WO2011069345A1

WO2011069345A1 - Chemical-mechanical polishing slurry and use thereof

Info

Publication number: WO2011069345A1
Application number: PCT/CN2010/002034
Authority: WO
Inventors: 荆建芬; 蔡鑫元
Original assignee: 安集微电子（上海）有限公司
Priority date: 2009-12-11
Filing date: 2010-12-13
Publication date: 2011-06-16
Also published as: CN102093818A

Abstract

A chemical-mechanical polishing slurry and the use thereof are provided. The polishing slurry is used for chemical-mechanical polishing of copper. The polishing slurry comprises a star polymer surfactant containing pigment-affinity groups, and also abrasive particles, a complexing agent, a corrosion inhibitor, and an oxidant. By applying the polishing slurry, the static corrosion rate of copper can be reduced, and dishing-pits of a polished copper wire can be ameliorated.

Description

Chemical mechanical polishing slurry and application thereof

The invention relates to a chemical mechanical polishing liquid and an application thereof. technical background

With the development of microelectronics technology, the integration of very large integrated circuit chips has reached several billion components, and the feature size has entered the nanometer level, which requires hundreds of processes in the microelectronics process, especially multilayer wiring. The substrate and the medium must be chemically mechanically planarized. Very large scale integrated wiring is being converted from traditional A1 to Cu. Compared with A1, Cu wiring has low resistivity, high electromigration resistance, and short RC delay time. The advantages of Cu wiring have made it a replacement metal for semiconductor fabrication.

However, there is currently no known technique for effective plasma etching or wet etching of copper to form a copper interconnect in an integrated circuit. Therefore, the chemical mechanical polishing method of copper is considered to be the most effective process. The chemical mechanical polishing method of copper generally works by removing a large amount of copper on the surface of the substrate with a fast and efficient removal rate. When it is approaching the barrier layer, it softly land, reducing the removal rate and polishing the remaining metal copper and stopping it. Floor. At present, a series of chemical mechanical polishing slurries suitable for polishing Cu have appeared, such as: US Pat. No. 6,616,717 discloses a composition and method for metal CMP; US Pat. No. 5,527,423 discloses a A chemical mechanical polishing slurry of a metal layer; US Pat. No. 6,821,897 discloses a method of copper CMP using a polymer complexing agent; Patent No. CN 02114147.9 discloses a copper chemical-mechanical polishing process polishing liquid; No. CN 01818940.7 discloses a slurry for chemical mechanical polishing of copper; Patent No. CN 98120987.4 discloses a CMP slurry manufacturing process for copper and for integrated electricity The manufacturing method of the road. However, after the above-mentioned polishing slurry for copper is used, there are defects, scratches, stains, and residual copper on the surface of the substrate, or the depression of the copper block after polishing is excessive, or local or overall corrosion occurs during polishing. The problem of high static corrosion rate of copper at normal temperature and polishing temperature (such as 50 ° C). Therefore, it is necessary to develop a new chemical mechanical polishing slurry for copper.

SUMMARY OF THE INVENTION The technical problem to be solved by the present invention is to provide a chemical mechanical polishing slurry capable of reducing the static etching rate of copper, improving the dishing recess of the polished copper wire, and its use in polishing copper. The polishing slurry contains at least one star-structured polymer surfactant having a pigment affinity group, abrasive particles, a complexing agent, a corrosion inhibitor, and an oxidizing agent.

The pigment-affinity group in the star-structured polymer surfactant having a pigment-affinity group is one or more of a hydroxyl group, an amino group and a carboxyl group.

The polymerizable monomer forming the star-shaped polymer containing the pigment-affinity group includes one or more of the following: an acrylic monomer, an acrylate monomer, an acrylamide monomer, and an epoxy acetamidine. .

The acrylic monomer is acrylic acid and/or methacrylic acid; the acrylate monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, A One or more of propyl acrylate, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate; the acrylamide monomer is acrylamide and/or methyl Acrylamide.

The monomer forming the star polymer containing the pigment-affinity group also includes other vinyl monomers.

The other vinyl monomer is ethylene, propylene, styrene or p-methylstyrene.

The star-shaped polymer containing the pigment affinity group is a polyacrylic acid star homopolymer, styrene and Binary star copolymer of hydroxyethyl acrylate, binary star copolymer of p-methylstyrene and epoxy oxime, binary star copolymer of styrene and ethylene oxide, methyl methacrylate a binary star copolymer with epoxy oxime, a binary star copolymer of methyl acrylate and hydroxyethyl acrylate, a binary star copolymer of acrylic acid and hydroxyethyl acrylate, and acrylic acid, butyl acrylate and One or more of the ternary star copolymers of acrylamide.

The star polymer containing the pigment-affinity group has a number average molecular weight of 800 to 50,000. The content of the star-type polymer containing the pigment-affinity group is 0.0001 to 5% by mass. The abrasive particles are one or more of silica, alumina, aluminum-doped silica, aluminum-coated silica, ceria, titania, and polymer abrasive particles. The content of the abrasive particles is 0.1 to 20% by mass. The abrasive particles have a particle diameter of 20 to 150 nm.

The complexing agent is an amino acid and a salt thereof, an organic carboxylic acid and a salt thereof, an organic phosphonic acid and a salt thereof. Specifically, glycine, alanine, valine, leucine, valine, phenylalanine, tyrosine, tryptophan, lysine, arginine, histidine, serine, aspartame Acid, glutamic acid, asparagine, glutamine, ammonia triacetic acid, ethylenediaminetetraacetic acid, cyclohexyltetraacetic acid, ethylenediamine disuccinic acid, diethylenetriaminepentaacetic acid and triethylenetetramine hexaacetic acid One or more of the organic carboxylic acids are acetic acid, oxalic acid, citric acid, tartaric acid, maleic acid, malonic acid, succinic acid, malic acid, lactic acid, gallic acid, and sulfosalicylic acid. One or more of the organic phosphonic acids are 2-phosphonic acid butyl phosphonium-1, 2, 4-tricarboxylic acid, aminotrimethylidene phosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediamine tetramethylidene One of phosphonic acid, diethylenetriamine pentamethylphosphonic acid, polyhydric phosphonate, 2-hydroxyphosphonic acid, ethylenediaminetetramethylenephosphonic acid, and polyaminopolyether methylphosphonic acid or A plurality of; the complexing agent is contained in an amount of 0.01 to 10% by mass. The corrosion inhibitor is one of azole, imidazole, thiazole, pyridine and pyrimidine Or a variety. The azole compound is selected from one or more of the group consisting of benzotriazole, 5-methyl-1,2,3-benzotriazole, 5-carboxybenzotriazole, 1-hydroxyl Tribenzotriazole, 1,2,4-triazole, 3-amino-1, 2,4-triazole, 4-amino-1, 2,4-triazole, 3, 5-di Amino-1, 2, 4-triazole, 5-carboxy-3-amino-1, 2,4-triazole, 3-amino-5-mercapto-1, 2,4-triazole, 5- Acetic acid-1H-tetrazole, 5-methyltetrazole, 5-phenyltetrazolium, 5-amino-1H-tetrazole and 1-phenyl-5-mercapto-tetrazolium; The imidazole compound is benzimidazole and/or 2-mercaptobenzimidazole; the thiazole compound is selected from one or more of the following: 2-indolyl-benzothiazole, 2-mercaptothiadiazole and 5 -amino-2-mercapto-1,3,4-thiadiazole; the pyridine is selected from one or more of the following: 2, 3-diaminopyridine, 2-aminopyridine and 2-picolinic acid; The pyrimidine is a 2-aminopyrimidine.

The content of the corrosion inhibitor is 0.005 to 5% by mass.

The oxidizing agent is hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, persulfate, percarbonate, periodic acid, perchloric acid, perboric acid, potassium permanganate and ferric nitrate. One or more.

The content of the oxidizing agent is 0.05 to 10% by mass.

The polishing solution has a pH of from 3 to 11, preferably from 4 to 8.

The polishing liquid of the present invention may further contain other conventional additives in the art such as a pH adjuster, a viscosity modifier, an antifoaming agent, a bactericide, and the like.

The polishing liquid of the present invention can prepare a concentrated sample which is diluted with deionized water and added with an oxidizing agent before use.

The positive progressive effect of the present invention is that the polishing liquid of the present invention can significantly improve the degree of dishing of the copper block after polishing while maintaining a high polishing rate, and the surface of the polished chip is non-corrosive, and the copper is significantly lowered at room temperature. And static corrosion rate at polishing temperature to improve the dish shape of the polished copper wire (dishing) a depression. DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the surface corrosion observed by SEM after polishing and immersing a patterned copper wafer with the polishing liquid of Example 51. Summary of the invention

The invention is further illustrated by the following examples, but the invention is not limited thereto.

Example 1~49

Table 1 shows Examples 1 to 49 of the chemical mechanical polishing liquid of the present invention. According to the formulation given in the table, the components other than the oxidizing agent were uniformly mixed, and the mass percentage was made up to 100% with water. Adjust to the desired pH with KOH or HNO ₃ . Add oxidizing agent before use and mix well. Examples 1 to 49

Real research month particle corrosion preparation complexing agent oxidant star polymer

Application Content Specific content Content Specific content Specific content Specific content pH wt% Specific substance Example wt% Quality wt% Substance wt% Substance wt%

Methyl acrylate and

3-amino

Si0 ₂

1 3 5 peroxygen

-1,2,4- 10

(35nm) oxalic acid 2 3 acrylamide star

3 hydrogen

Triazole-type copolymer,

Mn=3000 hydroxyethyl acrylate

Si0 ₂ benzotriene

2 1 0.005 peroxygen

0.01 with acrylamide (35nm) succinic acid 1 2 3 azole hydrogenated star copolymer,

Mn=5000

5-amino hydroxyethyl acrylate

Si0 ₂ |3⁄4 fierce

3 1 0.05 -1H-four 0.1 with acrylic star

(50nm) malonic acid 3 1.5 3 potassium acid

Azazole-shaped copolymer,

Mn=2500 methyl acrylate and

Si0 ₂ 1,2,4-

4 1 2 Nitric acid Hydroxyethyl acrylate

0.5

Star polymerization of (50nm) malic acid 0.5 1 3 triazole

Object, Mn=5000 Hydroxyethyl acrylate

2-mercapto

Si0 ₂

1 0.01 Peroxygen with methacrylic acid

-benzo-1 lactate 5 0.1 3 (70nm)

Star copolymerization of thiazole hydrogen

, Mn=15000 acrylic acid and propylene

A1 ₂ 0 ₃ 5-phenyl gallate

3 peroxygen

0.005 1 8 2 amide star-like 3 (30 nm) tetrazine hydrogen hydride polymer,

Mn=5000

5-amino hydroxyethyl acrylate

Si0 ₂ sulfo water

0.5 0.3 peroxygen

-1H-tetra 5 10 1.5 with acrylamide (70nm) 3

Hydrogen hydride star copolymer, azole

Mn=5000

Si0 ₂

1 benzotriene

0.2 3 peroxygen

(70nm) acetic acid 1 1 star polyacrylic acid 3

Azozolium Mn=3000

Methyl methacrylate

1, 2,

Ce0 ₂ ester and methacryl

2 citric acid

2 peroxygen

4-trinitrogen 8 5 0.5

(50 hydroxyethyl ester star 3

Azole hinge acetic acid

Copolymer,

Mn=15000 methyl acrylate, hydroxyethyl acrylate

Ti0 ₂ benzopyral acid

1 sulfur

0.01 2 0.5 0.8

(120nm) and styrene three 3

Zinc potassium potassium sulfate

Yuan star copolymer, Mn=30000

1-phenyl butyl acrylate,

2-phosphonic acid

Si0 ₂ -5-fluorene acrylamide and C

3 0.02 2 butyl sulfhydryl peroxy

3 1

(150nm) ternary star of enoic acid 3

Base-four-l j 4-acetic acid

Azazole-shaped copolymer,

Mn=10000 ethyl acrylate,

Si0 _{2 2} -mercapto hydroxyethylenediamine methacrylate

2. Sulfur

0.5 ethyl ester and styrene (80nm) - benzo 2 tetramethylene 4 0.5 3

Potassium acid

Triazole star-based phosphonic acid of thiazole

Polymer,

Mn=20000 diethylene methacrylic acid and

Si0 ₂ methacrylate

0.5 benzopyrene triamine

0.08 2 2.5

(lOOnm) 0.5

Starch of azole ethyl ester

Methyl phosphonium phosphonate

Polymer,

Mn=3000 methacrylate

Si0 _{2 2} -mercaptohydroxyl ester, hydroxy acrylate

0.5 0.5 Peroxyethyl ester and styrene Benzomid 2 3.5 0.5

(70nm) 3

Ternary star co-phosphonic acid

Polymer,

Mn = 10000 propyl acrylate and

Si0 ₂ 5-aminoamino three

0.5 0.5 peroxygen

-1H-tetra 2 methylene 4.5 0.8 acrylamide star (80nm) 3

Urea

Azazole-shaped copolymer,

Phosphonic acid

Mn=5000 Si0 _{2 2} -hydroxyethyl hydroxyethyl acrylate

0.5 benzotriene

0.2 peroxygen

2 phosphonic acid group 0.8 0.1 with acrylamide (100 nm) 3

Azoleacetic acid

Acetic acid star copolymer,

Mn=50000

1-phenyl

Si0 ₂

0.5 - 5 - Sulphur

1 2 im 0.8 star polypropylene

0.002

(lOOnm) 3

Base-tetramethylene acid acid, Mn=8000 azole phosphinic acid

Diethyl methacrylate

Si0 _{2 2} -decyl ester and hydroxy acrylate

0.5 supersulfur

1 3 triamine five

0.05 0.05

(lOOnm) - star of benzoethyl ester 4

Methyl phosphonium phosphonate

Thiazole polymer,

Potassium acid

Mn=7000 hydroxyethyl acrylate

Si0 ₂ ethylene diamine

Benzomethacrylate, acrylamide

0.5 0.3 3 peroxygen

(lOOnm) Sijia fork 0.1 0.05

Triazole and acrylic three 4

Hydrogen

Phosphonic acid star copolymer

Mn=3000 ethyl acrylate,

2-mercapto-hydroxy methacrylate

Si0 ₂ polyol

0.5 0.3 peroxygen

(lOOnm) benzopyrene 3 3 0.01 ethyl ester and styrene

4 ternary star copolymer of zoledronate urea,

Mn=8000 methyl acrylate, ethylenediamine hydroxyethyl acrylate

0.5 Si0 ₂ 5-phenyl

0.6 1 peroxygen

Tetraacetic acid 3

(lOOnm) 0.01 and styrene three 3

Tetrazolium acetate

Disodium metastar copolymer

Mn=3000 methyl acrylate and

-3-aminoethylenediamine

Si0 ₂

5 0.3 peroxygen

1 star (70nm) diammon 1 0.05 acrylamide 3

Hydrogen

-1,2,4-shaped copolymer,

Acid

Mn=5000 triazole

Ethyl acrylate and

4-amino

Si0 ₂ cyclohexane persulfate

0.5 0.3 -1,2,4- 1 1

(lOOnm) 0.001 acrylamide star

3 potassium tetraacetate

Triazole-type copolymer,

Mn=3000 diethylene butyl acrylate and

Si0 ₂ benzotriene

0.5 supersulfur

0.01 1

(lOOnm) triamine five 1 0.001 acrylamide star 3

Azinamide hinge copolymer,

Acetic acid

Mn=6000 hydroxyethyl acrylate

Si0 ₂ benzotriene

0.5 0.05 ammonia triethyl

3 peroxygen

5 with acrylamide (lOOnm) 0.01 3

Aziridine hydrogen star copolymer,

Mn=5000 methacrylic acid

2-phosphonic acid

5-acetate and ethylene oxide

Si0 ₂

2 0.2 -1H-tetra 1 butyl sulfhydryl peroxy

2 0.01 binary star total (70nm) 3

-1,2,4-hydrogenation

Azazole,

Mn=3000 2-mercaptomethacrylic acid

-iS.sm.ta 1 Benzomethoxazole and Methyl Propylene Persulfur

1 Si. ₂ azole 10 glycine 2 0.005 amide star-shaped ammonium tetraacetate

(70nm) benzotrimer, Mn=800

0.01

Azole

Styrene and propylene doped aluminum 5-amino

Two of hydroxyethyl peroxyacid

0.5 Si0 ₂ 0.1 -1H-tetra-5 alanine 2 0.005 4 hydrogen

(20nm) Yuan Star Copolymer

Azole

, Mn=6000 methyl acrylate,

5-hydroxyethyl methacrylate

5 enoic acid 0.1 5 peroxygen

Proline 2 0.0005 and ethylene ternary 5 methyl ester tetrazolium urea

(150nm) star copolymer,

Mn=30000 ethyl acrylate, polystyrene methacrylate

5-phenyl

4 ene 0.2 6 peroxygen

Leucine 5 0.1 ethyl ester and propylene 5 tetrazolium

(120nm) hydrogen

Ternary star copolymer, Mn=6000 hydroxyethyl acrylate

3-amino

Ester, acrylamide

Si0 ₂ -1, 2, phenylalanine

0.1 0.3 peroxygen

6 3 0.2

(70nm) and acrylic three 5

4-trihydrogen

Meta-star copolymer

Object, Mn=3000

2-mercapto-acrylic acid and propylene

Si0 ₂

0.1 2 peroxygen

8 threonine 2 0.02

(70nm) amide star

Polymer, Mn = 10000 propyl methacrylate and methacryl

Si0 _{2 2} -asparagine

0.2 2 peroxygen

8 2 0. 2

(70nm) pyrimidine amide star-like 6 arsine

Polymer, Mn=5000 methyl acrylate and

Si0 _{2 2} -amino

0.2 1 13⁄4 atmosphere

5 acrylamide star (70nm) serine 2 0.02 6 pyridine acid copolymer,

Mn=3000

5-butyl methacrylate,

1 proline

Si0 ₂ 1,2,3-acrylamide and C

0.3 0.02 peroxygen

3 0.05

(70nm) ternary star of benzotrienoic acid

Azole 2 tyrosine copolymer,

Mn = 5000 propyl methacrylate and methacryl

2,3-two 0.0005 amide star

Si0 ₂

1 0.5 peroxygen

(70nm) aminopyridyl 3 tryptophan 1 polymer, 6 hydrogen

Acridine Mn=8000 star polypropylene

0.3

Acid, Mn=10000 Peroxygen

1 ethyl acrylate and

Si0 _{2 2} -pyridine

2 hydrogen

0.5 3 acrylamide star methionine 0.05 6 (70 nm) formic acid persulfate

0.5-shaped copolymer,

Acid hinge Mn=8000

3,5-dimethyl acrylate and

Si0 ₂ Aspartame

3 0.5 amino 3 2 hydroxyethyl acrylate

7 (80nm) -1,2,4-star copolymerization

Triazole is 0.0001

, Mn = 10000 methacrylate

1-hydroxy ester, hydroxy acrylate

Si0 ₂ 13⁄4

3 iodine

0.5 monobenzo 3 ethyl ester and styrene glutamic acid 2 0.01 8 (80 nm) acid

a ternary star copolymer of triazole,

Mn=5000 p-methylstyrene

Si0 ₂ benzotriene

1 0.01 Peroxygen with ethylene oxide

1

(80nm) arginine 1 0.5 8 azole hydrogenation binary star copolymer, Mn=6000

5-amino methacrylate

Si0 ₂

1 0.03 peroxygen

-1H-tetra 2 ester and acrylic acid

Lysine 1 1 of 9 (80 nm) hydrogenated star copolymer, azole

Mn=3000

5-amino

Styrene and epoxy -2-pyrene

Si0 ₂

1 peroxygen

0.5 2 Ethylene binary star (80 nm) Histidine 3 0.01 9 Hydrogen

-1,3,4-type copolymer, thiadiazole Mn=8000

3-amino

Butyl methacrylate -5-fluorene

Si0 ₂

0.5 0.5 peroxygen

2 Diethylene 3 0.01 ester and acrylic acid 10 (80 nm) hydrogenated star copolymer, triamine

Mn=12000 methacrylic acid B

Si0 ₂ polythene

0.5 peroxygen

0.5 benzene 1 3 0.05 ester and acrylic acid 11 (80 nm) polyaminated hydrogen star copolymer, azole

Mn=6000 styrene and epoxy

SiO _z benzotriene

0.5 peroxygen

0.05 1 3 0.05 binary star of ethane

11 (80 nm) azole, tetrahydrogenation type copolymer,

Mn = 10000 methyl methacrylate and ethylene oxide

SiO _z benzotritetraethylene

0.5 0.05 peroxygen

1 2 0.05

(80nm) binary star type 11 azole pentamine hydrogenation

Polymer,

Mn=10000 styrene and epoxy

Si0 ₂ benzotriene

0.5 glutamyl

0.05 peroxygen

0.05 2 0.05

(80nm) binary star of ethane 10 oxazolidine formic acid

Copolymer, Mn = 10000

Effect embodiment 1

Table 2 shows the comparative polishing liquids 1 to 3 and the polishing liquids 50 to 52 of the present invention. According to the formulation given in the table, the components other than the oxidizing agent are uniformly mixed, and the mass percentage is made up to 100% with water, using KOH or HN0 _{3 is} adjusted to the desired pH. Add oxidizing agent before use and mix well.

Table 2 Comparative polishing solution 1~3 and polishing solution 50~52

Abrasive particles corrosion inhibitor complexing agent oxygen oxime agent star polymer pH polishing

Content specific content concrete content content specific content specific

Liquid content

Wt% specific substance substance wt% substance wt% substance wt% substance wt%

Si0 ₂ 5-phenylperoxy

Comparison 1 0.5 0.05 0.8 Maleic acid 3 \ 4

(50nm) tetrazolium hydrogenation

Si0 ₂

1,2,4- comparison 2 0.5 peroxygen

(lOOnm 0.03 1.1 glycine 1 . \ 6 triazole hydrogenation

)

Si0 ₂ 4-amino

Peroxygen

Comparison 3 0.5 0.1 -1,2,4- 1.5 glycine 2 \ 8

(80nm) hydrogen

Triazole and styrene

Si0 ₂ hydroxy acrylate

5-phenyl peroxygen

50 0.5 0.05 0.8 maleic acid 3 0.05 ethyl ester 2 4

(50nm) tetrazolium hydrogenation

Yuan star copolymer Mn=6000 methacrylic acid butyl ester, C

Si0 ₂

1,2,4-enoic acid

51 0.5 peroxygen

(lOOnm 0.03 1 glycoside 1 0.02 ester and phenylethyl 6 triazole hydrogenation

Triene

Star copolymer, Mn=3000 Acrylic acid B

4-amino ester and propylene

52 0.5 0.1 -1,2,4- 1.5 glycine 2 peroxygen

0.03 amide star 8

Hydrogen

Triazole copolymer

Mn = 5000 The copper (Cu) was polished by using the comparative polishing liquids 1 to 3 and the polishing liquids 50 to 52 of the present invention. And measure the static corrosion rate of copper in the polishing solution. The removal rate and static corrosion rate are shown in Table 3. Empty sheet polishing conditions: Copper wafer: Downforce 3Psi/lpsi; Polishing disc and polishing head speed 70/80rpm, polishing pad PPG MX710, polishing fluid flow rate 100ml/min, polishing machine for Logitech PM5 Polisher Static Corrosion Rate Test Conditions: Copper wafers were immersed in room temperature and 50 ^Q C polishing solution, soaking time: 30 minutes at room temperature and 5 minutes at 50 °C. Table 3 Copper removal rate and static corrosion rate

As can be seen from the table, in comparison with the comparative examples in which the star polymer was not added, the star polymers were added in Examples 50 to 52, and the star polymer was more effective in suppressing the removal rate of copper under low pressure. It is beneficial to reduce the depression on the patterned copper wafer, and maintain a high copper removal rate under high pressure without affecting the production capacity. The star polymer can effectively inhibit the static corrosion rate of copper at normal temperature and polishing temperature (such as 50 ^Q C), which is beneficial to reduce defects and butterfly depression after polishing. Effect Example 2

The patterned copper wafer is polished using the comparative polishing liquid 2 and the polishing liquid 51 of the present invention. The polished trap values of the 80um*80um copper block on the patterned copper wafer after polishing were measured by XE-300P atomic force microscope.

Polishing conditions: 3 psi under pressure, polished patterned copper wafer to residual copper of approximately 2000 A, and then the residual copper was removed and oversprayed for 30 seconds at 1 psi. Polishing disc and polishing head speed 70/80rpm, polishing pad PPG MX710, polishing liquid flow rate 100ml/min, polishing machine is Logitech PM5 Polisher.

Table 4: Butterfly trap value of copper block

From the surface of JL, compared with Comparative Example 2 in which no star polymer was added, Example 51 added a star polymer which can effectively reduce the butterfly shape on the patterned copper wafer. Depression. Effect Example 3

The patterned copper wafer is polished and immersed using the polishing liquid 51 of the present invention.

Polishing process conditions: polishing disc and polishing head speed 70/80rpm, polishing pad PPG MX710, polishing liquid flow rate 100ml/min, polishing machine for Logitech PM5 Polishes down 3psi, polishing patterned copper wafer to residual copper about 2000A, then The remaining copper was removed by lpsi and left for 30 seconds. After immersing the polished copper wafer in the polishing solution for 30 minutes, it is taken out and cleaned and then scanned. A submicroscope (SEM) was used to observe the corrosion of the wafer surface.

As shown in Fig. 1, on the patterned copper wafer polished and immersed by the polishing liquid of the present invention, the surface has no scratches and the like, and the surface and edge of the copper wire are smooth and free from corrosion.

Claims

Rights request

A chemical mechanical polishing slurry comprising: at least one star-structured polymeric surfactant having a pigment affinity group, abrasive particles, a complexing agent, a corrosion inhibitor, and an oxidizing agent.

The polishing slurry according to claim 1, wherein the pigment affinity group is one or more selected from the group consisting of a hydroxyl group, an amino group, and a carboxyl group.

3. The polishing paddle according to claim 1, wherein the polymerizable monomer forming the star-shaped polymerization group containing the pigment-affinity group comprises one or more of the following: an acrylic monomer , acrylate monomers, acrylamide monomers and ethylene oxide.

4. The polishing slurry according to claim 3, wherein the acrylic monomer is acrylic acid and/or methacrylic acid; and the acrylate monomer is selected from the group consisting of methyl acrylate and methacrylic acid. One or more of methyl ester, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate The acrylamide monomer is acrylamide and/or methacrylamide.

The polishing slurry according to claim 3, wherein the monomer forming the star-shaped polymer of the pigment-containing affinity group further comprises other vinyl-based monomers.

The polishing slurry according to claim 5, wherein the other vinyl monomer is one or more selected from the group consisting of ethylene, propylene, styrene, and p-methylstyrene.

The polishing slurry according to claim 1 or 2, wherein the star-type polymer containing a pigment-affinity group is selected from the group consisting of polyacrylic acid star homopolymer, styrene and hydroxyethyl acrylate. Binary star copolymer, binary star copolymer of p-methylstyrene and epoxy oxime, binary star copolymer of styrene and epoxy oxime, methyl methacrylate and epoxy a binary star copolymer of hydrazine, a binary star copolymer of methyl acrylate and hydroxyethyl acrylate, a binary star copolymer of acrylic acid and hydroxyethyl acrylate, and three of acrylic acid, butyl acrylate and acrylamide. One or more of the meta star copolymers.

The polishing slurry according to claim 1, wherein the pigment-containing affinity group The star polymer has a number average molecular weight of 800 to 50,000.

The polishing slurry according to claim 1, wherein the content of the star-type polymer containing the pigment-affinity group is 0.0001 to 5% by mass.

The polishing slurry according to claim 1, wherein the abrasive particles are selected from the group consisting of silica, alumina, aluminum-doped silica, aluminum-covered silica, and dioxide. One or more of cerium, titanium dioxide and polymer abrasive particles.

The polishing slurry according to claim 10, wherein the abrasive particles are contained in an amount of 0.1 to 20% by mass, and the abrasive particles have a particle diameter of 20 to 150 nm.

The polishing slurry according to claim 1, wherein the complexing agent is selected from the group consisting of amino acids and salts thereof, organic carboxylic acids and salts thereof, organic phosphonic acids, and salts thereof.

The polishing slurry according to claim 12, wherein the amino acid is specifically selected from the group consisting of glycine, alanine, valine, leucine, valine, phenylalanine, and tyrosine. , tryptophan, lysine, arginine, histidine, serine, aspartic acid, glutamic acid, asparagine, glutamine, ammonia triacetic acid, ethylenediaminetetraacetic acid, cyclohexane One or more of acetic acid, ethylenediamine disuccinic acid, diethylenetriaminepentaacetic acid and triethylenetetraamine hexaacetic acid; the organic carboxylic acid is selected from the group consisting of acetic acid, oxalic acid, citric acid, tartaric acid, and Malay One or more of acid, malonic acid, succinic acid, malic acid, lactic acid, gallic acid, and sulfosalicylic acid; the organic phosphonic acid is 2-phosphonic acid butane-1, 2, 4 -tricarboxylic acid, aminotrimethylene phosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylene phosphonic acid, diethylenetriamine pentamethylphosphonic acid, polyol phosphonate, 2-hydroxyphosphonic acid acetic acid And one or more of ethylenediaminetetramethylenephosphonic acid and polyaminopolyether methylphosphonic acid.

The polishing slurry according to claim 1, wherein the complexing agent is contained in an amount of 0.01% by mass to 10% by mass.

The polishing slurry according to claim 1, wherein the corrosion inhibitor is nitrogen One or more of an azole, an imidazole, a thiazole, a pyridine, and a pyrimidine compound.

The polishing slurry according to claim 15, wherein the azole compound is one or more selected from the group consisting of benzotriazole, 5-methyl-1, 2, 3 -benzotriazole, 5-carboxybenzotriazole, 1-hydroxy-benzotriazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 5-carboxy-3-amino-1, 2,4-triazole, 3 -amino-5-mercapto-1,2,4-triazole, 5-acetic acid: 1H-tetrazole, 5-methyltetrazolium, 5-phenyltetrazolium, 5-amino-1H-tetra a azole and 1-phenyl-5-mercapto-tetrazole; the imidazole compound is benzimidazole and/or 2-mercaptobenzimidazole; the thiazole compound is selected from one of the following or a variety of: 2-mercapto-benzothiazole, 2-mercaptothiadiazole and 5-amino-2-mercapto-1,3,4-thiadiazole; the pyridine is selected from one or more of the following : 2,3-diaminopyridine, 2-aminopyridine and 2-picolinic acid; the pyrimidine is 2-aminopyrimidine.

The polishing slurry according to claim 1, wherein the corrosion inhibitor is contained in an amount of 0.005 to 5% by mass.

18. The polishing paddle according to claim 1, wherein the oxidizing agent is hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, persulfate, percarbonate, periodic acid, One or more of perchloric acid, perboric acid, potassium permanganate, and ferric nitrate.

The polishing slurry according to claim 1, wherein the oxidizing agent is contained in an amount of 0.05 to 10% by mass.

20. Use of a chemical mechanical polishing fluid according to any one of claims 1 to 19 for inhibiting static corrosion of copper.