KR20170074003A - Cleaning solution composition - Google Patents

Cleaning solution composition Download PDF

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KR20170074003A
KR20170074003A KR1020150182957A KR20150182957A KR20170074003A KR 20170074003 A KR20170074003 A KR 20170074003A KR 1020150182957 A KR1020150182957 A KR 1020150182957A KR 20150182957 A KR20150182957 A KR 20150182957A KR 20170074003 A KR20170074003 A KR 20170074003A
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acid
cleaning liquid
liquid composition
triazole
group
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KR1020150182957A
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Korean (ko)
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윤주형
이혜희
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주식회사 케이씨텍
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3218—Alkanolamines or alkanolimines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

[0001] The present invention relates to a cleaning liquid composition, wherein the cleaning liquid composition according to an embodiment of the present invention comprises an amine-containing compound; Chelating agents; And a corrosion inhibitor which is used in a cleaning process after chemical mechanical polishing of a wafer containing tungsten and which is alkaline having a negative zeta potential and which is capable of etching the metal significantly or preventing the oxidation and corrosion of tungsten, Residual particles, organic residues and metal contaminants can be removed after tungsten film polishing without leaving or contamination of the wafer. In addition, it is possible to effectively prevent the re-deposition on the wafer after removing the contaminants, thereby improving the defects to occur in the subsequent process.

Description

CLEANING SOLUTION COMPOSITION [0002]

The present invention relates to a cleaning composition, and more particularly, to a cleaning composition used after a chemical mechanical polishing process of a wafer containing tungsten.

Market demands such as high performance and miniaturization have resulted in a demand for more integrated semiconductor devices on microelectronic devices. For example, there is a need for a high level planarization technique to form a good circuit pattern, wherein a chemical mechanical polishing (CMP) step of polishing the wafer surface is performed using a CMP slurry composition containing microparticles of alumina or silica use. However, in this CMP step, abrasive fine particles, alumina and silica in the CMP slurry composition, an aqueous solution of iron nitrate added to promote polishing, an anticorrosion agent added to suppress the corrosion of the metal, A residue of a metal used on the side of the wiring remains on the wafer surface and can have a short-circuited side effect on the electrical properties of the semiconductor. Therefore, it is necessary to perform a cleaning process in order to improve the reliability of the device by removing contamination of particles, metal atoms, and the like generated in the manufacturing process of the semiconductor device before proceeding to the next manufacturing step. CMP cleaners typically use aqueous hydrochloric acid and aqueous hydrogen peroxide in combination with aqueous ammonia and aqueous hydrogen peroxide solutions or dilute aqueous hydrofluoric acid solutions. However, in such a method, there is a problem that the cleaning ability is lowered, the particle removing performance is insufficient, protrusion of the tungsten film occurs, excessive etching of the oxide film occurs, and steps are generated. Therefore, there is a need for a cleaning liquid composition capable of effectively removing residual particles and metal contaminants.

It is an object of the present invention to solve the above-mentioned problems, and an object of the present invention is to provide a method for cleaning a wafer containing tungsten, which is used in a cleaning process after chemical mechanical polishing to prevent oxidation and corrosion of metal, And to prevent the re-deposition after removing the contaminants.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.

According to one embodiment of the present invention, an amine-containing compound; Chelating agents; And a corrosion inhibitor.

The pH of the cleaning liquid composition may be in the range of 9 to 11.

The cleaning composition may be tetra-methyl ammonium hydroxide-free.

The amine-containing compound may include an amine including an alkyl group and a hydroxyl group.

The amine-containing compound may be at least one selected from the group consisting of monoethanolamine, 2-ethylhexylamine, methylamine, dimethylamine, ethylamine, diethylamine, ethanolamine, diethanolamine, methyldiethanolamine, triethylamine, trimethylamine, triethanol Amines, isopropanolamine, diisopropanolamine, triisopropanolamine, nitrosodiethanolamine, n-butylamine, 3-methoxypropylamine, tert-butylamine, benzylamine, n-hexylamine, cyclohexylamine, n-octyl Amines such as N-methyl-N-butylamine, N- (3-aminopropyl) morpholine, 2-aminoethanol, o-xylylenediamine, m-xylylenediamine, And at least one selected from the group consisting of dodecylamine, (hydroxyethyloxymethyl) diethylamine, dimethylhydroxylamine, diethylhydroxylamine and dibutylhydroxylamine.

The amine-containing compound may be 0.01% by weight to 5% by weight of the cleaning liquid composition.

The chelating agent may be selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexanediamine-N, N, N ', N'-tetraacetic acid (CDTA), iminodiacetic acid (IDA) ) Is selected from the group consisting of iminodiacetic acid (HIDA), acetic acid, citric acid, nitrilotriacetic acid, picolinic acid, nicotinic acid, isonicotinic acid, fusaric acid, dinicotinic acid, dipiconic acid, lutidonic acid, quinolic acid, glutamic acid, alanine, , Histidine, asparagine, guanidine hydrazine, formic acid, acetic acid, benzoic acid, oxalic acid, succinic acid, malic acid, maleic acid, malonic acid, citric acid, lactic acid, tricarboxylic acid, tartaric acid, aspartic acid, And may contain at least any one selected from the group consisting of acid, fumaric acid, phthalic acid, and pyridinecarboxylic acid.

The chelating agent may be 0.01 wt% to 2 wt% of the cleaning liquid composition.

The chelating agent may be one that forms a complex with the metal to be polished off during polishing of the tungsten-containing wafer.

The corrosion inhibitor may include an azole compound having a cyclic structure.

The corrosion inhibitor may be selected from the group consisting of imidazole, indazole, benzothiazole, benzotriazole, 1,2,4-triazole (TAZ), tolytriazole, 5-phenyl-benzotriazole, , 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, hydroxybenzotriazole, 2- (5-amino-pentyl) Sol, 1,2,3-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, Triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 5-phenylthiol-benzotriazole, halo-benzotriazole , Cl, Br or I), naphthotriazole, 2-mercaptobenzimidazole (MBI), 2-mercaptobenzothiazole, 4-methyl- Thiadiazole-2-thiol, thiazole, methyltetrazole, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, 4-methyl-4H -1,2,4-triazole-3-thiol and 5-amino-1,3,4-thiadiazole-2- OLLO may be to include at least one selected from the group consisting of.

The corrosion inhibitor may be 0.01 wt% to 2 wt% of the cleaning liquid composition.

The cleaning liquid composition according to an embodiment of the present invention may contain at least one selected from the group consisting of nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, hydrobromic acid, iodic acid, formic acid, malonic acid, maleic acid, oxalic acid, acetic acid, adipic acid, At least one selected from the group consisting of propionic acid, fumaric acid, lactic acid, salicylic acid, pimelic acid, benzoic acid, succinic acid, phthalic acid, butyric acid, glutaric acid, glutamic acid, glycolic acid, lactic acid, aspartic acid, Acidic substances; And an alkaline substance comprising at least one selected from the group consisting of ammonia, ammonium methyl propanol (AMP), potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, sodium hydrogencarbonate, sodium carbonate, imidazole Lt; RTI ID = 0.0 > pH < / RTI >

The zeta potential of the cleaning liquid composition may be -40 mV to -80 mV.

The cleaning liquid composition may be one used as a cleaning liquid after wafer polishing containing tungsten.

The cleaning liquid composition according to an embodiment of the present invention is used in a cleaning process after chemical mechanical polishing of a wafer containing tungsten and is alkaline having a negative zeta potential to significantly etch the metal while preventing oxidation and corrosion of tungsten Residual residues, organic residues and metal contaminants can be removed after tungsten film polishing without leaving deposits or contamination of wafers. In addition, it is possible to effectively prevent the re-deposition on the wafer after removing the contaminants, thereby improving the defects to occur in the subsequent process.

1 is a scanning electron microscope (SEM) image of a tungsten surface after adsorption measurement using the cleaning liquid composition of Comparative Example 1-3 of the present invention.
2 is a scanning electron microscope (SEM) image of the surface of tungsten after adsorption measurement using the cleaning liquid composition of Comparative Example 2-3 of the present invention.
3 is a scanning electron microscope (SEM) image of a tungsten surface after adsorption measurement using the cleaning composition of Example 1-3 of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. In addition, terms used in this specification are terms used to appropriately express the preferred embodiments of the present invention, which may vary depending on the user, the intention of the operator, or the practice of the field to which the present invention belongs. Therefore, the definitions of these terms should be based on the contents throughout this specification. Like reference symbols in the drawings denote like elements.

Throughout the specification, when an element is referred to as "comprising ", it means that it can include other elements as well, without excluding other elements unless specifically stated otherwise.

Hereinafter, the cleaning liquid composition of the present invention will be specifically described with reference to examples and drawings. However, the present invention is not limited to these embodiments and drawings.

According to one embodiment of the present invention, an amine-containing compound; Chelating agents; And a corrosion inhibitor.

The cleaning liquid composition according to an embodiment of the present invention is used in a cleaning process after chemical mechanical polishing of a wafer containing tungsten and is alkaline having a negative zeta potential to significantly etch the metal while preventing oxidation and corrosion of tungsten Residual residues, organic residues and metal contaminants can be removed after tungsten film polishing without leaving deposits or contamination of wafers. In addition, it is possible to effectively prevent the re-deposition on the wafer after removing the contaminants, thereby improving the defects to occur in the subsequent process.

The pH of the washing liquid composition may be alkaline to be in the range of 9 to 11, preferably 9.5 to 10.5. In tungsten chemical mechanical polishing (CMP), a silica slurry composition is used, but the zeta potential of silica has a positive charge in acidity, whereas the silicon oxide film constituting the wafer surface has a negative charge. Therefore, an alkaline cleaning liquid is used so that the zeta potential of the slurry composition and the oxide film have negative charges together. When the pH is alkaline, particles are effectively removed due to the electrostatic repulsion of the residual particles from the charged tungsten surface, similar to the charge on the particles having a high surface negative charge.

The cleaning composition may be tetra-methyl ammonium hydroxide-free. The quaternary ammonium hydroxide is selected from the group consisting of choline hydroxide, tetraalkylammonium hydroxide, (hydroxyalkyl) trialkylammonium hydroxide, bis (hydroxyalkyl) dialkylammonium hydroxide, tris ) Alkylammonium hydroxide, and specifically include, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, (hydroxyethyl ) Trimethylammonium hydroxide < / RTI > choline. Addition of such quaternary ammonium hydroxide to the cleaning liquid composition of the present invention tends to lower abrasive particle removal performance, so it is preferable not to add quaternary ammonium hydroxide to the cleaning liquid composition of the present invention.

The amine-containing compound can remove residual particles from the surface of the wafer containing tungsten. The amine-containing compound may include an amine including an alkyl group and a hydroxyl group.

The amine-containing compound may be at least one selected from the group consisting of monoethanolamine, 2-ethylhexylamine, methylamine, dimethylamine, ethylamine, diethylamine, ethanolamine, diethanolamine, methyldiethanolamine, triethylamine, trimethylamine, triethanol Amines, isopropanolamine, diisopropanolamine, triisopropanolamine, nitrosodiethanolamine, n-butylamine, 3-methoxypropylamine, tert-butylamine, benzylamine, n-hexylamine, cyclohexylamine, n-octyl Amines such as N-methyl-N-butylamine, N- (3-aminopropyl) morpholine, 2-aminoethanol, o-xylylenediamine, m-xylylenediamine, And at least one selected from the group consisting of dodecylamine, (hydroxyethyloxymethyl) diethylamine, dimethylhydroxylamine, diethylhydroxylamine and dibutylhydroxylamine.

The amine-containing compound may be 0.01% by weight to 5% by weight of the cleaning liquid composition. If the amine-containing compound is less than 0.01% by weight in the cleaning liquid composition, it may be difficult to completely remove the tungsten residue, and if it exceeds 5% by weight, the corrosion resistance to the tungsten film may be increased.

The chelating agent removes tungsten, oxide residues from the wafer surface during polishing of the tungsten-containing wafer, forms a complex with the metal to be polished and removed, and prevents the removed metal from re-depositing on the surface of the semiconductor material And the function of securing the stability of the performance can be performed by keeping the cleaning liquid composition in a buffered state. The chelating agent may include an organic acid.

The chelating agent may be selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexanediamine-N, N, N ', N'-tetraacetic acid (CDTA), iminodiacetic acid (IDA) ) Is selected from the group consisting of iminodiacetic acid (HIDA), acetic acid, citric acid, nitrilotriacetic acid, picolinic acid, nicotinic acid, isonicotinic acid, fusaric acid, dinicotinic acid, dipiconic acid, lutidonic acid, quinolic acid, glutamic acid, alanine, , Histidine, asparagine, guanidine hydrazine, formic acid, acetic acid, benzoic acid, oxalic acid, succinic acid, malic acid, maleic acid, malonic acid, citric acid, lactic acid, tricarboxylic acid, tartaric acid, aspartic acid, And may contain at least any one selected from the group consisting of acid, fumaric acid, phthalic acid, and pyridinecarboxylic acid.

The chelating agent may be 0.01 wt% to 2 wt% of the cleaning liquid composition. When the chelating agent is less than 0.01 wt%, the solubility of the tungsten oxide in the cleaning composition tends to decrease. When the chelating agent is more than 2 wt%, the cleaning composition tends to corrode or dissolve the tungsten wiring.

In the case of the cleaning liquid composition after the tungsten film polishing according to the present invention, the alkaline region is in the range of pH 9 to 11 and the corrosion inhibitor is added because the dissolution rate is high. The corrosion inhibitor may include azole compounds having a ring structure for not only the corrosion inhibiting effect but also the cleaning speed and the storage stability of the cleaning composition.

The corrosion inhibitor may be selected from the group consisting of imidazole, indazole, benzothiazole, benzotriazole, 1,2,4-triazole (TAZ), tolytriazole, 5-phenyl-benzotriazole, , 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, hydroxybenzotriazole, 2- (5-amino-pentyl) Sol, 1,2,3-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, Triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 5-phenylthiol-benzotriazole, halo-benzotriazole , Cl, Br or I), naphthotriazole, 2-mercaptobenzimidazole (MBI), 2-mercaptobenzothiazole, 4-methyl- Thiadiazole-2-thiol, thiazole, methyltetrazole, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, 4-methyl-4H -1,2,4-triazole-3-thiol and 5-amino-1,3,4-thiadiazole-2- OLLO may be to include at least one selected from the group consisting of.

The corrosion inhibitor may be 0.01 wt% to 2 wt% of the cleaning liquid composition. If the corrosion inhibitor is less than 0.01 wt%, the corrosion of the tungsten can not be suppressed. If the corrosion inhibitor is more than 2 wt%, the particles may remain in the tungsten film.

The cleaning liquid composition according to an embodiment of the present invention may further comprise water as a solvent. The water may contain at least 50% by weight of the cleaning liquid composition, and ultrapure water used for semiconductor manufacturing may be used as the water.

The cleaning liquid composition according to an embodiment of the present invention may contain at least one selected from the group consisting of nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, hydrobromic acid, iodic acid, formic acid, malonic acid, maleic acid, oxalic acid, acetic acid, adipic acid, At least one selected from the group consisting of propionic acid, fumaric acid, lactic acid, salicylic acid, pimelic acid, benzoic acid, succinic acid, phthalic acid, butyric acid, glutaric acid, glutamic acid, glycolic acid, lactic acid, aspartic acid, Acidic substances; And an alkaline substance comprising at least one selected from the group consisting of ammonia, ammonium methyl propanol (AMP), potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, sodium hydrogencarbonate, sodium carbonate, imidazole Lt; RTI ID = 0.0 > pH < / RTI >

The pH can be adjusted by adding the above-mentioned pH adjusting agent. The cleaning composition of the present invention is alkaline, having a pH of 9 to 11, preferably a pH of 9.5 to 10.5, which is similar to the charge on a particle with a high surface negatively charged particle removed due to the electrostatic repulsion of residual particles from the charged surface . Further, the semiconductor substrate is excellent in corrosion inhibition property of tungsten, and it is possible to sufficiently remove the photoresist, the anti-reflection film, the plasma etching residue and the ashing residue as well as the cleaning of the residual particles, the oxidized contaminants and the tungsten residues after polishing.

The zeta potential of the cleaning liquid composition may be -40 mV to -80 mV. The cleaning liquid composition of the present invention implements a negative zeta potential of -40 mV to -80 mV in an alkaline solution to prevent residual particles, oxidative contaminants, tungsten residues, and the like from being resorbed after electrostatic repulsion .

The cleaning liquid composition may have a SER (Static Etch Rate) value per minute on the tungsten surface of 10 Å / min or less, preferably 5 Å / min or less.

The cleaning liquid composition of the present invention may be cleaned by directly contacting a wafer for a semiconductor device, and the wafer for a semiconductor device to be cleaned may include a substrate for a semiconductor device such as a semiconductor, metal, magnetic material, or superconductor. Particularly, among them, the cleaning liquid composition of the present invention may be particularly suitable for a wafer for a semiconductor device containing a metal or a metal compound on the surface of a wiring or the like. The metal used for the semiconductor wafer may include tungsten, copper, titanium, chromium, cobalt, zinc, hafnium, molybdenum, rubidium, gold, platinum, silver and the like as the metal compound. Nitride, oxide, silicide, and the like. Among them, the present invention can be a cleaning object to which tungsten and a compound containing them are suitably used, and preferably, the cleaning fluid composition of the present invention can be used as a cleaning fluid after tungsten polishing.

Hereinafter, the present invention will be described in detail with reference to the following examples and comparative examples. However, the technical idea of the present invention is not limited or limited thereto.

< Experimental Example  1>

Amine - Selective compound selection test

[Example 1-1]

1.5% by weight of triethanolamine (TEA) as an amine-containing compound was added to ultrapure water to prepare a cleaning liquid composition having a pH of 6.

[Example 1-2]

In Example 1-1, a cleaning liquid composition was prepared in the same manner except that the pH was changed to 8.

[Example 1-3]

In Example 1-1, a cleaning liquid composition was prepared in the same manner except that the pH was changed to 10.

[Comparative Example 1-1]

1.5% by weight of trimethyl ammonium hydroxide (TMAH) as an amine-containing compound was added to ultrapure water to prepare a cleaning liquid composition having a pH of 6.

[Comparative Example 1-2]

In Comparative Example 1-1, a cleaning liquid composition was prepared in the same manner except that the pH was changed to 8.

[Comparative Example 1-3]

In Comparative Example 1-1, a cleaning liquid composition was prepared in the same manner except that the pH was changed to 10.

[Comparative Example 2-1]

A cleaning liquid composition having a pH of 6 was prepared by adding 3 wt% of choline hydroxide as an amine-containing compound to ultrapure water.

[Comparative Example 2-2]

In Comparative Example 2-1, a cleaning liquid composition was prepared in the same manner except that the pH was changed to 8

[Comparative Example 2-3]

In Comparative Example 2-1, a cleaning liquid composition was prepared in the same manner except that the pH was changed to 10

The etching rate (SER) and zeta potential of the tungsten substrate after cleaning the tungsten substrate using the cleaning liquid compositions of Examples 1-1 to 1-3 and Comparative Examples 1-1 to 2-3 are shown below.

[Method for measuring zeta potential]

210 ml of a solution containing 1% by weight of silica was prepared and then measured using a ZetaFinder instrument.

[Method of Measuring Etching Rate (SER)] [

Cleaning liquid composition of 60 ℃ 30 g of hydrogen peroxide and 6 g 2 cm 2 of 5,000 Å in a container containing the The tungsten coupon wafer was immersed for 10 minutes and then cleaned. The SER value per minute was measured after measuring the thickness of the tungsten wafer before and after immersion using a 4-point probe of tungsten wafer at 5 mm intervals from the center of the wafer. The unit is Å / min.

SER (static Etch Rate) = (wafer thickness before immersion - wafer thickness after immersion) / 10

Table 1 shows SER and zeta potentials according to the amine-containing compounds and pH according to Examples 1-1 to 1-3 and Comparative Examples 1-1 to 2-3 of the present invention.

Amine-containing
compound pH SER
(Å / min) Zeta potential
(mV) Comparative Example 1-1 TMAH 6 108.6 -31.83 Comparative Example 1-2 8 145.6 -30.56 Comparative Example 1-3 10 121.0 -20.95 Comparative Example 2-1 Choline hydroxide 6 105.0 -25.67 Comparative Example 2-2 8 151.7 -21.67 Comparative Example 2-3 10 142.4 -27.75 Example 1-1 Triethanolamine 6 79.0 -22.49 Examples 1-2 8 86.1 -32.78 Example 1-3 10 29.0 -46.68

Referring to Table 1, the addition of triethanolamine (TEA) of the present invention compared with the addition of TMAH and choline hydroxide confirmed that the SER value was lower. In particular, in the case of the cleaning liquid composition prepared by adding triethanolamine as in Example 1-3 and having a pH of 10, since the zeta potential was as high as -46.68 mV, the removal effect due to the electrostatic repulsive force with the residual particles was improved Able to know.

[Measurement of Adsorption Property]

The cleaning liquid composition (60) of Comparative Examples 1-3, 2-3, and 1-3 was placed in a 125 ml bottle, and the 2x2 cm 2 tungsten coupon wafer was immersed for 10 minutes. Washed with ultrapure water and dried with N 2 .

FIG. 1 is a scanning electron microscope (SEM) image of a tungsten surface after measurement of adsorption using a cleaning liquid composition of Comparative Example 1-3 of the present invention. FIG. 2 is a graph showing the results of the adsorption measurement using the cleaning liquid composition of Comparative Example 2-3 of the present invention 3 is a scanning electron microscope (SEM) image of a tungsten surface after adsorption measurement using the cleaning composition of Example 1-3 of the present invention. Fig. 3 is a scanning electron microscope (SEM) image of a tungsten surface. As a result of observation with a scanning electron microscope (SEM), as shown in Figs. 1 to 3, in the case of a cleaning liquid composition containing triethanolamine (TEA) of Example 1-3, the addition of TMAH of Comparative Example 1-3 And the number of particles remaining on the surface is much smaller than that in the case of adding the choline hydroxide of Comparative Example 2-3.

< Experimental Example  2>

Chelating agent selection test

To select the chelating agent, a cleaning composition having a pH of 10 was prepared using various kinds of organic acids, and the SER and zeta potential were determined to evaluate the detergency.

[Example 2]

0.3 wt% of ethylenediaminetetraacetic acid (EDTA) as a chelating agent was added to ultrapure water to prepare a cleaning liquid composition having a pH of 10.

[Example 3]

In Example 2, a cleaning liquid composition was prepared in the same manner except that the chelating agent was changed to oxalic acid.

[Example 4]

In Example 2, a cleaning liquid composition was prepared in the same manner except that the chelating agent was changed to succinic acid.

[Example 5]

In Example 2, the cleaning liquid composition was prepared in the same manner except that the chelating agent was changed to malic acid.

[Example 6]

In Example 2, a cleaning liquid composition was prepared in the same manner except that the chelating agent was changed to tartaric acid.

[Example 7]

In Example 2, a cleaning liquid composition was prepared in the same manner except that the chelating agent was changed to citric acid.

[Example 8]

In Example 2, a cleaning liquid composition was prepared in the same manner except that the chelating agent was changed to glycine.

[Example 9]

In Example 2, a cleaning liquid composition was prepared in the same manner except that the chelating agent was changed to cysteine.

[Method of Measuring Etching Rate (SER)] [

Of 5,000 Å in the cleaning liquid composition container containing 30 g of 60 ℃ 2 cm 2 The tungsten coupon wafer was immersed for 10 minutes and then cleaned. The SER value per minute was measured after measuring the thickness of the tungsten wafer before and after immersion using a 4-point probe of tungsten wafer at 5 mm intervals from the center of the wafer. The unit is Å / min.

SER (static Etch Rate) = (wafer thickness before immersion - wafer thickness after immersion) / 10

Table 2 shows SER and zeta potentials according to the chelating agent types and pH according to Examples 2 to 8 of the present invention.

Chelating agent pH SER
(Å / min) Zeta potential
(mV) Example 2 EDTA 10 0.95 -48.30 Example 3 Oxalic acid 10 1.57 -48.47 Example 4 Suche mountain 10 1.45 -57.37 Example 5 Malian 10 1.48 -67.17 Example 6 Tartaric acid 10 1.35 -62.01 Example 7 Citric acid 10 0.91 -41.79 Example 8 Glycine 10 1.35 -43.93 Example 9 Cysteine 10 0.75 -12.63

Referring to Examples 2 to 8 in Table 2, it can be seen that even when the type of organic acid in the chelating agent is changed, the SER value is less than 2 ANGSTROM / min. Therefore, it can be seen that the same effect is obtained when organic acid is added regardless of the type of organic acid.

It can be seen that a low SER value reduces the phenomenon of being etched when cleaning using a cleaning composition.

< Experimental Example  3>

Evaluation of cleaning liquid composition characteristics

From the results of Experiment 1, triethanolamine was selected as an amine-containing compound exhibiting excellent performance and EDTA was selected as a chelating agent exhibiting excellent performance from the results of Experimental Example 2 to prepare a cleaning solution composition.

[Example 10-1]

1.5% by weight of triethanolamine (TEA) as an amine-containing compound and 0.03% by weight of ethylenediaminetetraacetic acid (EDTA) as a chelating agent were added to ultrapure water to prepare a cleaning liquid composition having a pH of 10.

[Example 10-2]

A cleaning liquid composition was prepared in the same manner as in Example 10-1, except that 0.15% by weight of ethylenediaminetetraacetic acid (EDTA) was added in Example 10-1.

[Example 10-3]

A cleaning liquid composition was prepared in the same manner as in Example 10-1, except that 0.3% by weight of ethylenediaminetetraacetic acid (EDTA) was added.

[Example 10-4]

0.65 wt% of triethanolamine (TEA) as an amine-containing compound and 0.03 wt% of ethylenediaminetetraacetic acid (EDTA) as a chelating agent were added to ultrapure water to prepare a cleaning liquid composition having a pH of 10.

[Example 10-5]

A cleaning liquid composition was prepared in the same manner as in Example 10-4, except that 0.15% by weight of ethylenediaminetetraacetic acid (EDTA) was added in Example 10-4.

[Example 10-6]

In Example 10-4, a cleaning liquid composition was prepared in the same manner as in Example 10-4, except that 0.3% by weight of ethylenediaminetetraacetic acid (EDTA) was added.

[Example 10-7]

0.15% by weight of triethanolamine (TEA) as an amine-containing compound and 0.03% by weight of ethylenediaminetetraacetic acid (EDTA) as a chelating agent were added to ultrapure water to prepare a cleaning composition having a pH of 10.

[Example 10-8]

In Example 10-7, a cleaning liquid composition was prepared in the same manner as in Example 10-7, except that 0.15% by weight of ethylenediaminetetraacetic acid (EDTA) was added.

[Example 10-9]

In Example 10-7, a cleaning liquid composition was prepared in the same manner as in Example 10-7, except that 0.3% by weight of ethylenediaminetetraacetic acid (EDTA) was added.

[Example 11]

1.5% by weight of triethanolamine (TEA) as an amine-containing compound, 0.3% by weight of ethylenediaminetetraacetic acid (EDTA) as a chelating agent and 0.3% by weight of imidazole as a corrosion inhibitor were added to ultrapure water to prepare a cleaning composition having a pH of 10 .

SER was measured under the condition of no hydrogen peroxide as in <Experimental Example 2>.

Table 3 below shows SER values and zeta potentials according to the concentrations of the TEA and EDTA compositions of Examples 10-1 to 10-9 and Example 11 of the present invention.

Composition (concentration) SER
(Å / min) Zeta potential
(mV) Example 10-1 TEA (1.5% by weight) + EDTA (0.03% by weight) 3.29 -76.07 Example 10-2 TEA (1.5% by weight) + EDTA (0.15% by weight) 3.05 -74.90 Example 10-3 TEA (1.5% by weight) + EDTA (0.3% by weight) 2.64 -50.95 Example 10-4 TEA (0.65 wt.%) + EDTA (0.03 wt.%) 2.84 -62.48 Examples 10-5 TEA (0.65 wt.%) + EDTA (0.15 wt.%) 2.55 -56.81 Examples 10-6 TEA (0.65 wt.%) + EDTA (0.3 wt.%) 2.77 -57.33 Examples 10-7 TEA (0.15 wt%) + EDTA (0.03 wt%) 2.07 -78.10 Examples 10-8 TEA (0.15 wt.%) + EDTA (0.15 wt.%) 2.79 -56.82 Examples 10-9 TEA (0.15% by weight) + EDTA (0.3% by weight) 3.00 -57.16 Example 11 TEA (1.5% by weight) + EDTA (0.3% by weight)
+ &Lt; / RTI &gt; imidazole (0.3% by weight) 4.89 -52.67

Referring to Table 3, it can be seen that the SER value increases with increasing triethanolamine (TEA) concentration, and the SER value decreases with decreasing EDTA concentration. Zeta potential also has a large value of -50 mV or more in general, which shows that the effect of removing the residues due to the electrostatic repulsive force with the residual particles is improved.

From these results, it was confirmed that when the SER value is less than 5 Å / min and the absolute value of zeta potential is higher than -50 mV, the cleaning agent composition exhibits excellent performance as a cleaning composition.

While the invention has been shown and described with reference to certain 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. This is possible. Therefore, the scope of the present invention should not be limited by the described embodiments, but should be determined by the equivalents of the appended claims, as well as the appended claims.

Claims (15)

Amine-containing compounds;
Chelating agents; And
Corrosion inhibitors;
&Lt; / RTI &gt;
The method according to claim 1,
Wherein the pH of the cleaning liquid composition is in the range of 9 to 11. &lt; Desc / Clms Page number 18 &gt;
The method according to claim 1,
Wherein the cleaning composition is tetra-methyl ammonium hydroxide-free.
The method according to claim 1,
Wherein the amine-containing compound comprises an amine comprising an alkyl group and a hydroxy group.
The method according to claim 1,
The amine-containing compound may be at least one selected from the group consisting of monoethanolamine, 2-ethylhexylamine, methylamine, dimethylamine, ethylamine, diethylamine, ethanolamine, diethanolamine, methyldiethanolamine, triethylamine, trimethylamine, triethanol Amines, isopropanolamine, diisopropanolamine, triisopropanolamine, nitrosodiethanolamine, n-butylamine, 3-methoxypropylamine, tert-butylamine, benzylamine, n-hexylamine, cyclohexylamine, n-octyl Amines such as N-methyl-N-butylamine, N- (3-aminopropyl) morpholine, 2-aminoethanol, o-xylylenediamine, m-xylylenediamine, Wherein the cleaning liquid composition comprises at least any one selected from the group consisting of dodecylamine, dodecylamine, (hydroxyethyloxymethyl) diethylamine, dimethylhydroxylamine, diethylhydroxylamine, and dibutylhydroxylamine.
The method according to claim 1,
Wherein the amine-containing compound is present in an amount ranging from 0.01% to 5% by weight of the cleaning composition.
The method according to claim 1,
The chelating agent may be selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexanediamine-N, N, N ', N'-tetraacetic acid (CDTA), iminodiacetic acid (IDA) ) Is selected from the group consisting of iminodiacetic acid (HIDA), acetic acid, citric acid, nitrilotriacetic acid, picolinic acid, nicotinic acid, isonicotinic acid, fusaric acid, dinicotinic acid, dipiconic acid, lutidonic acid, quinolic acid, glutamic acid, alanine, , Histidine, asparagine, guanidine hydrazine, formic acid, acetic acid, benzoic acid, oxalic acid, succinic acid, malic acid, maleic acid, malonic acid, citric acid, lactic acid, tricarboxylic acid, tartaric acid, aspartic acid, Wherein the cleaning liquid composition contains at least any one selected from the group consisting of acid, fumaric acid, phthalic acid, and pyridinecarboxylic acid.
The method according to claim 1,
Wherein the chelating agent is 0.01% to 2% by weight of the cleaning composition.
The method according to claim 1,
Wherein the chelating agent forms a complex with the metal to be polished and removed upon polishing of the tungsten-containing wafer.
The method according to claim 1,
Wherein the corrosion inhibitor comprises an azole compound having a cyclic structure.
The method according to claim 1,
The corrosion inhibitor may be selected from the group consisting of imidazole, indazole, benzothiazole, benzotriazole, 1,2,4-triazole (TAZ), tolytriazole, 5-phenyl-benzotriazole, , 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, hydroxybenzotriazole, 2- (5-amino-pentyl) Sol, 1,2,3-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, Triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 5-phenylthiol-benzotriazole, halo-benzotriazole , Cl, Br or I), naphthotriazole, 2-mercaptobenzimidazole (MBI), 2-mercaptobenzothiazole, 4-methyl- Thiadiazole-2-thiol, thiazole, methyltetrazole, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, 4-methyl-4H -1,2,4-triazole-3-thiol and 5-amino-1,3,4-thiadiazole-2- It is to include at least one selected from the group consisting OLLO, the cleaning liquid composition.
The method according to claim 1,
Wherein the corrosion inhibitor is 0.01 wt% to 2 wt% of the cleaning liquid composition.
The method according to claim 1,
But are not limited to, nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, bromic acid, formic acid, malonic acid, maleic acid, oxalic acid, acetic acid, adipic acid, citric acid, adipic acid, acetic acid, propionic acid, fumaric acid, An acidic substance comprising at least any one selected from the group consisting of benzoic acid, succinic acid, phthalic acid, butyric acid, glutaric acid, glutamic acid, glycolic acid, lactic acid, aspartic acid, and tartaric acid and salts thereof; And an alkaline substance comprising at least one selected from the group consisting of ammonia, ammonium methyl propanol (AMP), potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, sodium hydrogencarbonate, sodium carbonate, imidazole Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;
The method according to claim 1,
Wherein the zeta potential of the cleaning liquid composition is from -40 mV to -80 mV.
The method according to claim 1,
Wherein the cleaning liquid composition is used as a cleaning liquid after tungsten polishing.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180151427A1 (en) * 2016-11-29 2018-05-31 Taiwan Semiconductor Manufacturing Company, Ltd. Method of Cleaning Wafer After CMP

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180151427A1 (en) * 2016-11-29 2018-05-31 Taiwan Semiconductor Manufacturing Company, Ltd. Method of Cleaning Wafer After CMP
US10109523B2 (en) * 2016-11-29 2018-10-23 Taiwan Semiconductor Manufacturing Company, Ltd. Method of cleaning wafer after CMP
US10510594B2 (en) 2016-11-29 2019-12-17 Taiwan Semiconductor Manufacturing Company, Ltd. Method of cleaning wafer after CMP
US10916473B2 (en) 2016-11-29 2021-02-09 Taiwan Semiconductor Manufacturing Company, Ltd. Method of cleaning wafer after CMP

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