KR101693237B1 - Slurry composition for tungsten polishing - Google Patents

Slurry composition for tungsten polishing Download PDF

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Publication number
KR101693237B1
KR101693237B1 KR1020150112432A KR20150112432A KR101693237B1 KR 101693237 B1 KR101693237 B1 KR 101693237B1 KR 1020150112432 A KR1020150112432 A KR 1020150112432A KR 20150112432 A KR20150112432 A KR 20150112432A KR 101693237 B1 KR101693237 B1 KR 101693237B1
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South Korea
Prior art keywords
abrasive grains
abrasive
slurry composition
tungsten
polishing
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KR1020150112432A
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Korean (ko)
Inventor
공현구
황진숙
박한터
윤영호
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주식회사 케이씨텍
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Priority to KR1020150112432A priority Critical patent/KR101693237B1/en
Priority to US15/205,684 priority patent/US10077381B2/en
Priority to TW106115948A priority patent/TWI633163B/en
Priority to TW105122690A priority patent/TWI609057B/en
Priority to CN201610575493.0A priority patent/CN106366934B/en
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Publication of KR101693237B1 publication Critical patent/KR101693237B1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1409—Abrasive particles per se
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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

Abstract

The present invention relates to a slurry composition for tungsten comprising at least two types of abrasive particles selected among first abrasive particles, second abrasive particles and third abrasive particles, wherein the specific surface area of the abrasive particles satisfies equation 1, 20 m^2/g <= (T_AK_A) + (T_BK_B) + (T_CK_C) <= 100 m^2/g. In equation 1, T_A is the specific surface area of the first abrasive particles; T_B is the specific surface area of the second abrasive particles; T_C is the specific surface area of the third abrasive particles; one among T_A, T_B and T_C may be 0; the K_A is the content of the first abrasive particles; the K_B is the content of the second abrasive particles; K_C is the content of the third abrasive particles; K_A is equal to or greater than 0 and less than 1; K_B is equal to or greater than 0 and less than 1; and K_C is equal to or greater than 0 and less than 1.

Description

[0001] SLURRY COMPOSITION FOR TUNGSTEN POLISHING [0002]

The present invention relates to a slurry composition for tungsten polishing.

As the design rule of the product is reduced, the aspect ratio (depth / floor width) is rapidly increasing due to the narrow width and height of the structure, and the influence of the scratches generated in the conventional 50- It affects the process more than 2 times. As a result, the influence of the flatness as well as the scratches on the surface of the film was also sensitized. The most important factors to be considered in the polishing process are the amount of polishing and the quality of the polishing surface. Recently, as the semiconductor design rule is reduced, the importance of the quality of the polishing surface is maximized.

On the other hand, as the degree of integration of semiconductors has increased recently, a lower current leakage is required, and a high-permittivity dielectric and a metal gate structure have been devised to satisfy this demand. Aluminum has been widely used as a metal gate material in general. However, due to problems such as difficulty in complete deposition due to reduction in design rule and difficulty in polishing aluminum oxide having high hardness, much research has been conducted on using tungsten as a gate material have. However, as the material is changed from an aluminum gate to a tungsten gate, tungsten forms a topography due to the tungsten crystal grain size after deposition, which causes a short between the undesired metals, resulting in a reduction in semiconductor yield. In order to improve the polishing surface quality of such tungsten, i.e., to improve the flatness, polishing is essential for the next generation process. The slurry composition which is not improved in flatness causes tungsten over etch or unetch in the post-polishing process, resulting in a process failure or unstable operation of the device, thereby drastically lowering the semiconductor yield. In addition, since the conventional slurry compositions for tungsten polishing are optimized for the polishing rate and the selectivity ratio to the titanium and silicon oxide films, the slurry composition is designed to have a low flatness improvement characteristic.

An object of the present invention is to provide a tungsten polishing slurry composition which has a high polishing rate and is excellent in flatness, by polishing a tungsten film.

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.

The slurry composition for tungsten polishing according to one embodiment of the present invention comprises at least two kinds of abrasive grains among first abrasive grains, second abrasive grains and third abrasive grains, and the specific surface area of the abrasive grains satisfies the following conditional expression 1: &lt; RTI ID = 0.0 &gt;

[Conditional expression 1]

20 m 2 / g ≤ (T A × K A) + (T B × K B) + (T C × K C) ≤ 100 m 2 / g

(Wherein T A is one of the specific surface area, the T B is a specific surface area of the second abrasive grain, the T C is and the specific surface of the third abrasive grain, the T A, T B, T C of the first abrasive particles 0 may be, the K a is the content ratio, K B is the content ratio of the K C of the second abrasive particles of the first abrasive particles and the content ratio of the third abrasive grain, 0≤K a <1, 0 ≤K B <1, 0≤K C <satisfies 1).

The specific surface area of the first abrasive grains, the second abrasive grains or the third abrasive grains may be 10 m 2 / g to 120 m 2 / g, respectively.

The specific surface area of the first abrasive grains is 70 m 2 / g to 120 m 2 / g, the specific surface area of the second abrasive grains is 25 m 2 / g to 70 m 2 / g, The specific surface area may be 10 m 2 / g to 25 m 2 / g.

Wherein the content of the first abrasive grains is 10 wt% to 70 wt% of the total abrasive grains, the content of the second abrasive grains is 10 wt% to 70 wt% of the total abrasive grains, May be 10 wt% to 70 wt% of the total abrasive grains.

Wherein the two or more kinds of abrasive grains each independently include at least one selected from the group consisting of a metal oxide coated with a metal oxide, an organic or inorganic material, and a metal oxide in a colloidal state, , Ceria, zirconia, alumina, titania, barium titania, germania, manganese, and magnesia.

And a part of the abrasive grains may be replaced by metal ions.

The metal ion may have a tetrahedral coordination.

The metal ion may be at least one selected from the group consisting of Fe, Al, As, Ga, B, Ber, C, Cr, (Ti), vanadium (V), zinc (Zn), and zirconium (Zr), in addition to the elements selected from the group consisting of indium (In), magnesium (Mg), manganese Or at least one of them.

The abrasive particles may be colloidal silica, the metal ion may be iron (Fe) ions, and some of the surfaces of the colloidal silica abrasive grains may be substituted with iron (Fe) ions.

And ammonium iodide, ammonium persulfate, ammonium persulfate, tetramethylammonium chlorate, tetramethylammonium iodate, potassium iodate, potassium iodate, ammonium permanganate, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium perchlorate, tetramethylammonium chlorate, At least one oxidizing agent selected from the group consisting of tetramethylammonium, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, 4-methylmorpholine N-oxide, pyridine-N-oxide and urea hydrogen peroxide As shown in Fig.

The oxidizing agent may be 0.005 wt% to 5 wt% of the slurry composition for tungsten polishing.

The slurry composition for tungsten polishing may be one which polishes tungsten having a thickness of 1,000 A / min to 2,200 A / min.

The flatness of the surface of the tungsten-containing wafer using the slurry composition for tungsten polishing may be 5% or less.

The surface of the tungsten-containing wafer using the slurry composition for tungsten polishing may have a peak to valley (Rpv) value of 100 nm or less and a surface roughness of 10 nm or less.

The pH of the slurry composition for tungsten polishing may be in the range of 1 to 12.

The slurry composition for tungsten polishing according to the present invention can realize a high polishing rate for a tungsten film, shortening the polishing process time and providing excellent flatness. Surface defects such as erosion phenomenon, dishing phenomenon and formation of a residue of a metal layer on the surface of the object to be polished can be significantly lowered, thereby reducing metal shorts and erroneous defects Thereby enabling a next-generation high integration process.

1 is an infrared absorption spectrum (FT-IR) graph of Fe ion-substituted colloidal silica abrasive particles and general colloidal silica abrasive particles 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 slurry composition for tungsten polishing 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.

The slurry composition for tungsten polishing according to the present invention comprises at least two kinds of abrasive grains: first abrasive grains, second abrasive grains and third abrasive grains, wherein the specific surface area of the abrasive grains satisfies the following conditional expression 1 Lt; / RTI &gt;

[Conditional expression 1]

20 m 2 / g ≤ (T A × K A) + (T B × K B) + (T C × K C) ≤ 100 m 2 / g

(Wherein T A is one of the specific surface area, the T B is a specific surface area of the second abrasive grain, the T C is and the specific surface of the third abrasive grain, the T A, T B, T C of the first abrasive particles 0 may be, the K a is the content ratio, K B is the content ratio of the K C of the second abrasive particles of the first abrasive particles and the content ratio of the third abrasive grain, 0≤K a <1, 0 ≤K B <1, 0≤K C <satisfies 1).

The reason why one of T A , T B and T C can be 0 is that the specific surface area value of one of the first abrasive particle, the second abrasive particle and the third abrasive particle can be 0, Means that only particles having a surface area are added.

The sum of the content ratios of the respective abrasive grains satisfies K A + K B + K C = 1, and one of the K A , K B and K C may be 0. The fact that one of K A , K B and K C can be 0 means that the content ratio of one of the first abrasive grain, the second abrasive grain and the third abrasive grain can be 0, Is added.

The ratio of the specific surface area to the specific surface area of each of the first abrasive grains, the second abrasive grains and the third abrasive grains is set to (T A × K A ) + (T B × K B ) + (T C × K C ) The sum of the multiplied values may be from 20 m 2 / g to 100 m 2 / g. If the sum of the specific surface area of each of the first abrasive grains, the second abrasive grains and the third abrasive grains is less than 20 m 2 / g, the polishing rate may be increased during the polishing step, but scratches may occur. If it is larger than 100 m 2 / g, there is a problem that a sufficient polishing rate can not be obtained.

The slurry composition for tungsten polishing according to the present invention can realize a high polishing rate for a tungsten film, shortening the polishing process time and providing excellent flatness. By including two or more kinds of mixed abrasive grains, surface defects such as erosion phenomenon, dishing phenomenon, and formation of a residue of a metal layer on the surface of an object to be polished can be significantly lowered. As a result, metal shorts and erroneous defects can be reduced and a next-generation high integration process can be performed.

In the present specification, "two or more types of abrasive grains" describes two or three kinds of abrasive grains. However, the present invention is not limited to this, and may include four or more kinds of abrasive grains. When the two or more types of abrasive grains are two types of abrasive grains, the abrasive grains having different specific surface areas are mixed by controlling the calcination condition and / or the milling condition, so that the abrasive grains having a bimodal- Lt; / RTI &gt; Or when the two or more types of abrasive grains are three kinds of abrasive grains, three types of abrasive grains having different specific surface areas may be mixed to have a particle size distribution showing three peaks.

Wherein the first abrasive grains have a primary particle size of 20 nm or more and less than 45 nm, a primary particle size of the second abrasive grains is 45 nm or more and less than 130 nm, nm. &lt; / RTI &gt;

The second abrasive grains have a secondary particle size of 30 nm or more and less than 100 nm, a secondary particle size of the second abrasive grains of 100 nm or more and less than 250 nm, and a secondary particle size of the third abrasive grains of 250 nm Or more and less than 500 nm.

The abrasive grains may be prepared by mixing the first abrasive grains and the second abrasive grains, or by mixing the first abrasive grains with the second abrasive grains, or by mixing the first abrasive grains with the second abrasive grains, The first abrasive grains and the third abrasive grains or the second abrasive grains and the third abrasive grains may be mixed to have a bimodal shape size distribution. Or the first abrasive grains, the second abrasive grains, and the third abrasive grains may be mixed to have a particle size distribution showing three peaks. The relatively large abrasive grains and the relatively small abrasive grains can be mixed to have better dispersibility and the effect of reducing the scratch on the wafer surface can be expected.

In one embodiment of the present invention, the specific surface area of the first abrasive grains, the second abrasive grains or the third abrasive grains may be 10 m 2 / g to 120 m 2 / g, respectively. If the specific surface area of the abrasive grains is less than 10 m 2 / g, there is a possibility of occurrence of scratches between the polishing processes, and if it is more than 120 m 2 / g, it may be difficult to obtain excellent flatness.

For example, the specific surface area of the first abrasive grains is 70 m 2 / g to 120 m 2 / g, the specific surface area of the second abrasive grains is 25 m 2 / g to 70 m 2 / g, May have a specific surface area of 10 m 2 / g to 25 m 2 / g, but the present invention is not limited thereto and may be a mixture of two or three kinds of abrasive grains having a specific surface area of 10 m 2 / g to 120 m 2 / g &Lt; / RTI &gt; in any case.

When two or more types of abrasive grains are mixed, abrasive grains having a relatively large specific surface area and abrasive grains having a relatively small specific surface area are mixed, and thus the polishing speed can be 1.5 times or more higher than that of a single abrasive grains Excellent dispersibility and excellent flatness on the wafer surface can be expected.

Wherein the content of the first abrasive grains is 10 wt% to 70 wt% of the total abrasive grains, the content of the second abrasive grains is 10 wt% to 70 wt% of the total abrasive grains, May be 10 wt% to 70 wt% of the total abrasive grains. If the content of the abrasive grains is less than 10% by weight, a sufficient polishing rate can not be obtained in the polishing step. If the abrasive grains content is more than 70% by weight, scratches may occur between the polishing steps.

The polishing and topographic improvement of the tungsten-containing wafer is related to the contact area between the abrasive particles and the tungsten-containing film, and the abrasive grains in which the first abrasive grains, the second abrasive grains and the third abrasive grains are mixed in the above- When used, topography improvement effect is excellent. Particularly, the content of the first abrasive grains, the second abrasive grains and the third abrasive grains is determined within a range of improving the dispersion stability by calculating the contact area between each abrasive grain and the tungsten-containing film according to the mixing ratio .

Wherein the two or more kinds of abrasive grains each independently include at least one selected from the group consisting of a metal oxide coated with a metal oxide, an organic or inorganic material, and a metal oxide in a colloidal state, , Ceria, zirconia, alumina, titania, barium titania, germania, manganese, and magnesia.

On the other hand, the two or more types of abrasive grains may include metal-substituted abrasive grains in which a part of the abrasive grains are substituted with metal ions, and at least one of the first abrasive grains, the second abrasive grains, Or more may be metal-substituted abrasive grains. A part of the abrasive grains may be up to 30% from the surface of the abrasive grains or from the surface to the center of the abrasive grains. Refers to a point where the length from the surface to the center of the abrasive grains is regarded as 100%. In the surface of the abrasive grains, the metal ion may be one in which the component of the abrasive grains is replaced with the metal ion have.

The metal ion may have a tetrahedral coordination. The metal ion may be at least one selected from the group consisting of Fe, Al, As, Ga, B, Ber, C, Cr, (Ti), vanadium (V), zinc (Zn), and zirconium (Zr), in addition to the elements selected from the group consisting of indium (In), magnesium (Mg), manganese Or at least one of them.

The two or more kinds of abrasive grains may be colloidal silica, the metal ion may be iron (Fe) ion, and some of the surfaces of the colloidal silica abrasive grains may be substituted with iron (Fe) ions.

The metal-substituted abrasive particles may have a zeta potential of -10 mV to -70 mV at a pH of 1 to 12 at a zeta potential of -1 mV to -100 mV, preferably at a pH of 1 to 6. An absolute value of the zeta potential is also exhibited in the acidic region, whereby the dispersion stability is high and an excellent polishing force can be realized.

The method for producing the metal-substituted abrasive particles comprises: preparing a mixture by mixing abrasive particles with a metal salt, a metal ion compound, or both; And synthesizing the mixture under hydrothermal synthesis conditions. And substitutes the metal oxide element and metal ion of the abrasive particles by the property that the metal ion has a tetrahedral coordination in an alkali condition.

The metal salt may be at least one selected from the group consisting of Fe, Al, As, Ga, B, Ber, Cb, Cr, Hf, At least one selected from the group consisting of In, Mg, Mn, Ni, P, Ti, V, Zn and Zr, Or a salt of any one of the metals. As a salt of iron of the metal salt, iron nitrate (Fe (NO 3) 3, ferric nitrate), iron sulfate (Fe 2 (SO 4) 3 , ferric sulfate), iron oxide (Fe 2 O 3, ferric oxide) and iron ( FeCl 3 , and ferric chloride. In the case of iron nitrate, it is dissociated from water to provide iron ions (Fe 2+ , Fe 3 ).

The metal ion compound is selected from the group consisting of sodium nitrate, lithium nitrate, potassium nitrate, sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium sulfate, lithium sulfate, potassium sulfate, sodium chloride, lithium chloride, potassium chloride, lithium carbonate and potassium carbonate And may include at least any one selected.

The metal salt may be 0.001 to 20 parts by weight based on 100 parts by weight of the abrasive grains. When the amount of the metal salt is less than 0.001 part by weight, it is difficult to obtain sufficient zeta charge and dispersion stability is poor. When the amount of the metal salt exceeds 20 parts by weight, there is a possibility that the unreacted metal salt may cause a contamination problem.

The metal ion compound may be 0.001 to 20 parts by weight based on 100 parts by weight of the abrasive grains. If the amount of the metal ion compound is less than 0.001 part by weight, the metal ion may not be smoothly substituted. If the amount of the metal ion compound exceeds 20 parts by weight, a problem of contamination may occur and a dispersion stability may be deteriorated Can be.

The step of synthesizing the mixture under the hydrothermal synthesis condition, which is carried out in order to proceed the metal substitution reaction efficiently, may be a hydrothermal synthesis in a temperature range of 100 ° C to 300 ° C for 0.5 hours to 72 hours.

The pH of the mixture may be adjusted to 9 to 12 before proceeding with the hydrothermal synthesis, and the pH may be adjusted to 1 to 5 after the hydrothermal synthesis is completed. The pH adjusting agent used herein may be an acid or base without limitation and may be any one of potassium hydroxide, sodium hydroxide, ammonia, ammonia derivatives, hydrochloric acid, nitric acid, sulfuric acid, acetic acid, phosphoric acid, boric acid, amino acid, citric acid, tartaric acid, formic acid, Oxalic acid, tartaric acid, and acetic acid may be used to prepare metal-substituted abrasive grains in an amount such that the desired pH can be adjusted.

The metal ion is not simply bonded to the surface of the metal-substituted abrasive grains, but the metal ion having the tetrahedral coordination in the alkali region is used, And the surface is modified by replacing the metal ion, whereby the dispersion stability is high even in the acidic region. In addition, the metal oxide element ion and the substituted metal ion on the surface of the abrasive grains can promote the oxidation of the metal film, thereby realizing a high polishing characteristic capable of easily polishing the tungsten film.

The shape of each of the first abrasive grains, the second abrasive grains and the third abrasive grains may be at least one selected from the group consisting of spherical, angular, acicular, and plate- .

The slurry composition for tungsten polishing according to the present invention may contain at least one selected from the group consisting of hydrogen peroxide, ferric nitrate, potassium iodate, potassium permanganate, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium periodate, ammonium tetrachloride Methylmorpholine N-oxide, pyridine-N-oxide, and urea hydrogen peroxide, in a solvent selected from the group consisting of methyl ammonium, tetramethylammonium chlorate, tetramethylammonium iodide, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, And at least one oxidizing agent selected from the group consisting of Among them, it is preferable to use hydrogen peroxide in view of the oxidative power and the dispersion stability of the slurry composition for tungsten polishing and economical efficiency.

The oxidizing agent may be 0.005 wt% to 5 wt%, preferably 0.05 wt% to 1 wt% of the slurry composition for tungsten polishing. When the oxidizing agent is less than 0.005 wt% in the polishing slurry composition, the polishing rate and the etching rate with respect to tungsten may be lowered. When the oxidizing agent is more than 5 wt%, the oxide film on the tungsten surface becomes hard, The oxide film grows, and the topography can be deteriorated due to corrosion and aging of tungsten. Since the oxidizing agent directly affects the polishing rate and the etching rate of tungsten, it is necessary to reduce the concentration of hydrogen peroxide in the present invention, which considers the quality of the tungsten surface.

The slurry composition for tungsten polishing according to the present invention may further include a material used for preventing corrosion of a metal or a polishing machine and for realizing a pH range in which metal oxidation easily occurs. The pH adjusting agent may be an inorganic acid or an inorganic acid salt including at least one selected from the group consisting of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, bromic acid, iodic acid and salts thereof; And organic acids such as formic acid, malonic acid, maleic acid, oxalic acid, acetic acid, citric acid, adipic acid, acetic acid, propionic acid, fumaric acid, lactic acid, salicylic acid, pimelic acid, benzoic acid, succinic acid, phthalic acid, butyric acid, glutaric acid, An organic acid or an organic acid salt containing at least one selected from the group consisting of glycolic acid, lactic acid, aspartic acid, tartaric acid and salts thereof.

The slurry composition for tungsten polishing may be one which polishes tungsten having a thickness of 1,000 A / min to 2,200 A / min.

The flatness of the surface of the tungsten-containing wafer using the slurry composition for tungsten polishing may be 5% or less. Examples of the tungsten-containing wafers include tungsten, tantalum, titanium, ruthenium, hafnium, other refractory metals, nitrides and silicides thereof.

The surface of the tungsten-containing wafer using the slurry composition for tungsten polishing may have a peak to valley (Rpv) value of 100 nm or less and a surface roughness of 10 nm or less. The peak-to-valley value can be measured with an atomic force microscope.

The pH of the slurry composition for tungsten polishing according to the present invention is preferably adjusted to provide dispersion stability and proper polishing rate depending on the abrasive grain, and the pH of the slurry composition for tungsten polishing is 1 to 12, preferably 1 to 6 It may be one having an acidic pH range.

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.

[Example 1]

Two kinds of abrasive grains were mixed at a ratio of 50% of the first abrasive grains of colloidal silica (Fuso Chemical Co.) and 50% of the second abrasive grains of colloidal silica to obtain abrasive grains having a total specific surface area of 69.9089 m 2 / g 3 parts by weight of a slurry composition, 0.5 parts by weight of hydrogen peroxide as an oxidizing agent, 0.1 parts by weight of malonic acid as a reaction inhibitor and nitric acid as a pH adjusting agent were added to prepare a polishing slurry composition having a pH of 2.5.

[Example 2]

Except that abrasive grains having a specific surface area of 55.2498 m 2 / g were used as a mixture of two kinds of abrasive grains in a ratio of 50% of colloidal silica first abrasive grains and 50% of colloidal silica third abrasive grains. 1 &lt; / RTI &gt; to prepare a polishing slurry composition.

[Example 3]

Except that abrasive grains having a specific surface area of 29.4898 m 2 / g were used as a mixture of two abrasive grains in a ratio of 50% colloidal silica second abrasive grains and 50% colloidal silica third abrasive grains. 1 &lt; / RTI &gt; to prepare a polishing slurry composition.

[Example 4]

Three types of abrasive grains were mixed at a ratio of 40% of colloidal silica first abrasive grains, 40% of colloidal silica second abrasive grains and 40% of colloidal silica third abrasive grains, and the sum of specific surface areas was 58.8933 m 2 / g The abrasive slurry composition was prepared under the same conditions as in Example 1, except that the abrasive grains were used.

[Example 5]

Three kinds of abrasive grains were mixed at a ratio of 40% of colloidal silica first abrasive grains, 20% of colloidal silica second abrasive grains and 40% of colloidal silica third abrasive grains, and the sum of specific surface areas was 53.0296 m 2 / g The abrasive slurry composition was prepared under the same conditions as in Example 1, except that the abrasive grains were used.

[Example 6]

Three kinds of abrasive grains were mixed at a ratio of 20% of colloidal silica first abrasive grains, 40% of colloidal silica second abrasive grains and 40% of colloidal silica third abrasive grains, and the sum of specific surface areas was 42.7256 m 2 / g The abrasive slurry composition was prepared under the same conditions as in Example 1, except that the abrasive grains were used.

[Example 7]

Three kinds of abrasive grains were mixed at a ratio of 40% of colloidal silica first abrasive grains, 30% of colloidal silica second abrasive grains and 30% of colloidal silica third abrasive grains, and the sum of specific surface areas was 55.9614 m 2 / g The abrasive slurry composition was prepared under the same conditions as in Example 1, except that the abrasive grains were used.

[Example 8]

Three kinds of abrasive grains were mixed at a ratio of 30% of colloidal silica first abrasive grains, 40% of colloidal silica second abrasive grains and 30% of colloidal silica third abrasive grains, and the sum of specific surface areas was 50.8094 m 2 / g The abrasive slurry composition was prepared under the same conditions as in Example 1, except that the abrasive grains were used.

[Example 9]

Three types of abrasive grains were mixed at a ratio of 30% of colloidal silica first abrasive grains, 30% of colloidal silica second abrasive grains and 40% of colloidal silica third abrasive grains, and the sum of specific surface areas was 47.8776 m 2 / g The abrasive slurry composition was prepared under the same conditions as in Example 1, except that the abrasive grains were used.

[Example 10]

Three kinds of abrasive grains were mixed at a ratio of 33% of colloidal silica first abrasive grains, 33% of colloidal silica second abrasive grains and 34% of colloidal silica third abrasive grains, and the sum of specific surface areas was 51.0340 m 2 / g The abrasive slurry composition was prepared under the same conditions as in Example 1, except that the abrasive grains were used.

[Example 11]

As the colloidal silica abrasive grains, Fe ion-substituted colloidal silica abrasive grains were used. The method for producing the Fe ion-substituted colloidal silica abrasive particles was such that 5 wt% of colloidal silica abrasive grains, 0.17 wt% of iron nitrate ((FeNO 3 ) 3 ) and 0.484 wt% of sodium nitrate (NaNO 3 ) The mixed solution was prepared and titrated with sodium hydroxide (NaOH) until the pH reached 11. The mixed solution containing colloidal silica with controlled pH was placed in a hydrothermal reactor and subjected to hydrothermal reaction at 140 for 24 hours to prepare Fe ion-substituted colloidal silica abrasive particles.

In order to confirm the Fe ion substitution of the Fe ion-substituted colloidal silica abrasive particles, the Fe ion-substituted colloidal silica abrasive particles were centrifuged and the cake was dried at 110 to 24 hours. KBr Pellets were prepared by mixing and measured with an infrared spectroscope. 1 is an infrared absorption spectrum (FT-IR) graph of Fe ion-substituted colloidal silica abrasive particles and general colloidal silica abrasive particles of the present invention. The horizontal axis represents the wave number and the vertical axis represents the transmittance. Referring to FIG. 1, a Si-O-Fe bonding peak can be confirmed at 668 cm -1 . This analysis shows that the Fe-substitution is well done.

In a ratio of 40% of the Fe ion-substituted colloidal silica first abrasive grains, 20% of the Fe ion-substituted colloidal silica second abrasive grains and 40% of the Fe ion-substituted colloidal silica third abrasive grains, Of abrasive grains were mixed to prepare a polishing slurry composition under the same conditions as in Example 1, except that abrasive grains having a specific surface area of 58.8933 m 2 / g were used.

[Example 12]

In the ratio of 30% of the Fe ion-substituted colloidal silica first abrasive grains, 40% of the Fe ion-substituted colloidal silica second abrasive grains and 30% of the Fe ion-substituted colloidal silica third abrasive grains, Were mixed to prepare a polishing slurry composition under the same conditions as in Example 1, except that abrasive grains having a specific surface area of 50.8094 m 2 / g were used.

[Comparative Example 1]

The polishing slurry composition was prepared under the same conditions as in Example 1, except that only the first abrasive grains of colloidal silica having a specific surface area of 95.6689 m 2 / g were used.

[Comparative Example 2]

The polishing slurry composition was prepared under the same conditions as in Example 1 except that only the second abrasive grains of colloidal silica having a specific surface area of 44.1489 m 2 / g were used.

[Comparative Example 3]

A polishing slurry composition was prepared under the same conditions as in Example 1 except that only the third abrasive grains of colloidal silica having a specific surface area of 14.8307 m 2 / g were used.

The polishing slurry compositions of Examples 1 to 12 and Comparative Examples 1 to 3 of the present invention were used to polish a tungsten wafer under the following polishing conditions.

[Polishing condition]

1. Polishing equipment: Bruker's CETR CP-4

2. Wafer: 6 cm x 6 cm tungsten wafer

3. Platen pressure: 3 psi

4. Spindle speed: 69 rpm

5. Platen speed: 70 rpm

6. Flow rate: 100 ml / min

7. Slurry solids content: 3 wt%

Table 1 below shows the abrasive grain content, specific surface area, tungsten polishing rate and flatness after polishing of tungsten wafers using the respective slurry compositions in the slurry compositions of Examples 1 to 12 and Comparative Examples 1 to 3 of the present invention will be.

No. 1st
Abrasive particle
(%) Second
Abrasive particle
(%) Third
Abrasive particle
(%) Specific surface area
(m 2 / g) tungsten
Abrasion rate
(Å / min) flatness Example 1 50 50 0 69.9089 647 4.67 Example 2 50 0 50 55.2498 783 4.86 Example 3 0 50 50 29.4898 809 4.99 Example 4 40 40 20 58.8933 775 3.13 Example 5 40 20 40 53.0296 847 3.56 Example 6 20 40 40 42.7256 891 3.69 Example 7 40 30 30 55.9614 772 2.54 Example 8 30 40 30 50.8094 874 2.73 Example 9 30 30 40 47.8776 933 2.97 Example 10 33 33 34 51.0340 943 2.59 Example 11 40 40 20 58.8933 1571 4.13 Example 12 30 40 30 50.8094 1759 3.79 Comparative Example 1 100 0 0 95.6689 334 6.94 Comparative Example 2 0 100 0 44.1489 421 7.15 Comparative Example 3 0 0 100 14.8307 540 7.89

Examples 1 to 3, which contained two or more types of abrasive grains in Examples 1 to 12 and Comparative Examples 1 to 3 of the present invention and had a specific surface area value of mostly 20 m 2 / g or more and 70 m 2 / g or less It can be seen that the tungsten polishing slurry composition of the present invention has a larger tungsten polishing rate than that of the slurry compositions of Comparative Examples 1 to 3 which are slurry compositions for tungsten polishing including single species of specific surface polishing particles, Value of 5% or less. In particular, in Examples 11 and 12 using three kinds of Fe ion-substituted silica abrasive grains, it can be seen that the tungsten polishing rate is high.

As a result, it was found that the use of the slurry composition for tungsten polishing mixed with two or three kinds of silica particles resulted in a higher tungsten polishing rate and improved flatness compared to the polishing slurry composition containing colloidal silica particles having a single composition have.

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)

At least two kinds of abrasive grains among the first abrasive grains, the second abrasive grains and the third abrasive grains,
Wherein the specific surface area of the first abrasive grains, the second abrasive grains or the third abrasive grains satisfies the following conditional expression 1 within a range of 10 m 2 / g to 120 m 2 / g, respectively: Composition:
[Conditional expression 1]
20 m 2 / g ≤ (T A × K A) + (T B × K B) + (T C × K C) ≤ 100 m 2 / g
(Wherein T A is one of the specific surface area, the T B is a specific surface area of the second abrasive grain, the T C is and the specific surface of the third abrasive grain, the T A, T B, T C of the first abrasive particles 0 may be, the K a is the content ratio, K B is the content ratio of the K C of the second abrasive particles of the first abrasive particles and the content ratio of the third abrasive grain, 0≤K a <1, 0 ≤K B <1, 0≤K C <satisfies 1).
delete The method according to claim 1,
The specific surface area of the first abrasive grains is 70 m 2 / g to 120 m 2 / g,
The specific surface area of the second abrasive grains is 25 m 2 / g to 70 m 2 / g,
And the specific surface area of the third abrasive grains is 10 m 2 / g to 25 m 2 / g.
The method according to claim 1,
The content of the first abrasive grains is 10 wt% to 70 wt% of the total abrasive grains,
The content of the second abrasive grains is 10 wt% to 70 wt% of the total abrasive grains,
Wherein the content of the third abrasive grains is 10 wt% to 70 wt% of the total abrasive grains.
The method according to claim 1,
The two or more kinds of abrasive grains are, independently of each other,
At least one selected from the group consisting of a metal oxide coated with a metal oxide, an organic or inorganic material, and a metal oxide in a colloidal state,
Wherein the metal oxide comprises at least one selected from the group consisting of silica, ceria, zirconia, alumina, titania, barium titania, germania, manganese, and magnesia.
The method according to claim 1,
Wherein the abrasive grains have a component part of the abrasive grains substituted with metal ions.
The method according to claim 6,
Wherein the metal ion has a tetrahedral coordination.
The method according to claim 6,
The metal ion may be at least one selected from the group consisting of Fe, Al, As, Ga, B, Ber, C, Cr, (Ti), vanadium (V), zinc (Zn), and zirconium (Zr), in addition to the elements selected from the group consisting of indium (In), magnesium (Mg), manganese And at least one of them is contained.
The method according to claim 6,
Wherein the abrasive grains are colloidal silica and the metal ions are iron (Fe) ions, wherein some of the surfaces of each of the colloidal silica abrasive grains are substituted with iron (Fe) ions. Composition.
The method according to claim 1,
And ammonium persulfate, ammonium persulfate, tetramethylammonium chlorate, tetramethylammonium iodate, potassium iodate, potassium iodate, potassium permanganate, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium perchlorate, tetramethylammonium chlorate, At least one oxidizing agent selected from the group consisting of tetramethylammonium, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, 4-methylmorpholine N-oxide, pyridine-N-oxide and urea hydrogen peroxide Further comprising a slurry composition for tungsten polishing.
11. The method of claim 10,
Wherein the oxidizing agent is 0.005 wt% to 5 wt% of the slurry composition for tungsten polishing.
The method according to claim 1,
Wherein the slurry composition for tungsten polishing is a tungsten polishing slurry composition having a thickness of 1,000 A / min to 2,200 A / min.
The method according to claim 1,
Wherein the flatness of the surface of the tungsten-containing wafer using the slurry composition for tungsten polishing is 5% or less after polishing.
The method according to claim 1,
Wherein the surface of the tungsten-containing wafer using the slurry composition for tungsten polishing has a peak to valley (Rpv) value of 100 nm or less and a surface roughness of 10 nm or less. .
The method according to claim 1,
Wherein the pH of the slurry composition for tungsten polishing is in the range of 1 to 12. 5. The tungsten polishing slurry composition according to claim 1,
KR1020150112432A 2015-07-20 2015-08-10 Slurry composition for tungsten polishing KR101693237B1 (en)

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KR1020150112432A KR101693237B1 (en) 2015-08-10 2015-08-10 Slurry composition for tungsten polishing
US15/205,684 US10077381B2 (en) 2015-07-20 2016-07-08 Polishing slurry composition
TW106115948A TWI633163B (en) 2015-07-23 2016-07-19 Polishing slurry composition
TW105122690A TWI609057B (en) 2015-07-23 2016-07-19 Polishing slurry composition
CN201610575493.0A CN106366934B (en) 2015-07-23 2016-07-19 Polishing material paste composition

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100623963B1 (en) * 2005-01-12 2006-09-19 제일모직주식회사 Metal CMP Slurry And Metal Polishing Method Using Thereof
KR20120134105A (en) * 2010-02-01 2012-12-11 제이에스알 가부시끼가이샤 Aqueous dispersion for chemical mechanical polishing, and chemical mechanical polishing method using same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100623963B1 (en) * 2005-01-12 2006-09-19 제일모직주식회사 Metal CMP Slurry And Metal Polishing Method Using Thereof
KR20120134105A (en) * 2010-02-01 2012-12-11 제이에스알 가부시끼가이샤 Aqueous dispersion for chemical mechanical polishing, and chemical mechanical polishing method using same

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