CN102051283B - Hydroxylamine-containing cleaning solution and use thereof - Google Patents
Hydroxylamine-containing cleaning solution and use thereof Download PDFInfo
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- CN102051283B CN102051283B CN200910197954.5A CN200910197954A CN102051283B CN 102051283 B CN102051283 B CN 102051283B CN 200910197954 A CN200910197954 A CN 200910197954A CN 102051283 B CN102051283 B CN 102051283B
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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 in the specification. 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 containing azanol.
Background technology
In semiconductor components and devices manufacturing processed, the coating of photoresist layer, exposure and imaging are necessary processing steps to the pattern manufacture of components and parts.Before last (after coating, imaging, implanted ions and the etching at photoresist layer) of patterning carries out next processing step, the residue of photoresist layer material need thoroughly be removed.Can sclerosis photoresist layer polymkeric substance in the bombardment of doping step intermediate ion, thus therefore make photoresist layer not soluble being more difficult to that become remove.So far in semi-conductor industry, the general two-step approach (dry ashing and wet etching) of using is removed this layer of photoresistance tunic.The first step utilizes dry ashing to remove the major part of photoresist layer (PR); Second step utilizes 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 as aluminium lamination.
In current wet clean process, scavenging solution with the most use is the scavenging solution that contains azanol class, the exploitation of the at present main Shi You EKCHeACTLiang of this based cleaning liquid company, and occupy the larger 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 toxic substance, in many countries, has started restriction and used.So along with environmental consciousness strengthens, increasing company wishes can be with do not remove to carry out the removing residues of photoresist layer material containing the hydroxylamine containing solutions of pyrocatechol, to guarantee operator's health and better operating environment.
Summary of the invention
The object of the invention is to overcome the above-mentioned scarce filling existing in prior art.The scavenging solution containing azanol that a kind of comparatively environmental protection is provided, this scavenging solution has kept the cleansing power of traditional azanol based cleaning liquid, simultaneously less to metal and nonmetallic erosion rate.
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%;
In the present invention, described solvent can be selected from one or more in sulfoxide, sulfone, imidazolidone, pyrrolidone, imidazolone, ether, acid amides and hydramine, preferably hydramine.Wherein, described sulfoxide is preferably dimethyl sulfoxide (DMSO); Described sulfone is preferably tetramethylene sulfone; Described imidazolidone is preferably 1,3-dimethyl-2-imidazolidone; Described pyrrolidone is preferably N-Methyl pyrrolidone; Described imidazolone is preferably DMI (DMI); Described acid amides is preferably dimethyl formamide; Described ether is preferably propylene glycol monomethyl ether, dipropylene glycol monomethyl ether.Described hydramine is preferably monoethanolamine, diethanolamine, trolamine, α-amino isopropyl alcohol, 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 refers to the organism that contains following structure.
Wherein: substituent R 1, R2, R3, R4 can be hydrogen atom independently, hydroxyl, thiol group, the organic substituent of carboxyl, sulfonic group, C1-C6.Preferred R1, R2, R3, in R4, having two or more substituting groups is the mercaptan benzothiazole type organic of hydroxyl.
Scavenging solution of the present invention can be made by the simple evenly mixing of mentioned component.
Scavenging solution of the present invention is used for removing photoresist layer residue, and after by etch residue on photoresistance scavenging solution removal wafer, rinsing is afterwards also dry.
Positive progressive effect of the present invention is: by adding mercaptan benzothiazole type organic, successfully substituted the toxic substance pyrocatechol using in traditional azanol based cleaning liquid, retained the stronger cleansing power of current azanol based cleaning liquid, simultaneously less to metal and nonmetallic erosion rate; Comparatively friendly to environment, be conducive to guarantee operator's health and better operating environment.
Embodiment
With embodiment, further illustrate the present invention below.
Embodiment 1～20
Table 1 embodiment 1～20
In order to further illustrate effect of the present invention, we have selected some embodiment, have tested metallic aluminium, and the erosion rate of the silicon-dioxide (PETEOS) that nonmetal plasma body strengthens 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 the resistance initial value (Rs1) of the blank silicon chip of Napson four-point probe instrument test 4*4cm aluminium;
2) the blank silicon chip of this 4*4cm aluminium is immersed in advance to constant temperature by the solution of design temperature 60 minutes;
3) take out the blank silicon chip of this 4*4cm aluminium, after rinsing, high pure nitrogen dries up, the resistance value (Rs2) of the blank silicon chip of recycling Napson four-point probe instrument test 4*4cm aluminium;
4) above-mentioned resistance value and soak time are input to suitable program computability and go out its erosion rate.
The nonmetal erosion rate testing method of solution:
1) utilize the thickness (T1) of Nanospec6100 thickness tester test 4*4cm PETEOS silicon chip;
2) this 4*4cmPETEOS silicon chip is immersed in advance to constant temperature by the solution of design temperature 60 minutes;
3) take out this 4*4cmPETEOS silicon chip, after rinsing, high pure nitrogen dries up, the thickness (T2) of recycling Nanospec6100 thickness tester test 4*4cmPETEOS silicon chip;
4) above-mentioned one-tenth-value thickness 1/10 and soak time are input to suitable program computability and go out its erosion rate.
The method of wafer cleaning:
1) wafer to be cleaned is put in advance to 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, after rinsing, high pure nitrogen dries up; 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 metal (as metallic aluminium) and nonmetal (as PETEOS) used substantially can not corrode, the equal major part of its erosion rate is less than conventionally desired 2 dust per minutes of semi-conductor industry.With this solution article on plasma etch residue, clean discovery, its plasma etching residues is all removed, and there is no 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) provide a kind of comparatively environmental protection and kept the cleansing power semiconductor crystal wafer scavenging solution of traditional azanol based cleaning liquid.Be conducive to guarantee operator's health and better operating environment;
2) it is less to metal and nonmetallic erosion rate.
Claims (6)
1. containing the scavenging solution of azanol, by solvent, azanol, mercaptan benzothiazole type organic forms, and described solvent comprises water and other solvent, and the mass percentage content of wherein said other 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%, and described mercaptan benzothiazole type organic contains following structure:
Described substituent R 1, R2, R3, R4 is independently selected from hydrogen atom, hydroxyl, thiol group, a kind of in carboxyl and sulfonic group.
2. scavenging solution as claimed in claim 1, is characterized in that, described other solvent is selected from one or more in sulfoxide, sulfone, imidazolidone, pyrrolidone, imidazolone, ether, acid amides and hydramine.
3. scavenging solution as claimed in claim 2, is characterized in that, described sulfoxide is dimethyl sulfoxide (DMSO); Described sulfone is tetramethylene sulfone; Described imidazolidone is 1,3-dimethyl-2-imidazolidone; Described pyrrolidone is N-Methyl pyrrolidone; Described imidazolone is DMI; Described acid amides is dimethyl formamide; Described ether is propylene glycol monomethyl ether and/or dipropylene glycol monomethyl ether; Described hydramine is for being selected from one or more in monoethanolamine, diethanolamine, trolamine, α-amino isopropyl alcohol, 2-(diethylin) ethanol, ethyldiethanolamine and diglycolamine.
4. scavenging solution as claimed in claim 2, is characterized in that, described other solvent is selected from one or more in monoethanolamine, diethanolamine, trolamine, α-amino isopropyl alcohol, 2-(diethylin) ethanol, ethyldiethanolamine and diglycolamine.
5. scavenging solution as claimed in claim 1, is characterized in that, described substituent R 1, and R2, R3, has in R4 and is no less than the mercaptan benzothiazole type organic that the substituting group of two is hydroxyl.
6. the application of scavenging solution for removing photoresist layer residue as described in claim 1～5 any one.
Priority Applications (1)
| 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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| Publication Number | Publication Date |
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| CN102051283A CN102051283A (en) | 2011-05-11 |
| CN102051283B true CN102051283B (en) | 2014-11-05 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114350454B (en) * | 2022-01-17 | 2022-10-18 | 嘉庚创新实验室 | Polyfunctional group metal corrosion inhibitor, 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999060083A1 (en) * | 1998-05-19 | 1999-11-25 | Arch Specialty Chemicals, Inc. | Cleaning composition and method for removing residues |
| CN1277682A (en) * | 1998-03-03 | 2000-12-20 | 硅谷化学实验室公司 | Composition and method for removing resist and etching residues using hydroxylammonium carboxylates |
| CN1813223A (en) * | 2003-05-23 | 2006-08-02 | 空气产品及化学制品股份有限公司 | Compositions suitable for removing photoresist, photoresist byproducts and etching residue, and use thereof |
| 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 |
| CN101371199A (en) * | 2005-08-13 | 2009-02-18 | 韩国泰科诺赛美材料株式会社 | Photoresist stripper composition for semiconductor manufacturing |
-
2009
- 2009-10-30 CN CN200910197954.5A patent/CN102051283B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1277682A (en) * | 1998-03-03 | 2000-12-20 | 硅谷化学实验室公司 | Composition and method for removing resist and etching residues using hydroxylammonium carboxylates |
| WO1999060083A1 (en) * | 1998-05-19 | 1999-11-25 | Arch Specialty Chemicals, Inc. | Cleaning composition and method for removing residues |
| CN1813223A (en) * | 2003-05-23 | 2006-08-02 | 空气产品及化学制品股份有限公司 | Compositions suitable for removing photoresist, photoresist byproducts and etching residue, and use thereof |
| CN101371199A (en) * | 2005-08-13 | 2009-02-18 | 韩国泰科诺赛美材料株式会社 | 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 |
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