auxiliary oxidizing agent and a specific perhydrogen stabilizer, and the etching composition of the present invention includes hydrogen peroxide; an auxiliary oxidizing agent which is an organic or inorganic compound containing one or more ions selected from silver, iron, copper, nickel, manganese, and cerium; corrosion inhibitor; and an aliphatic cyclic ketone compound, a lactone compound, or a water stabilizer that is a mixture thereof.

The water stabilizer according to an embodiment of the present invention may be included in an amount of 0.1 to 5% by weight based on the total weight of the etching composition.

Preferably, the aliphatic cyclic ketone compound according to an embodiment of the present invention is a compound represented by Formula 1 below, and the lactone compound may be a compound represented by Formula 2 or 3 below.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

(In Formulas 1 to 4,

R ₁ to R ₈ , R ₁₁ to R ₁₆ and R ₂₁ to R ₂₄ and R ₃₁ to R ₃₄ are each independently hydrogen, hydroxy, (C1-C10)alkyl, hydroxy (C1-C10)alkyl or (C1 -C10) alkoxy;

A is O or CR ₃₅ R ₃₆ ;

R ₃₅ to R ₃₆ are each independently hydrogen hydroxy, (C1-C10)alkyl, hydroxy(C1-C10)alkyl, (C1-C10)alkoxy or (C6-C12)aryl; n and m are independently of each other an integer from 0 to 7.)

In Formulas 1 to 4 of the present invention, R ₁ to R ₈ are each independently hydrogen or (C1-C10)alkyl; R ₁₁ to R ₁₆ are each independently hydrogen, hydroxy, (C1-C10)alkyl or hydroxy(C1-C10)alkyl; R ₂₁ to R ₂₄ are each independently hydrogen or (C1-C10)alkyl; R ₃₁ to R ₃₆ are each independently hydrogen, (C1-C10)alkyl, (C1-C10)alkoxy or (C6-C12)aryl; n and m may be each independently an integer of 0 to 5.

Specifically, the water stabilizer of the present invention may be selected from the following compounds.

The auxiliary oxidizing agent according to an embodiment of the present invention may be included in an amount of 0.02 to 10 parts by weight based on 100 parts by weight of hydrogen peroxide, and may be an inorganic acid salt containing copper or iron ions.

The corrosion inhibitor according to one embodiment of the present invention may be a heterocyclic compound containing one or two or more heteroatoms selected from oxygen, sulfur and nitrogen in a molecule.

The etching composition according to an embodiment of the present invention may further include a fluorine-containing compound and a compound containing a sulfonic acid group, and the fluorine-containing compound is dissociated to provide fluorine (F ^- ) or hydrogen fluoride (HF ₂ ^- ) ions. The compound containing a sulfonic acid group may be an alkyl sulfonate, an alkylene disulfonic acid, an alkyl benzene sulfonate, an alkyl naphthalene sulfonate, an alkylphenyl Ether disulfonic acid (alkyl phenyl ether disulfonate), polymer of formaldehyde and naphthalene sulfonate, polymer of acrylamide methylpropane sulfonate, acrylic acid and acrylamidomethyl propane It may be one or two or more selected from the group consisting of a copolymer of acrylamide methylpropane sulfonate and a polymer of vinylbenzene sulfonate.

Preferably, the etching composition of the present invention contains 5 to 30% by weight of hydrogen peroxide, 0.0001 to 2% by weight of an auxiliary oxidizing agent, 0.01 to 2% by weight of a corrosion inhibitor, 0.01 to 1% by weight of a fluorine-containing compound, and 0.01 to 5% by weight of a corrosion inhibitor. It may include a water stabilizer, 0.001 to 2% by weight of a compound containing a sulfonic acid group, and the remaining amount of water.

The etching composition of the present invention includes an auxiliary oxidizing agent and an aliphatic cyclic ketone compound, a lactone compound, or a mixture thereof as a water stabilizer, thereby stabilizing the etching composition so that the etching rate, etching uniformity, etc. It has excellent etching performance and etching characteristics because there is no change in etching characteristics.

In addition, the etching method of the present invention has excellent etching performance by etching using the etching composition of the present invention.

1 is a photograph of a cross-section of a specimen observed with a scanning electron microscope after etching a molybdenum-titanium alloy film (MoTi) for 80 s using an etchant 0 and 5 days after preparing the etchant composition according to Example 1, respectively. .
Figure 2 is a copper / molybdenum-titanium alloy double film (upper copper thickness 5000Å lower molybdenum-titanium 300Å) using an etchant 0 days and 5 days after preparing the etchant composition according to Example 1, respectively, after etching for 150 s This is a photograph of a cross-section of the specimen observed with a scanning electron microscope.
3 is a photograph of a cross section of a specimen observed with a scanning electron microscope after etching a molybdenum-titanium alloy film (MoTi) for 80 s using an etchant 0 days and 5 days after preparing the etchant composition according to Comparative Example 1, respectively. .
4 is a copper / molybdenum-titanium alloy double film (upper copper thickness 5000Å lower molybdenum-titanium 300Å) using an etchant 0 days and 5 days after preparation of the etchant composition according to Comparative Example 1, respectively, after etching for 150 s This is a photograph of a cross-section of the specimen observed with a scanning electron microscope.

The present invention provides an etching composition having excellent stability and improved etching characteristics by including an auxiliary oxidizing agent and a specific hydrogen stabilizer,

The etching composition of the present invention, hydrogen peroxide; an auxiliary oxidizing agent which is an organic or inorganic compound containing one or more ions selected from silver, iron, copper, nickel, manganese, and cerium; corrosion inhibitor; and an aliphatic cyclic ketone compound, a lactone compound, or a water stabilizer that is a mixture thereof.

Korean Patent Publication No. 2016-0041873 improves etching characteristics with hydrogen peroxide as the main oxidizing agent and one or more ions selected from silver, iron, copper, nickel, manganese and cerium as the auxiliary oxidizing agent or a combination of organic or inorganic compounds containing these ions Improved the problem of precipitates while doing it.

However, the inventors of the present invention found a problem in that the composition of the etching composition is changed due to the decomposition of hydrogen peroxide and organic matter, which are the main oxidizing agent, by the transition metal of the auxiliary oxidizing agent of Korean Patent Publication No. 2016-0041873. and, at the same time, it was found that the etching characteristics could be improved, and the present invention was completed.

The etching composition of the present invention includes hydrogen peroxide as a main oxidizing agent; At least one ion selected from silver, iron, copper, nickel, manganese, and cerium, or an aliphatic cyclic ketone compound, a lactone compound, or these as a hydrostatic stabilizer specific to a combination of an auxiliary oxidizing agent and a corrosion inhibitor, which are organic or inorganic compounds containing these ions By including a mixture of the hydrogen peroxide of the etching composition is extremely stabilized to increase the stability of the etching composition.

That is, the hydrogen peroxide stabilizer, which is an aliphatic cyclic ketone compound, a lactone compound or a mixture thereof of the present invention, suppresses the decomposition reaction of hydrogen peroxide, which proceeds as the metal ion concentration increases during the etching process, and maintains the etching characteristics for a long time. .

Therefore, compared to the conventional etching composition, the etching composition of the present invention has excellent etching performance because hydrogen peroxide is stabilized during the etching process, and there is no change in etching characteristics such as etching rate and etching uniformity even when the number of etching sheets and processing time increase. .

In addition, the etching composition of the present invention stabilizes hydrogen peroxide during the etching process and at the same time selectively protects the intermetallic interface during the etching process of a double or multiple transition metal film, thereby suppressing over-etching of the interface to enable a stable etching process, and the etching composition It keeps the hydrogen peroxide content constant, suppresses the decomposition of corrosion inhibitors, and improves etching characteristics such as etch speed, etch bias, and suppression of metal damage.

Furthermore, the etching composition of the present invention suppresses the decomposition of the corrosion inhibitor and does not cause etching of copper, thereby suppressing the etching of metal under the pixel electrode, especially copper, to prevent defects due to disconnection of the wiring and oxidation of the metal film. .

Preferably, the water stabilizer according to one embodiment of the present invention may be included in an amount of 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, based on the total weight of the etching composition.

Preferably, the aliphatic cyclic ketone compound according to an embodiment of the present invention is a compound represented by Formula 1 below, and the lactone compound may be a compound represented by Formula 2 or 4 below.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

(In Formulas 1 to 4,

R ₁ to R ₈ , R ₁₁ to R ₁₆ and R ₂₁ to R ₂₄ and R ₃₁ to R ₃₄ are each independently hydrogen, hydroxy, (C1-C10)alkyl, hydroxy (C1-C10)alkyl or (C1 -C10) alkoxy;

A is O or CR ₃₅ R ₃₆ ;

R ₃₅ to R ₃₆ are each independently hydrogen hydroxy, (C1-C10)alkyl, hydroxy(C1-C10)alkyl, (C1-C10)alkoxy or (C6-C12)aryl;

n and m are independently of each other an integer from 0 to 7.)

In Formulas 1 to 3 of the present invention, R ₁ to R ₈ are each independently hydrogen or (C1-C10)alkyl; R ₁₁ to R ₁₆ are each independently hydrogen, hydroxy, (C1-C10)alkyl or hydroxy(C1-C10)alkyl; R ₂₁ to R ₂₄ are each independently hydrogen or (C1-C10)alkyl; n and m may be each independently an integer of 0 to 5, R ₃₁ to R ₃₆ are each independently hydrogen, (C1-C10) alkyl, (C1-C10) alkoxy or (C6-C12) aryl, more preferably Preferably, R ₁ to R ₈ are each independently hydrogen or (C1-C7)alkyl; R ₁₁ to R ₁₆ are each independently hydrogen, hydroxy, (C1-C7)alkyl or hydroxy(C1-C7)alkyl; R ₂₁ to R ₂₄ are each independently hydrogen or (C1-C7)alkyl; R ₃₁ to R ₃₆ are each independently hydrogen, (C1-C10)alkyl or (C1-C10)alkoxy; n and m may be each independently an integer of 0 to 4.

Specifically, the water stabilizer of the present invention may be selected from the following compounds, but is not limited thereto.

"Alkyl" and "alkoxy" described in the present invention include both straight-chain or branched forms, and "hydroxyalkyl" refers to OH-alkyl in which a hydroxy group is bonded to the alkyl group defined above.

In addition, the (C1-C10)alkyl group described in the present invention is preferably (C1-C7)alkyl, more preferably (C1-C5)alkyl.

Hereinafter, the present invention will be described in detail for each component of the etching composition.

a) hydrogen peroxide

In the etching composition of the present invention, hydrogen peroxide acts as the main oxidizing agent of the transition metal or metal of the transition metal or metal film.

Hydrogen peroxide according to an embodiment of the present invention may be included in an amount of 5 to 30% by weight based on the total weight of the etching composition. When hydrogen peroxide is included in less than 10% by weight, the oxidizing power of the transition metal is not sufficient, so that etching may not be performed. It is possible to implement a desirable etching rate to prevent etching residues and etching defects, and in terms of reducing CD loss and facilitating process control, it may be included in an amount of 5 to 25% by weight, preferably 15 to 25% by weight. there is.

b) auxiliary oxidizing agent

The auxiliary oxidizing agent according to an embodiment of the present invention may be one or more ions selected from silver, iron, copper, nickel, manganese, and cerium, or an organic or inorganic compound containing these ions.

Preferably, the auxiliary oxidizing agent of the present invention may be an inorganic acid salt containing one or more ions selected from silver (Ag), iron (Fe), copper (Cu), nickel (Ni), manganese (Mn) and cerium (Ce), , preferably an inorganic acid salt containing copper or iron ions.

In terms of increasing the etching rate and not generating precipitates, the auxiliary oxidizing agent of the present invention preferably has an amount of 0.02 to 10 parts by weight, preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of hydrogen peroxide, which is the main oxidizing agent. parts by weight, more preferably 1 to 5 parts by weight.

c) corrosion inhibitor

The corrosion inhibitor acts to prevent etching of a metal film used as a source-drain electrode, particularly a copper film, and may be a heterocyclic compound containing one or two or more heteroatoms selected from oxygen, sulfur, and nitrogen in a molecule.

The heterocyclic compound described in the present invention includes a monocyclic heterocyclic compound and a polycyclic heterocyclic compound having a condensation structure of a monocyclic heterocyclic ring and a benzene ring, specifically selected from heterocyclic aromatic compounds and heterocyclic aliphatic compounds. It can be one or more than one.

Specific examples of the corrosion inhibitor according to an embodiment of the present invention include oxazole, imidazole, pyrazole, triazole, tetrazole , 5-aminotetrazole ( 5-aminotetrazole), methyltetrazole , piperazine, methylpiperazine, hydroxyethylpiperazine, benzimidazole, benzpyrazole , tolute It may be tolutriazole, hydrotolutriazole or hydroxytolutriazole, preferably one or two or more selected from tetrazole, 5-aminotetrazole and methyltetrazole. can

The corrosion inhibitor according to an embodiment of the present invention has sufficient anti-corrosion performance to sufficiently suppress corrosion of a metal film used as a source-drain electrode, while a molybdenum alloy film, an indium and tin oxide film, or a molybdenum alloy film and indium and tin constituting a pixel electrode It may be included in an amount of 0.01 to 2% by weight, preferably 0.1 to 2% by weight, based on the total weight of the composition in order not to reduce the etching rate of the multilayer oxide film.

The etching composition of the present invention may further include a fluorine-containing compound and a compound containing a sulfonic acid group.

d) Fluorinated compounds

The fluorine-containing compound that may be further included in the etching composition of the present invention improves the etching rate of the molybdenum film to reduce tail length when a copper/molybdenum film is simultaneously etched as an example of a double metal film, and removes molybdenum that is inevitably generated during etching. It works by removing residue. An increase in the molybdenum tail can reduce the luminance, and if the residue remains on the substrate and the lower film, it must be removed because it reduces electrical shorts, poor wiring, and luminance.

The fluorinated compound according to an embodiment of the present invention can be any compound capable of dissociating to generate F ^- or HF ₂ ^- , but specific examples include HF, NaF, KF, AlF ₃ , HBF ₄ , NH ₄ F, It may be one or two or more selected from NH ₄ HF ₂ , NaHF ₂ , KHF ₂ and NH ₄ BF ₄ , 0.01 to 2% by weight based on the total weight of the etching composition, metal residues, for example, residues of molybdenum in a copper / molybdenum film In terms of effective removal and suppression of etching of a lower film such as a glass substrate, it may preferably be included in an amount of 0.01 to 1% by weight.

e) compounds containing sulfonic acid groups

The compound containing a sulfonic acid group serves to reduce the etching rate of SiNx while maintaining the etching rate of the molybdenum alloy and indium and tin oxide films in the presence of a fluorine compound by protecting SiNx, which is an insulating film. That is, the sulfonic acid group-containing compound can adjust the selectivity of SiNx etching compared to the etching of the molybdenum alloy film and the indium/tin oxide film.

The compound having a sulfonic acid group may be included in an amount of 0.001 to 2% by weight, or 0.01 to 2% by weight, or 0.01 to 1% by weight based on the total weight of the composition in order to improve the effect of controlling the selectivity of SiNx etching.

Compounds having a sulfonate group according to an embodiment of the present invention include alkyl sulfonate, alkyl disulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, and alkylphenyl Ether disulfonic acid (alkyl phenylether disulfonate), polymer of formaldehyde and naphthalene sulfonate, polymer of acrylamide methylpropane sulfonate, acrylic acid and acrylamidomethylpropane sulfonic acid (acrylamide methylpropane sulfonate) copolymer and vinylbenzene sulfonate polymer, etc., may be at least one selected from the group consisting of low-molecular and high-molecular compounds having sulfonic acid groups and their salts, preferably acrylic acid (acrylic acid) and acrylamidomethylpropane sulfonic acid (acrylamide methylpropane sulfonate), and a specific example thereof may be poly(acrylic acid-acrylamido-2-methylpropane sulfonic acid).

f) water

In the etching composition of the present invention, water is not particularly limited, but deionized water may be preferable, and deionized water having a resistivity value of 18 MQ/cm or more, which is a degree of removal of ions in water, may be more preferable.

The water may be included in an amount such that the total weight of the etching composition is 100% by weight.

The etching composition of the present invention preferably contains 5 to 30% by weight of hydrogen peroxide, 0.0001 to 2% by weight of an auxiliary oxidizing agent, 0.01 to 2% by weight of a corrosion inhibitor, 0.01 to 1% by weight of a fluorine-containing compound, and 0.01 to 5% by weight of a corrosion inhibitor. It may include a water stabilizer, 0.001 to 2% by weight of a compound containing a sulfonic acid group, and the remaining amount of water.

In addition, the present invention provides a method of etching a metal film using the etching composition of the present invention, and the etching method of the present invention includes the step of etching the metal by bringing the etching composition of the present invention into contact with the metal wiring film.

The metal or metal film described in the present invention means to include all metals, non-metals, or transition metals, transition metals, and may preferably be transition metals, and may include metals or transition metals alone, or metals or transition metals. It can be a mixed metal.

Specifically, it may be a single metal film, a metal alloy film, or a metal oxide film, and examples of the metal oxide film include ITO, IZO, IGZO, and the like.

The transition metal or metal film to which the etching composition according to an embodiment of the present invention can be applied is copper, molybdenum, titanium, indium, zinc, tin, tungsten, silver, gold, chromium, manganese, iron, cobalt, nickel, and niobium. It may be a film containing one or more selected metals or transition metals, and as a specific example, it may be a copper film, a molybdenum film, a titanium film, a molybdenum alloy film, or an indium alloy film, and preferably a molybdenum alloy film.

A transition metal or metal film according to an embodiment of the present invention can be applied to all of a single film, a double film, or a multilayer film.

A copper/molybdenum film or a copper/molybdenum alloy film according to an embodiment of the present invention is a multi-layer in which one or more copper (Cu) films and one or more molybdenum (Mo) films and/or molybdenum alloy films (Mo-alloy) are mutually stacked. The multilayer may include a Cu/Mo(Mo-alloy) double layer, a Cu/Mo(Mo-alloy)/Cu or a Mo(Mo-alloy)/Cu/Mo(alloy) triple layer. The order of the films may be appropriately adjusted according to the material and bonding properties of the substrate.

Molybdenum alloy film according to an embodiment of the present invention is molybdenum-tungsten (Mo-W), molybdenum-titanium (Mo-Ti), molybdenum-niobinium (Mo-Nb), molybdenum It may be composed of denium-chromium (Mo-Cr) or molybdenum-tantalum (Mo-Ta), and the molybdenum film or molybdenum alloy film is 100 to 500 Å in terms of effective etching without residue. The copper film may be deposited to have a thickness of 1000 to 10,000 Å.

Preferably, the metal interconnection film of the present invention may be a single film selected from a molybdenum film, a molybdenum alloy film, and an indium and tin oxide film, or a multi-layer stacked of two or more of them.

Any contact time between the etching composition of the present invention and the metal film according to an embodiment of the etching method of the present invention is within a range recognized by those skilled in the art.

The etching method of the present invention is a very efficient method that can be easily and efficiently etched to have improved etching characteristics by using an etching composition that is a specific combination of hydrogen peroxide, a secondary oxidizing agent, an etching inhibitor, and a specific fruit water stabilizer as the main oxidizing agent of the present invention. am.

Specifically, the etching method of the present invention includes depositing a metal film on a substrate; patterning after forming a photoresist film on the metal film; and etching the metal film on which the patterned photoresist film is formed using the etching composition of the present invention.

The metal film formed on the substrate may be a single film, a double metal film, or a multi-metal film (multi-layer metal film), and in the case of a double metal film or a multi-metal film, the stacking order is not particularly limited.

In addition, the etching method may include forming a semiconductor structure between the substrate and the transition metal film, that is, between the substrate and the transition metal film, for example, between the substrate and the copper film or between the substrate and the molybdenum film in the case of a copper / molybdenum film. .

The semiconductor structure may be a semiconductor structure for a display device such as a liquid crystal display device or a plasma display panel. Specifically, the semiconductor structure may include one or more layers of a film selected from a dielectric film, a conductive film, and an amorphous or polycrystalline silicon film, and these semiconductor structures may be manufactured according to a conventional method.

Hereinafter, the present invention will be described in detail by examples. However, the following examples are merely illustrative of the present invention, and the content of the present invention is not limited to the following examples.

[Examples 1 to 11 and Comparative Examples 1 to 9]

Etching compositions of Examples 1 to 11 and Comparative Examples 1 to 9 according to the present invention were prepared by mixing each component in the component content shown in Table 1 below.

Examples and Comparative Examples hydrogen peroxide
[weight%] auxiliary oxidizer
[weight%] corrosion inhibitor
[weight%] fluorine-containing compounds
[weight%] fruit tree stabilizer
[weight%] Compounds containing sulfonic acid groups
[weight%] deionized water
[weight %] Example 1 21 _CuSO4 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 ε-Caprolactone 1.0 SI 0.5 75.5 Example 2 21 _CuSO4 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 δ-Caprolactone 1.0 SI 0.5 75.5 Example 3 21 _CuSO4 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 γ-Caprolactone 1.0 SI 0.5 75.5 Example 4 21 _CuSO4 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 butyrolactone 1.0 SI 0.5 75.5 Example 5 21 _CuSO4 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 propiolactone 1.0 SI 0.5 75.5 Example 6 21 _CuSO4 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 δ-Gluconolactone 1.0 SI 0.5 75.5 Example 7 21 _CuSO4 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 cyclohexanone 1.0 SI 0.5 75.5 Example 8 21 _CuSO4 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 cyclopentanone 1.0 SI 0.5 75.5 Example 9 21 _CuSO4 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 Cycloheptanone 1.0 SI 0.5 75.5 Example 10 21 _CuSO4 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 ε-Caprolactone 2.0 SI 0.5 74.5 Example 11 21 Fe(NO3)3 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 ε-Caprolactone 1.0 SI 0.5 75.5 Comparative Example 1 21 _CuSO4 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 - - SI 0.5 76.5 Comparative Example 2 21 Fe(NO3)3 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 - - SI 0.5 76.5 Comparative Example 3 21 _CuSO4 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 PEG 1.0 SI 0.5 75.5 Comparative Example 4 21 _CuSO4 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 Cyclohexanol 1.0 SI 0.5 75.5 Comparative Example 5 21 _CuSO4 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 Glycerin 1.0 SI 0.5 75.5 Comparative Example 6 21 _CuSO4 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 Phenyl urea 1.0 SI 0.5 75.5 Comparative Example 7 - _CuSO4 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 ε-Caprolactone 1.0 SI 0.5 96.5 Comparative Example 8 21 - - BTA 1.0 NH ₄ HF ₂ 0.5 ε-Caprolactone 1.0 SI 0.5 76 Comparative Example 9 21 _CuSO4 0.5 - - NH ₄ HF ₂ 0.5 ε-Caprolactone 1.0 SI 0.5 76.5

Abbreviations used in Table 1 are as follows.

BTA: benzotriazole,

PEG: Poly(ethylene glycol, average weight molecular weight 400),

SI: poly(Acrylic Acid-2-Acrylamido-2-Methylpropane Sulfonic Acid, average weight molecular weight 20000)

<Experimental Example 1> Performance test of etching composition

The performance of the etching compositions of Examples 1 to 11 and Comparative Examples 1 to 9 was tested to determine the characteristics of the etching compositions.

First, in order to confirm the decomposition of hydrogen peroxide according to the passage of time, the water content of each of the etching compositions of Examples 1 to 11 and Comparative Examples 1 to 9 after 5 days of passage of time was analyzed to obtain a water decomposition rate compared to 0 days of passage.

In addition, a 300 Å thick molybdenum-titanium alloy single film and a copper/molybdenum-titanium alloy double film (upper copper thickness 5000 Å, lower molybdenum-titanium 300 Å) are separately deposited on a glass substrate, and then a photolithography process is performed to form a pattern. Formed to prepare a specimen. Etching was performed in a sprayable equipment (Mini-etcher ME-001).

In order to check the etching characteristics, the molybdenum-titanium alloy film was etched for 80 seconds, and to check the extent of damage to the copper film used as the source-drain wiring, it was etched for 150 seconds.

After etching, the etching characteristics of the molybdenum alloy film and the thickness change of the copper film were observed using a scanning electron microscope (Hitachi, S-4800).

In addition, Figure 1 is a photograph of a cross section of a specimen observed with a scanning electron microscope after etching a molybdenum-titanium alloy film (MoTi) for 80 s using an etchant 0 days and 5 days after the preparation of the etchant composition according to Example 1, respectively. 3 is a molybdenum-titanium alloy film (MoTi) etched for 80 s using an etchant 0 days and 5 days after preparing the etchant composition according to Comparative Example 1, respectively, and then observing the cross section of the specimen with a scanning electron microscope. As a photograph, in the case of FIG. 1, it can be seen that the etch bias, which can confirm the MoTi etching characteristics, remains the same at 0.26 and 0.25um even after the storage days of the etching composition are 0 and 5 days. On the other hand, in the case of FIG. 3 without the fruit water stabilizer, after 5 days of aging, the etch bias decreased to a level of 40%, confirming that the etching performance was poor. FIGS. 2 and 4 are respectively Example 1 and Comparative After preparing the etchant composition according to Example 1, the copper/molybdenum-titanium alloy double layer (upper copper thickness 5000 Å, lower molybdenum-titanium 300 Å) was etched for 150 s using the etchant after 0 and 5 days had elapsed, respectively, and then the cross section of the specimen was cut. In contrast to FIGS. 2 and 4 with each photograph observed with a scanning electron microscope, in the case of FIG. 2, even after 0 days and 5 days of storage of the etching composition, the damage to the Cu copper film, which is a material forming the lower film, is 150 s to the etching composition. It was shown to be 0 even when exposed for a period of time. These results show that compositional changes such as decomposition of hydrogen peroxide and decomposition of organic substances (eg, copper etch inhibitor) do not occur, so that etching characteristics do not change.

On the other hand, in the case of FIG. 4 without applying the hydrostatic stabilizer, the damage to the copper film is 0 on the 0th day of aging, but 3930 Å of copper film damage when exposed to the etching composition for 150s after 5 days of aging. Therefore, it can be confirmed that the etching composition without the fruit water stabilizer of the present invention causes defects by increasing the damage to the lower copper film while promoting the decomposition of fruit water or organic matter (copper corrosion inhibitor).

In order to confirm the degree of decomposition of the copper etching inhibitor, the etching characteristics of each of the etching compositions of Examples 1 to 11 and Comparative Examples 1 to 9 over time of 5 days were compared, and the experimental results are summarized in Table 2.

Examples and Comparative Examples molybdenum titanium
alloy film etching
bias(㎛)/ 80s etching 5-day hydrogen peroxide decomposition rate (%) Copper/molybdenum-titanium double layer
Etch thickness at 150 s etch
(Å) 0 days 5 days 5 days 0 days 5 days Example 1 0.26 0.25 0.1 0 0 Example 2 0.25 0.24 0.2 0 0 Example 3 0.25 0.23 0.2 0 0 Example 4 0.25 0.24 0.1 0 0 Example 5 0.25 0.23 0.2 0 0 Example 6 0.25 0.22 0.8 0 0 Example 7 0.26 0.23 0.2 0 0 Example 8 0.25 0.23 0.4 0 0 Example 9 0.26 0.23 0.7 0 0 Example 10 0.25 0.25 0.0 0 0 Example 11 0.16 0.17 0.0 0 0 Comparative Example 1 0.25 0.10 39.7 0 3,930 Comparative Example 2 0.16 0.10 26.4 0 2,740 Comparative Example 3 0.26 0.12 32.1 0 3,627 Comparative Example 4 0.24 0.11 34.2 0 3,720 Comparative Example 5 0.25 0.12 37.4 0 3,889 Comparative Example 6 0.23 0.11 36.2 0 3,756 Comparative Example 7 0.02 0.02 - 0 0 Comparative Example 8 0.06 0.06 0.7 0 0 Comparative Example 9 0.25 0.25 0.8 5,000 5,000

As shown in Table 2, as a result of evaluation of the etching compositions of Comparative Examples 1 and 2, the etching compositions containing compounds containing transition metal ions as auxiliary oxidants such as CuSO ₄ and Fe(NO ₃ ) ₃ molybdenum at 0 days of age. The etch bias of the titanium alloy film increased, but after 5 days, the etch bias decreased due to hydrogen peroxide decomposition, and the etching thickness of the copper film forming the lower film increased due to the decomposition of the corrosion inhibitor.

To improve these problems, PEG, glycerin, phenyl urea, etc. were applied as hydrogen peroxide stabilizers, but the change due to the passage of time was not reduced.

In addition, as in Comparative Examples 1, 7, 8, and 9, when the four combinations of hydrogen peroxide, auxiliary oxidant, corrosion inhibitor, and hydrogen peroxide stabilizer are not made as components of the present invention, MoTi etch bias, hyperhydrolysis, Cu damage, etc. The etching characteristics were found to be poor.

On the other hand, the etching composition having the four combinations of Examples 1 to 11 according to the present invention includes an aliphatic cyclic ketone compound or lactone compound, which is a specific hydrogen peroxide stabilizer, so that hydrogen peroxide of the composition after 5 days even when a transition metal is used as an auxiliary oxidizing agent It was confirmed that the etch bias reduction phenomenon was reduced due to low decomposition, and the etching performance was maintained because the etching thickness of the copper film did not increase due to the reduced decomposition of the corrosion inhibitor.

Claims (12)

hydrogen peroxide,
An auxiliary oxidizing agent that is an organic or inorganic compound containing one or more ions selected from silver, iron, copper, nickel, manganese, and cerium, or these ions;
preservatives, and
An etching composition comprising an aliphatic cyclic ketone compound, a lactone compound, or a water stabilizer that is a mixture thereof. According to claim 1,
The etching composition is contained in an amount of 0.1 to 5% by weight based on the total weight of the etching composition. According to claim 1,
The aliphatic cyclic ketone compound is a compound represented by Formula 1, and the lactone compound is a compound represented by Formula 2, Formula 3 or 4 below.
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

(In Formulas 1 to 4,
R ₁ to R ₈ , R ₁₁ to R ₁₆ and R ₂₁ to R ₂₄ and R ₃₁ to R ₃₄ are each independently hydrogen, hydroxy, (C1-C10)alkyl, hydroxy (C1-C10)alkyl, (C1 -C10) alkoxy or (C6-C12) aryl;
A is O or CR ₃₅ R ₃₆ ;
R ₃₅ to R ₃₆ are each independently hydrogen, hydroxy, (C1-C10)alkyl, hydroxy(C1-C10)alkyl, (C1-C10)alkoxy or (C6-C12)aryl;
n and m are independently of each other an integer from 0 to 7.) According to claim 3,
R ₁ to R ₈ are each independently hydrogen or (C1-C10)alkyl;
R ₁₁ to R ₁₆ are each independently hydrogen, hydroxy, (C1-C10)alkyl or hydroxy(C1-C10)alkyl;
R ₂₁ to R ₂₄ are each independently hydrogen or (C1-C10)alkyl;
R ₃₁ to R ₃₆ are each independently hydrogen, (C1-C10)alkyl, (C1-C10)alkoxy or (C6-C12)aryl;
n and m are independently of each other an integer of 0 to 5 etching composition. According to claim 1,
The hydrostatic stabilizer is an etching composition selected from the following compounds.

According to claim 1,
The auxiliary oxidizing agent is an etching composition containing 0.02 to 10 parts by weight relative to 100 parts by weight of hydrogen peroxide. According to claim 1,
The auxiliary oxidizing agent is an inorganic acid salt containing copper or iron ions etching composition. According to claim 1,
The etching composition of claim 1, wherein the corrosion inhibitor is a heterocyclic compound containing one or two or more heteroatoms selected from oxygen, sulfur and nitrogen in a molecule. According to claim 1,
The etching composition further comprises a compound containing a fluorine-containing compound and a sulfonic acid group. According to claim 9,
The etching composition of claim 1 , wherein the fluorine-containing compound is a compound capable of dissociating to provide fluorine (F ^- ) or hydrogen fluoride (HF ₂ ^- ) ions. According to claim 9,
The compound having the sulfonic acid group is an alkyl sulfonic acid, an alkylene disulfonic acid, an alkyl benzene sulfonic acid, an alkyl naphthalene sulfonic acid, an alkyl phenyl Ether disulfonic acid, polymer of formaldehyde and naphthalene sulfonic acid, polymer of acrylamide methylpropane sulfonic acid, acrylic acid and acrylamide At least one etching composition selected from the group consisting of copolymers of acrylamide methylpropane sulfonic acid and vinylbenzene sulfonic acid polymers. According to claim 9,
The etching composition contains 5 to 30% by weight of hydrogen peroxide, 0.0001 to 2% by weight of an auxiliary oxidizing agent, 0.01 to 2% by weight of a corrosion inhibitor, 0.01 to 1% by weight of a fluorine-containing compound, 0.01 to 5% by weight of a hydrogen peroxide stabilizer, 0.001 To 2% by weight of a compound containing a sulfonic acid group and the remaining amount of water.