CN103060831A - Cleaning liquid and application thereof - Google Patents
Cleaning liquid and application thereof Download PDFInfo
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- CN103060831A CN103060831A CN2012105755386A CN201210575538A CN103060831A CN 103060831 A CN103060831 A CN 103060831A CN 2012105755386 A CN2012105755386 A CN 2012105755386A CN 201210575538 A CN201210575538 A CN 201210575538A CN 103060831 A CN103060831 A CN 103060831A
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Abstract
The invention discloses a cleaning liquid which comprises at least one carrier and a metallic anticorrosion inhibitor. The invention further discloses application of the cleaning liquid in cleaning of a metal substrate. Compared with typical cleaning liquid, the cleaning liquid provided by the invention has the following advantages since the cleaning liquid substantially reduces the corrosion degree of a metal material: (1) the ratio of defects on the surface of a metal is obviously reduced; (2) flatness of the surface of the metal is substantially improved; (3) product quality is improved, and yield is increased; and (4) cleaning efficiency is improved.
Description
Technical field
The present invention relates to a kind of scavenging solution and uses thereof, relate in particular to a kind of scavenging solution that cleans integrated circuit (IC) wafer.
Background technology
Typical scavenging solution mainly is deionized water, superoxol and weak ammonia etc. in the prior art, and these scavenging solutions are mainly used in cleaning the debris in the preorder technique.This preorder technique is such as being: 1) CMP (Chemical Mechanical Polishing) process, through the residual a small amount of polishing fluid of the meeting of the metallic surface after the chemically machinery polished; 2) etching is gone high light resistance technique, also can residually go the high light blocking solution after this technique; 3) depositing operation and other techniques etc.After debris wherein is cleaned totally, but the corrosion of metallic surface still exists.The corrosion of metallic surface can affect the metallic surface Flatness, also makes defect level high, thereby reduces product yield and earning rate.
Some scavenging solutions are disclosed, such as US Patent No. 2004/0204329, US2003/0216270, US2004/0082180, US6147002, US6443814, US6719614, US6767409, US6482749 etc., it all is the using method about scavenging solution or scavenging solution.Be scavenging solution about a kind of acidic aqueous solution such as the scavenging solution among the patent US6147002, it also comprises the fluorine-containing material of 0.5～5 % by 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 not 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
The objective of the invention is provides a kind of scavenging solution in order to address the above problem.
A kind of scavenging solution, it comprises at least a carrier, it also comprises a kind of anti-corrosion of metal inhibitor.
Wherein, described anti-corrosion of metal inhibitor preferably is polycarboxylic acid and/or its salt.
Described polycarboxylic acid and/or its salt preferably are polyacrylic compounds and/or its salt.
Described polycarboxylic acid preferably is polyacrylic compounds, perhaps be acrylic compounds and cinnamic copolymerization, it perhaps is the copolymerization of acrylic compounds and MALEIC ANHYDRIDE, it perhaps is the copolymerization of acrylic compounds and esters of acrylic acid, their molecular weight are 2,000～1, and 000, between 000, preferably between 10000～500000.
Described polycarboxylic acid and/or its salt preferred formula I compound:
The formula I
Wherein, R
1, R
2Be hydrogen atom or carbonatoms by oneself less than 3 alkyl, R
3Be H, K, Na or NH
4
Described polyacrylic compounds and/or its salt is polyacrylic acid more preferably, and its molecular weight is preferably 10,000～30, and 000.
Scavenging solution of the present invention can also comprise pH adjusting agent.
Scavenging solution of the present invention also preferably comprises nitrogen-containing heterocycle compound, with further raising cleaning performance.
The preferred benzotriazole of described nitrogen-containing heterocycle compound, pyrazoles and/or imidazoles, more preferably benzotriazole.
Described carrier preferably is alcohols and/or water, and described alcohols can be glycerol.
In scavenging solution of the present invention, the mass concentration of this anti-corrosion of metal inhibitor preferably is 0.0001～20%, and this carrier is surplus.
Another object of the present invention provides the purposes of described scavenging solution in metal substrate, and described metal substrate is aluminium, copper, tantalum, tantalum nitride, titanium, titanium nitride, silver, gold, preferred aluminium.
Positive progressive effect of the present invention is: compare with typical scavenging solution, scavenging solution provided by the invention greatly reduces the extent of corrosion of metallic substance, thereby has following advantage: (1) so that the ratio of defects of metallic surface obviously descend; (2) greatly improve the Flatness of metallic surface; (3) improve the quality of products, the additional income rate, (4) improve cleaning efficiency.
Description of drawings
Figure 1A is for using scanning electronic microscope (SEM) figure of the metallic surface after washed with de-ionized water liquid cleans;
Figure 1B is for using the SEM figure of the metallic surface after scavenging solution of the present invention cleans;
Fig. 2 A is atomic force microscope (AFM) figure of the Metal Surface Roughness after the use washed with de-ionized water;
Fig. 2 B is for using the atomic force microscope figure of the Metal Surface Roughness after scavenging solution of the present invention cleans;
Fig. 3 A is for using deionized water to brush the opticmicroscope details in a play not acted out on stage, but told through dialogues figure on the metallic aluminium surface after the cleaning, and the black matrix among the figure is metallic aluminium, and white round dot is corrosion;
Fig. 3 B is for using scavenging solution of the present invention to brush the opticmicroscope details in a play not acted out on stage, but told through dialogues figure on the metallic aluminium surface after the cleaning.
Embodiment
Embodiment 1
The scavenging solution (pH=5.3) that will contain 800ppm polyacrylic acid (molecular weight is 30,000) and water and be surplus cleans with the aluminum metal surface after the chemical mechanical polishing liquid polishing.(1) technique of chemical mechanical polishing liquid polished aluminum metal is: the rotating speed 100rpm of overdraft 1psi, polishing disk, rubbing head rotating speed 105rpm, scavenging solution flow velocity 200ml/min, scavenging period 1min; (2) and then respectively with this clear Xian's liquid and PVA round brush 1min is scrubbed on the aluminum metal surface on the wafer with deionized water and polyvinyl alcohol (PVA) round brush, the round brush rotating speed is 100rpm; (3) take out again with deionized water and PVA round brush and scrub 1min.Wash result is seen Figure 1B.
The result shows, compares with the wafer (such as Figure 1A) that uses washed with de-ionized water liquid to clean, and uses the ratio of defects of the metallic surface (such as Figure 1B) after scavenging solution of the present invention cleans obviously to descend, and the Flatness of metallic surface improves.
Embodiment 2
To contain 600ppm polyacrylic acid (molecular weight is 30,000), 500ppm BTA(azimidobenzene) and water be that the scavenging solution (pH=4.3) of surplus cleans with the aluminum metal surface after the chemical mechanical polishing liquid polishing.(1) technique of chemical mechanical polishing liquid polished aluminum metal is: the rotating speed 100rpm of overdraft 1psi, polishing disk, rubbing head rotating speed 105rpm, scavenging solution flow velocity 200ml/min, scavenging period 1min; (2) and then respectively with this clear Xian's liquid and PVA round brush 1min is scrubbed on the aluminum metal surface on the wafer with deionized water and polyvinyl alcohol (PVA) round brush, the round brush rotating speed is 100rpm; (3) take out again with deionized water and PVA round brush and scrub 1min.Wash result is seen Fig. 2 B.
The result shows, the roughness of doing wafer (such as Fig. 2 A) surface of scavenging solution cleaning with deionized water is 3.72A, and use the roughness of the metallic surface (such as Fig. 2 B) after scavenging solution of the present invention cleans to be 3.00A, and the metallic surface spot corrosion obviously descends, and the roughness of metallic surface improves.
Embodiment 3
To contain 1200ppm polyacrylic acid (molecular weight is 30,000), 500ppmBTA and water are that the scavenging solution (pH=4.4) of surplus cleans with the aluminum metal surface on the wafer after the chemical mechanical polishing liquid polishing.(1) technique of chemical mechanical polishing liquid polished aluminum metal is: the rotating speed 100rpm of overdraft 1psi, polishing disk, rubbing head rotating speed 105rpm, scavenging solution flow velocity 200ml/min; (2) and then respectively with this clear Xian's liquid and PVA round brush 1min is scrubbed on the aluminum metal surface on the wafer with deionized water and PVA round brush, the round brush rotating speed is 100rpm; (3) be statically placed in 30min in the ionized water after scrubbing; (4) take out again with deionized water and PVA round brush and scrub 1min.
The result shows: used the clear Xian's liquid that contains the anti-corrosion of metal inhibitor of the present invention can effectively prevent metal Corrosion of Al (seeing Fig. 3 A) in step (2), and on the metallic aluminium of use washed with de-ionized water a large amount of corrosion (seeing Fig. 3 B) has been arranged.
Embodiment 4
To contain 1200ppm polyacrylic acid (molecular weight is 10,000), 500ppm BTA and water are the aluminum metal surface after the scavenging solution (pH=4.6) of surplus cleans the chemical mechanical polishing liquid polishing.(1) technique of chemical mechanical polishing liquid polished aluminum metal is: the rotating speed 100rpm of overdraft 1psi, polishing disk, rubbing head rotating speed 105rpm, scavenging solution flow velocity 200ml/min, scavenging period 1min; (2) and then respectively with this clear Xian's liquid and PVA round brush 1min is scrubbed on the aluminum metal surface on the wafer with deionized water and PVA round brush, the round brush rotating speed is 100rpm; (3) take out again with deionized water and PVA round brush and scrub 1min.
Embodiment 5
To contain 25ppm polyacrylic acid (molecular weight is 30,000), 500ppmBTA and water are that the scavenging solution (pH=3.0) of surplus cleans with the aluminum metal surface after the chemical mechanical polishing liquid polishing.(1) technique of chemical mechanical polishing liquid polished aluminum metal is: the rotating speed 100rpm of overdraft 1psi, polishing disk, rubbing head rotating speed 105rpm, scavenging solution flow velocity 200ml/min, scavenging period 1min(2) and then with this clear Xian's liquid and PVA round brush 1min is scrubbed on the aluminum metal surface on the wafer with deionized water and PVA round brush respectively, the round brush rotating speed is 100rpm; (3) take out again with deionized water and PVA round brush and scrub 1min.
Embodiment 6
To contain 10ppm polyacrylic acid (molecular weight is 10,000), 500ppm BTA and water are the copper metallic face after the scavenging solution (pH=3.0) of surplus cleans the chemical mechanical polishing liquid polishing.(1) technique of chemical mechanical polishing liquid polish copper metal is: the rotating speed 100rpm of overdraft 1psi, polishing disk, rubbing head rotating speed 105rpm, scavenging solution flow velocity 200ml/min, scavenging period 1min; (2) and then respectively with this clear Xian's liquid and PVA round brush the copper metallic face on the wafer is scrubbed 1min with deionized water and PVA round brush, the round brush rotating speed is 100rpm; (3) take out again with deionized water and PVA round brush and scrub 1min.
Embodiment 7
To contain 20% polyacrylic acid (molecular weight is 10,000), 500ppm BTA and water are the copper metallic face after the scavenging solution (pH=7.4) of surplus cleans the chemical mechanical polishing liquid polishing.(1) technique of chemical mechanical polishing liquid polish copper metal is: the rotating speed 100rpm of overdraft 1psi, polishing disk, rubbing head rotating speed 105rpm, scavenging solution flow velocity 200ml/min, scavenging period 1min; (2) and then respectively with this clear Xian's liquid and PVA round brush the copper metallic face on the wafer is scrubbed 1min with deionized water and PVA round brush, the round brush rotating speed is 100rpm; (3) take out again with deionized water and PVA round brush and scrub 1min.
Claims (17)
1. the purposes of an anti-corrosion of metal inhibitor in the clean metal substrate is characterized in that, described anti-corrosion of metal inhibitor is polycarboxylic acid and/or its salt.
2. purposes as claimed in claim 1, it is characterized in that, described polycarboxylic acid is polyacrylic compounds, perhaps being acrylic compounds and cinnamic copolymerization, perhaps is the copolymerization of acrylic compounds and MALEIC ANHYDRIDE, perhaps is the copolymerization of acrylic compounds and esters of acrylic acid, their molecular weight are 2,000～3, between 000,000.
3. purposes according to claim 1 is characterized in that, described polycarboxylic acid and/or its salt are formula I compound:
The formula I
Wherein, R
1, R
2Be hydrogen atom or carbonatoms by oneself less than 3 alkyl, R
3Be H, K, Na or NH
4
4. purposes according to claim 3 is characterized in that, described polyacrylic compounds is polyacrylic acid, and its molecular weight is 10,000～30,000.
5. purposes according to claim 1 is characterized in that, described metal substrate is aluminium, copper, tantalum, tantalum nitride, titanium, titanium nitride, silver or golden.
6. the purposes of a scavenging solution in metal substrate is characterized in that, described scavenging solution comprises at least a carrier and anti-corrosion of metal corrosion inhibitor.
7. purposes according to claim 6, described anti-corrosion of metal inhibitor is polycarboxylic acid and/or its salt.
8. purposes as claimed in claim 7, it is characterized in that, described polycarboxylic acid is polyacrylic compounds, perhaps being acrylic compounds and cinnamic copolymerization, perhaps is the copolymerization of acrylic compounds and MALEIC ANHYDRIDE, perhaps is the copolymerization of acrylic compounds and esters of acrylic acid, their molecular weight are 2,000～3, between 000,000.
9. purposes according to claim 7 is characterized in that, described polycarboxylic acid and/or its salt are formula I compound:
The formula I
Wherein, R
1, R
2Be hydrogen atom or carbonatoms by oneself less than 3 alkyl, R
3Be H, K, Na or NH
4
10. purposes according to claim 9 is characterized in that, described polyacrylic compounds is polyacrylic acid, and its molecular weight is 10,000～30,000.
11. purposes according to claim 6 is characterized in that, also comprises pH adjusting agent.
12. according to claim 6 or 11 described purposes, characterized by further comprising nitrogen-containing heterocycle compound.
13. purposes according to claim 12 is characterized in that, the nitrogen-containing heterocycle compound in the described scavenging solution is benzotriazole, pyrazoles and/or imidazoles.
14. purposes according to claim 6 is characterized in that, the carrier in the described scavenging solution is alcohols and/or water.
15. purposes according to claim 6 is characterized in that, the mass concentration of this anti-corrosion of metal inhibitor is 0.0001～20%, and this carrier is surplus.
16. purposes as claimed in claim 6 is characterized in that, described scavenging solution pH value is less than 7.
17. purposes as claimed in claim 6 is characterized in that, described metal substrate is aluminium, copper, tantalum, tantalum nitride, titanium, titanium nitride, silver or golden.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105755386A CN103060831A (en) | 2005-07-21 | 2005-07-21 | Cleaning liquid and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105755386A CN103060831A (en) | 2005-07-21 | 2005-07-21 | Cleaning liquid and application thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200510027989.6A Division CN1900363B (en) | 2005-07-21 | 2005-07-21 | Scavenging solution and uses thereof |
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| Publication Number | Publication Date |
|---|---|
| CN103060831A true CN103060831A (en) | 2013-04-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012105755386A Pending CN103060831A (en) | 2005-07-21 | 2005-07-21 | Cleaning liquid and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822670A (en) * | 2018-05-19 | 2018-11-16 | 保定维特瑞交通设施工程有限责任公司 | A kind of PCB circuit board welding ultrasonic wave antistatic on-line cleaning material and preparation method thereof |
| CN113151837A (en) * | 2021-04-27 | 2021-07-23 | 上海新阳半导体材料股份有限公司 | Preparation method of cleaning solution after chemical mechanical polishing |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004051761A (en) * | 2002-07-19 | 2004-02-19 | Daisan Kogyo Kk | Detergent composition having anticorrosive effect |
| US20050049168A1 (en) * | 2003-09-03 | 2005-03-03 | Laibin Yan | Aqueous compositions for cleaning gas turbine compressor blades |
-
2005
- 2005-07-21 CN CN2012105755386A patent/CN103060831A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004051761A (en) * | 2002-07-19 | 2004-02-19 | Daisan Kogyo Kk | Detergent composition having anticorrosive effect |
| US20050049168A1 (en) * | 2003-09-03 | 2005-03-03 | Laibin Yan | Aqueous compositions for cleaning gas turbine compressor blades |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822670A (en) * | 2018-05-19 | 2018-11-16 | 保定维特瑞交通设施工程有限责任公司 | A kind of PCB circuit board welding ultrasonic wave antistatic on-line cleaning material and preparation method thereof |
| CN113151837A (en) * | 2021-04-27 | 2021-07-23 | 上海新阳半导体材料股份有限公司 | Preparation method of cleaning solution after chemical mechanical polishing |
| CN113151837B (en) * | 2021-04-27 | 2022-08-05 | 上海新阳半导体材料股份有限公司 | Preparation method of cleaning solution after chemical mechanical polishing |
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Application publication date: 20130424 |