CN100549121C - Chemical Mechanical Polishing Composition - Google Patents
Chemical Mechanical Polishing Composition Download PDFInfo
- Publication number
- CN100549121C CN100549121C CNB2006100666408A CN200610066640A CN100549121C CN 100549121 C CN100549121 C CN 100549121C CN B2006100666408 A CNB2006100666408 A CN B2006100666408A CN 200610066640 A CN200610066640 A CN 200610066640A CN 100549121 C CN100549121 C CN 100549121C
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- CN
- China
- Prior art keywords
- content
- chemical mechanical
- mechanical polishing
- polishing composition
- composition according
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 239000000126 substance Substances 0.000 title claims abstract description 38
- 238000005498 polishing Methods 0.000 title claims abstract description 34
- 238000000227 grinding Methods 0.000 claims abstract description 67
- 229910052751 metal Chemical group 0.000 claims abstract description 66
- 239000002184 metal Chemical group 0.000 claims abstract description 66
- 239000003112 inhibitor Substances 0.000 claims abstract description 59
- 150000001875 compounds Chemical group 0.000 claims abstract description 53
- 238000005260 corrosion Methods 0.000 claims abstract description 29
- 230000007797 corrosion Effects 0.000 claims abstract description 29
- 239000012736 aqueous medium Substances 0.000 claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 43
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 26
- 239000013543 active substance Substances 0.000 claims description 21
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 13
- 235000019253 formic acid Nutrition 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
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- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 7
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- 125000000129 anionic group Chemical group 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
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- GUOVBFFLXKJFEE-UHFFFAOYSA-N 2h-benzotriazole-5-carboxylic acid Chemical compound C1=C(C(=O)O)C=CC2=NNN=C21 GUOVBFFLXKJFEE-UHFFFAOYSA-N 0.000 claims 1
- ZJJADRZINPLZGS-UHFFFAOYSA-N 3-hydrazinyl-1,2,4-triazol-4-amine Chemical compound NNC1=NN=CN1N ZJJADRZINPLZGS-UHFFFAOYSA-N 0.000 claims 1
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- 238000004519 manufacturing process Methods 0.000 description 15
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- 239000002002 slurry Substances 0.000 description 13
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- 230000000052 comparative effect Effects 0.000 description 10
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- 239000006061 abrasive grain Substances 0.000 description 7
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- 210000004080 milk Anatomy 0.000 description 7
- 235000013336 milk Nutrition 0.000 description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
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- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N Lactic Acid Natural products CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VKWHEBRSOGACFC-UHFFFAOYSA-N pent-2-enoic acid Chemical compound CCC=CC(O)=O.CCC=CC(O)=O VKWHEBRSOGACFC-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- JOFWLTCLBGQGBO-UHFFFAOYSA-N triazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1Cl JOFWLTCLBGQGBO-UHFFFAOYSA-N 0.000 description 1
- 229960003386 triazolam Drugs 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Landscapes
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
A chemical mechanical polishing composition having a pH ranging from 2 to 5 and comprising a mixture of: an aqueous medium, a grinding material, a corrosion inhibitor, a surfactant, diacid compound and a metal residue inhibitor, wherein the metal residue inhibitor is selected from the group consisting of compounds represented by the following chemical formulas: the formula , the formula (II), the formula (III), the formula (IV), the formula (V) and combinations of these compounds, wherein the structures of the formulae (II) to (V) and the definitions of the individual substituents are defined in the description and the claims. When the chemical mechanical polishing composition is used for polishing the surface of a semiconductor wafer, a good metal polishing rate can be obtained, metal pits can be effectively reduced, and metal residues on the surface of the wafer can be reduced.
Description
Technical field
The present invention relates to a kind of Chemicomechanically grinding composition, be meant a kind of Chemicomechanically grinding composition that is used for manufacture of semiconductor and comprises a metal residual inhibitor especially.
Background technology
Cmp (chemical mechanical polishing abbreviates " CMP " as) technology is to result in the planarization that problem developed that is difficult on the micro-photographing process focus on for the plated film height difference that solves when making because of unicircuit (IC).The cmp technology at first is applied in the manufacturing of 0.5 micron element on a small quantity, but along with the dwindling of component size, and the probability that the cmp technology is employed is also along with increase, and has become the indispensable planarization of industry at present.
In the semiconductor crystal wafer processing procedure, there is two types layer to grind, one type is the middle layer (interlayer) such as silicon oxide (silicon oxide) and silicon nitride (silicon nitride), and another type is the metallic circuit (for example tungsten, copper, aluminium etc.) that is used to connect main drive.The Ginding process that generally is used for metallic circuit (metal wire) is that semiconductor crystal wafer is placed a spin finishing platform that is provided with a grinding head (polishing head), and the grinding milk that coating one contains abrasive grains (abrasive particles) on this crystal column surface, with effective enhancement integral grinding effect.When utilizing a grinding milk to carry out the grinding of metallic circuit, general supposition can select following first mechanism (mechanism) or second mechanism to carry out.In first mechanism, the component in the grinding milk (needing the extra oxygenant that adds usually) can form the monoxide layer with the metallic circuit reaction earlier continuously in the metallic surface, and the mechanical abrasive action of the abrasive grains in the grinding milk can worn this oxide skin.In second mechanism, do not form this oxide skin, but use the component in this grinding milk to corrode and dissolve this metallic circuit, and increase dissolution rate by the mechanical effect of abrasive grains as first mechanism, and then make the thickness attenuation of metallic circuit, to reach worn purpose.Because the CMP processing procedure has the uneven problem of grinding, so after bestowing this processing procedure, though the metal oxide of crystal column surface can still also may be caused part metals to be ground and produce depression (dishing) by worn, crystal column surface then may residually have unwanted metal.Therefore, the depression of how removing metal residue fast and reducing metallic circuit is quickened production capacity simultaneously, a big problem that need overcome for the CMP processing procedure utmost point.
Existing many at present document and patents of mentioning that relevant utilization grinding milk comes the metal level on the polishing semiconductor wafers.For example United States Patent (USP) announces the 6th, 447, No. 563 a kind of slurries systems (slurry system) that are used for grinding metal layer of announcement, and this slurries system comprises a first part and a second section, and has the pH value between 2 to 11.A dispersion liquid that is made of abrasive grains, a stablizer and a tensio-active agent is in fact contained in this first part, this second section contains an accelerator solution (activator solution), and this accelerator solution contains at least two and is selected from by the component in the following group that constitutes: oxygenant, acid, amine, sequestrant (chelating agent), fluorochemicals, corrosion inhibitor (corrosion inhibitor), biotechnological formulation (biological agent), tensio-active agent, buffer reagent and composition thereof.This patent mentions that spendable acid comprises: formic acid, acetate, caproic acid, lactic acid organic acids such as (lactic acid), and mineral acid such as hydrochloric acid, sulfuric acid.And the preferable acid that contains one or more carboxyl and replace through hydroxyl, for example oxysuccinic acid (malic acid), tartrate (tartaric acid), glyconic acid (gluconic acid) and the citric acid (citric acid) of using.In addition, the type of this tensio-active agent can be non-ionic type, anionic, cationic and amphoteric.In the embodiment 1 of this patent, at first prepare by the silica of being fuming (fumed silica) of 4wt%, the hydrogen peroxide of 1wt% and the slurries system that propionic acid constituted of 0.1M, then utilizing this slurries system to carry out the grinding test of copper wafer, find that at last worn speed (removal rate) is to surpass 450nm, and heterogeneity is less than 5%.The slurries system of this patent is used to improve grinding rate, and not mentioned metal residual problem about crystal column surface.
United States Patent (USP) announces the 6th, 864, disclose the method that a kind of metal wire that is used to make semiconductor device meets bolt (metal line contact plug) for No. 177, this manufacture method comprises following two steps: (1) uses first slurries to carry out the CMP process of fs, these first slurries contain the abrasive grains of 1～20wt%, the oxygenant of 0.1～15wt% and the complexing agent (complexing agent) of 0.01～10wt%, and have a pH scope of 2～9, have etching selectivity (etchingselectivity) at the insulator/metal film in addition greater than 10; (2) use second slurries to carry out the CMP process of subordinate phase, these second slurries contain the abrasive grains of 5～30wt% and the oxygenant of 0.01～5wt%, and have 6～12 pH scope, have etching selectivity less than 3 at the insulator/metal film in addition.Complexing agent in first slurries of this patent is to be selected from the group that is made of following: the salt or the mixture of citric acid, tartrate, Succinic Acid (succinic acid), oxysuccinic acid, maleic acid (maleic acid), FUMARIC ACID TECH GRADE (fumaric acid), propanedioic acid (malonicacid), ethylene dinitrilotetra-acetic acid salt (ethylenediamine tetraacetate), oxyacetic acid (glycolic acid) and these compounds.In this patent, do not provide any test data, yet not mentioned use tensio-active agent and corrosion inhibitor.
This case applicant had before also obtained the TaiWan, China patent of a relevant Chemicomechanically grinding composition, and just No. the 574352nd, the TaiWan, China patent announcement, and it discloses a kind of chemical and mechanical grinding fluid composition and using method thereof.This serosity combination is the aqueous medium that comprises 70～99.5wt%, the abrasive grains of 0.1～25wt%, the corrosion inhibitor of 0.01～1wt%, and the chemical of 0.01～1wt%.This chemical is to be selected from the group that is made of following: following formula (A), following formula (B) and both combinations, wherein, X, Y and Z are selected from hydrogen or C respectively
1～C
6Alkyl.The purpose of this patent is mainly preventing copper depression, do not address about the residual improvement of the copper of grinding rate and crystal column surface, in addition, in this patent and not mentioned use tensio-active agent.
Because the composition of chemical and mechanical grinding fluid can influence the sinking degree of grinding rate, metallic circuit and the metal residual of crystal column surface, therefore, how effectively under higher grinding rate, reduce the sinking degree of metallic circuit and the metal residual of crystal column surface simultaneously, for present industry, still there is a demand.
Summary of the invention
Therefore, purpose of the present invention is to provide a kind of good grinding rate of keeping, and effectively reduces the Chemicomechanically grinding composition of sinking degree and metal residual simultaneously.
The pH scope of Chemicomechanically grinding composition of the present invention is between 2 to 5, and comprise a mixture with following component: an aqueous medium, an abrasive (abrasive), a corrosion inhibitor, a tensio-active agent, two acid compounds and a metal residual inhibitor, this metal residual inhibitor are the groups that compound constituted that is selected from by shown in the following chemical formula:
In this formula (II)～(V), R
1, R
2, R
3And R
4Be selected from the group that constitutes by following respectively: hydrogen, C
1～C
6Alkyl, C
2～C
6Thiazolinyl and C
2～C
6Inferior thiazolinyl (alkylidyne), and R
5, R
6, R
7And R
8, R
9And R
10Be selected from hydrogen or C respectively
1～C
6Alkyl.
Chemicomechanically grinding composition of the present invention is by adding the metal residual that a metal residual inhibitor reduces crystal column surface, employed metal residual inhibitor has at least one carboxyl and reactive splendid with metal (for example copper), thereby can reduce the metal residual of crystal column surface, add and add two acid compounds, tensio-active agent, abrasive and corrosion inhibitor, can keep good grinding rate simultaneously and reduce sinking degree.
Embodiment
Chemicomechanically grinding composition of the present invention has a pH value scope between 2 to 5, and comprise a mixture with following component: an aqueous medium, an abrasive, a corrosion inhibitor, a tensio-active agent, two acid compounds and a metal residual inhibitor, this metal residual inhibitor are the groups that compound constituted that is selected from by shown in the following chemical formula:
And a combination of these compounds,
In this formula (II)～(V), R
1, R
2, R
3And R
4Be selected from the group that constitutes by following respectively: hydrogen, C
1～C
6Alkyl, C
2～C
6Thiazolinyl and C
2～C
6Inferior thiazolinyl, and R
5, R
6, R
7And R
8, R
9And R
10Be selected from hydrogen or C respectively
1～C
6Alkyl.
Chemicomechanically grinding composition of the present invention can carry out the content adjustment according to subsequent use, preferably, is that 100wt% calculates with the gross weight of this mixture, and each components contents is as follows:
The content of this abrasive: 0.10～25.00wt%
The content of this corrosion inhibitor: 0.01～1.00wt%
The content of this tensio-active agent: 0.01～1.00wt%
The content of this two acid compounds: 0.01～1.00wt%
The content of this metal residual inhibitor: 0.01～1.00wt%
Aqueous medium: all the other content
Above-mentioned " all the other content " is meant that the content of aqueous medium and other component concentrations add up to 100wt%.
Optionally, when this metal residual inhibitor was the compound that is selected from shown in this formula (I), this formula (II), this formula (III) or this formula (IV), the preferable content of each component in this mixture was as follows:
The content of this abrasive: 0.50～10.00wt%
The content of this corrosion inhibitor: 0.01～0.50wt%
The content of this tensio-active agent: 0.01～0.50wt%
The content of this two acid compounds: 0.05～1.00wt%
The content of this metal residual inhibitor: 0.01～0.50wt%
Aqueous medium: all the other content
Again more preferably, each components contents in this mixture is as follows: the content of this abrasive is 0.50～5.00wt%, the content of this corrosion inhibitor is 0.01～0.20wt%, the content of this tensio-active agent is 0.01～0.30wt%, the content of this two acid compounds is 0.10～1.00wt%, the content of this metal residual inhibitor is 0.01～0.30wt%, and all the other content are this aqueous medium.It will be further appreciated that when this metal deactivator is during by the compound shown in this formula (I), its content is more preferred from 0.01～0.10wt%.
In addition optionally, when this metal residual inhibitor is by shown in this formula V the time, the preferable content of each component in this mixture is as follows:
The content of this abrasive: 0.50～10.00wt%
The content of this corrosion inhibitor: 0.01～0.50wt%
The content of this tensio-active agent: 0.01～0.50wt%
The content of this two acid compounds: 0.05～1.00wt%
The content of this metal residual inhibitor: 0.05～1.00wt%
Aqueous medium: all the other content
Again more preferably, each components contents in this mixture is as follows: the content of this abrasive is 0.50～5.00wt%, the content of this corrosion inhibitor is 0.01～0.20wt%, the content of this tensio-active agent is 0.01～0.30wt%, the content of this two acid compounds is 0.10～1.00wt%, the content of this metal residual inhibitor is 0.05～0.50wt%, and all the other content are this aqueous medium.
Be noted that, when grinding rate is lower than
During/min, can be by increasing the content of two acid compounds and abrasive, to increase grinding rate.When sinking degree is too high, then can reduce by increasing surfactant content.And when crystal column surface has metal residual, then can lower the metal residual situation by increasing this metal residual inhibitor content.
Preferably, compound shown in this formula (II) is to be selected from the group that is made of following: 2,2-dimethyl succinic acid (2,2-dimethylsuccinic acid), 2-ethyl-2-pyrovinic acid (2-ethyl-2-methylsuccinic acid), 2,3-dimethyl succinic acid (2,3-dimethylsuccinic acid) and methyne Succinic Acid (Itaconic acid or Methylenesuccinic acid).And in a specific example of the present invention, this formula (II) is the methyne Succinic Acid.
Compound shown in this formula (III) can be cis (cis-) compound or trans (trans-) compound, preferably, the compound shown in this formula (III) is to be selected from the group that is made of following: maleic acid, 2-methyl-maleic acid (2-methyl-maleic acid), FUMARIC ACID TECH GRADE and 2-methyl-FUMARIC ACID TECH GRADE (2-methyl-furmaric acid).In a specific example of the present invention, this formula (III) is a FUMARIC ACID TECH GRADE.
Preferably, compound shown in this formula (IV) is to be selected from the group that is made of following: 2-oxyacetic acid (2-hydroxy acetic acid or Glycolic acid), 2-methyl-2-oxyacetic acid (2-methyl-2-hydroxy acetic acid), 2-ethyl-2-oxyacetic acid (2-ethyl-2-hydroxy acetic acid), 2,2-diethyl-2-oxyacetic acid (2,2-diethyl-2-hydroxy acetic acid) and 2-ethyl-2-methyl-2-oxyacetic acid (2-ethyl-2-methyl-2-hydroxy acetic acid).In a specific example of the present invention, this formula (IV) is the 2-oxyacetic acid.
Preferably, compound shown in this formula V is to be selected from the group that is made of following: vinylformic acid (acrylic acid), 2-methacrylic acid (2-methyl acrylicacid), 2-ethylacrylic acid (2-ethyl acrylic acid), 3-methacrylic acid (3-methyl acrylic acid), 3-ethylacrylic acid (3-ethyl acrylic acid) and 2,3-dimethacrylate (2,3-dimethyl acrylic acid).In a specific example of the present invention, this formula V is a vinylformic acid.
Tensio-active agent of the present invention can be selected suitable commercially available prod according to actual needs, and preferably, this tensio-active agent can be anionic (anionic type) or non-ionic type (nonionic type).
Abrasive in this Chemicomechanically grinding composition can be selected any commercially available prod for use according to actual needs, particularly select for use have higher degree, the commercially available prod of the advantage of high-specific surface area and narrow size distribution.Preferably, this abrasive is to be selected from the group that is made of following material: silicon oxide (SiO
2), aluminum oxide (Al
2O
3), zirconium white (ZrO
2), cerium oxide (CeO
2), silicon carbide (SiC), titanium oxide (TiO
2), silicon nitride (Si
3N
4) and these compounds one the combination.And in a specific example of the present invention, this abrasive is a silicon oxide.In addition, the particle size range of this abrasive can be adjusted according to actual needs, and preferably, the particle size range of this abrasive is between 15nm and 30nm.
This corrosion inhibitor can be selected any existing commercially available prod that is used for semiconductor applications and can suppresses corrosion phenomenon for use.Preferably, this corrosion inhibitor is the material that is selected from by in the following group that constitutes: benzotriazole (benzotriazole), tricyanic acid (1,3,5-triazine-2,4,6-triol), 1,2,3-triazole (1,2,3-triazole), 3-amido-1,2,4-triazole (3-amino-1,2,4-triazole), 3-nitro-1,2,4-triazole (3-nitro-1,2,4-triazole), 4-amido-3-diazanyl-1,2,4-triazolyl-5-mercaptan (4-amino-3-hydrazino-1,2,4-triazol-5-thiol, commodity Popeye by name get (
)), benzotriazole-5-carboxylic acid (benzotriazole-5-carboxylic acid), 3-amido-1,2,4-triazole-5-carboxylic acid (3-amino-1,2,4-triazole-5-carboxylic acid), one of I-hydroxybenzotriazole (1-hydroxy benzotriazole), nitrobenzene and triazolam (nitrobenzotriazole) and these compounds combination.And in a specific example of the present invention, this corrosion inhibitor is a benzotriazole.
Two acid compounds that the optional usefulness of this two acid compounds generally is used for the straight chain of grinding milk and is unsubstituted, preferably, this two acid compounds is to be selected from the group that is made of following: a combination of Succinic Acid, hexanodioic acid, pentanedioic acid and these compounds.
Aqueous medium in the Chemicomechanically grinding composition of the present invention mainly is to be used to make this chemical and mechanical grinding fluid can present the slurries shape after mixing, and therefore can use and be familiar with the existing various aqueous mediums of this operator.And in a specific example of the present invention, this aqueous medium is a deionized water.
The production method of Chemicomechanically grinding composition of the present invention is mixed this abrasive, this tensio-active agent, this corrosion inhibitor, this two acid compounds, this metal residual inhibitor and this aqueous medium earlier at normal temperatures, making this mixture, then be adjusted between 2 to 5 with acid or alkali pH value with this mixture.Preferably, the pH value is between 3 to 4.The acid or the alkali that are used to adjust the pH value of said composition are not limited to them, and preferably, this acid can be hydrochloric acid or nitric acid, and this alkali can be ammoniacal liquor or tetramethyl ammonium hydroxide (tetramethylammonium hydroxide abbreviates " TMAH " as).
Preferably, this Chemicomechanically grinding composition also comprises an oxygenant, its objective is the oxidation of the metal level that is used to quicken this crystal column surface.More preferably, this oxygenant is to be selected from the group that is made of following: hydrogen peroxide (hydrogen peroxide, H
2O
2), iron nitrate (ferric nitrate, Fe (NO
3)
3), Potassium Iodate (potassium iodate, KIO
3), peracetic acid (acetic hydroperoxide, CH
3COOOH) and potassium permanganate (potassium permanganate, KMnO
4).In a specific example of the present invention, this oxygenant is a hydrogen peroxide.
The content of this oxygenant can use according to reality and adjust, and preferably, the content ratio of the mixture in this oxygenant and this Chemicomechanically grinding composition is 1: 9～1: 30.And in a specific example of the present invention, the content ratio of this oxygenant and this mixture is 1: 11.
Preferably, the mixture in this Chemicomechanically grinding composition has more formic acid, the sinking degree that can increase grinding rate and more effectively reduce this crystal column surface.
And the content range of this formic acid can be adjusted according to the reality use, preferably, gross weight with this mixture is that 100wt% calculates, the content of this abrasive is 0.10～25.00wt%, the content of this corrosion inhibitor is 0.01～1.00wt%, the content of this tensio-active agent is 0.01～1.00wt%, the content of this two acid compounds is 0.01～1.00wt%, the content of this metal residual inhibitor is 0.01～1.00wt%, and the content of this formic acid is that 0.01～1.00wt% and all the other content are aqueous medium.
＜embodiment 〉
The present invention will be described further with regard to following examples, but will be appreciated that, described embodiment only is the example explanation, and should not be interpreted as restriction of the invention process.
[chemical]
Following examples and comparative example select for use following chemical to be prepared respectively:
(1) aqueous medium: be ionized water.
(2) abrasive: be silicon oxide, commercially available product is called silicic acid glue (colloidal silica).
(3) corrosion inhibitor: be benzotriazole, by company of TaiWan, China Fine Machinery Research and Development Center (PMC) manufacturing.
(4) two acid compounds: embodiment uses hexanodioic acid, and comparative example uses pentanedioic acid, all by the manufacturing of U.S. TEDIA company.
(5) tensio-active agent: be aniorfic surfactant.
(6) metal residual inhibitor: be respectively 1 according to following table 1,2,3,4-tetracarboxylic acid butane (1,2,3,4-butanetetracarboxylic acid, following table 1 will be called " formula (I) compound "), methyne Succinic Acid, FUMARIC ACID TECH GRADE, 2-oxyacetic acid and vinylformic acid, and described metal residual inhibitor is by the manufacturing of U.S. Aldrich company.
(7) oxygenant: be hydrogen peroxide, by TaiWan, China Bo Lv limited-liability company (TAIWANMAXWAVE CO., LTD.) manufacturing.
(8) formic acid: be by the manufacturing of U.S. Aldrich company.
[test]
Following examples and comparative example will grind test and analysis according to following condition and step:
1. test condition:
(1) instrument: employed grinder station is that (model is AMAT/Mirra for APPLIEDMATERIALS, INC.) manufacturing by limited-liability company of Applied Materials.
(2) instrument is set:
Mould (membrane pressure) 1.0～1.5psi
(inner tube) exhaust (vent) of interior pipe
Keep ring compression (retaining ring) 1.8psi
Grinding plate rotating speed (platen speed) 70rpm
Carrier rotating speed (carrier speed) 74rpm
25 ℃ of temperature
Grinding pad (polishing pad) base pattern CUP4410
Slurry flow rate 200mL/min
(3) wafer: be coated with pattern (pattern) wafer of copper metal layer, by the manufacturing of U.S. Sematech company, live width is 0.18 μ m.
2. test procedure:
Use the prepared Chemicomechanically grinding composition of following examples and comparative example respectively, and on above-mentioned grinder station, carry out the grinding of a wafer, the inductor block (End Point System) that the process of lapping required time then utilizes board to set up is responded to the wafer that is ground and has been reached the signal that produces behind the grinding endpoint [this signal will as endpoint signal (EP2)] and judge, to be ground to the EP2 generation, carry out 20% excessive polishing (over-polishing) again, and then with a cleaning machine (by the solid-state instrument company of the U.S. (SlidState Equipment Corporation) manufacturing, model is " EvergreenModel 10X ") carry out the cleaning of wafer, and with nitrogen wafer is dried up.Carry out following analysis at last again.
3. analyze:
(1) grinding rate: with the model of US business's KLA-Tencor company (KLA-TENCOR) manufacturing is that the film thickness measuring instrument (resistivitymeasurement system) of KLA-Tencor RS-75 is measured the copper metal layer thickness after grinding.Grinding rate be with 1 minute worn metal layer thickness (
/ min) define, and preferable with
/ min is above to be the acceptable scope of industry.
(2) sinking degree: with a contact-type surface profiler (Surface Profiler, model by US business's KLA-Tencor company (KLA-TENCOR) manufacturing is KLA-Tencor P-11) measure, be measurement point with live width 100 μ m copper cash during mensuration, and measure the relative depression situation of this copper cash and a barrier layer (barrier layer).Generally speaking, the numerical value of sinking degree is the smaller the better, and the best is that sinking degree is
/ min.
(3) the metal residual situation of crystal column surface: get by naked-eye observation.
[embodiment 1～9]
According to following table 1, at room temperature the abrasive of 2.00wt%, the corrosion inhibitor of 0.05wt%, the hexanodioic acid of 0.4wt%, tensio-active agent, metal residual inhibitor and the selectivity interpolation formic acid (content is as shown in table 1) of 0.2wt% are mixed, adding an amount of aqueous medium again is 100wt% until gross weight, to make a mixture respectively.Then according to oxygenant: the ratio of mixture=1: 11, this mixture and this oxygenant are mixed, and whether test pH value is between 3 to 4, as not in this pH scope, then utilize hydrochloric acid or ammoniacal liquor again, the pH value is adjusted into 3～4, obtains the Chemicomechanically grinding composition of embodiment 1～9 at last respectively.
The Chemicomechanically grinding composition of embodiment 1～9 is tested according to above-mentioned test and analytical procedure respectively, and the result who is obtained puts in order respectively in following table 1.
[comparative example 1～4]
In these comparative examples, except not adding this metal residual inhibitor and optionally adding industry other two acid compounds (as pentanedioic acid) or other acid (as formic acid) commonly used, utilization prepares Chemicomechanically grinding composition with abrasive, corrosion inhibitor and hexanodioic acid and the preparation method of embodiment 1 identical type and content, and the variation of surfactant content, two acid compounds and other sour kinds and content thereof is as shown in table 1 in each comparative example.
The Chemicomechanically grinding composition of comparative example 1～4 is tested according to above-mentioned test and analytical procedure respectively, and the result who is obtained also puts in order respectively in following table 1.
Table 1
A. "-" expression is not added.
[result]
1. the influence of metal residual inhibitor:
The embodiment 1～9 of table 1 is compared with comparative example 1～4 respectively, can find: comparative example 1～4 all has the metal residual situation, and by the result of embodiment 1～9, when using this metal deactivator, can allow crystal column surface not have the metal residual situation, and sinking degree also exist
Below, and keep and be higher than
The grinding rate of/min, obvious utilization metal residual inhibitor can suppress the metal residual situation really effectively.
In addition, by the result of embodiment 1 and embodiment 2, when the content of increase formula (I) compound, can effectively promote the situation that grinding rate and crystal column surface do not have metal residual.And by the result of embodiment 3 and 4, when metal deactivator was the combination of formula (I) compound and methyne Succinic Acid, can promote grinding rate and crystal column surface did not have the metal residual situation yet, similarly, identical result was arranged also in embodiment 6 and 7.Prove that so this metal deactivator can be selected compound or these combination of compounds of above-mentioned formula (I) to (V) according to need, promote grinding rate and allow crystal column surface not have the purpose of metal residual situation and reach simultaneously.
2. the influence of formic acid:
The embodiment 9 of table 1 is compared with embodiment 1, can find can promote grinding rate effectively, and can reduce sinking degree when adding formic acid, obvious interpolation formic acid more can obtain good grinding rate and lower sinking degree.
Really can under higher grinding rate, reduce sinking degree and metal residual situation simultaneously by the provable Chemicomechanically grinding composition of the present invention of above result.
Conclude above-mentioned, Chemicomechanically grinding composition of the present invention is owing to comprise a metal residual inhibitor, can reduce the metal residual situation of crystal column surface effectively, add being used of abrasive, tensio-active agent, two acid compounds and corrosion inhibitor, more can allow sinking degree and grinding rate maintain the acceptable preferred range of industry.In addition, when adding formic acid, can allow grinding rate further promote, and allow sinking degree descend simultaneously in this Chemicomechanically grinding composition.
The above only is preferred embodiment of the present invention; so it is not in order to limit scope of the present invention; any personnel that are familiar with this technology; without departing from the spirit and scope of the present invention; can do further improvement and variation on this basis, so the scope that claims were defined that protection scope of the present invention is worked as with the application is as the criterion.
Claims (22)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100666408A CN100549121C (en) | 2006-04-17 | 2006-04-17 | Chemical Mechanical Polishing Composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100666408A CN100549121C (en) | 2006-04-17 | 2006-04-17 | Chemical Mechanical Polishing Composition |
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| CN100549121C true CN100549121C (en) | 2009-10-14 |
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| JP6051632B2 (en) * | 2011-07-20 | 2016-12-27 | 日立化成株式会社 | Abrasive and substrate polishing method |
| CN111378372B (en) * | 2018-12-28 | 2022-05-13 | 安集微电子（上海）有限公司 | Application of acetic acid in STI polishing |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1282775A (en) * | 1999-07-28 | 2001-02-07 | 长兴化学工业股份有限公司 | Chemical mechanical polishing composition and method |
| CN1493640A (en) * | 2002-10-31 | 2004-05-05 | 长兴化学工业股份有限公司 | chemical mechanical polishing slurry composition and method of use thereof |
| CN1650403A (en) * | 2002-04-30 | 2005-08-03 | 日立化成工业株式会社 | Polishing fluid and polishing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1282775A (en) * | 1999-07-28 | 2001-02-07 | 长兴化学工业股份有限公司 | Chemical mechanical polishing composition and method |
| CN1650403A (en) * | 2002-04-30 | 2005-08-03 | 日立化成工业株式会社 | Polishing fluid and polishing method |
| CN1493640A (en) * | 2002-10-31 | 2004-05-05 | 长兴化学工业股份有限公司 | chemical mechanical polishing slurry composition and method of use thereof |
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