CN102051283A - Hydroxylamine-containing cleaning solution and use thereof - Google Patents
Hydroxylamine-containing cleaning solution and use thereof Download PDFInfo
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- CN102051283A CN102051283A CN 200910197954 CN200910197954A CN102051283A CN 102051283 A CN102051283 A CN 102051283A CN 200910197954 CN200910197954 CN 200910197954 CN 200910197954 A CN200910197954 A CN 200910197954A CN 102051283 A CN102051283 A CN 102051283A
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Abstract
The invention discloses hydroxylamine-containing cleaning solution and use thereof. The cleaning solution is characterized by containing solvent, water, hydroxylamine and 2-mercaptobenzothiazole organic matters. The general structural formula of the 2-mercaptobenzothiazole organic matters is shown below. The cleaning solution retains the strong cleaning capability of the conventional hydroxylamine cleaning solution and has a small metal and nonmetal corrosion rate. The novel cleaning solution has a bright application prospect in field of microelectronics such as metal cleaning and semiconductor chip cleaning.
Description
Technical field
The present invention relates to a kind of scavenging solution and application thereof that contains azanol.
Background technology
In the semiconductor components and devices manufacturing processed, the coating of photoresist layer, exposure and imaging are necessary process steps to the pattern manufacturing of components and parts.Before last (promptly after coating, imaging, ion implantation and the etching at photoresist layer) of patterning carried out next processing step, the residue of photoresist layer material need thoroughly be removed.Can sclerosis photoresist layer polymkeric substance in doping step intermediate ion bombardment, thus therefore making photoresist layer become to be difficult for dissolving more is difficult to remove.So far the general two-step approach (dry ashing and wet etching) of using is removed this layer photoresistance tunic in semi-conductor industry.The first step utilizes dry ashing to remove the major part of photoresist layer (PR); Second step utilized composite corrosion inhibitor wet etching/cleaning to remove and wash remaining photoresist layer, and its step is generally scavenging solution cleaning/rinsing/rinsed with deionized water.In this process, can only remove residual polymkeric substance photoresist layer and inorganics, and can not attack infringement metal level such as aluminium lamination.
In present wet clean process, scavenging solution with the most use is the scavenging solution that contains the azanol class, and this based cleaning liquid mainly is that EKC and the exploitation of ACT two companies are arranged at present, and occupies the bigger market share.Its typical patent has US6110881, US6319885, US5672577, US6030932, US6825156 and US5419779 etc.The principal character of this based cleaning liquid is to use pyrocatechol as one of its main ingredient; And pyrocatechol is a toxic substance, has begun restriction in many countries and has used.So along with environmental consciousness strengthens, increasing company wishes to go to carry out with the hydroxylamine containing solutions that does not contain pyrocatechol the removing residues of photoresist layer material, with health and the better operating environment that guarantees operator.
Summary of the invention
The objective of the invention is to overcome the above-mentioned scarce filling that exists in the prior art.A kind of scavenging solution that contains azanol of comparatively environmental protection is provided, and this scavenging solution has kept the cleansing power of traditional azanol based cleaning liquid, and is less to metal and nonmetallic erosion rate simultaneously.
Scavenging solution of the present invention contains:
1) solvent: 10～80%;
2) water: 10～45%;
3) azanol: 1～40%;
4) mercaptan benzothiazole type organic: 0.1～10%;
Among the present invention, described solvent can be selected from one or more in sulfoxide, sulfone, imidazolidone, pyrrolidone, imidazolone, ether, acid amides and the hydramine, preferred hydramine.What wherein, described sulfoxide was preferable is dimethyl sulfoxide (DMSO); What described sulfone was preferable is tetramethylene sulfone; What described imidazolidone was preferable is 1,3-dimethyl-2-imidazolidone; What described pyrrolidone was preferable is N-Methyl pyrrolidone; What described imidazolone was preferable is 1,3-dimethyl-2-imidazolone (DMI); What described acid amides was preferable is dimethyl formamide; What described ether was preferable is propylene glycol monomethyl ether, dipropylene glycol monomethyl ether.What described hydramine was preferable is monoethanolamine, diethanolamine, trolamine, Yi Bingchunan, 2-(diethylin) ethanol, ethyldiethanolamine and diglycolamine.
The present invention also further comprises water.
The present invention also further comprises azanol.
In the present invention, described mercaptan benzothiazole type organic is meant the organism that contains following structure.
Wherein: substituent R 1, R2, R3, R4 can be a hydrogen atom independently, hydroxyl, thiol group, the organic substituent of carboxyl, sulfonic group, C1-C6.Preferred R1, R2, R3, it is the mercaptan benzothiazole type organic of hydroxyl that two or more substituting groups are arranged among the R4.
Scavenging solution of the present invention can be made by the simple uniform mixing of mentioned component.
Scavenging solution of the present invention is used to remove the photoresist layer residue, after etch residue on the usefulness photoresistance scavenging solution removal wafer, and rinsing afterwards and dry getting final product.
Positive progressive effect of the present invention is: by adding the mercaptan benzothiazole type organic, successfully substituted the toxic substance pyrocatechol that uses in traditional azanol based cleaning liquid, kept the stronger cleansing power of present azanol based cleaning liquid, less to metal and nonmetallic erosion rate simultaneously; Comparatively friendly to environment, help guaranteeing operator's health and better operating environment.
Embodiment
Further specify the present invention with embodiment below.
Embodiment 1～20
Table 1 embodiment 1～20
In order to further specify effect of the present invention, we have selected some embodiment, have tested metallic aluminium, and the erosion rate of nonmetal plasma body enhanced silicon-dioxide (PETEOS) is also cleaned three kinds of dissimilar wafers, and it the results are shown in Table 2.
The rate of metal corrosion testing method of solution:
1) utilize Napson four-point probe instrument to test the resistance initial value (Rs1) of the blank silicon chip of 4*4cm aluminium;
2) the blank silicon chip of this 4*4cm aluminium is immersed in advance constant temperature in the solution of design temperature 60 minutes;
3) take out the blank silicon chip of this 4*4cm aluminium, high pure nitrogen dries up after the rinsing, utilizes the resistance value (Rs2) of the blank silicon chip of Napson four-point probe instrument test 4*4cm aluminium again;
4) above-mentioned resistance value and soak time are input to suitable procedure and can calculate its erosion rate.
The nonmetal erosion rate testing method of solution:
1) utilize the Nanospec6100 thickness tester to test the thickness (T1) of 4*4cm PETEOS silicon chip;
2) this 4*4cmPETEOS silicon chip is immersed in advance constant temperature in the solution of design temperature 60 minutes;
3) take out this 4*4cmPETEOS silicon chip, high pure nitrogen dries up after the rinsing, utilizes the thickness (T2) of Nanospec6100 thickness tester test 4*4cmPETEOS silicon chip again;
4) above-mentioned one-tenth-value thickness 1/10 and soak time are input to suitable procedure and can calculate its erosion rate.
The method that wafer cleans:
1) wafer to be cleaned is put in advance constant temperature to the solution of design temperature;
2) principle of soaking 30 minutes according to metal wire immersion 20 minutes, passage and metal gasket is soaked wafer;
3) after soak time arrives, take out this wafer, high pure nitrogen dries up after the rinsing; Send SEM test.
The guide look of table 2 part embodiment The performance test results
As can be seen from Table 2: cleaning liquid composition of the present invention during semi-conductor is made used metal (as metallic aluminium) and nonmetal (as PETEOS) can not corrode substantially, its erosion rate is all most of less than semi-conductor industry desired 2 dust per minutes usually.Clean discovery with this solution article on plasma etch residue, its plasma etching residues all is removed, and does not have corroding metal and nonmetal.Illustrate that scavenging solution of the present invention has lower metal and nonmetallic erosion rate, can clean metal wire, passage and three kinds of wafers of metal gasket simultaneously.
To sum up, positive progressive effect of the present invention is:
1) provides a kind of comparatively environmental protection and kept the cleansing power semiconductor crystal wafer cleaning fluid of traditional azanol based cleaning liquid. Be conducive to guarantee operating personnel's health and better operating environment;
2) it is littler to metal and nonmetallic corrosion rate.
Claims (9)
1. scavenging solution that contains azanol, it contains: solvent, water, azanol, mercaptan benzothiazole type organic.
2. scavenging solution as claimed in claim 1 is characterized in that, the mass percentage content of described solvent is 10～80%; The mass percentage content of described water is 10～45%; The mass percentage content of described azanol is 1～40%; The mass percentage content of described mercaptan benzothiazole type organic is 0.1～10%.
3. scavenging solution as claimed in claim 1 is characterized in that described solvent is selected from one or more in sulfoxide, sulfone, imidazolidone, pyrrolidone, imidazolone, ether, acid amides and the hydramine.
4. scavenging solution as claimed in claim 3 is characterized in that, described sulfoxide is a dimethyl sulfoxide (DMSO); Described sulfone is a tetramethylene sulfone; Described imidazolidone is 1,3-dimethyl-2-imidazolidone; Described pyrrolidone is a N-Methyl pyrrolidone; Described imidazolone is 1,3-dimethyl-2-imidazolone; Described acid amides is a dimethyl formamide; Described ether is propylene glycol monomethyl ether and/or dipropylene glycol monomethyl ether; Described hydramine is for being selected from monoethanolamine, diethanolamine, trolamine, Yi Bingchunan, 2-(diethylin) ethanol, ethyldiethanolamine and the diglycolamine one or more.
5. scavenging solution as claimed in claim 3 is characterized in that, described solvent is selected from one or more in monoethanolamine, diethanolamine, trolamine, Yi Bingchunan, 2-(diethylin) ethanol, ethyldiethanolamine and the diglycolamine.
6. scavenging solution as claimed in claim 1 is characterized in that, described mercaptan benzothiazole type organic contains following structure:
7. scavenging solution as claimed in claim 6 is characterized in that, described substituent R 1, and R2, R3, R4 is independently selected from hydrogen atom, hydroxyl, thiol group, one or more in carboxyl and the sulfonic group.
8. scavenging solution as claimed in claim 7 is characterized in that, described substituent R 1, and R2, R3, it is the mercaptan benzothiazole type organic of hydroxyl that two or more substituting groups are arranged among the R4.
9. as claim 1～8 application that scavenging solution is used to remove the photoresist layer residue as described in each.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910197954.5A CN102051283B (en) | 2009-10-30 | 2009-10-30 | Hydroxylamine-containing cleaning solution and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910197954.5A CN102051283B (en) | 2009-10-30 | 2009-10-30 | Hydroxylamine-containing cleaning solution and use thereof |
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| CN102051283A true CN102051283A (en) | 2011-05-11 |
| CN102051283B CN102051283B (en) | 2014-11-05 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107765514A (en) * | 2017-11-17 | 2018-03-06 | 上海新阳半导体材料股份有限公司 | A kind of cleaning fluid containing azanol, its preparation method and application |
| TWI749964B (en) * | 2020-12-24 | 2021-12-11 | 達興材料股份有限公司 | Alkaline cleaning composition, cleaning method, and manufacturing method of semiconductor |
| CN114350454A (en) * | 2022-01-17 | 2022-04-15 | 嘉庚创新实验室 | Polyfunctional group metal corrosion inhibitor, preparation method and application thereof |
| CN115595217A (en) * | 2022-10-08 | 2023-01-13 | 浙江奥首材料科技有限公司（Cn） | Stable solution containing hydroxylamine, semiconductor cleaning solution containing hydroxylamine, preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6030932A (en) * | 1996-09-06 | 2000-02-29 | Olin Microelectronic Chemicals | Cleaning composition and method for removing residues |
| US6432209B2 (en) * | 1998-03-03 | 2002-08-13 | Silicon Valley Chemlabs | Composition and method for removing resist and etching residues using hydroxylazmmonium carboxylates |
| US6951710B2 (en) * | 2003-05-23 | 2005-10-04 | Air Products And Chemicals, Inc. | Compositions suitable for removing photoresist, photoresist byproducts and etching residue, and use thereof |
| KR100718532B1 (en) * | 2005-08-13 | 2007-05-16 | 테크노세미켐 주식회사 | Photoresist stripper composition for semiconductor manufacturing |
| CN101201557A (en) * | 2006-12-15 | 2008-06-18 | 安集微电子（上海）有限公司 | Detergent for cleaning thick film photoresist |
-
2009
- 2009-10-30 CN CN200910197954.5A patent/CN102051283B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107765514A (en) * | 2017-11-17 | 2018-03-06 | 上海新阳半导体材料股份有限公司 | A kind of cleaning fluid containing azanol, its preparation method and application |
| CN107765514B (en) * | 2017-11-17 | 2019-03-05 | 上海新阳半导体材料股份有限公司 | One kind cleaning solution containing azanol, preparation method and application |
| TWI749964B (en) * | 2020-12-24 | 2021-12-11 | 達興材料股份有限公司 | Alkaline cleaning composition, cleaning method, and manufacturing method of semiconductor |
| CN114350454A (en) * | 2022-01-17 | 2022-04-15 | 嘉庚创新实验室 | Polyfunctional group metal corrosion inhibitor, preparation method and application thereof |
| CN115595217A (en) * | 2022-10-08 | 2023-01-13 | 浙江奥首材料科技有限公司（Cn） | Stable solution containing hydroxylamine, semiconductor cleaning solution containing hydroxylamine, preparation method and application thereof |
| CN115595217B (en) * | 2022-10-08 | 2024-04-30 | 浙江奥首材料科技有限公司 | Stable solution containing hydroxylamine, semiconductor cleaning solution containing hydroxylamine, preparation method and application thereof |
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| CN102051283B (en) | 2014-11-05 |
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