KR20180047386A - etching composition - Google Patents

Abstract

The present invention relates to an etching composition and an etching method using the same, wherein the etching solution of the present invention contains: hydrogen peroxide; a co-oxidant which is one or more ions selected from silver, iron, copper, nickel, manganese, and cerium or an organic or inorganic compound including the ions; a corrosion inhibitor; and an aliphatic cyclic ketone compound, a lactone compound, or a mixture thereof. The etching composition has excellent stability and improved etching characteristics.

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 or the like of a TFT-LCD display.

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

The pixel electrode is generally laminated on a substrate by a method such as sputtering, a photoresist is uniformly applied on the substrate, light is irradiated through a mask engraved with a pattern, and then a photoresist of a desired pattern is formed Lithography process in which a pattern is transferred to a metal film under the photoresist by dry or wet etching and then unnecessary photoresist is removed by a peeling process.

When the etching of the molybdenum alloy film and the indium oxide film is performed by using the same etching solution, the manufacturing process can be simplified. However, the molybdenum alloy film generally has a problem in that wet etching is not easy because of its excellent chemical resistance, There is a problem that the molybdenum alloy film can not be etched with the oxalic acid based etching solution.

To solve this problem, Korean Patent Laid-Open Publication No. 2016-0041873 contains hydrogen peroxide as a main oxidizing agent and silver (Ag), iron (Fe), copper (Cu), nickel (Ni), manganese (Ce), or an organic or inorganic compound containing these ions. The present invention also provides an etchant composition for a metal wiring film. However, when the transition metal is used as the auxiliary oxidizing agent in the above composition, or when the etching substance is a transition metal, the hydrogen peroxide is decomposed by the fenton reaction between the hydrogen peroxide and the metal, or the etching composition itself is decomposed, .

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

In particular, the cyclic amine compound is bonded to the copper ion generated when the copper film is etched. In this case, when the chlorine ion is present in the etching composition, And a poorly soluble precipitate is generated when the bonded product is reacted.

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

The present invention provides an etching composition comprising a transition metal co-oxidant and a hydrous stabilizer.

The present invention provides an etch composition having excellent stability and improved etch characteristics by including a co-oxidant and a specific hydrous stabilizer, wherein the etch composition of the present invention comprises hydrogen peroxide; Silver, at least one ion selected from iron, copper, nickel, manganese and cerium, or a co-oxidant which is an organic or inorganic compound comprising these ions; Corrosion inhibitors; And an aliphatic cyclic ketone compound, a lactone compound, or a mixture thereof.

The hydrous 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 the following formula (1), and the lactone compound may be a compound represented by the following formula (2) or (3).

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

(In the above Chemical 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 independently hydrogen, hydroxy, (C1-C10) alkyl, hydroxy (C1-C10) alkyl or (C1 each other -C10) alkoxy;

A is O or CR ₃₅ R ₃₆ a;

R ₃₅ to R ₃₆ independently of one another are hydrogen, (C 1 -C 10) alkyl, hydroxy (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy or (C 6 -C 12) aryl; n and m are independently of each other an integer of 0 to 7)

In the formulas (1) to (4) of the present invention, R ₁ to R ₈ independently of one another are hydrogen or (C 1 -C 10) alkyl; R ₁₁ to R ₁₆ are independently of each other hydrogen, hydroxy, (C 1 -C 10) alkyl or hydroxy (C 1 -C 10) alkyl; R ₂₁ to R ₂₄ independently from each other are hydrogen or (C 1 -C 10) alkyl; R ₃₁ to R ₃₆ are independently of each other hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy or (C 6 -C 12) aryl; n and m may be an integer of 0 to 5 independently of each other.

Specifically, the hydrous stabilizer of the present invention can be selected from the following compounds.

The auxiliary oxidant 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 ion.

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 the molecule.

The etching composition according to an embodiment of the present invention may further include a fluorinated compound and a compound containing a sulfonic acid group, and the fluorinated compound may dissociate to provide fluorine (F ^- ) or hydrogen fluoride (HF ₂ ^- ) ions And the compound containing a sulfonic acid group may be a compound capable of reacting with an alkyl sulfonate, an alkyl disulfonate, an alkyl benzene sulfonate, an alkyl naphthalene sulfonate, an alkylphenyl sulfonate, Polymers such as alkyl phenyl ether disulfonate, polymers of formaldehyde and naphthalene sulfonate, polymers of acrylamide methylpropane sulfonate, acrylic acid and acrylamidomethylpropane A copolymer of acrylamide methylpropane sulfonate and a vinylbenzene sulfonate polymer. Emitter can be more than one or two are selected.

Preferably, the etching composition of the present invention comprises from 5 to 30% by weight of hydrogen peroxide, from 0.0001 to 2% by weight of co-oxidant, from 0.01 to 2% by weight of corrosion inhibitor, from 0.01 to 1% by weight of fluorine compound, from 0.01 to 5% A hydrous stabilizer, a compound containing a sulfonic acid group in an amount of 0.001 to 2% by weight, and a residual amount of water.

The etching composition of the present invention stabilizes the etching composition by incorporating a co-oxidant and an aliphatic cyclic ketone compound, a lactone compound, or a mixture thereof as a hydrous stabilizer to increase the etching rate and etch uniformity There is no change in etching characteristics, and therefore, it has excellent etching performance and etching characteristics.

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

FIG. 1 is a photograph of a cross section of a specimen after a 80s etching of a molybdenum titanium alloy film (MoTi) using an etchant which has elapsed from 0 day and 5 days, respectively, after preparation of the etching composition according to Example 1 by a scanning electron microscope .
FIG. 2 is a graph showing the results of etching the copper / molybdenum-titanium alloy double layer (upper copper thickness 5000 Å, lower molybdenum-titanium 300 Å) 150 s using an etchant that has elapsed from 0 day and 5 days after the preparation of the etchant composition according to Example 1 The cross section of the specimen was observed with a scanning electron microscope.
FIG. 3 is a photograph of a cross section of a specimen obtained by etching a molybdenum titanium alloy film (MoTi) for 80 seconds using an etchant having elapsed from 0 day and 5 days after the preparation of the etchant composition according to Comparative Example 1, using a scanning electron microscope .
FIG. 4 is a graph showing the results of etching the copper / molybdenum-titanium alloy double layer (upper copper thickness: 5000 Å, lower molybdenum-titanium: 300 Å) for 150 seconds using an etchant that has elapsed from 0 day and 5 days after the preparation of the etchant composition according to Comparative Example 1 The cross section of the specimen was observed with a scanning electron microscope.

The present invention provides an etch composition having excellent stability and improved etch characteristics by including a co-oxidant and a specific hydrous stabilizer,

The etching composition of the present invention comprises hydrogen peroxide; Silver, at least one ion selected from iron, copper, nickel, manganese and cerium, or a co-oxidant which is an organic or inorganic compound comprising these ions; Corrosion inhibitors; And an aliphatic cyclic ketone compound, a lactone compound, or a mixture thereof.

Korean Patent Laid-Open Publication No. 2016-0041873 discloses a method for improving etching properties by using hydrogen peroxide as a main oxidizing agent and at least one ion selected from silver, iron, copper, nickel, manganese and cerium as an auxiliary oxidizing agent or a combination of organic or inorganic compounds containing these ions Thereby improving the problem of precipitation.

However, the inventors of the present invention discovered a problem of decomposition of hydrogen peroxide and organic compounds as peroxides by the transition metal of the co-oxidant of Korean Patent Laid-Open Publication No. 2016-0041873, thereby causing a change in the composition of the etching composition, and by including a specific hydrous stabilizer, And at the same time, etch characteristics can be improved. Thus, the present invention has been completed.

The etching composition of the present invention comprises hydrogen peroxide as a peroxide; The present invention relates to a combination of a corrosion inhibitor and a co-oxidant which is an organic or inorganic compound containing at least one ion selected from iron, copper, nickel, manganese and cerium, or an organic or inorganic compound containing these ions and an aliphatic cyclic ketone compound, To thereby extremely stabilize the hydrogen peroxide of the etching composition to enhance the stability of the etching composition.

That is, the hydrous cyclic ketone compound, the lactone compound, or a mixture thereof, of the present invention is an etchant that retains etch characteristics for a long time by suppressing the decomposition reaction of hydrogen peroxide as the metal ion concentration increases during the etching process .

Accordingly, the etching composition of the present invention has excellent etching performance because the hydrogen peroxide is stabilized in the etching process as compared with the conventional etching composition, and the etching characteristics such as the etching rate and the etching uniformity do not change even if the etching treatment number and the treatment time are increased .

In addition, the etching composition of the present invention stabilizes the peroxidic acid in the etching process and protects the intermetallic interface selectively in the etching process of the double or multiple transition metal film, The etching rate, etch bias, and the occurrence of metal damage are suppressed, thereby improving the etching characteristics such as keeping the content of hydrogen peroxide in the etching solution at a constant level and suppressing decomposition of the corrosion inhibitor.

Further, the etching composition of the present invention suppresses the decomposition of the corrosion inhibitor and does not cause copper etching, thereby suppressing the etching of the metal under the pixel electrode, particularly the wiring formed of copper, thereby causing no disconnection due to wiring and oxidation due to oxidation of the metal film .

Preferably, the hydrous stabilizer according to an embodiment of the present invention may be contained 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 one embodiment of the present invention is a compound represented by the following formula (1), and the lactone compound may be a compound represented by the following formula (2) or (4).

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

(In the above Chemical 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 independently hydrogen, hydroxy, (C1-C10) alkyl, hydroxy (C1-C10) alkyl or (C1 each other -C10) alkoxy;

A is O or CR ₃₅ R ₃₆ a;

R ₃₅ to R ₃₆ independently of one another are hydrogen, (C 1 -C 10) alkyl, hydroxy (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy or (C 6 -C 12) aryl;

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

In the formulas (1) to (3) of the present invention, R ₁ to R ₈ independently of one another are hydrogen or (C 1 -C 10) alkyl; R ₁₁ to R ₁₆ are independently of each other hydrogen, hydroxy, (C 1 -C 10) alkyl or hydroxy (C 1 -C 10) alkyl; R ₂₁ to R ₂₄ independently from each other are hydrogen or (C 1 -C 10) alkyl; n and m may independently be an integer of 0 to 5, and R ₃₁ to R ₃₆ independently of one another are hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy or (C 6 -C 12) To R &_lt; ₈ > independently from each other are hydrogen or (C1-C7) alkyl; R ₁₁ to R ₁₆ are independently of each other hydrogen, hydroxy, (C 1 -C 7) alkyl or hydroxy (C 1 -C 7) alkyl; R ₂₁ to R ₂₄ independently from each other are hydrogen or (C 1 -C 7) alkyl; R ₃₁ to R ₃₆ independently from each other are hydrogen, (C 1 -C 10) alkyl or (C 1 -C 10) alkoxy; n and m may be an integer of 0 to 4 independently of each other.

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

"Alkyl" and "alkoxy" described in the present invention include both linear and branched forms, and "hydroxyalkyl" means OH-alkyl in which a hydroxy group is bonded to an alkyl group as defined above.

Further, 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 more detail with respect to each component of the etching composition.

a) Hydrogen peroxide

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

The 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 the hydrogen peroxide is contained in an amount less than 10% by weight, the oxidizing power of the transition metal is not sufficient and etching may not be performed. If the hydrogen peroxide is contained in an amount exceeding 30% by weight, the etching speed becomes too fast. It is possible to realize a preferable etching rate and to prevent etch residue and etch failure, and it can be contained in an amount of 5 to 25% by weight, preferably 15 to 25% by weight in view of reduction of CD loss and easiness of process control have.

b) auxiliary oxidant

The co-oxidant 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 at least one ion selected from silver (Ag), iron (Fe), copper (Cu), nickel (Ni), manganese (Mn) , Preferably an inorganic acid salt containing copper or iron ions.

The auxiliary oxidizing agent of the present invention preferably has a content of the auxiliary oxidizing agent of 0.02 to 10 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of hydrogen peroxide which is the main oxidizing agent, from the viewpoint of increasing the etching rate, By weight, more preferably 1 to 5 parts by weight.

c) Corrosion inhibitor

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

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, the heterocyclic compound is selected from a heterocyclic aromatic compound and a heterocyclic aliphatic compound Lt; / RTI >

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 , tolutole , May be a tolutriazole, hydrotolutriazole or hydroxytolutriazole, preferably one or more than one selected from tetrazole, 5-aminotetrazole and methyltetrazole .

The corrosion inhibitor according to an embodiment of the present invention can be used as a source electrode and a drain electrode because it has sufficient corrosion inhibiting performance and can sufficiently prevent corrosion of a metal film used as a source drain electrode, 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 lower the etching rate of the oxide film.

The etching composition of the present invention may further contain a fluorinated compound and a compound containing a sulfonic acid group.

d) Fluorine compounds

The fluorine compound which can be further included in the etching composition of the present invention is a double metal film, for example, when the copper / molybdenum film is etched at the same time, the etching rate of the molybdenum film is improved to reduce the tail length, and the molybdenum It acts to remove residues. Increasing the tail of the molybdenum can reduce the brightness, and the residues left on the substrate and underlying film must be removed since they reduce electrical shorts, poor wiring and brightness.

The fluorine compound according to an embodiment of the present invention can be any compound that can dissociate to generate F ^- or HF ₂ ^- . Specific examples thereof include HF, NaF, KF, AlF ₃ , HBF ₄ , NH ₄ F, NH ₄ HF ₂ , NaHF ₂ , KHF _2, and NH ₄ BF ₄ and may be used in an amount of 0.01 to 2 wt% based on the total weight of the etching composition, and a metal residue, for example, a residue of molybdenum in a copper / molybdenum film It may preferably be contained in an amount of 0.01 to 1% by weight in view of effective removal and suppression of etching of a lower film such as a glass substrate.

e) Compounds containing sulfonic acid groups

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

The compound having a sulfonic acid group may be contained 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, from the viewpoint of improving the selective control effect of etching of SiNx.

The compound having a sulfonate group according to an embodiment of the present invention includes alkyl sulfonate, alkyldisulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkylphenyl sulfonate, Polymers such as alkyl phenylether disulfonate, polymers of formaldehyde and naphthalene sulfonate, polymers of acrylamide methylpropane sulfonate, acrylic acid and acrylamidomethylpropanesulfonic acid, a copolymer of acrylamide methylpropane sulfonate and a vinylbenzene sulfonate polymer, a low molecular weight and a high molecular compound having a sulfonic acid group and a salt thereof, preferably acrylic acid, And acrylamide methylpropane sulfonate. And a specific example thereof may be poly (acrylic acid-acrylamido-2-methylpropanesulfonic 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 at which ions are removed 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 wt%.

The etching composition of the present invention preferably comprises 5 to 30 wt% of hydrogen peroxide, 0.0001 to 2 wt% of a co-oxidant, 0.01 to 2 wt% of a corrosion inhibitor, 0.01 to 1 wt% of a fluorine compound, 0.01 to 5 wt% A hydrous stabilizer, a compound containing a sulfonic acid group in an amount of 0.001 to 2% by weight, and a residual amount of water.

The present invention also provides a method of etching a metal film using the etching composition of the present invention, wherein the etching method of the present invention includes 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 includes both a metal, a nonmetal, or a transition metal transition metal, and may be preferably a transition metal. A metal or a transition metal may be included alone, or a metal or a transition metal Mixed metal.

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

The transition metal or metal film to which the etching composition according to an embodiment of the present invention can be applied is selected from copper, molybdenum, titanium, indium, zinc, tin, tungsten, silver, gold, chromium, manganese, iron, cobalt, And may be a film containing one or more metals or transition metals selected therefrom. Specific examples thereof may include a copper film, a molybdenum film, a titanium film, a molybdenum alloy film and an indium alloy film, and preferably a molybdenum alloy film.

The transition metal or metal film according to an embodiment of the present invention is applicable to a single film, a double film or a multi-film.

The copper / molybdenum film or the copper / molybdenum alloy film according to an embodiment of the present invention may be a multi-layer film in which at least one copper (Cu) film and at least one molybdenum (Mo) film and / or a molybdenum alloy film (Mo- And the multilayer may comprise a triple layer of a Cu / Mo (Mo-alloy) double layer, a Cu / Mo / Cu or Mo / Cu / Mo alloy. The order of the film can be appropriately adjusted according to the material and bonding property of the substrate.

The molybdenum alloy film according to one embodiment of the present invention may be a molybdenum-tungsten (Mo-W), molybdenum-titanium (Mo-Ti), molybdenum-niobium The molybdenum film or the molybdenum alloy film may have a thickness of 100 to 500 angstroms in order to efficiently etch without residue, and the molybdenum- The copper film can be deposited to have a thickness of 1000 to 10,000 ANGSTROM.

Preferably, the metal interconnection film of the present invention may be a single film selected from a molybdenum film, a molybdenum alloy film, an indium and tin oxide film, or a multiple film in which two or more thereof are laminated.

The 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 all within a range that can be recognized by those skilled in the art.

The etching method of the present invention is a highly efficient method which can etch easily and efficiently to have improved etching characteristics by using a specific combination of hydrogen peroxide, the auxiliary oxidizing agent, the etching inhibitor and the specific hydrous stabilizer, which are the main oxidizing agents of the present invention, to be.

More specifically, the etching method of the present invention includes: depositing a metal film on a substrate; Forming a photoresist film on the metal film and patterning the 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 (multilayer metal film), and in the case of a double metal film or a multi metal film, the order of lamination 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, in the case of a copper / molybdenum film, between the substrate and the copper film or between the substrate and the molybdenum film .

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

Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are illustrative of the present invention and are not intended to limit the scope of the present invention.

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

The respective components were mixed with the component contents shown in Table 1 below to prepare the etching compositions of Examples 1 to 11 and Comparative Examples 1 to 9 according to the present invention.

Examples and Comparative Examples Hydrogen peroxide
[weight%] Auxiliary oxidant
[weight%] Corrosion inhibitor
[weight%] Fluorine compound
[weight%] Fruit stabilizer
[weight%] Sulfonic acid group-containing compound
[weight%] Deionized water
[weight %] Example 1 21 CuSO ₄ 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 ε-Caprolactone 1.0 SI 0.5 75.5 Example 2 21 CuSO ₄ 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 δ-Caprolactone 1.0 SI 0.5 75.5 Example 3 21 CuSO ₄ 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 γ-Caprolactone 1.0 SI 0.5 75.5 Example 4 21 CuSO ₄ 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 butyrolactone 1.0 SI 0.5 75.5 Example 5 21 CuSO ₄ 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 propiolactone 1.0 SI 0.5 75.5 Example 6 21 CuSO ₄ 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 δ-Gluconolactone 1.0 SI 0.5 75.5 Example 7 21 CuSO ₄ 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 cyclohexanone 1.0 SI 0.5 75.5 Example 8 21 CuSO ₄ 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 cyclopentanone 1.0 SI 0.5 75.5 Example 9 21 CuSO ₄ 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 Cycloheptanone 1.0 SI 0.5 75.5 Example 10 21 CuSO ₄ 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 CuSO ₄ 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 CuSO ₄ 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 PEG 1.0 SI 0.5 75.5 Comparative Example 4 21 CuSO ₄ 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 Cyclohexanol 1.0 SI 0.5 75.5 Comparative Example 5 21 CuSO ₄ 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 Glycerin 1.0 SI 0.5 75.5 Comparative Example 6 21 CuSO ₄ 0.5 BTA 1.0 NH ₄ HF ₂ 0.5 Phenyl urea 1.0 SI 0.5 75.5 Comparative Example 7 - CuSO ₄ 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 CuSO ₄ 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: Polyethylene glycol (ethylene glycol, average molecular weight 400,

SI: Poly (Acrylic Acid-2-Acrylamido-2-Methylpropane Sulfonic Acid, average molecular weight 20,000)

EXPERIMENTAL EXAMPLE 1 Performance Test of Etching Composition

The properties of the etching compositions of Examples 1 to 11 and Comparative Examples 1 to 9 were tested to evaluate their performance.

First, in order to confirm the decomposition of hydrogen peroxide with respect to the aged days, the hydrolysis rate of the etch compositions of Examples 1 to 11 and Comparative Examples 1 to 9, in which aged 5 days had elapsed, was analyzed.

A single layer of a molybdenum-titanium alloy film having a thickness of 300 angstroms and a double-layered copper / molybdenum-titanium alloy film (having a top copper thickness of 5000 angstroms and a lower molybdenum-titanium angles of 300 angstroms) were separately deposited on a glass substrate, and then a photolithography process was performed. To prepare a specimen. The etching was carried out in a sprayable apparatus (Mini-etcher ME-001).

In order to confirm the etch characteristics, a molybdenum titanium alloy film was etched for 80 seconds and etched for 150 seconds in order to check the damage of the copper film used in the source drain wiring.

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

FIG. 1 is a photograph showing a cross section of a specimen by a scanning electron microscope after etching a molybdenum titanium alloy film (MoTi) for 80 seconds using an etchant that has elapsed from 0 day and 5 days after the preparation of the etchant composition according to Example 1 And FIG. 3 is a graph showing the results of etching of a molybdenum titanium alloy film (MoTi) by 80 s using an etchant that has elapsed from 0 day and 5 days after the preparation of the etchant composition according to Comparative Example 1, 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 0.25 mu even if the storage days of the etching composition elapse after 0 and 5 days. On the other hand, in the case of FIG. 3 in which the hydrous stabilizer is not included, it is confirmed that the etch bias is reduced to 40% After the etching solution composition according to Example 1 was etched for 150 seconds, a copper / molybdenum-titanium alloy double layer (upper copper thickness 5000 Å, lower molybdenum-titanium 300 Å) was etched using etchant which had passed for 0 day and 5 days respectively, 2 and FIG. 4 in comparison with FIG. 2 and FIG. 4, the damage of Cu copper film, which is a material for forming the lower film, was not found in the etching composition after 150 days And 0 when exposed. These results show that there is no change in etching characteristics such as decomposition of hydrogen peroxide and decomposition of organic materials (eg, copper etching inhibitor).

On the other hand, in the case of FIG. 4 in which the hydrous stabilizer is not applied, the damage to the copper film is 0 at the time of aging, but when exposed to the etching composition for 5 seconds after the aging, the copper film is damaged by 3930Å. Therefore, it can be confirmed that the etching composition not containing the hydrous stabilizer of the present invention accelerates the decomposition of fruit water or organic matter (copper corrosion inhibitor), thereby increasing damage to the lower copper film and causing defects.

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

Examples and Comparative Examples Molybdenum titanium
Alloy film etching
bias (탆) / 80s etching Decomposition rate of hydrogen peroxide (%) at 5 days Copper / molybdenum-titanium double layer
Etch Thickness during 150s etch
(A) 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, the etching compositions of Comparative Examples 1 and 2 showed that the etching composition containing a compound containing a transition metal ion as a co-oxidant such as CuSO ₄ and Fe (NO ₃ ) ₃ was molybdenum The etch bias of the titanium alloy film increases, but the etch bias decreases by the hydrogen peroxide decomposition after 5 days, and the etching thickness of the copper film forming the lower film increases due to decomposition of the corrosion inhibitor.

To solve these problems, PEG, glycerin, and Phenyl urea were applied as hydrogen peroxide stabilizers, but the change with time was not reduced.

As in the case of Comparative Examples 1, 7, 8, and 9, when four combinations of hydrogen peroxide, a co-oxidant, a corrosion inhibitor, and a hydrous stabilizer were not provided as constituent elements of the present invention, MoTi etch bias, hydrolysis, Cu damage The etching characteristics were found to be defective.

On the other hand, the etching composition having the four combinations of Examples 1 to 11 according to the present invention contains an aliphatic cyclic ketone compound or a lactone compound, which is a specific hydrous stabilizer, so that even after using the transition metal as the auxiliary oxidizing agent, And the etch thickness of the copper film was not increased due to the decrease of decomposition of the corrosion inhibitor. As a result, it was confirmed that the etching performance was maintained.

Claims (12)

Hydrogen peroxide,
Silver, at least one ion selected from iron, copper, nickel, manganese and cerium, or a co-oxidant which is an organic or inorganic compound containing these ions,
A corrosion inhibitor, and
An aliphatic cyclic ketone compound, a lactone compound, or a mixture thereof. The method according to claim 1,
Wherein the hydrothermal stabilizer is included in an amount of 0.1 to 5% by weight based on the total weight of the etching composition. The method according to claim 1,
Wherein the aliphatic cyclic ketone compound is a compound represented by the following formula (1), and the lactone compound is a compound represented by the following formula (2), (3) or (4)
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

(In the above Chemical 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 independently of one another are hydrogen, hydroxy, (C 1 -C 10) alkyl, hydroxy (C 1 -C 10) -C10) alkoxy or (C6-C12) aryl;
A is O or CR ₃₅ R ₃₆ a;
R ₃₅ to R ₃₆ independently of one another are hydrogen, (C 1 -C 10) alkyl, hydroxy (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy or (C 6 -C 12) aryl;
n and m are independently of each other an integer of 0 to 7) The method of claim 3,
Wherein R ₁ to R ₈ are independently of each other hydrogen or (C 1 -C 10) alkyl;
R ₁₁ to R ₁₆ are independently of each other hydrogen, hydroxy, (C 1 -C 10) alkyl or hydroxy (C 1 -C 10) alkyl;
R ₂₁ to R ₂₄ independently from each other are hydrogen or (C 1 -C 10) alkyl;
R ₃₁ to R ₃₆ are independently of each other hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy or (C 6 -C 12) aryl;
n and m are independently of each other an integer from 0 to 5. The method according to claim 1,
Wherein the hydrous stabilizer is selected from the following compounds.

The method according to claim 1,
Wherein the auxiliary oxidizing agent is included in an amount of 0.02 to 10 parts by weight based on 100 parts by weight of hydrogen peroxide. The method according to claim 1,
Wherein the co-oxidant is an inorganic acid salt comprising copper or iron ions. The method according to claim 1,
Wherein the corrosion inhibitor is a heterocyclic compound containing one or more heteroatoms selected from oxygen, sulfur and nitrogen in the molecule. The method according to claim 1,
Wherein the etching composition further comprises a fluorine compound and a compound comprising a sulfonic acid group. 10. The method of claim 9,
Wherein the fluorinated compound is a compound which is dissociated to provide fluorine (F ^- ) or hydrogen fluoride (HF ₂ ^- ) ions. 10. The method of claim 9,
The sulfonate group-containing compound may be an alkyl sulfonate, an alkyl disulfonate, an alkyl benzene sulfonate, an alkyl naphthalene sulfonate, an alkylphenyl ether disulfonate phenyl ether disulfonate, a polymer of formaldehyde and naphthalene sulfonate, a polymer of acrylamide methylpropane sulfonate, a polymer of acrylic acid and acrylamide methylpropane sulfonate ) And a vinylbenzene sulfonate polymer. ≪ RTI ID = 0.0 > [0002] < / RTI > 10. The method of claim 9,
The etch composition comprises 5 to 30% by weight of hydrogen peroxide, 0.0001 to 2% by weight of a co-oxidant, 0.01 to 2% by weight of a corrosion inhibitor, 0.01 to 1% by weight of a fluorine compound, 0.01 to 5% To 2% by weight of a compound comprising a sulfonic acid group and a balance of water.

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