CN101842747A - Corrosion inhibitor for semiconductor chip metal substrate and use method thereof - Google Patents
Corrosion inhibitor for semiconductor chip metal substrate and use method thereof Download PDFInfo
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- CN101842747A CN101842747A CN200880114829A CN200880114829A CN101842747A CN 101842747 A CN101842747 A CN 101842747A CN 200880114829 A CN200880114829 A CN 200880114829A CN 200880114829 A CN200880114829 A CN 200880114829A CN 101842747 A CN101842747 A CN 101842747A
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Abstract
A metal corrosion inhibitor for semiconductor chip includes polycarboxylic acid, polymer containing pigment affiliation group, and water. A method includes: residues on the semiconductor chip which is etched or etched/ashed is treated with cleaning composition, then semiconductor chip is directly cleaned with the metal corrosion inhibitor and dried. The metal corrosion inhibitor for semiconductor chip has low etch rate for metals, in particular for aluminum.
Description
A kind of corrosion inhibitor for semiconductor chip metal substrate and its application method technical field
The present invention relates to a kind of cleaning fluid in semiconductor manufacturing cleaning and its application method, a kind of corrosion inhibitor for semiconductor chip metal substrate and its application method are specifically related to.
Technical background
In semiconductor components and devices manufacturing process, coating, exposure and the imaging of photoresist layer are necessary processing steps for the pattern manufacture of component.In the last of patterning（Coating i.e. in photoresist layer, be imaged, be ion implanted and etch after）Carry out before next processing step, the residue of photoresistance layer material need to be removed thoroughly.Photoresist layer polymer can be hardened in doping step intermediate ion bombardment, hence in so that photoresist layer becomes to not readily dissolve to be more difficult to remove.So far two-step method is typically used in the semiconductor manufacturing industry（Dry ashing and wet etching）Remove this layer of photoresistance tunic.The first step removes the major part of photoresist layer (PR) using dry ashing.Second step removes remaining photoresist layer using composite corrosion inhibitor wet etching/cleaning, and its specific steps is generally cleaning fluid cleaning/rinsing/deionized water rinsing.In the process, the polymer light resistance layer and inorganic matter of residual can only be removed, and infringement metal level can not be attacked（Such as aluminium lamination）.
In current wet clean process, with more cleaning fluid is the cleaning fluid of the class containing azanol and the cleaning fluid of fluoride.In addition, also a small amount of be not only free of azanol but also not fluorine-containing cleaning fluid.The cleaning fluid of azanol class is due to larger to the corrosion rate of metallic aluminium when it is rinsed in water, after plasma etching thing has been cleaned, frequently with solvent rinse.Solvent used mainly has isopropanol and 1-METHYLPYRROLIDONE.The former has progressively been eliminated because flash-point is than relatively low, volatile in some Semiconductor Manufacturing Companies；And the latter because flash-point is higher, not volatile used always in a lot of Semiconductor Manufacturing Companies.But with environmental consciousness and cost pressure, increasing company wishes to directly be rinsed with deionized water, without causing corrosion of metal.For fluorine-containing cleaning fluid, when directly being rinsed with deionized water, its rate of metal corrosion has one has a high to Low curve again from low to high（As Fig. 1 shows）.
It is fast frequently with substantial amounts of water during reality in order to reduce corrosion of the rinsing to metal base
Speed rinsing, so as to faster speed and shorter time by the larger region of corrosion rate, to reduce corrosion of metal.And this often brings the problem of rinse cycle action pane is too small.
Brief summary of the invention
The technical problems to be solved by the invention are to solve the problems, such as the metal erosion in wet-cleaning rinse step, and provide a kind of with relatively low rate of metal corrosion, while environmentally friendly, cheap and easy to use corrosion inhibitor for semiconductor chip metal substrate and its application method.
The corrosion inhibitor for semiconductor chip metal substrate of the present invention contains：The polymer and water of carbonyl bearing polymer, the affinity groups containing pigment.
In the present invention, described metal base especially aluminium is such as applied to standard aluminum, Al-Si-Cu alloy or the aluminium copper aluminium alloy of semiconductor technology.
In the present invention, the one or more of described carbonyl bearing polymer preferably in carboxylic homopolymer, carboxylic homopolymer salt, carboxylic copolymer and carboxylic copolymer salt.
Wherein, described carboxylic homopolymer is preferably HPMA（HPMA), polyacrylic acid（PAA the one or more) and in polymethylacrylic acid, more preferably HPMA and/or polyacrylic acid.
Wherein, described carboxylic copolymer is preferably the copolymer of carboxyl group-containing monomer（Such as acrylic acid and the copolymer and/or methacrylic acid and the copolymer of maleic acid of maleic acid）And/or the copolymer of vinyl-containing monomers and carboxyl group-containing monomer（Such as the one or more in the copolymer of the copolymer of the copolymer of styrene and acrylic acid, the copolymer of styrene and maleic acid, acrylonitrile and maleic acid, the copolymer of ethene and acrylic acid, acrylonitrile and acrylic acid, the copolymer of styrene and methacrylic acid, ethene and the copolymer and acrylonitrile of methacrylic acid and the copolymer of methacrylic acid）.Wherein, the preferred copolymer of acrylic acid and maleic acid.
Wherein, described salt is the one or more in ammonium salt, sylvite and sodium salt；It is preferred that ammonium salt, such as ammonium polyacrylate（SD).
In the present invention, as long as existing carboxylic polymer is used equally for the corrosion inhibitor for semiconductor chip metal substrate of the present invention in the prior art, on condition that the polymer has certain solubility in water.
In general, carboxylic polymer molecular weight size has no effect on and realizes the purpose of the present invention.If having in the corrosion inhibitor for semiconductor chip metal substrate of the present invention also correspondingly has certain density carboxyl in the polymer of certain mass concentration, the corrosion inhibitor for semiconductor chip metal substrate.Because for the polymer of certain mass concentration, if the molecular weight of polymer is big, the molal quantity of polymer is just correspondingly few in corrosion inhibitor for semiconductor chip metal substrate；If the molecular weight of polymer is small, the molal quantity of polymer is also just correspondingly more in corrosion inhibitor for semiconductor chip metal substrate.That is, also just correspondingly containing certain density carboxyl on the certain polymer of composition, the polymer of its certain mass concentration.No matter the molecular size range of the polymer, as long as the carboxyl on the polymer reaches certain concentration in slow-releasing agent system.In the corrosion inhibitor for semiconductor chip metal substrate of the present invention, the content of described carbonyl bearing polymer is preferably mass percent 0.0001 ~ 3%.
In the present invention, described pigment affinity groups are preferably hydroxyl or amino.It is well known that carboxyl is also a kind of pigment affinity groups, but can contain carboxyl in the so-called polymer of affinity groups containing pigment in the present invention, carboxyl can also not contained.In the present invention, the molecular weight of the polymer of the affinity groups containing pigment is had no special requirements.
In the present invention, the polymer of the described affinity groups containing pigment is preferably the polyacrylate polymers of the affinity groups containing pigment, it is preferred that the copolymer of hydroxy-ethyl acrylate and acrylamide, the copolymer of acrylic ester monomer and hydroxy-ethyl acrylate class monomer, the copolymer of acrylic ester monomer and hydroxyethyl methacrylate class monomer, the copolymer of acrylic ester monomer and acrylamide monomers, acrylic ester monomer, the terpolymer of hydroxy-ethyl acrylate class monomer and vinyl-containing monomers, acrylic ester monomer, the terpolymer of hydroxyethyl methacrylate class monomer and vinyl-containing monomers, and acrylic ester monomer, one or more in the terpolymer of acrylamide monomers and vinyl-containing monomers.
Wherein, the terpolymer of the preferred methyl acrylate of the terpolymer of described acrylic ester monomer, hydroxy-ethyl acrylate class monomer and vinyl-containing monomers, hydroxy-ethyl acrylate and styrene；Described acrylic ester monomer, the preferred butyl acrylate of the terpolymer of acrylamide monomers and vinyl-containing monomers, the terpolymer of acrylamide and acrylic acid.
Wherein, described acrylic ester monomer is preferably methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, EMA, propyl methacrylate
Or butyl methacrylate.
In the present invention, the content of the polymer of the affinity groups containing pigment is preferably mass percent
0 Fine 1 ~ 3%.
Agents useful for same and raw material of the present invention are commercially available.The corrosion inhibitor for semiconductor chip metal substrate of the present invention is simply hooked mixing by mentioned component and can be prepared by.
The invention further relates to the application method of the corrosion inhibitor for semiconductor chip metal substrate of the present invention：Removed with cleaning fluid after the residue on semiconductor wafer after etched or etching/ashing, directly semiconductor wafer is cleaned with described corrosion inhibitor for semiconductor chip metal substrate, dried afterwards.
Wherein, described semiconductor wafer is preferably chip containing aluminum semiconductor；After being cleaned with corrosion inhibitor for semiconductor chip metal substrate to semiconductor wafer, preferably cleaned again with water.The time cleaned using the corrosion inhibitor for semiconductor chip metal substrate of the present invention to semiconductor wafer is preferably no more than 15 minutes.The present invention corrosion inhibitor for semiconductor chip metal substrate can be to the cleaning way of semiconductor wafer：Overflow infusion method, quick descending liquid method or rotary spray method.
The positive effect of the present invention is：The corrosion inhibitor for semiconductor chip metal substrate of the present invention is not only to metal（Especially aluminium）With relatively low corrosion rate, while having environmentally friendly, cheap, easy to use and effect outstanding feature.The corrosion inhibitor for semiconductor chip metal substrate of the present invention can be after being cleaned using the cleaning fluid of the class containing azanol, rinsed instead of conventional solvent isopropanol and 1-METHYLPYRROLIDONE, also can be after being cleaned using the cleaning fluid of fluoride, rinsed, to improve action pane when deionized water is directly rinsed.The corrosion inhibitor for semiconductor chip metal substrate of the present invention has a good application prospect in the microelectronic such as metal cleaning and cleaning semiconductor chip.
Brief description of the drawings
Fig. 1 is metallic aluminium corrosion rate and fluorine-containing cleaning solution and the graph of a relation of the dilution ratio of water.
The content of the invention
The present invention is further illustrated below by the mode of embodiment, but is not therefore limited the present invention to
Among described scope of embodiments.In following embodiments, percentage is mass percent.Embodiment 1 ~ 22
Table 1 gives the formula of the corrosion inhibitor for semiconductor chip metal substrate embodiment 1 ~ 22 of the present invention, by listed component and its content in table 1, and uniform, i.e., obtained each corrosion inhibitor for semiconductor chip metal substrate is simply mixed.The corrosion inhibitor for semiconductor chip metal substrate 1 22 of the present invention of table 1
Embodiment of the method 1
The application method of corrosion inhibitor for semiconductor chip metal substrate, specific steps：
1. with azanol based cleaning liquid in table 2（F1) the wafer after 65 times cleaning plasma etchings 20 minutes.
2. rotary spraying type is carried out to wafer with metal erosion protective liquid 8 in table 1 to clean 10 minutes.
3. dry afterwards.The application method of the corrosion inhibitor for semiconductor chip metal substrate of embodiment of the method 2, specific steps：
1. with azanol based cleaning liquid in table 2（F1) the clock of wafer 15 under 65 °C after cleaning plasma etching.
2. rotary spraying type is carried out to wafer with metal erosion protective liquid 8 in table 1 to clean 5 minutes.
3. 2 minutes rotary spraying types are carried out to wafer with deionized water to clean.
4. dry afterwards.The application method of the corrosion inhibitor for semiconductor chip metal substrate of embodiment of the method 3, specific steps：
1. with azanol based cleaning liquid in table 2（F1) the clock of wafer 25 under 65 °C after cleaning plasma etching.
2. overflow immersion type is carried out to wafer with metal erosion protective liquid 8 in table 1 to clean 15 minutes.
3. 5 minutes overflow immersion types are carried out to wafer with deionized water to clean.
4. dry afterwards.The application method of the corrosion inhibitor for semiconductor chip metal substrate of embodiment of the method 4, specific steps：
1. with fluorine-containing based cleaning liquid in table 2（F2) the clock of wafer 20 under 35 °C after cleaning plasma etching
2. quick descending liquid formula is carried out to wafer with metal erosion protective liquid 8 in table 1 to clean 10 minutes.
3. 8 minutes quick descending liquid formulas are carried out to wafer with deionized water to clean.
4. dry afterwards.
Effect example
In order to illustrate the effect of the present invention, the cleaning fluid (referring to table 2) of cleaning fluid and fluorinated containing U.S. amine has been prepared according to the published patent with typical meaning, and has tested the metallic aluminium corrosion rate (referring to table 3) when the water of the two and different proportion is diluted.
2 liang of classes of table often use cleaning fluid and its composition
Metallic aluminium corrosion rate method of testing：
1) the resistance initial value of 4*4cm aluminium bare silicon wafers is tested using Napson four-point probes instrument（Rsl );
2) the 4*4cm aluminium bare silicon wafers are immersed in advance constant temperature into 35 °C of solution 30 minutes;
3) the 4*4cm aluminium bare silicon wafers are taken out, are cleaned with deionized water, high pure nitrogen drying recycles Napson four-point probes instrument to test the resistance value of 4*4cm aluminium bare silicon wafers（Rs2);
4) if it is necessary, repeat second and the 3rd step re-test once, resistance value is designated as Rs3;
5) above-mentioned resistance value and soak time are input to suitable program computability and go out its corrosion rate.Metallic aluminium corrosion rate when the water of 3 liang of common cleaning fluids of class of table and different proportion is diluted
(35。C)
From table 3：Metallic aluminium corrosion rate is larger when azanol based cleaning liquid dilutes in water, and this is also the reason for based cleaning liquid can not be rinsed directly with water.At present, semi-conductor industry circle is after using the cleaning of azanol based cleaning liquid, common solvent rinsing.Solvent used is mainly isopropanol and 1-METHYLPYRROLIDONE.The former once occurred fire because flash-point is than relatively low, volatile in individual semiconductor manufacturing company, therefore
Progressively it is eliminated；And the latter because flash-point is higher, it is not volatile used always in a lot of Semiconductor Manufacturing Companies, but its price is higher.And with environmental consciousness and cost pressure, increasing company is wished under the premise of the corrosion of metallic aluminium is not caused, and can directly be rinsed with deionized water.
And for fluorine-containing cleaning fluid, when being diluted with deionized water, its metallic aluminium corrosion rate is with dilution ratio（Dilution/fluorine-containing cleaning solution）Increase exist one from low to high again have a high to Low curve
(as shown in Figure 1）.In order to reduce corrosion of the rinsing to metal aluminium base, current semi-conductor industry circle is during reality frequently with substantial amounts of water short rinse, to pass through the larger region of corrosion rate with faster speed and shorter time, to reduce the corrosion of metallic aluminium, and this often brings the problem of rinse cycle action pane is too small.If the peak shape height shown in reduction Fig. 1, is beneficial to reduce the corrosion of metallic aluminium in rinse cycle, while bringing larger action pane.
By taking the metal erosion protective liquid embodiment 8 of the present invention as an example, the effect of the metal erosion protective liquid of the present invention is illustrated, method of testing ibid, the results are shown in Table 4.The metal erosion protective liquid of the common cleaning fluid embodiment 8 of 4 liang of classes of table
Metallic aluminium corrosion rate (35 °C) when being diluted
From table 4：The metal erosion protective liquid embodiment 8 of the present invention itself is smaller to the corrosion rate of metallic aluminium（0. 53/1. 39) .When with the dilution of the azanol based cleaning liquid of different proportion, all with relatively low corrosion rate（Respectively less than l.OA/min).And in the fluorinated cleaning solution dilution with different proportion,
Compared with water, the elevated peak of corrosion rate is dropped into below 56A/min in table 4 by 89 ~ 109.36A/min in table 3（That is the peak height in reduction Fig. 1), this can provide bigger action pane for the rinse step after being cleaned using fluorine-containing based cleaning liquid.
To sum up, positive effect of the invention is：
1) provide that a kind of environmentally friendly, cheap, operation is simple and the rinsing metal erosion protective liquid after the significant semiconductor crystal wafer cleaning of effect, itself is smaller to corrosion of metal speed（Such as:The corrosion rate of aluminium<1.5^1^11)
2) in the cleaning fluid wet clean process containing azanol class, it can instead corrosion of the solvent rinse without causing metal base（Such as：The corrosion rate of metallic aluminium<1.0A/min) .
3) in the cleaning fluid wet clean process containing fluorine class, metal erosion maximum rate when can reduce its rinsing（That is the peak height in reduction Fig. 1）, bigger action pane can be provided for rinsing.
Claims (1)
- Claim1. a kind of corrosion inhibitor for semiconductor chip metal substrate, it is characterised in that contain：The polymer and water of carbonyl bearing polymer, the affinity groups containing pigment.2. corrosion inhibitor for semiconductor chip metal substrate as claimed in claim 1, it is characterised in that：Described metal base is aluminium.3. corrosion inhibitor for semiconductor chip metal substrate as claimed in claim 2, it is characterised in that：Described aluminium is applied to the standard aluminum of semiconductor technology, Al-Si-Cu alloy or aluminium copper.4. corrosion inhibitor for semiconductor chip metal substrate as claimed in claim 1, it is characterised in that：One or more of the described carbonyl bearing polymer in carboxylic homopolymer, carboxylic homopolymer salt, carboxylic copolymer and carboxylic copolymer salt.5. corrosion inhibitor for semiconductor chip metal substrate as claimed in claim 4, it is characterised in that：Described carboxylic homopolymer is the one or more in HPMA, polyacrylic acid and polymethylacrylic acid；Described carboxylic copolymer is the copolymer of carboxyl group-containing monomer and/or the copolymer of vinyl-containing monomers and carboxyl group-containing monomer；Described salt is the one or more in ammonium salt, sylvite and sodium salt.6. corrosion inhibitor for semiconductor chip metal substrate as claimed in claim 5, it is characterised in that：The copolymer of described carboxyl group-containing monomer is the copolymer and/or methacrylic acid and the copolymer of maleic acid of acrylic acid and maleic acid；One or more in the described copolymer of vinyl-containing monomers and the copolymer of carboxyl group-containing monomer selected from styrene and acrylic acid, the copolymer of styrene and maleic acid, the copolymer of acrylonitrile and maleic acid, the copolymer of ethene and acrylic acid, the copolymer of acrylonitrile and acrylic acid, the copolymer of styrene and methacrylic acid, the copolymer and acrylonitrile of ethene and methacrylic acid and the copolymer of methacrylic acid；Described ammonium salt is ammonium polyacrylate.7. corrosion inhibitor for semiconductor chip metal substrate as claimed in claim 1, it is characterised in that：Institute The content for the carbonyl bearing polymer stated is mass percent 0.0001 3%.8. corrosion inhibitor for semiconductor chip metal substrate as claimed in claim 1, it is characterised in that：The polymer of the described affinity groups containing pigment is the polyacrylate polymers of the affinity groups containing pigment.9. the corrosion inhibitor for semiconductor chip metal substrate as described in claim 1 or 8, it is characterised in that：Described pigment affinity groups are hydroxyl or amino.10. corrosion inhibitor for semiconductor chip metal substrate as claimed in claim 8, it is characterised in that：The polyacrylate polymers of the described affinity groups containing pigment are selected from the copolymer of hydroxy-ethyl acrylate and acrylamide, the copolymer of acrylic ester monomer and hydroxy-ethyl acrylate class monomer, the copolymer of acrylic ester monomer and hydroxyethyl methacrylate class monomer, the copolymer of acrylic ester monomer and acrylamide monomers, acrylic ester monomer, the terpolymer of hydroxy-ethyl acrylate class monomer and vinyl-containing monomers, acrylic ester monomer, the terpolymer of hydroxyethyl methacrylate class monomer and vinyl-containing monomers, and acrylic ester monomer, one or more in the terpolymer of acrylamide monomers and vinyl-containing monomers.11. corrosion inhibitor for semiconductor chip metal substrate as claimed in claim 10, it is characterised in that：The terpolymer of described acrylic ester monomer, hydroxy-ethyl acrylate class monomer and vinyl-containing monomers is the terpolymer of methyl acrylate, hydroxy-ethyl acrylate and styrene；The terpolymer of described acrylic ester monomer, acrylamide monomers and vinyl-containing monomers is the terpolymer of butyl acrylate, acrylamide and acrylic acid.12. the corrosion inhibitor for semiconductor chip metal substrate as described in claim 10 or 11, it is characterised in that：Described acrylic ester monomer is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, EMA, propyl methacrylate or first Base butyl acrylate.13. corrosion inhibitor for semiconductor chip metal substrate as claimed in claim 1, it is characterised in that：The content of the polymer of the described affinity groups containing pigment is mass percent 0.0001 3%.14. the application method of corrosion inhibitor for semiconductor chip metal substrate as claimed in claim 1, it is characterised in that：Removed with cleaning fluid after the residue on semiconductor wafer after etched or etching/ashing, directly semiconductor wafer is cleaned with described corrosion inhibitor for semiconductor chip metal substrate, dried afterwards.15. application method as claimed in claim 14, it is characterised in that：Described semiconductor wafer is chip containing aluminum semiconductor.16. method as claimed in claim 14, it is characterised in that：Cleaned after being cleaned with corrosion inhibitor for semiconductor chip metal substrate, then with water.17. method as claimed in claim 14, it is characterised in that：The described time cleaned with corrosion inhibitor for semiconductor chip metal substrate to semiconductor wafer is no more than 15 minutes.18. method as claimed in claim 14, it is characterised in that：The described mode cleaned with corrosion inhibitor for semiconductor chip metal substrate to semiconductor wafer is overflow immersion type, quick descending liquid formula or rotary spraying type.
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| CN2008801148297A CN101842747B (en) | 2007-11-02 | 2008-10-31 | Corrosion inhibitor for semiconductor chip metal substrate and use method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200710047790.9 | 2007-11-02 | ||
| CNA2007100477909A CN101424887A (en) | 2007-11-02 | 2007-11-02 | Semiconductor wafer metal substrate web corrosion prevention liquid and its use method |
| PCT/CN2008/001829 WO2009062397A1 (en) | 2007-11-02 | 2008-10-31 | Corrosion inhibitor for semiconductor chip metal substrate and use method thereof |
| CN2008801148297A CN101842747B (en) | 2007-11-02 | 2008-10-31 | Corrosion inhibitor for semiconductor chip metal substrate and use method thereof |
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| CN101842747A true CN101842747A (en) | 2010-09-22 |
| CN101842747B CN101842747B (en) | 2012-07-25 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111441060A (en) * | 2020-04-13 | 2020-07-24 | 南通科星化工有限公司 | Neutral metal cleaning agent and preparation method thereof |
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| US5338347A (en) * | 1992-09-11 | 1994-08-16 | The Lubrizol Corporation | Corrosion inhibition composition |
| US5516459A (en) * | 1994-08-12 | 1996-05-14 | Buckeye International, Inc. | Aircraft cleaning/degreasing compositions |
| WO2000066810A1 (en) * | 1999-05-03 | 2000-11-09 | Betzdearborn Inc. | Method and composition for inhibiting corrosion in aqueous systems |
| JP2005002370A (en) * | 2003-06-09 | 2005-01-06 | Nippon Paint Co Ltd | Surface treatment method for aluminum-based substrate, and surface-treated substrate |
| CN1900363B (en) * | 2005-07-21 | 2016-01-13 | 安集微电子（上海）有限公司 | Scavenging solution and uses thereof |
| CN1982426B (en) * | 2005-12-16 | 2011-08-03 | 安集微电子（上海）有限公司 | Slow-releasing agent system for cleaning semiconductor chip |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111441060A (en) * | 2020-04-13 | 2020-07-24 | 南通科星化工有限公司 | Neutral metal cleaning agent and preparation method thereof |
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