CN105273636A - Chemical mechanical polishing liquid - Google Patents
Chemical mechanical polishing liquid Download PDFInfo
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- CN105273636A CN105273636A CN201410351205.4A CN201410351205A CN105273636A CN 105273636 A CN105273636 A CN 105273636A CN 201410351205 A CN201410351205 A CN 201410351205A CN 105273636 A CN105273636 A CN 105273636A
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Abstract
The invention discloses a chemical mechanical polishing liquid containing abrasive particles, a corrosion inhibitor, an antioxidant, water and two complexing agents. The chemical mechanical polishing liquid can maintain higher copper removal rate after a polishing pad cleaning liquid is used.
Description
Technical field
The present invention relates to a kind of chemical mechanical polishing liquid.
Background technology
Along with the development of microelectronics, very large scale integration chip integration has reached tens components and parts, characteristic dimension enters nano level, and this just requires the hundreds of procedure in microelectronic technique, especially multilayer wiring, substrate, medium must through chemical-mechanical planarization.Very large-scale integrated wiring is just transformed to Cu by traditional Al.Compared with Al, to have resistivity low in Cu wiring, and deelectric transferred energy rate is high, and RC is short for time of lag, and the advantage of Cu wiring has made its substitute for Al become interconnected metal in semiconductor fabrication.
But also do not carry out plasma etching or wet etching effectively to copper material, the known technology fully formed in integrated circuits to make copper-connection at present, therefore the cmp method of copper is considered to the most effective processing method.The principle of work of the cmp method of copper is generally first with fast and remove copper a large amount of on speed removing substrate surface efficiently, when soon close to during blocking layer and soft landing, reduces and removes the remaining metallic copper of speed polishing and be also parked in blocking layer.At present, there is a series of chemical mechanical polishing slurry being suitable for polishing Cu, as: the patent No. is US6, and 616,717 disclose a kind of composition for metal CMP and method; The patent No. is US5, and 527,423 disclose a kind of chemical mechanical polishing slurry for metal level; The patent No. is US6, and 821,897 disclose a kind of method using the copper CMP of polymer complexing agent; The patent No. is that CN02114147.9 discloses a kind of polishing liquid used in copper chemical mechanical polishing technology; The patent No. is that CN01818940.7 discloses the chemically machinery polished of copper slurry used; The patent No. is that CN98120987.4 discloses the manufacture of a kind of CMP slurry liquid for copper and the manufacture method for unicircuit.But use removal due to copper in the polishing process of copper more, usually can remain on polishing pad, affect polishing performance, therefore need to use after a polish acid polishing pad scavenging solution to make a return journey remaining of copper removal.But the polishing slurries that polishing slurries, particularly pH value are higher is often incompatible with polishing pad scavenging solution, cause the removal rate reduction using copper after scavenging solution.Therefore be necessary to develop the chemical mechanical polishing slurry for copper made new advances.
Summary of the invention
Technical problem to be solved by this invention is incompatible with polishing pad scavenging solution for the chemical mechanical polishing liquid of polish copper, cause the removal rate reduction of copper, thus a kind of chemical mechanical polishing liquid that higher copper also can be kept after using polishing pad scavenging solution to remove speed is provided.
Chemical mechanical polishing liquid of the present invention, containing abrasive grains, corrosion inhibitor, oxygenant, the combination of water and following two kinds of complexing agents:
First complexing agent, containing amino compound and salt thereof;
Second complexing agent, organic acid and salt thereof, described salt be selected from sylvite, sodium salt and/or ammonium salt one or more.
In the present invention, described is amino acid and/or polyamines containing amino compound.
In the present invention, described amino acid be selected from glycine, L-Ala, α-amino-isovaleric acid, leucine, proline(Pro), phenylalanine, methionine(Met), Threonine, tyrosine, tryptophane, Methionin, arginine, Histidine, Serine, aspartic acid, L-glutamic acid, l-asparagine and/or glutamine one or more.
In the present invention, described polyamines be selected from quadrol, diethylenetriamine, pentamethyl-diethylenetriamine, triethylene tetramine, tetraethylene pentamine and/or polyethylene polyamine one or more.
In the present invention, described organic acid is organic carboxyl acid and/or organic phospho acid.
In the present invention, described organic carboxyl acid be selected from acetic acid, oxalic acid, citric acid, tartrate, propanedioic acid, succinic acid, oxysuccinic acid, lactic acid, toxilic acid, gallic acid and/or sulphosalicylic acid one or more.
In the present invention, described organic phospho acid is selected from 2-phosphonobutane-1, one or more in 2,4-tricarboxylic acid, Amino Trimethylene Phosphonic Acid, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid and/or polyamino polyether base methylenephosphonic acid.
In the present invention, the described mass percentage containing amino compound and salt thereof is 0.01 ~ 10%.
In the present invention, described organic acid and the mass percentage of salt thereof are 0.01 ~ 3%.
In the present invention, described oxygenant be selected from hydrogen peroxide, urea peroxide, peroxyformic acid, Peracetic Acid, persulphate, percarbonate, Periodic acid, perchloric acid, high boric acid, potassium permanganate and/or iron nitrate one or more.The mass percentage of described oxygenant is 0.01 ~ 10%.
In the present invention, described abrasive grains be selected from silicon-dioxide, aluminium sesquioxide, the silicon-dioxide of adulterated al, the silicon-dioxide of aluminium coating, cerium dioxide, titanium dioxide and/or polymer abrasive grains one or more.The mass percentage of described abrasive grains is 0.1 ~ 5%.The particle diameter of described abrasive grains is 20 ~ 150nm.
In the present invention, described corrosion inhibitor be selected from nitrogen azoles, imidazoles, thiazole, pyridine and/or pyrimidines one or more.
In the present invention, described nitrogen azole compounds is selected from benzotriazole, 5-methyl isophthalic acid, 2, 3-benzotriazole, 5-carboxy benzotriazole, 1-hydroxyl-benzotriazole, 1, 2, 4-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 3, 5-diaminostilbene, 2, 4-triazole, 5-carboxyl-3-amino-1, 2, 4-triazole, 3-amino-5-sulfydryl-1, 2, 4-triazole, 5-acetic acid-1H-tetrazole, 5-methyl tetrazole, 5-phenyl tetrazole, one or more in 5-amino-1H-tetrazole and/or 1-phenyl-5-sulfydryl-tetrazole.
In the present invention, described glyoxaline compound is benzoglyoxaline and/or 2-mercaptobenzimidazole.
In the present invention, described thiazole compound be selected from 2-Mercapto-benzothiazole, 2-dimercaptothiodiazole and/or 5-amino-2-mercapto phenyl formic-1,3,4-thiadiazoles one or more.
In the present invention, described pyridine be selected from 2,3 diamino pyridine, PA and/or 2-pyridine carboxylic acid one or more.
In the present invention, described pyrimidine is 2-aminopyrimidine.
In the present invention, described corrosion inhibition mass percentage is 0.001 ~ 5%.
The polishing fluid of invention, pH is 4 ~ 11, is preferably 5 ~ 8.
In polishing fluid of the present invention, can also other conventional additives of this area be contained, as one or more in pH adjusting agent, viscosity modifier, defoamer and/or sterilant.
Polishing fluid of the present invention can concentrate preparation as required, dilutes and add oxygenant to mix before using with deionized water.Agents useful for same of the present invention and raw material are all commercially.
Positive progressive effect of the present invention is: can still keep higher polishing speed after use polishing pad scavenging solution.
Embodiment
preparation embodiment 1
Further illustrate the present invention by embodiment below, but the present invention is not limited.
Table 1 gives the embodiment 1 ~ 24 of chemical mechanical polishing liquid of the present invention, by table in give formula, other components except oxygenant are mixed, supply mass percent to 100% with water.With KOH or HNO
3be adjusted to required pH value.Use front oxidizer, mix.
Table 1 chemical mechanical polishing liquid embodiment 1 ~ 24 of the present invention
preparation embodiment 2
Table 2 gives contrast polishing fluid 1 ~ 2 and the preparation embodiment of polishing fluid of the present invention 25 ~ 28, by table 2 give formula, supply mass percent to 100% with water, other components except oxygenant mixed, with KOH or HNO
3be adjusted to required pH value.Use front oxidizer, mix.
Table 2 chemical mechanical polishing liquid embodiment 25 ~ 28 of the present invention and comparative example 1 ~ 2
effect example
Adopt the polishing fluid of comparative example 1 ~ 2 and the polishing fluid of the embodiment of the present invention 25 ~ 28 to carry out polishing to empty sheet copper (Cu) wafer, remove speed in table 3.
Polishing material: empty sheet copper wafer; Polishing condition: overdraft 3Psi, polishing disk and rubbing head rotating speed 70/80rpm, polishing pad PPGMX710, polishing fluid flow velocity 100ml/min, polishing machine platform is LogitechPM5Polisher.；
Polishing pad cleans: after 25 milliliters of polishing pad scavenging solution (1% citric acid) cleanings, then use 1 liter of washed with de-ionized water polishing pad.
Table 3 comparative example 1 ~ 2 and embodiment 25 ~ 28 polishing fluid are to the removal speed of metallic copper
From table 3, compared with the comparative example 1 ~ 2 of not adding the second complexing agent, after use polishing pad scavenging solution, the removal speed of copper significantly reduces.And after with the addition of the second complexing agent of different concns in the polishing fluid of embodiments of the invention 25 ~ 28, the removal speed of copper is substantially constant, and the removal speed of copper also can be kept constant after use polishing pad scavenging solution.
Claims (18)
1. a chemical mechanical polishing liquid, containing abrasive grains, corrosion inhibitor, oxygenant, the combination of water and following two kinds of complexing agents:
First complexing agent, containing amino compound and salt thereof;
Second complexing agent, organic acid and salt thereof.
2. polishing fluid according to claim 1, described is amino acid and/or polyamines containing amino compound.
3. polishing fluid according to claim 2, described amino acid be selected from glycine, L-Ala, α-amino-isovaleric acid, leucine, proline(Pro), phenylalanine, methionine(Met), Threonine, tyrosine, tryptophane, Methionin, arginine, Histidine, Serine, aspartic acid, L-glutamic acid, l-asparagine and/or glutamine one or more.
4. polishing fluid according to claim 2, described polyamines be selected from quadrol, diethylenetriamine, pentamethyl-diethylenetriamine, triethylene tetramine, tetraethylene pentamine and/or polyethylene polyamine one or more.
5. polishing fluid according to claim 1, described organic acid is organic carboxyl acid and/or organic phospho acid.
6. polishing fluid according to claim 5, described organic carboxyl acid be selected from acetic acid, oxalic acid, citric acid, tartrate, propanedioic acid, succinic acid, oxysuccinic acid, lactic acid, toxilic acid, gallic acid and/or sulphosalicylic acid one or more.
7. polishing fluid according to claim 5, described organic phospho acid is selected from 2-phosphonobutane-1, one or more in 2,4-tricarboxylic acid, Amino Trimethylene Phosphonic Acid, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid and/or polyamino polyether base methylenephosphonic acid.
8. polishing fluid according to claim 1, described salt be selected from sylvite, sodium salt and/or ammonium salt one or more.
9. polishing fluid according to claim 1, the described mass percentage containing amino compound and salt thereof is 0.01 ~ 10%.
10. polishing fluid according to claim 1, described organic acid and the mass percentage of salt thereof are 0.01 ~ 3%.
11. polishing fluids according to claim 1, described oxygenant be selected from hydrogen peroxide, urea peroxide, peroxyformic acid, Peracetic Acid, persulphate, percarbonate, Periodic acid, perchloric acid, high boric acid, potassium permanganate and/or iron nitrate one or more.
12. polishing fluids according to claim 1, the mass percentage of described oxygenant is 0.01 ~ 10%.
13. polishing fluids according to claim 1, described abrasive grains be selected from silicon-dioxide, aluminium sesquioxide, the silicon-dioxide of adulterated al, the silicon-dioxide of aluminium coating, cerium dioxide, titanium dioxide and/or polymer abrasive grains one or more.
14. polishing fluids according to claim 1, the mass percentage of described abrasive grains is 0.1 ~ 5%.
15. polishing fluids according to claim 1, the particle diameter of described abrasive grains is 20 ~ 150nm.
16. polishing fluids according to claim 1, described corrosion inhibition mass percentage is 0.001 ~ 5%.
17. polishing fluids according to claim 1, pH is 4 ~ 11.
18. polishing fluids according to claim 1, containing one or more in pH adjusting agent, viscosity modifier, defoamer and/or sterilant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410351205.4A CN105273636A (en) | 2014-07-23 | 2014-07-23 | Chemical mechanical polishing liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410351205.4A CN105273636A (en) | 2014-07-23 | 2014-07-23 | Chemical mechanical polishing liquid |
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|---|---|
| CN105273636A true CN105273636A (en) | 2016-01-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410351205.4A Pending CN105273636A (en) | 2014-07-23 | 2014-07-23 | Chemical mechanical polishing liquid |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107189695A (en) * | 2017-04-15 | 2017-09-22 | 浙江晶圣美纳米科技有限公司 | A kind of polishing fluid for being efficiently applied to stainless steel lining bottom CMP process |
| CN107267991A (en) * | 2017-06-28 | 2017-10-20 | 合肥博之泰电子科技有限公司 | A kind of polishing fluid and preparation method thereof |
| CN113122147A (en) * | 2019-12-31 | 2021-07-16 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing solution and use method thereof |
| CN116144323A (en) * | 2022-12-15 | 2023-05-23 | 上海应用技术大学 | Composite microsphere with mesoporous core-shell structure for copper CMP, preparation method thereof, chemical mechanical polishing solution and application thereof |
-
2014
- 2014-07-23 CN CN201410351205.4A patent/CN105273636A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107189695A (en) * | 2017-04-15 | 2017-09-22 | 浙江晶圣美纳米科技有限公司 | A kind of polishing fluid for being efficiently applied to stainless steel lining bottom CMP process |
| CN107267991A (en) * | 2017-06-28 | 2017-10-20 | 合肥博之泰电子科技有限公司 | A kind of polishing fluid and preparation method thereof |
| CN113122147A (en) * | 2019-12-31 | 2021-07-16 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing solution and use method thereof |
| CN113122147B (en) * | 2019-12-31 | 2024-03-12 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing solution and application method thereof |
| CN116144323A (en) * | 2022-12-15 | 2023-05-23 | 上海应用技术大学 | Composite microsphere with mesoporous core-shell structure for copper CMP, preparation method thereof, chemical mechanical polishing solution and application thereof |
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Application publication date: 20160127 |