CN101842747B - 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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- CN101842747B CN101842747B CN2008801148297A CN200880114829A CN101842747B CN 101842747 B CN101842747 B CN 101842747B CN 2008801148297 A CN2008801148297 A CN 2008801148297A CN 200880114829 A CN200880114829 A CN 200880114829A CN 101842747 B CN101842747 B CN 101842747B
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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
Technical field
The present invention relates to semiconductor and make a kind of cleaning fluid and method of application thereof in the cleaning, concrete a kind of corrosion inhibitor for semiconductor chip metal substrate and the method for application thereof of relating to.
Technical background
In the semiconductor components and devices manufacture process, 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 remaining photoresist layer, and its concrete steps are generally cleaning fluid 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 (like aluminium lamination).
In present wet clean process, the cleaning fluid of using morely is to contain the cleaning fluid of azanol class and the cleaning fluid of fluoride.In addition, also has a spot of not fluorine-containing again cleaning fluid of azanol that neither contains.The cleaning fluid of azanol class after having cleaned the plasma etching thing, often adopts the solvent rinsing because it is bigger to the corrosion rate of metallic aluminium during rinsing in water.Used solvent mainly contains isopropyl alcohol and N-Methyl pyrrolidone.The former progressively is eliminated in some semiconductor manufacturing companies because flash-point is lower, volatile; And the latter since flash-point use in good multiple semiconductor manufacturing company than higher, not volatile always.But along with environmental consciousness and cost pressure, increasing company hopes can be with the direct rinsing of deionized water, and does not cause corrosion of metal.For fluorine-containing cleaning fluid, with the direct rinsing of deionized water the time, its rate of metal corrosion exists one to have high to a low curve (showing like Fig. 1) from low to high again.
In order to reduce the corrosion of rinsing to metal base, often in the process of reality adopt a large amount of quick rinsings of water so that with fast speeds and short time through the bigger zone of corrosion rate, to reduce corrosion of metal.And this often brings the too small problem of rinse cycle action pane.
Brief summary of the invention
Technical matters to be solved by this invention is in order to solve the metal erosion problem in the wet-cleaned rinse step; And a kind of lower rate of metal corrosion that has is provided, environmentally friendly simultaneously, low price and corrosion inhibitor for semiconductor chip metal substrate and method of application thereof easy to use.
Corrosion inhibitor for semiconductor chip metal substrate of the present invention contains: carbonyl bearing polymer, the polymkeric substance that contains the pigment affinity groups and water.
Among the present invention, described metal base especially refers to aluminium, as is applied to the aluminium alloys such as standard aluminum, Al-Si-Cu alloy or aluminium copper of semiconductor technology.
Among the present invention, described carbonyl bearing polymer is preferable is selected from carboxylic homopolymer, carboxylic homopolymer salt, carboxylic multipolymer and the carboxylic copolymer salt one or more.
Wherein, described carboxylic homopolymer is preferable is in HPMA (HPMA), polyacrylic acid (PAA) and the polymethylacrylic acid one or more, and better is HPMA and/or polyacrylic acid.
Wherein, described carboxylic multipolymer preferable for containing the multipolymer (like the multipolymer of acrylic acid and maleic acid and/or the multipolymer of methacrylic acid and maleic acid) and/or the vinyl-containing monomers of carboxylic monomer and containing the multipolymer (like in the multipolymer of the multipolymer of multipolymer, ethene and the methacrylic acid of multipolymer, ethene and acrylic acid multipolymer, vinyl cyanide and acrylic acid multipolymer, styrene and the methacrylic acid of multipolymer, vinyl cyanide and the maleic acid of styrene and acrylic acid multipolymer, styrene and maleic acid and vinyl cyanide and methacrylic acid one or more) of carboxylic monomer.Wherein, the multipolymer of preferred acrylic acid and maleic acid.
Wherein, described salt is one or more in ammonium salt, sylvite and the sodium salt; Preferred ammonium salt is like ammonium polyacrylate (SD).
Among the present invention, so long as existing carboxylic polymkeric substance all can be used for corrosion inhibitor for semiconductor chip metal substrate of the present invention in the prior art, prerequisite is that this polymkeric substance has certain solubleness in water.Generally speaking, carboxylic polymer molecular weight size does not influence realization the object of the invention.If the polymkeric substance that has certain mass concentration in the corrosion inhibitor for semiconductor chip metal substrate of the present invention also correspondingly has certain density carboxyl in this corrosion inhibitor for semiconductor chip metal substrate.This is because for the polymkeric substance of certain mass concentration, if the molecular weight of polymkeric substance is big, the molal quantity of polymkeric substance is just correspondingly few in the corrosion inhibitor for semiconductor chip metal substrate; If the molecular weight of polymkeric substance is little, the molal quantity of polymkeric substance is also just correspondingly many in the corrosion inhibitor for semiconductor chip metal substrate.That is to say, form certain polymkeric substance, also just correspondingly contain certain density carboxyl on the polymkeric substance of its certain mass concentration.No matter the molecular weight of this polymkeric substance size is as long as the carboxyl on this polymkeric substance 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%.
Among the present invention, what described pigment affinity groups was preferable is hydroxyl or amino.As everyone knows, carboxyl also is a kind of pigment affinity groups, but what is called contains in the pigment affinity groups polymkeric substance and can contain carboxyl in the present invention, also can not contain carboxyl.Among the present invention, the molecular weight of the polymkeric substance that contains the pigment affinity groups is had no special requirements.
Among the present invention; The described polymkeric substance that contains the pigment affinity groups preferable for containing the polyacrylate polymers of pigment affinity groups; The multipolymer of multipolymer, acrylic ester monomer and the hydroxy-ethyl acrylate class monomer of preferred hydroxy-ethyl acrylate and acrylic amide; The multipolymer of acrylic ester monomer and hydroxyethyl methacrylate class monomer; The multipolymer of acrylic ester monomer and acrylamide monomers; The terpolymer of acrylic ester monomer, hydroxy-ethyl acrylate class monomer and vinyl-containing monomers, the terpolymer of acrylic ester monomer, hydroxyethyl methacrylate class monomer and vinyl-containing monomers, and in the terpolymer of acrylic ester monomer, acrylamide monomers and vinyl-containing monomers one or more.
Wherein, the preferred methyl acrylate of terpolymer, hydroxy-ethyl acrylate and the cinnamic terpolymer of described acrylic ester monomer, hydroxy-ethyl acrylate class monomer and vinyl-containing monomers; The preferred butyl acrylate of the terpolymer of described acrylic ester monomer, acrylamide monomers and vinyl-containing monomers, acrylic amide and acrylic acid terpolymer.
What wherein, described acrylic ester monomer was preferable is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate or butyl methacrylate.
Among the present invention, the content of the described polymkeric substance that contains the pigment affinity groups is preferable is mass percent 0.0001～3%.
Agents useful for same of the present invention and raw material are all commercially available to be got.Corrosion inhibitor for semiconductor chip metal substrate of the present invention can be made by the simple evenly mixing of mentioned component.
The invention still further relates to the method for application of corrosion inhibitor for semiconductor chip metal substrate of the present invention: after the residue after etching or etching/ashing on the cleaning fluid removal semiconductor wafer; Directly semiconductor wafer is cleaned with described corrosion inhibitor for semiconductor chip metal substrate, dry afterwards.
Wherein, described semiconductor wafer preferable for containing the aluminum semiconductor wafer; After with corrosion inhibitor for semiconductor chip metal substrate semiconductor wafer being cleaned, preferable water again cleans.What the time of using corrosion inhibitor for semiconductor chip metal substrate of the present invention that semiconductor wafer is cleaned was preferable is no more than 15 minutes.Corrosion inhibitor for semiconductor chip metal substrate of the present invention can be the cleaning way of semiconductor wafer: overflow infusion method, fast prompt drop liquid method or rotary spray method.
Positive progressive effect of the present invention is: corrosion inhibitor for semiconductor chip metal substrate of the present invention not only has lower corrosion rate to metal (especially aluminium), has environmental protection, low price, easy to use and obvious results characteristics simultaneously.After corrosion inhibitor for semiconductor chip metal substrate of the present invention can clean at the cleaning fluid that employing contains the azanol class; Replace solvent isopropyl alcohol and N-Methyl pyrrolidone commonly used to carry out rinsing; Also can be after the cleaning fluid that adopts fluoride cleans; Carry out rinsing, the action pane during with the direct rinsing of raising deionized water.Corrosion inhibitor for semiconductor chip metal substrate of the present invention has a good application prospect at microelectronics such as metal cleaning and semiconductor wafer cleanings.
Summary of the invention
Mode through embodiment further specifies the present invention below, but does not therefore limit the present invention among the described scope of embodiments.Among the following embodiment, number percent is mass percent.
Description of drawings
Fig. 1 is the graph of a relation of the dilution ratio of metallic aluminium corrosion rate and fluorine-containing cleaning fluid and water.
Embodiment 1～22
Table 1 has provided the prescription of corrosion inhibitor for semiconductor chip metal substrate embodiment 1～22 of the present invention, presses listed component and content thereof in the table 1, simply mixes, and promptly makes each corrosion inhibitor for semiconductor chip metal substrate.
Table 1 corrosion inhibitor for semiconductor chip metal substrate 1～22 of the present invention
Method embodiment 1
The method of application of corrosion inhibitor for semiconductor chip metal substrate, concrete steps:
1. clean the wafer 20 minutes behind the plasma etchings down with 65 ℃ of azanol based cleaning liquids (F1) in the table 2.
2. being rotated fountain with 8 pairs of wafers of metal erosion protective liquid in the table 1 cleaned 10 minutes.
3. dry afterwards.
Method embodiment 2
The method of application of corrosion inhibitor for semiconductor chip metal substrate, concrete steps:
1. clean the wafer 15 minutes behind the plasma etchings down with 65 ℃ of azanol based cleaning liquids (F1) in the table 2.
2. being rotated fountain with 8 pairs of wafers of metal erosion protective liquid in the table 1 cleaned 5 minutes.
3. with deionized water wafer being carried out 2 minutes rotary spray formulas cleans.
4. dry afterwards.
Method embodiment 3
The method of application of corrosion inhibitor for semiconductor chip metal substrate, concrete steps:
1. clean the wafer 25 minutes behind the plasma etchings down with 65 ℃ of azanol based cleaning liquids (F1) in the table 2.
2. carrying out the overflow immersion type with 8 pairs of wafers of metal erosion protective liquid in the table 1 cleaned 15 minutes.
3. with deionized water wafer being carried out 5 minutes overflow immersion types cleans.
4. dry afterwards.
Method embodiment 4
The method of application of corrosion inhibitor for semiconductor chip metal substrate, concrete steps:
1. clean the wafer 20 minutes behind the plasma etchings down with 35 ℃ of fluorinated cleaning fluids (F2) in the table 2
2. carrying out fast prompt drop liquid formula with 8 pairs of wafers of metal erosion protective liquid in the watch 1 cleaned 10 minutes.
3. with deionized water wafer being carried out 8 minutes fast prompt drop liquid formulas cleans.
4. dry afterwards.
Effect embodiment
For effect of the present invention is described; Prepared the cleaning fluid that contains the azanol class and the cleaning fluid (seeing table 2 for details) of fluorinated according to disclosed patent with typical meaning, and the metallic aluminium corrosion rate (see table 3) of the water of having tested the two and different proportion when diluting.
Two types of cleaning fluids commonly used of table 2 and composition thereof
Metallic aluminium corrosion rate method of testing:
1) utilize Napson four-point probe appearance 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 in the solution of constant temperature to 35 ℃ 30 minutes;
3) take out the blank silicon chip of this 4*4cm aluminium, use washed with de-ionized water, high pure nitrogen dries up, and utilizes the resistance value (Rs2) of the blank silicon chip of Napson four-point probe appearance test 4*4cm aluminium again;
4) if necessary, repeated for the second and the 3rd step and test once, resistance value is designated as Rs3;
5) be input to suitable procedure to above-mentioned resistance value and soak time and can calculate its corrosion rate.
Metallic aluminium corrosion rate (35 ℃) when the water of two types of common cleaning fluids of table 3 and different proportion dilutes
Visible by table 3: the metallic aluminium corrosion rate was bigger when the azanol based cleaning liquid diluted in water, this also be this based cleaning liquid can not be directly with the reason of water rinse.At present, semi-conductor industry circle after adopting the azanol based cleaning liquid to clean, the common solvent rinsing.Used solvent is mainly isopropyl alcohol and N-Methyl pyrrolidone.The former is because flash-point is lower, volatile, once in the breaking out of fire of indivedual semiconductor manufacturing companies, so progressively be eliminated; And the latter is because flash-point uses in good multiple semiconductor manufacturing company than higher, not volatile always, but its price is higher.And along with environmental consciousness and cost pressure, increasing company not hopes causing under the corrosion prerequisite of metallic aluminium, can be with the direct rinsing of deionized water.
And for fluorine-containing cleaning fluid, when diluting with deionized water, its metallic aluminium corrosion rate exists one to have high to a low curve (as shown in Figure 1) from low to high again with the increase of dilution ratio (dilution/fluorine-containing cleaning fluid).In order to reduce the corrosion of rinsing to the metallic aluminium base material; Semi-conductor industry circle a large amount of quick rinsing of water of normal employing in the process of reality at present; So that with fast speeds and short time through the bigger zone of corrosion rate; With the corrosion of minimizing metallic aluminium, and this often brings the too small problem of rinse cycle action pane.If can reduce peak shape height shown in Figure 1, will help reducing the corrosion of metallic aluminium in the rinse cycle, bring bigger action pane simultaneously.
With metal erosion protective liquid embodiment 8 of the present invention is example, illustrates the effect of metal erosion protective liquid of the present invention, and method of testing is the same, and the result sees table 4.
Metallic aluminium corrosion rate (35 ℃) when two types of common cleaning fluids of table 4 dilute with the metal erosion protective liquid of embodiment 8
Visible by table 4: metal erosion protective liquid embodiment of the present invention 8 itself is to the corrosion rate of metallic aluminium less (0.53/1.39).When the azanol based cleaning liquid with different proportion dilutes, all has lower corrosion rate (all less than 1.0A/min).And the time with the fluorinated cleaning solution dilution of different proportion; With the water ratio; The peak that corrosion rate is raise is dropped in the table 4 by 89～109.36A/min in the table 3 and (promptly reduces the peak height among Fig. 1) below the 56A/min, and this can provide bigger action pane for adopting the rinse step after the fluorinated cleaning fluid cleans.
To sum up, positive progressive effect of the present invention is:
1) provide a kind of environmental protection, low price, operation is simple and easy and the rinsing metal erosion protective liquid of obvious results semiconductor crystal wafer after cleaning, itself is to the less (as: corrosion rate of aluminium＜1.5A/min) of corrosion of metal speed.
2) in containing the cleaning fluid wet clean process of azanol class, can replace the solvent rinsing and can not cause the corrosion (as: corrosion rate of metallic aluminium＜1.0A/min) of metal base.
3) in containing the cleaning fluid wet clean process of fluorine class, metal erosion maximum rate in the time of can reducing its rinsing (reducing the peak height among Fig. 1) can provide bigger action pane for rinsing.
Claims (11)
1. corrosion inhibitor for semiconductor chip metal substrate is characterized in that containing: carbonyl bearing polymer, the polymkeric substance that contains the pigment affinity groups and water, wherein:
Described carbonyl bearing polymer is for to be selected from: one or more in the multipolymer of multipolymer, ethene and the methacrylic acid of the multipolymer of multipolymer, vinyl cyanide and the maleic acid of the multipolymer of the multipolymer of acrylic acid and maleic acid and/or methacrylic acid and maleic acid, styrene and acrylic acid multipolymer, styrene and maleic acid, ethene and acrylic acid multipolymer, vinyl cyanide and acrylic acid multipolymer, styrene and methacrylic acid and the multipolymer of vinyl cyanide and methacrylic acid;
The described polymkeric substance that contains the pigment affinity groups is the multipolymer of the multipolymer, acrylic ester monomer and the hydroxy-ethyl acrylate class monomer that are selected from hydroxy-ethyl acrylate and acrylic amide; The multipolymer of acrylic ester monomer and hydroxyethyl methacrylate class monomer; The multipolymer of acrylic ester monomer and acrylamide monomers; The terpolymer of acrylic ester monomer, hydroxy-ethyl acrylate class monomer and vinyl-containing monomers; The terpolymer of acrylic ester monomer, hydroxyethyl methacrylate class monomer and vinyl-containing monomers, and in the terpolymer of acrylic ester monomer, acrylamide monomers and vinyl-containing monomers one or more
Wherein: described acrylic ester monomer is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate or butyl methacrylate.
2. corrosion inhibitor for semiconductor chip metal substrate as claimed in claim 1 is characterized in that: described metal base is an aluminium.
3. corrosion inhibitor for semiconductor chip metal substrate as claimed in claim 2 is characterized in that: described aluminium is standard aluminum, Al-Si-Cu alloy or the aluminium copper that is applied to semiconductor technology.
4. corrosion inhibitor for semiconductor chip metal substrate as claimed in claim 1 is characterized in that: the content of described carbonyl bearing polymer is mass percent 0.0001～3%.
5. corrosion inhibitor for semiconductor chip metal substrate as claimed in claim 1 is characterized in that: the terpolymer of described acrylic ester monomer, hydroxy-ethyl acrylate class monomer and vinyl-containing monomers is methyl acrylate, hydroxy-ethyl acrylate and cinnamic terpolymer; The terpolymer of described acrylic ester monomer, acrylamide monomers and vinyl-containing monomers is butyl acrylate, acrylic amide and acrylic acid terpolymer.
6. corrosion inhibitor for semiconductor chip metal substrate as claimed in claim 1 is characterized in that: the described content that contains the polymkeric substance of pigment affinity groups is mass percent 0.0001～3%.
7. the method for application of corrosion inhibitor for semiconductor chip metal substrate as claimed in claim 1; It is characterized in that: after the residue after etching or etching/ashing on the cleaning fluid removal semiconductor wafer; Directly semiconductor wafer is cleaned with described corrosion inhibitor for semiconductor chip metal substrate, dry afterwards.
8. method of application as claimed in claim 7 is characterized in that: described semiconductor wafer is for containing the aluminum semiconductor wafer.
9. method as claimed in claim 7 is characterized in that: after cleaning with corrosion inhibitor for semiconductor chip metal substrate, water cleans again.
10. method as claimed in claim 7 is characterized in that: the described time of semiconductor wafer being cleaned with corrosion inhibitor for semiconductor chip metal substrate is no more than 15 minutes.
11. method as claimed in claim 7 is characterized in that: the described corrosion inhibitor for semiconductor chip metal substrate that uses is overflow immersion type, fast prompt drop liquid formula or rotary spray formula to the mode that semiconductor wafer cleans.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008801148297A CN101842747B (en) | 2007-11-02 | 2008-10-31 | Corrosion inhibitor for semiconductor chip metal substrate and use method thereof |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100477909A CN101424887A (en) | 2007-11-02 | 2007-11-02 | Semiconductor wafer metal substrate web corrosion prevention liquid and its use method |
| CN200710047790.9 | 2007-11-02 | ||
| 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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| Publication Number | Publication Date |
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| CN101842747A CN101842747A (en) | 2010-09-22 |
| CN101842747B true CN101842747B (en) | 2012-07-25 |
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| CN2008801148297A Active CN101842747B (en) | 2007-11-02 | 2008-10-31 | Corrosion inhibitor for semiconductor chip metal substrate and use method thereof |
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| CN111441060B (en) * | 2020-04-13 | 2022-09-30 | 南通科星化工股份有限公司 | Neutral metal cleaning agent and preparation method thereof |
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| US5516459A (en) * | 1994-08-12 | 1996-05-14 | Buckeye International, Inc. | Aircraft cleaning/degreasing compositions |
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| CN1900363A (en) * | 2005-07-21 | 2007-01-24 | 安集微电子（上海）有限公司 | Cleaning liquid and its use |
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| CN1083835A (en) * | 1992-09-11 | 1994-03-16 | 鲁布里佐尔公司 | Suppress the corrosion composition |
| US5516459A (en) * | 1994-08-12 | 1996-05-14 | Buckeye International, Inc. | Aircraft cleaning/degreasing compositions |
| CN1359430A (en) * | 1999-05-03 | 2002-07-17 | 贝茨迪尔博恩公司 | Inhibition of corrosion in aqueous systems |
| CN1572913A (en) * | 2003-06-09 | 2005-02-02 | 日本油漆株式会社 | Aluminium base material surface treatment method and surface treated base material |
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| CN101842747A (en) | 2010-09-22 |
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