CN102560510A - Cleaning solution for metal corrosion resistance - Google Patents
Cleaning solution for metal corrosion resistance Download PDFInfo
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- CN102560510A CN102560510A CN2010105821302A CN201010582130A CN102560510A CN 102560510 A CN102560510 A CN 102560510A CN 2010105821302 A CN2010105821302 A CN 2010105821302A CN 201010582130 A CN201010582130 A CN 201010582130A CN 102560510 A CN102560510 A CN 102560510A
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- scavenging solution
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- ether
- scavenging
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- 238000004140 cleaning Methods 0.000 title abstract description 20
- 230000007797 corrosion Effects 0.000 title abstract description 11
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- Cleaning Or Drying Semiconductors (AREA)
Abstract
The invention discloses a cleaning solution for metal corrosion resistance. The cleaning solution for metal corrosion resistance contains at least one phosphate surfactant. The cleaning solution for metal corrosion resistance can prevent corrosion or corrosive pitting of metal in cleaning, and effectively remove polishing residues.
Description
Technical field
The present invention relates to a kind of anticorrosion scavenging solution that is used for metal.
Background technology
Development along with microelectronics; The very large scale integration chip integration has reached tens components and parts; Characteristic dimension has got into nano level, and this just requires hundreds of procedure, especially multilayer wiring, substrate, medium in the microelectronic technique must pass through chemical-mechanical planarization.After chemical mechanical planarization, can remain on the surface of wafer by the pollutent that reaction product constituted in particle, chemicaladditives and the polishing process of polishing slurries.These pollutents must clean up before entering into next step, to avoid reducing the safety of device.For metallic substance, also want and can in cleaning process, do not corroded by the protective money metal surface, avoid producing defective and cause the performance of semiconductor device variation.
Typical scavenging solution mainly is deionized water, superoxol and weak ammonia etc. in the prior art, and these scavenging solutions are mainly used in the debris of cleaning in the preorder technology.This preorder technology is such as being: 1) CMP process, through the residual a spot of polishing fluid of the meeting of the metallic surface after the chemically machinery polished; 2) etching is gone high light resistance technology, also can residually go the high light blocking solution after this technology; 3) depositing operation and other technologies or the like.After debris wherein is cleaned totally, but the corrosion of metallic surface still exists.The corrosion of metallic surface can influence the metallic surface Flatness, also makes defect level high, thereby reduces product yield and earning rate.
Certain cleaning liquid is disclosed, like U.S. Pat 2004/0204329, US2003/0216270, US2004/0082180; US6147002, US6443814, US6719614; US6767409, US6482749 etc., it all is the method for use about scavenging solution or scavenging solution.Like the scavenging solution among the patent US6147002 is the scavenging solution about a kind of acidic aqueous solution, and it also comprises the fluorine-containing material of 0.5～5 weight %, and this scavenging solution is suitable for cleaning the ic component of copper metal semiconductor wafer.But the scavenging solution in the above-mentioned patent, or contain toxicant, unfriendly to environment; Or the high inadequately defective of cleaning efficiency; Or the cleaning use range is narrow, and for example the scavenging solution of US6443814 patent is merely able to clean the wafer of copper-containing metal layer.
Summary of the invention
In order to address the above problem, the present invention proposes a kind of new anti-corrosion of metal scavenging solution.
The present invention has disclosed and has cleaned after the new chemically machinery polished that is used for metal level and other relate to the scavenging solution that the metallic surface is cleaned.This scavenging solution contains one or more phosphoric acid ester tensio-active agents at least.
In detail in fact, concrete grammar of the present invention is in scavenging solution, to have added one or more phosphoric acid ester tensio-active agents.Described phosphoric acid ester tensio-active agent has following structure:
Wherein R is alkyl or korenyl, the glyceryl (C of C8～C22
3H
5O
3-) etc.; N=3～30, M=H, K, NH
4, (CH
2CH
2O)
1～3NH
3～1And/or Na.
The content of the phosphoric acid ester tensio-active agent described in the present invention is weight percentage 0.0005～2%, is preferably 0.001～1%.
Can also contain metal chelating agent among the present invention, described metal chelating agent is ammonia carboxylation compound and salt, organic carboxyl acid and salt thereof, organic phospho acid and salt thereof, organic amine.Be specially glycocoll, L-Ala, Xie Ansuan, leucine, proline(Pro), phenylalanine(Phe), tyrosine, tryptophane, Methionin, l-arginine, Histidine, Serine, aspartic acid, L-glutamic acid, Threonine, l-asparagine, Stimulina, nitrilotriacetic acid(NTA), YD 30, hexanaphthene tetraacethyl, EDDS, diethylene triamine pentacetic acid (DTPA) and triethylenetetramine hexaacetic acid, acetic acid, oxalic acid, Hydrocerol A, tartrate, propanedioic acid, Succinic Acid, toxilic acid, oxysuccinic acid, lactic acid, gallic acid and sulphosalicylic acid, 2-phosphonic acids butane-1; 2,4-tricarboxylic acid, ATMP, HEDP, ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid, ethylene diamine tetra methylene phosphonic acid, polyamino polyether base methylenephosphonic acid, quadrol, carbinolamine, thanomin, diethylenetriamine, pentamethyl-diethylenetriamine, polyethylene polyamine, triethylene tetramine, TEPA etc.Described salt is one or more of sylvite, sodium salt and/or ammonium salt; The content of described complexing agent is mass percent 0.01～10%.
Other amount waters are supplied.
Scavenging solution pH of the present invention is 2-11.
In the scavenging solution of the present invention, can also contain alcohols and/or ether equal solvent, said alcohols is ethanol, terepthaloyl moietie, USP Kosher, and said ether is ethylene glycol monomethyl ether, ethylene glycol bisthioglycolate monomethyl ether, propylene glycol monomethyl ether and/or dihydroxypropane single-ether.The content of described alcohol and/or ether is mass percent 0.5～10%.
Also contain the conventional additive in this areas such as pH regulator agent, viscosity modifier, skimmer and sterilant in the scavenging solution of the present invention and reach cleaning performance.
Scavenging solution of the present invention can prepare concentrating sample, is diluted to concentration range of the present invention with deionized water before use.
Use scavenging solution of the present invention can effectively remove the polishing residue, prevent the integral body and the local corrosion of metallic substance, defective is obviously descended, improve surface quality.
Description of drawings
Accompanying drawing 1～8 is for soaking back aluminium surface optical microscope figure, and wherein Fig. 1 is contrast 1, and Fig. 2 is contrast 2, and Fig. 3～8 are embodiment 53～58.
Accompanying drawing 9～12 is for cleaning back copper graphical wafer surface optical microscope figure, and wherein Fig. 9 is contrast 3, and Figure 10～12 are embodiment 59～61.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.
Embodiment 1～52
Table 1 has provided the embodiment 1～52 of scavenging solution of the present invention, by the prescription of giving in the table, component is mixed, and water is supplied mass percent to 100%.With KOH or HNO
3Be adjusted to needed pH value.
Table 1 embodiment 1～52
Effect embodiment 1
Table 2 has provided comparative example 1～2 and scavenging solution embodiment 53～58 components of the present invention, by the prescription of giving in the table, all components is mixed, and water is supplied mass percent to 100%, with KOH or HNO
3Be adjusted to needed pH value.
Empty sheet aluminium (Al) wafer is put into comparative example 1～2 soak with scavenging solution embodiment 53～58 of the present invention, soak time 30 minutes, with the condition of surface that observation by light microscope soaks back aluminium wafer, its condition of surface is seen table 2 and Fig. 1～8.
The condition of surface of table 2 comparative example 1～2 aluminium wafer with scavenging solution 53～58 components of the present invention and after soaking
Visible by Fig. 1～8; Compare with the comparative example who does not add SULPHOSUCCINIC ACID ESTER 1～2; Added the phosphate ester surfactants of different amounts among the embodiment 53～58; Can improve and prevent the spot corrosion and the corrosion of aluminium wafer effectively, prevent in cleaning process, to produce metallic corrosion, improve the surface quality after cleaning simultaneously.
Effect embodiment 2
Table 3 has provided comparative example 3 and scavenging solution embodiment 59～61 components of the present invention, by the prescription of giving in the table, all components is mixed, and water is supplied mass percent to 100%, with KOH or HNO
3Be adjusted to needed pH value.
Copper wafer with the band figure behind comparative example 3 and scavenging solution embodiment 59～61 cleaning polishings of the present invention; Cleaning condition is: scrubbed 1 minute with scavenging solution; Scrub with deionized water then and dry up with nitrogen after 1 minute, used cleaning brush is the Z 150PH brush.With its surface contaminant Restzustand of observation by light microscope.Cleaning performance is seen table 3 and Fig. 9～12.
The condition of surface of the copper graphical wafer after table 2 comparative example 3 cleans with scavenging solution 59～61 components of the present invention and with it
Visible by Fig. 9～12, the copper graphical wafer after the polishing can not effectively be removed the polishing fluid residue after cleaning with Comparative Examples 3 (deionized water).And after using the scavenging solution that has added SULPHOSUCCINIC ACID ESTER to clean, can effectively remove the polishing fluid residue.The adding of complexing agent helps the metal remained ion remaval.
Claims (11)
1. an anti-corrosion of metal scavenging solution is characterized in that, contains one or more phosphoric acid ester tensio-active agents at least.
2. scavenging solution according to claim 1 is characterized in that described phosphoric acid ester tensio-active agent has following structure:
Wherein R is alkyl or korenyl, the glyceryl (C of C8～C22
3H
5O
3-); N=3～30, M=H, K, NH
4, (CH
2CH
2O)
1～3NH
3～1And/or Na.
3. like the said scavenging solution of claim 2, it is characterized in that the content of described phosphoric acid ester tensio-active agent is weight percentage 0.0005～2%.
4. like the said scavenging solution of claim 3, it is characterized in that the content of described phosphoric acid ester tensio-active agent is weight percentage 0.001～1%
5. scavenging solution according to claim 1 is characterized in that said scavenging solution also contains metal chelating agent, and described metal chelating agent is ammonia carboxylation compound and salt, organic carboxyl acid and salt thereof, organic phospho acid and salt thereof, organic amine.
6. like the said scavenging solution of claim 5; It is characterized in that; Said metal chelating agent is glycocoll, L-Ala, Xie Ansuan, leucine, proline(Pro), phenylalanine(Phe), tyrosine, tryptophane, Methionin, l-arginine, Histidine, Serine, aspartic acid, Threonine, L-glutamic acid, l-asparagine, Stimulina, nitrilotriacetic acid(NTA), YD 30, hexanaphthene tetraacethyl, EDDS, diethylene triamine pentacetic acid (DTPA) and triethylenetetramine hexaacetic acid, acetic acid, oxalic acid, Hydrocerol A, tartrate, propanedioic acid, Succinic Acid, toxilic acid, oxysuccinic acid, lactic acid, gallic acid and sulphosalicylic acid, 2-phosphonic acids butane-1; 2; 4-tricarboxylic acid, ATMP, HEDP, ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid, ethylene diamine tetra methylene phosphonic acid and polyamino polyether base methylenephosphonic acid, quadrol, carbinolamine, thanomin, diethylenetriamine, pentamethyl-diethylenetriamine, polyethylene polyamine, triethylene tetramine, TEPA, described salt is one or more of sylvite, sodium salt and/or ammonium salt;
7. like claim 5 or 6 described scavenging solutions, it is characterized in that the content of described complexing agent is mass percent 0.01～10%.
8. scavenging solution according to claim 1 is characterized in that said scavenging solution also contains alcohols and/or ether.
9. like the said scavenging solution of claim 8, it is characterized in that said alcohols is that ethanol, terepthaloyl moietie, USP Kosher, said ether are ethylene glycol monomethyl ether, ethylene glycol bisthioglycolate monomethyl ether, propylene glycol monomethyl ether and/or dihydroxypropane single-ether.
10. like the said scavenging solution of claim 8, it is characterized in that the content of described alcohol and/or ether is mass percent 0.5～10%.
11. scavenging solution is characterized in that according to claim 1, said scavenging solution pH is 2-11.
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| CN103253778A (en) * | 2013-05-09 | 2013-08-21 | 陕西省石油化工研究设计院 | Steam condensate corrosion inhibitor for industrial boiler |
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| CN104862709A (en) * | 2015-04-28 | 2015-08-26 | 安徽不二越精工轴承有限公司 | Steel material anticorrosion conditioning fluid |
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| CN105696008A (en) * | 2016-02-18 | 2016-06-22 | 东莞市伟思化学科技有限公司 | Ultrasonic water-based cleaning fluid for hardware products and preparation method thereof |
| CN106591815A (en) * | 2016-10-31 | 2017-04-26 | 无锡市永兴金属软管有限公司 | Preparing method of antiseptic treatment liquid of metal bellows |
| CN109536972A (en) * | 2018-12-20 | 2019-03-29 | 新沂肽科生物科技有限公司 | A kind of intermetallic composite coating product surface cleansing composition and its preparation and application |
| CN113130292A (en) * | 2019-12-31 | 2021-07-16 | 安集微电子科技（上海）股份有限公司 | Plasma etching residue cleaning solution |
| CN112143574A (en) * | 2020-09-30 | 2020-12-29 | 常州时创新材料有限公司 | Cleaning solution used after CMP in IC copper process and preparation method thereof |
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