KR20160067522A - Cleaner composition - Google Patents

Abstract

The present invention relates to a cleaning composition for a microelectronic substrate. The cleaning composition comprises: hydrogen peroxide; a metal oxidation-reduction inhibitor; an inorganic compound including ammonium ions; an oxidation co-stabilizer; a metal anticorrosive; and water. The cleaning composition is stabilized by minimizing the amount of organic matter. According to the present invention, the cleaning composition can maintain residue removal rate with respect to changes according to time by preventing changes in the hydrogen peroxide content and suppressing changes in pH of the cleaning solution.

Description

Cleaner composition [

The present invention relates to a detergent composition, and more particularly, to a detergent composition for use in a cleaning process after plasma etching of a microelectronic substrate, which is capable of retarding a change in cleaning performance and maintaining a constant rate of residue removal .

In a back-end-of-line (BEOL) process of an electronic substrate, metallization is formed by photolithography. A low-K dielectric film (Black Diamond, SiC, etc.) formed on the substrate is patterned in the form of a via hole by etching gases (CF ₄ , C ₂ F ₄ ), and the remaining photoresist is removed by using oxygen plasma.

The residue after the plasma etching is deposited on the via hole on the substrate and can inhibit the contact formation if not properly removed. The residue after plasma etching may typically comprise chemical elements present on the substrate and on the plasma gas. In addition, when a TiN hard mask is applied over the low-K dielectric layer, the residue may include modified hardmask titanium-containing material and oil, inorganic residues.

The use of organic compounds in conventional detergent compositions generally results in a change in the cleaning agent composition containing hydrogen peroxide over time, which may result in lower cleaning rates or damage to metals and dielectric films. Therefore, there is a need for a detergent that does not damage the dielectric film and the unoxidized metal while removing residues, hardmask and oxidized metal.

A problem to be solved by the present invention is to provide a detergent composition capable of suppressing changes in pH and cleaning rate of the composition with time and maintaining a stable cleaning ability.

According to an aspect of the present invention,

Hydrogen peroxide;

Metal redox inhibitors;

An inorganic compound containing an ammonium ion;

Oxidation auxiliary stabilizers;

Metal corrosion inhibitors; And

Water. ≪ / RTI >

According to the detergent composition of the present invention, the change in the content due to the decomposition of hydrogen peroxide and the pH change of the detergent composition can be prevented, and stable cleaning conditions can be maintained.

In addition, it is possible to reduce the consumption due to the replacement of the cleaning agent by suppressing performance changes to the residue cleaning and maintaining the etching rate for the oxidized metal.

FIG. 1 is a graph showing changes in hard mask removal rate and hydrogen peroxide content with time for the composition of Example 1. FIG.
Fig. 2 is a photograph showing the residue removal state according to the hydrogen peroxide content. Fig.
Fig. 3 is a photograph showing the surface state of the pure copper substrate after cleaning. Fig.

Hereinafter, the present invention will be described in detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

According to the present invention, hydrogen peroxide; Metal redox inhibitors; An inorganic compound containing an ammonium ion; Oxidation auxiliary stabilizers; Metal corrosion inhibitors; And a balance of water.

Conventional organic buffers can be decomposed by reaction with hydrogen peroxide as the washing process proceeds. The organic buffer may be decomposed into, for example, CH ₃ radicals, which may cause decomposition of the organic buffer to proceed more quickly, thereby lowering the pH of the composition. If the pH of the composition is lowered, oxidation and decomposition of the detergent composition proceeds, thereby impairing the ability to remove residues, resulting in damage to the metal and dielectric film. If the dielectric film is damaged, the metal wires may be capped with each other to shorten the lifetime of the device and cause defects.

On the other hand, the inorganic compound included in the present invention can prevent the pH from being changed due to the decomposition of hydrogen peroxide by the reaction with organic substances in the detergent composition. That is, it is possible to maintain the removal ability of the residue and the etching rate for the oxidized metal by preventing the change of the pH.

According to one embodiment, the detergent composition may comprise a compound containing an ammonium ion as an inorganic compound.

According to one embodiment, the compound containing ammonium ions may include ammonia water or ammonium halide, and may be at least one of ammonium hydroxide, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium carbonate, ammonium sulfate, and ammonium nitrate .

On the other hand, when ammonium phosphate is used as the compound containing the ammonium ion, corrosion to the non-oxidized metal may occur. Thus, for example, it may be desirable to use compounds containing ammonium ions, but not phosphates, as the compound containing ammonium ions.

If the content of the inorganic compound is not appropriate, the pH change due to hydrogen peroxide decomposition can not be prevented, or corrosion to an unoxidized metal can be caused. Therefore, the inorganic compound may be used in an amount of 0.05 to 3 parts by weight based on 100 parts by weight of the total amount of the detergent composition to serve as a detergent. For example, the inorganic compound may be added in an amount of 0.1 to 2 parts by weight.

According to one aspect, during the cleaning process, the metal may generate a new covalent bond with hydrogen peroxide in accordance with the oxidation-reduction reaction to cause a condensation reaction, and may cause a coupling reaction to cause a chain decomposition reaction of hydrogen peroxide. If the hydrogen peroxide decomposes due to such a chemical reaction, the content of hydrogen peroxide on the basis of the total weight of the detergent composition may be reduced, resulting in a pH change of the detergent composition. Thus, to prevent this, the detergent composition may include a metal redox inhibitor.

According to one embodiment, the metal oxidation-reduction inhibitor may comprise a chelate compound, and typical examples of chelating materials are the following organic acids and their isomers and salts: (ethylenedinitrilo) tetraacetic acid , Ethylenediamine tetraacetic acid (EDTA), butylenediaminetetraacetic acid, (1,2-cyclohexylenedinitrilo) tetraacetic acid, CyDTA, diethylenetriaminepentaacetic acid, acid, DETPA, ethylenediaminetetrapropionic acid, (hydroxyethyl) ethylenediaminetriacetic acid (HEDTA), N, N, N ', N'-ethylenediaminetetra (methylenephosphonic acid, ) Acid (N, N, N ', N'-ethylenediaminetetra (methylenephosphonic acid), EDTMP), triethylenetetraminehexaacetic acid , TTHA), 1,3-diamino-2-hydroxypropane-N, N, N ', N'- tetraacetic acid, DHPTA), methyliminodiacetic acid, propylenediaminetetraacetic acid, nitrolotriacetic acid (NTA), citric acid, tartaric acid, gluconic acid gluconic acid, saccharic acid, glyceric acid, oxalic acid, phthalic acid, maleic acid, mandelic acid, malonic acid, Lactic acid, salicylic acid, cayechol acid, gallic acid, propyl gallate, 8-hydroxyquinoline, and cysteine. ).

Preferably, it may include, for example, at least one of aminocarboxylic acid, aminophosphonic acid, and phosphonic acid.

More specifically, it includes, for example, at least one of ethylenediamine tetraacetic acid, cyclohexylene dinitrilotetraacetic acid, diethylenetriamine pentaacetic acid, iminodiacetic acid, nitrilotriacetic acid and hydroxyethanediphosphonic acid .

The content of the metal oxidation-reduction inhibitor may be 0.001 to 0.1 part by weight, for example, 0.003 to 0.05 part by weight based on 100 parts by weight of the total amount of the detergent composition.

According to one embodiment, the detergent composition may include an oxidative auxiliary stabilizer and may serve to maintain the detergent composition in a more stable state due to hydrogen bonding with hydrogen peroxide. According to one embodiment, the oxidative auxiliary stabilizer may comprise at least one selected from the group consisting of polyhydric alcohols, alkanolamines, and morpholinoalkylamines.

More specifically, the oxidative auxiliary stabilizer may be, for example, a glycol, a polyethylene glycol, a glycerin, a xylitol, a sorbitol, a pyrogallol, a catechol, an aminoethoxyethanol, a monoethanolamine (MEA), a methylethanolamine (MDEA), diethanolamine (DEA), diethylethanolamine (DEEA), triethanolamine (TEA), and aminopropylmorpholine (APM).

In addition, the detergent composition according to the present invention may contain 0.03 to 1.5 parts by weight of the oxidative auxiliary stabilizer based on 100 parts by weight of the total amount of the detergent composition in order to minimize the decomposition of hydrogen peroxide as the organic content increases. For example, 0.05 to 1 part by weight. If the content of the oxidative auxiliary stabilizer is not proper, it may cause difficulty in decomposition of hydrogen peroxide and maintenance of the pH of the composition.

According to one embodiment, the detergent composition may comprise a metal corrosion inhibitor. The metal corrosion inhibitor may be a heterocyclic compound containing a nitrogen atom and may be selected from, for example, pyrazole, triazole, tetrazole, imidazole, adenine, pyridine, pyridazine, indazole, thiazole and oxazole-based compounds .

The metal corrosion inhibitor is a compound containing at least one nitrogen atom in an aromatic ring, and the nitrogen atom may be a compound in which hydrogen atoms capable of dissociating into hydrogen ions are directly bonded in the slurry.

According to one embodiment, the metal corrosion inhibitor may include a triazole compound, a benzotriazole compound, an imidazole compound, an adenine compound, a tetrazole compound, a thiazole compound, an oxazole compound and a pyrazole compound as an azole compound And these compounds can be used independently or in combination. For example, the metal corrosion inhibitor may include any one or more of the group consisting of a triazole compound, a benzotriazole compound, and an imidazole compound, either independently or in combination.

More specifically, examples of compounds that can be included in the metal corrosion inhibitor according to the present invention include triazole, 1H-1,2,3-triazole, 1,2,3-triazole-4,5-dicarboxylic acid , 1,2,4-triazole, 1-H-1,2,4-triazole-3-thiol, 3-amino-triazole and the like. These compounds can be used independently or in combination .

Other examples include benzotriazole compounds, such as benzotriazole, 1-amino-benzotriazole, 1-hydroxy-benzotriazole, 5-methyl-1H-benzotriazole, benzotriazole- These compounds can be used independently or in combination.

Examples of the imidazole compound include imidazole, 1-methylimidazole, benzimidazole, 1-methyl-benzimidazole, 2-methyl-benzimidazole and 5-methyl-benzimidazole. The compounds may be used independently or in combination.

Other examples include tetrazole compounds, such as 1H-tetrazole, 1H-tetrazole-5-acetic acid and 5-amino-tetrazole. These compounds may be used independently or in combination.

Another example is a thiazole compound, and examples thereof include benzothiazole, 2-methyl-benzothiazole, 2-amino-benzothiazole, 6-amino-benzothiazole and 2-mercapto-benzothiazole. The compounds may be used independently or in combination.

Another example is an oxazole compound, and examples thereof include isoxazole, benzoxazole, 2-methyl-benzoxazole, and 2-mercapto-benzoxazole, and these compounds can be used independently or in combination.

Pyrazole compounds, and pyrazole, 4-pyrazole-carboxylic acid, etc. These compounds can be used independently or in combination.

Also, according to one embodiment, the metal corrosion inhibitor may be at least one of pyridine and piperidine, and may include, for example, 3-methylpyridine, cysteamine.

According to one embodiment, the metal corrosion inhibitor may comprise at least one of pyrazole, triazole, benzotriazole, tolytriazole, aminotriazole, methyltetrazole, imidazole, pyridine, pyridazine and indazole have.

According to one embodiment, the metal corrosion inhibitor may increase the antioxidant effect of the metal when it contains a benzene group or includes a hydrophobic group such as a methyl group.

The content of the metal corrosion inhibitor may be 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of the detergent composition.

The metal film corrosion inhibitor may also serve to prevent galvanic corrosion. Galvanic corrosion refers to a phenomenon in which when two kinds of metals are in contact with each other in the electrolyte, a potential difference is generated, and corrosion of the metal on the cathode side, which is highly corrosion resistant due to flow of current between the metals, is suppressed, The galvanic corrosion phenomenon can be prevented by forming the corrosion prevention film on the metal film in the electric device applying the different metal film by the metal film corrosion inhibitor.

According to one embodiment, the detergent composition may comprise water as a solvent, and the water may be deionized water or deionized water, which is generally reduced in impurities used for semiconductor processing. For example, the water used may have a purity of greater than or equal to 18 MΩ / cm, and the remaining amount of the composition may be included based on 100 parts by weight of the detergent composition.

According to one embodiment, the pH of the detergent composition of the present invention may be from 7 to 11. Also, the change width of the pH may be 0 to 0.5 for 120 hours of the washing process time, and may have a variation range of 0 to 0.3 for 24 hours, for example.

According to one embodiment, the detergent composition may further comprise a surfactant. The surfactant may be added additionally to improve the wetting property of the applied surface to allow the detergent composition to act on the substrate uniformly, to improve the foam characteristics of the additive, and to improve solubility in other organic additives.

 The surfactant may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, a cationic surfactant and an amphoteric surfactant.

The nonionic surfactant may be used in admixture with other types of surfactants for the reason of not generating ions in the aqueous solution state. Nonionic surfactants include, for example, ethoxylated linear alcohols, ethoxylated alkylphenols, fatty acid esters, amine and amide derivatives, alkylpolyglycosides, ethylene oxide-propylene oxide interpolymers, polyalcohols and ethoxylates Polyhydric alcohol, polyhydric alcohol, polyhydric alcohol, polyhydric alcohol, polyhydric alcohol, polyhydric alcohol, polyhydric alcohol, polyhydric alcohol,

The anionic surfactant may include a sulfate, a sulfonate, an organophosphate, a sarcoside, an alkyl amino acid, lauryl sarcosinate, for example, an alkyl ester sulfate, an alkyl ethoxy ether sulfate, a dodecylbenzenesulfonate , Alkyl benzene sulfonic acid salts, alpha-olefin sulfonic acid salts, lignosulfonic acid salts, sulfo-carboxyl compounds.

The cationic surfactant can be adsorbed on the negative chargeable substrate and thus can serve as antistatic and softening agent. And can also serve as dispersants, flocculants, hydrophobic agents and corrosion inhibitors for solid particles. Cationic surfactants may include, for example, fatty acid amines, quaternary alkyl-ammonium, linear diamines, n-dodecylpyridinium chloride, imidazole and morpholine compounds.

The amphoteric surfactant has an anionic and cationic dissociation in the same molecule and has a constant isoelectric point, and includes, for example, amphocarboxylate, alkylbetaine, amidoalkylbetaine, amidoalkylsutaine, amphophosphate, Tine, pyrophosphobetaine, carboxyalkyl alkyl polyamines.

As the surfactant, for example, at least one of acetylenic diol, alkylamine, alkylcarboxylic acid, and pluronic-based polymer may be used. The pluronic polymers may include, for example, block copolymers of ethylene oxide and propylene oxide.

Surfactants that may be included in the detergent composition may be those commonly used in the art and are not limited to the surfactants described above.

 The surfactant may be added in an amount of 0.0005 to 5 parts by weight based on 100 parts by weight of the detergent composition. For example, 0.001 to 2 parts by weight of a nonionic surfactant, an amphoteric surfactant, or a mixture thereof may be added have. If the content of the surfactant is not appropriate, it is not expected to improve the wettability, improve the foam properties of the additive, and increase the solubility in the organic additive, or the surfactant precipitation problem may occur due to the solubility problem.

According to one aspect, the detergent composition according to the present invention can be advantageously used for cleaning a via hole portion in forming a metal wiring in a process for manufacturing a device having a semiconductor structure, for example, an electronic substrate for manufacturing a semiconductor having a high degree of integration .

BRIEF DESCRIPTION OF THE DRAWINGS The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings in which: . The following examples are intended to illustrate the present invention and should not be construed as limiting the scope of the present invention in any way whatsoever, and all changes, equivalents, and alternatives falling within the spirit and scope of the present invention are to be understood.

Examples 1 to 7 and Comparative Examples 1 to 4

Each component was mixed in the contents shown in the following Table 1 to prepare a detergent composition having 100% by weight. In the following table, a 29% aqueous solution of ammonium hydroxide was used.

ingredient Oxidant weapon
Buffer assistant
Stabilizer Redox inhibitor corrosion
Inhibitor Ultrapure water H ₂ O ₂ 29% NH ₄ OH AEE CyDTA DTPA EDTA IDA HEDP BTA Example 1 18 0.14 0.07 0.007 0 0 0 0 0.035 Balance Example 2 18 0.14 0.07 0.01 0 0 0 0 0.035 Balance Example 3 18 0.14 0.07 0 0.01 0 0 0 0.035 Balance Example 4 18 0.14 0.07 0 0 0.01 0 0 0.035 Balance Example 5 18 0.14 0.07 0 0 0 0.01 0 0.035 Balance Example 6 18 0.14 0.07 0 0 0 0 0.01 0.035 Balance Example 7 18 1.4 0.07 0.007 0 0 0 0 0.035 Balance Comparative Example 1 18 0 0.91 0 0 0 0 0 0.035 Balance Comparative Example 2 18 0 0.91 0.007 0 0 0 0 0.035 Balance Comparative Example 3 18 0.14 0.07 0 0 0 0 0 0.035 Balance Comparative Example 4 18 1.4 0 0.007 0 0 0 0 0.035 Balance

Abbreviations used in Table 1 above mean the following.

AEE: 2- (2-aminoethoxy) ethanol

CyDTA: cyclohexylene dinitrile, tetraacetic acid

DTPA: diethylenetriamine pentaacetic acid

EDTA: Ethylenediamine tetraacetic acid

IDA: iminodiacetic acid

HEDP: Hydroxyethane diphosphonic acid

BTA: 1H-benzotriazole

Experimental Example 1: Determination of composition stability and aging

As a test piece on which a via hole is formed, a structure in which a Cu metal film, a silicon nitride film, a silicon oxide film, a SiC dielectric (trade name BD2) and a TiN hard mask layer are laminated on a substrate, Specimens with modified dense hardmask titanium residues and polymer residues as organic and inorganic residues were prepared.

For the examples and comparative compositions having the contents shown in Table 1, the compositions were stored in a 50 ° C bath for 24 hours, and then H ₂ O ₂ content and pH were measured. The content of hydrogen peroxide was confirmed by potassium permanganate titration.

The thicknesses of the TiN hard mask, the Cu metal, and the insulator on the silicon wafer before and after cleaning, respectively, were measured using a cleaning agent composition after a cleaning process time of 15 seconds, 30 seconds, and 60 seconds, respectively, Respectively. The time taken to remove polymer residues was measured by scanning electron microscopy in 30 second increments.

As shown in FIG. 1, the detergent composition (Example 1) according to the present invention shows that the hard mask removal rate change and the hydrogen peroxide concentration change slowly progress for 120 hours, and the difference is small.

Fig. 2 is a scanning electron microscope (SEM, S-4800, Hitachi) photograph of a specimen subjected to a cleaning process using the cleaning composition according to Examples 1 to 5 and Comparative Example 1. Fig. It can be confirmed that the cleaning effect is excellent when the composition according to the present invention is used.

The insulation damage was measured using a specimen prepared after molding an insulator (trade name: BD2) of 5000 Å on a silicon wafer and measuring the thickness variation using a material specific refractive index with a K-MAC ST- Speed.

division H ₂ O ₂ content pH TiN removal rate
(Å / min) Cu etch rate
(Å / min) Insulator
Etching rate
(Å / min) Polymer
Removal time
(sec) Early 24h Early 24h Early 24h Early 24h Early 24h Early 24h Example 1 18 18 8.0 8.0 283 285 6.2 6.3 ≤2 ≤2 60 60 Example 2 18 18 8.0 8.0 288 281 6.5 6.4 ≤2 ≤2 60 60 Example 3 18 18 8.0 8.0 281 279 6.4 6.5 ≤2 ≤2 60 60 Example 4 18 18 8.0 8.0 295 288 6.5 6.5 ≤2 ≤2 60 60 Cixi Example 5 18 16 7.9 8.1 276 272 6.3 6.8 ≤2 ≤2 60 60 Example 6 18 18 7.8 7.5 323 286 9.1 7.2 ≤2 ≤2 60 60 Example 7 18 16 9.7 9.6 470 451 17.5 18.1 ≤2 ≤2 60 60 Comparative Example 1 18 4.3 8.0 6.8 187 26 6.8 2.6 ≤2 ≤2 60 Residue Comparative Example 2 18 18 8.0 6.8 191 49 7.1 4.4 ≤2 ≤2 60 120 Comparative Example 3 18 14 8.0 7.9 285 217 5.3 7.1 ≤2 ≤2 60 80 Comparative Example 4 18 11 9.3 9.5 481 243 14.8 17.3 ≤2 ≤2 60 60

As can be seen from the results in Table 2, in Comparative Examples 1 and 2 containing no inorganic compound, the hydrogen peroxide content and pH were greatly reduced after 24 hours of experiment, and as a result, the removal ability of the TiN hard mask was 3 to 7 times . Also in the result of Comparative Example 3 which did not use an oxidation-reduction inhibitor or Comparative Example 4 which did not use an auxiliary stabilizer, the content of hydrogen peroxide also drastically decreased, so that the removal ability of the TiN hard mask was reduced to nearly half after 24 hours of the cleaning process, The etching rate for the etching solution is considerably increased.

Examples 8 to 9 and Comparative Examples 5 to 8

A cleaning agent composition was prepared by mixing each component so that the total amount was 100% by weight in the contents shown in Table 3 below.

division Oxidant Buffer assistant
Stabilizer Redox
Inhibitor corrosion
Inhibitor Ultrapure water H ₂ O ₂ 29%
NH ₄ OH 40%
NH ₄ F 20%
TMAH EPPS Aac AP2 AEE CyDTA BTA Example 8 18 0.14 0 0 0 0 0 0.07 0.007 0.035 Balance Example 9 18 0 0.12 0 0 0 0 0.07 0.007 0.035 Balance Comparative Example 5 18 0 0 1.75 0 0 0 0.07 0.007 0.035 Balance Comparative Example 6 18 0 0 0 0.35 0 0 0.07 0.007 0.035 Balance Comparative Example 7 18 0 0 0 0 0.7 0 0.07 0.007 0.035 Balance Comparative Example 8 18 0 0 0 0 0 0.924 0.07 0.007 0.035 Balance

Abbreviations used in Table 3 above mean the following.

TMAH: tetramethylammonium hydroxide

EPPS: 4- (2-hydroxyethyl) piperazin-1-propanesulfonic acid

Aac: ammonium acetate

AP2: ammonium phosphate dibasic acid

AEE: 2- (2-aminoethoxy) ethanol

CyDTA: cyclohexylene dinitrile, tetraacetic acid

BTA: 1H-benzotriazole

Experimental Example 2: Effect of inorganic compound buffer

The cleaning compositions shown in Table 3 were used in the same manner as in Experimental Example 1, and the results are shown in Table 5 below.

ingredient H ₂ O ₂ pH TiN removal rate
(Å / min) Cu etch rate
(Å / min) Polymer
Removal time
(sec) Early 24 hours Early 24 hours △ Early 24 hours Early 24 hours Early 24 hours Example 8 18 18 8.0 8.0 0.0 283 285 6.2 6.3 60 60 Example 9 18 18 7.1 7.1 0.0 78 82 4.2 3.8 180 180 Comparative Example 5 18 1.6 8.0 10.4 -2.4 276 0 8.7 11.2 60 Residue Comparative Example 6 18 17 7.8 6.2 1.6 241 112 5.9 4.1 60 300 Comparative Example 7 18 18 7.0 7.1 -0.1 69 67 4.4 4.7 240 240 Comparative Example 8 18 18 7.3 7.3 0.0 197 212 16.1 17.4 120 120

As can be seen from the results in Table 4, when the detergent compositions according to Examples 8 and 9 were used, the content of hydrogen peroxide after 24 hours was the same as the first, the pH of the detergent composition was not changed, and the removal rate of the TiN hard mask There is no significant change and it can be confirmed that there is little damage to the copper metal. On the other hand, in the case of Comparative Examples 5 and 6, the content of hydrogen peroxide greatly decreases, and the pH change range of the detergent composition is large. In addition, Comparative Examples 7 and 8 show a long time consumed in removing the TiN hard mask and residues, and in particular, the damage to copper metal in Comparative Example 8 is large.

Examples 10 to 14 and Comparative Examples 10 to 11

The cleaning agent compositions of Examples 10 to 14 and Comparative Example 9 were prepared by mixing the components in the amounts shown in Table 5 so that the total amount was 100% by weight.

division Oxidant weapon
Buffer
Corrosion inhibitor assistant
stability
issue Oxidation
restoration
Inhibitor Ultrapure water H ₂ O ₂ 29%
NH ₄ OH BTA TTA PyZ TAZ ATZ IMD ADN AEE CyDTA Example 10 18 0.14 0.035 0 0 0 0 0 0 0.07 0.007 Balance Example 11 18 0.14 0 0.035 0 0 0 0 0 0.07 0.007 Balance Example 12 18 0.14 0 0 0.21 0 0 0 0 0.07 0.007 Balance Example 13 18 0.14 0 0 0 0.07 0 0 0 0.07 0.007 Balance Example 14 18 0.14 0 0 0 0 0.07 0 0 0.07 0.007 Balance Comparative Example 9 18 0.14 0 0 0 0 0 0 0 0.07 0.007 Balance

Abbreviations used in Table 5 above mean the following.

TTA: Tolythriazole

Pyz: Pyrazole

ATZ: Aminotetrazole

IMD: imidazole

ADN: Adenine

Experimental Example 3: Effect of corrosion inhibitor

The copper substrate etching rate was measured using each of the cleaning composition shown in Table 5. The results are shown in Table 6 below.

As pure copper substrate, a pure copper film etched with dilute hydrofluoric acid copper was used. As the copper oxide substrate, a copper substrate obtained by oxidizing at 200 ° C. for 30 minutes using an oven was used.

ingredient Copper substrate Etching rate (Å / min) Pure copper substrate Copper oxide substrate Copper oxide / pure copper etching rate ratio Example 10 6.2 10.8 1.7 Example 11 3.4 6.3 1.8 Example 12 9.9 12.0 1.2 Example 13 9.0 11.2 1.3 Example 14 8.5 9.2 1.1 Comparative Example 9 0.5 0.4 0.8

FIG. 3 is a photograph of a copper substrate cleaned using the cleaning compositions of Examples 10 to 13 and Comparative Example 9, washed with deionized water, dried with a high purity nitrogen gas, and then observed with a scanning electron microscope.

As can be seen from the results of Table 6 and FIG. 3, the detergent composition is considered to be preferable when the etching rate ratio to pure copper and copper oxide is 1.0 or more. In Comparative Example 9, And the copper oxide substrate is not etched.

While the present invention has been particularly shown and described with reference to the preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It is not.

Claims (12)

Hydrogen peroxide;
Metal redox inhibitors;
An inorganic compound containing an ammonium ion;
Auxiliary stabilizers;
Metal corrosion inhibitors; And
Water. The detergent composition according to claim 1, wherein the inorganic compound comprises an ammonium ion, but not a phosphate compound. The detergent composition according to claim 1, wherein the inorganic compound comprising ammonium ions is at least one of ammonium hydroxide, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium carbonate, ammonium sulfate and ammonium nitrate. The method according to claim 1,
Wherein the metal oxidation-reduction inhibitor comprises a chelate compound. The method according to claim 1,
Wherein the metal oxidation-reduction inhibitor comprises at least one selected from the group consisting of aminocarboxylic acids, aminophosphonic acids, and phosphonic acids. The method according to claim 1,
Wherein the auxiliary stabilizer comprises at least one selected from the group consisting of polyhydric alcohols, alkanolamines, and morpholinoalkylamines. The method according to claim 1,
The auxiliary stabilizer is selected from the group consisting of glycol, polyethylene glycol, glycerin, xylitol, sorbitol, pyrogallol, catechol, aminoethoxyethanol, monoethanolamine, methylethanolamine, methyldiethanolamine, diethanolamine, diethylethanolamine, And aminopropylmorpholine. ≪ Desc / Clms Page number 24 > The method according to claim 1,
Wherein the metal corrosion inhibitor comprises a nitrogen atom-containing heterocyclic compound. The method according to claim 1,
Wherein the metal corrosion inhibitor comprises at least one of substituted or unsubstituted pyrazole, triazole, tetrazole, imidazole, adenine, pyridine, pyridazine, indazole, thiazole and oxazole compounds. The method according to claim 1,
wherein the pH is in the range of 7 to 11 and the pH change range is in the range of 0 to 0.3 after being left for 24 hours. The method according to claim 1,
Based on 100 parts by weight of total cleaning composition,
5 to 30 parts by weight of hydrogen peroxide;
0.001 to 0.1 part by weight of a metal redox inhibitor;
0.05 to 3 parts by weight of an inorganic compound containing ammonium ions;
0.03 to 1.5 parts by weight of a secondary stabilizer;
0.01 to 5 parts by weight of a metal corrosion inhibitor; And
Lt; / RTI > water. A method for cleaning a microelectronic substrate after plasma etching using the cleaning composition of any one of claims 1 to 11.

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