CN103881848A - Cleaning fluid and its application - Google Patents
Cleaning fluid and its application Download PDFInfo
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- CN103881848A CN103881848A CN201210556881.6A CN201210556881A CN103881848A CN 103881848 A CN103881848 A CN 103881848A CN 201210556881 A CN201210556881 A CN 201210556881A CN 103881848 A CN103881848 A CN 103881848A
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- acid
- scavenging solution
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Abstract
The invention provides a cleaning fluid used after chemically mechanical polishing the metal, which comprises at least one organic acid, one complexone and one carboxylic acid polymer. The cleaning fluid can be used for cleaning surface of a metal-containing wafer after polishing. The cleaning fluid can remove the grinding particles, metal ions and a corrosion inhibitor on the wafer surface after being polished, wafer surface roughness is reduced, the hydrophilcity on the wafer surface after cleaning is improved, surface defect is reduced, and the metal surface corrosion can be avoided.
Description
Technical field
The present invention relates to a kind of scavenging solution and application thereof.
Background technology
Metallic substance is as copper, aluminium, and tungsten etc. are conductor materials conventional in unicircuit.In the time manufacturing device, chemically machinery polished (CMP) becomes the major technique of wafer planarization.Chemical mechanical polishing of metals liquid contains abrasive grains, complexing agent, metal corrosion inhibitor, oxygenant etc. conventionally.Wherein abrasive grains is mainly silicon-dioxide, cerium dioxide, titanium dioxide, polymer abrasive grains of silicon-dioxide, aluminium sesquioxide, adulterated al or aluminium coating etc.After metal CMP operation, wafer surface can be subject to the pollution of abrasive grains in metal ion and polishing fluid itself, and this pollution meeting exerts an influence to the reliability of semi-conductive electrical specification and device.The residual Flatness that all can affect wafer surface of these metal ions and abrasive grains, thus the performance impact subsequent handling of device or the operation of device may be reduced.So after metal CMP technique, remove the metal ion, metal corrosion inhibitor and the abrasive grains that remain in wafer surface, improve the wetting ability of the wafer surface after cleaning, reduce surface imperfection and be necessary.
Chinese patent CN100543124C provides for the clean-out system of substrate and purging method, removes basic surface granule metallic impurity, does not affect surface irregularity, not removing preventing metal corrosion agent-Cu coating simultaneously, removes the carbon defects that is present in substrate surface.Its clean-out system contains the complexing agent and at least one organic solvent that have the organic acid of at least 1 carboxyl, be made up of organic phospho acid.This scavenging solution also further contains at least a kind of material in the group of selecting free reductive agent, preventing metal corrosion agent and tensio-active agent composition.Wherein said tensio-active agent is selected from least one in the group of following substances composition: the nonionic class tensio-active agent in molecule with polyoxy alkylidene; In molecule, there is the anionic species tensio-active agent of the group that is selected from sulfonic group, carboxylic acid, phosphonate group, sulfoxylic acid base and phosphonato, amphoterics.It has used the organic solvent of not environmental protection.And the protection against corrosion inhibitor adding in scavenging solution is the protection against corrosion inhibitor containing in copper polish slurry, equally likely can remains in wafer surface and form carbon defects.In addition, prove to add the effect after at least one material in the group being formed by reductive agent, preventing metal corrosion agent and tensio-active agent without embodiment.
U.S. Pat 2001/0051597A1 provides a kind of scavenging solution with citric acid and sequestrant composition, and its object is the residual metal ion on wafer to remove.US2005/0197266 provides a kind of scavenging solution being made up of acidic chemical material and corrosion inhibitor, removes the residual metal ion of wafer surface, regulates the pH of scavenging solution with the pH coupling of polishing fluid.The problem of these patents has been only to solve the problem of removing metal ion.
U.S. Pat 2005/0199264A1 provides a kind of scavenging solution that contains hydroxycarboxylic acid/salt and sterilant, removes the growth of the bacterium of the residual abrasive grains of wafer surface and inhibition wafer surface.The problem of this patent has been only to solve the problem of removing abrasive grains and sterilization.
Taiwan patent TW416987B provides clean-out system and the purging method of substrate, and the method comprises at least one carboxyl organic acid and has the complexing agent clean semiconductor substrate surface of sequestering power.
Summary of the invention
The present invention, in order to solve above-mentioned problems of the prior art, provides a kind of scavenging solution.
Scavenging solution of the present invention, it comprises at least one organic acid, complexone, and at least one carboxylic-acid polymkeric substance and/or its salt.
In the present invention, described organic acid concentration is mass percent 0.05～5%, and the concentration of described complexone is mass percent 0.005～1%, and the concentration of described carboxylic-acid polymkeric substance and/or its salt is mass percent 0.0005～1%.Preferably, described organic acid concentration is mass percent 0.1～3%, and the concentration of described complexone is mass percent 0.01～0.5%, and the concentration of described carboxylic-acid polymkeric substance and/or its salt is mass percent 0.001～0.1%.
In the present invention, described organic acid is citric acid, oxysuccinic acid, oxalic acid, tartrate and/or Whitfield's ointment.
In the present invention, described complexone is selected from ethylenediamine tetraacetic acid (EDTA), ethylenediamine disuccinic acid, ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA), diethylene triamine pentacetic acid (DTPA), Oxyethylethylenediaminetriacetic acid, cyclohexanediaminetetraacetic acid, one or more in two [two (carboxymethyl) amine] diethyl ether of 2,2-and salt thereof.
In the present invention, described salt is ammonia salt, sylvite.
In the present invention, described carboxylic-acid polymkeric substance is acrylic polymers and salt thereof.
In the present invention, described carboxylic-acid polymkeric substance is polyacrylic acid, vinylformic acid and cinnamic multipolymer, the multipolymer of the multipolymer of vinylformic acid and MALEIC ANHYDRIDE and/or vinylformic acid and acrylate.
In the present invention, described carboxylic-acid polymericular weight is 1,000～300,000.Preferably, described carboxylic-acid polymericular weight is 1,000～30,000.
In the present invention, described scavenging solution pH value is less than 7.Preferably, described scavenging solution pH value is 2-5.
In the present invention, above-mentioned scavenging solution can be applicable in metal substrate.
In the present invention, described metal substrate is aluminium, copper, tantalum, tantalum nitride, titanium, titanium nitride, tungsten, nickel, nickel-phosphorus, iron, silver and/or golden.
In the present invention, above-mentioned scavenging solution can be applicable in cleaning machine clean wafers or after polishing finishes on polishing disk in clean wafers.
In the present invention, carboxylic-acid polymkeric substance can be applicable to the wetting ability of improving wafer surface, reduces surfaceness, suppress in corrosion of metal,
In the present invention, can also comprise pH adjusting agent, defoamer, the additive of this area routines such as sterilant.
In the present invention, above-mentioned scavenging solution can be prepared into concentrating sample, before using, is diluted to concentration range of the present invention with deionized water.
Technique effect of the present invention is:
1) by adding carboxylic-acid polymkeric substance, can reduce surfaceness, suppress corrosion of metal.
2) complexone can increase the removal of the residual metal ion in metallic surface and metal oxide.
3) adding of carboxylic-acid polymkeric substance, improve the wetting ability of wafer surface, be conducive to the cleaning of wafer.
4) being used in conjunction with of complexone and carboxylic-acid polymkeric substance, has increased the removal of abrasive grains.
Accompanying drawing explanation
Fig. 1 is the copper graphical wafer scanning electron microscope (SEM) photograph using after scavenging solution embodiment 10 of the present invention cleans;
Fig. 2 is the copper graphical wafer scanning electron microscope (SEM) photograph using after scavenging solution embodiment 10 of the present invention soaks.
Embodiment
Agents useful for same of the present invention and raw material be commercially available obtaining all.Scavenging solution of the present invention can be made by the simple evenly mixing of mentioned component.
Further set forth advantage of the present invention below by embodiment, but the present invention includes but be not limited to following embodiment.
Preparation Example
Table 1 has provided embodiment and the comparative example of scavenging solution of the present invention, by the formula of giving in table, all components is dissolved and is mixed, and water is supplied mass percent to 100%.With KOH, ammoniacal liquor or HNO
3be adjusted to needed pH value.The following stated percentage composition is mass percentage content.
Table 1 embodiment of the present invention and comparative example formula
Effect embodiment
The mensuration of wafer surface roughness: utilize XE-300P atomic force microscope to measure the copper wafer surface roughness Ra with scavenging solution cleaning and after soaking.
The removal aptitude tests of metal ion: blank silica wafers is immersed in the copper ion solution that 200 ml concns are C0, soak after 30 minutes and take out, with the scavenging solution washing wafer of same volume 3 times, and washing lotion and copper ion solution are collected together to (totally 800 milliliters), utilize ICP to measure the concentration of cupric ion in washing lotion and be multiplied by 4 for C1, C1/C0 is more close to 1, and the removal ability of metal ion is stronger.
Wetting ability test in metallic surface after scavenging solution cleans: scrub copper wafer surface 1 minute with scavenging solution in cleaning machine, then water is scrubbed 1 minute, after nitrogen drying, measure the contact angle α of water in wafer surface, the less wafer surface of contact angle is more hydrophilic, wafer surface is more easily cleaned, and surface imperfection is fewer.Cleaning brush used is PVA brush.
The dissolving power of metal oxide: add 0.1% copper oxide particle in scavenging solution, stirring 30min sampling is centrifugal, takes out supernatant liquid.Utilize ICP to measure the content of cupric ion in supernatant liquid.Content is higher, and the ability of scavenging solution dissolution of metals oxide compound is stronger.
The removal ability of abrasive grains: abrasive grains is added and measures the Zeta potential ξ of abrasive grains at solution in scavenging solution, the absolute value of Zeta potential | ξ | lower, abrasive grains is more easily reunited, in cleaning process, be easily cleaned brush and walk and be difficult for being adsorbed on wafer surface, scavenging solution is stronger to the removal ability of abrasive grains.
The mensuration of corrosion current: utilize chi660b electrochemical workstation, measure corrosion potential and the corrosion current of copper in scavenging solution.Corrosion current is larger, and scavenging solution causes the possibility of corrosion stronger to metal.
Table 2 has provided specific embodiment and comparative example removal ability, the metal oxide dissolving power at abrasive grains, the wetting ability of copper wafer surface, roughness and the metallic corrosion current data of copper wafer surface after cleaning.
The wafer cleaning situation of table 2 embodiment and comparative example
Can find out adding of carboxylic-acid polymkeric substance from comparative example 3 and embodiment, reduced the roughness of wafer surface and reduced scavenging solution to corrosion of metal.
From comparative example 1,2,3 and embodiment can see that being used in conjunction with of complexone and carboxylic-acid polymerization increased the removal of scavenging solution to the residual abrasive grains of wafer surface.
Can find out and increase the dissolving power of metal oxide adding of complexone from comparative example 2 and comparative example 3 and embodiment.
Can see adding of carboxylic-acid polymkeric substance from comparative example 3 and embodiment, the wetting ability of having improved wafer surface is conducive to the cleaning of wafer.
In scavenging solution, soak 30 minutes by the copper graphical wafer after scavenging solution 10 cleaning polishings of the present invention and by the graphical wafer after cleaning, after cleaning, be dried with scavenging solution after taking-up, by the situation of sem observation copper line surface, see Fig. 1 and 2.
Polishing technological conditions: polishing machine platform is 8 " Mirra, polishing disk and rubbing head rotating speed 93/87rpm, polishing fluid flow velocity 150ml/min, copper polishing polishing pad used is IC1010, barrier polishing polishing pad used is Fujibo H7000.Copper polishing fluid is the products A EP U3000 of An Ji company, and barrier polishing solution is the products A njiTCU2000H4 of An Ji company.
From attached Fig. 1 and 2, the copper graphical wafer surface no-pollution after cleaning with scavenging solution of the present invention, without grinding particle residue, the defect such as corrosion-free.Copper cash edge clear, the copper cash of the copper graphical wafer after soaking with scavenging solution are corrosion-free.
In sum, use the metallic wafer after scavenging solution cleaning polishing of the present invention, can remove chip surface after polishing residual abrasive grains, metal ion etc. residual, reduce the rough degree in metallic surface, improve the wetting ability of wafer surface after cleaning, reduce the surface imperfection after cleaning, and can prevent wafer issuable metallic corrosion in the process of waiting for next step operation.
Should be understood that, wt% of the present invention all refers to quality percentage composition.
Above specific embodiments of the invention be have been described in detail, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and alternative also all among category of the present invention.Therefore, equalization conversion and the modification done without departing from the spirit and scope of the invention, all should contain within the scope of the invention.
Claims (17)
1. a scavenging solution, it comprises at least one organic acid, complexone, and at least one carboxylic-acid polymkeric substance and/or its salt.
2. scavenging solution according to claim 1, it is characterized in that: described organic acid concentration is mass percent 0.05～5%, the concentration of described complexone is mass percent 0.005～1%, and the concentration of described carboxylic-acid polymkeric substance and/or its salt is mass percent 0.0005～1%.
3. scavenging solution according to claim 2, it is characterized in that: described organic acid concentration is mass percent 0.1～3%, the concentration of described complexone is mass percent 0.01～0.5%, and the concentration of described carboxylic-acid polymkeric substance and/or its salt is mass percent 0.001～0.1%.
4. scavenging solution according to claim 1, is characterized in that: described organic acid is citric acid, oxysuccinic acid, oxalic acid, tartrate and/or Whitfield's ointment.
5. scavenging solution according to claim 1, it is characterized in that: described complexone is selected from ethylenediamine tetraacetic acid (EDTA), ethylenediamine disuccinic acid, ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA), diethylene triamine pentacetic acid (DTPA), Oxyethylethylenediaminetriacetic acid, cyclohexanediaminetetraacetic acid, one or more in two [two (carboxymethyl) amine] diethyl ether of 2,2-and salt thereof.
6. scavenging solution according to claim 5, is characterized in that: described salt is ammonia salt, sylvite.
7. scavenging solution according to claim 1, is characterized in that: described carboxylic-acid polymkeric substance is acrylic polymers and salt thereof.
8. scavenging solution according to claim 7, it is characterized in that: described carboxylic-acid polymkeric substance is selected from polyacrylic acid, vinylformic acid and cinnamic multipolymer, one or more in the multipolymer of the multipolymer of vinylformic acid and MALEIC ANHYDRIDE and/or vinylformic acid and acrylate.
9. scavenging solution according to claim 7, is characterized in that: described carboxylic-acid polymericular weight is 1,000～300,000.
10. scavenging solution according to claim 9, is characterized in that: described carboxylic-acid polymericular weight is 1,000～30,000.
11. scavenging solutions according to claim 1, is characterized in that: described scavenging solution pH value is less than 7.
12. scavenging solutions according to claim 11, is characterized in that: described scavenging solution pH value is 2-5.
13. according to the scavenging solution described in claim 1-12 any one, the application in metal substrate.
14. application according to claim 13, is characterized in that: described metal substrate is aluminium, copper, tantalum, tantalum nitride, titanium, titanium nitride, tungsten, nickel, nickel-phosphorus, iron, silver and/or golden.
15. according to the scavenging solution described in claim 1-12 any one, clean wafers or the application in clean wafers on polishing disk after polishing finishes in cleaning machine.
16. 1 kinds comprise carboxylic-acid polymkeric substance and are improving the wetting ability of wafer surface, reduction surfaceness, the application in inhibition corrosion of metal.
17. application as claimed in claim 16, it is characterized in that: described carboxylic-acid polymkeric substance is selected from polyacrylic acid, vinylformic acid and cinnamic multipolymer, one or more in the multipolymer of the multipolymer of vinylformic acid and MALEIC ANHYDRIDE and/or vinylformic acid and acrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210556881.6A CN103881848A (en) | 2012-12-19 | 2012-12-19 | Cleaning fluid and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210556881.6A CN103881848A (en) | 2012-12-19 | 2012-12-19 | Cleaning fluid and its application |
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| CN103881848A true CN103881848A (en) | 2014-06-25 |
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| CN201210556881.6A Pending CN103881848A (en) | 2012-12-19 | 2012-12-19 | Cleaning fluid and its application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104330959A (en) * | 2014-10-25 | 2015-02-04 | 江阴市化学试剂厂有限公司 | Preparation method of photoresist stripping liquid |
| CN104388953A (en) * | 2014-10-30 | 2015-03-04 | 青岛昌安达药业有限公司 | Metal cleaning agent |
| CN109576090A (en) * | 2018-12-13 | 2019-04-05 | 中国科学院上海光学精密机械研究所 | Leftover cleaning agent and preparation method thereof after the chemically mechanical polishing of oxide optical element |
| CN110387549A (en) * | 2019-07-17 | 2019-10-29 | 武汉钢铁有限公司 | Inhibit the additive and method of coil of strip pickling rear surface residual ferrous powder |
| CN112064050A (en) * | 2020-09-18 | 2020-12-11 | 广州三孚新材料科技股份有限公司 | Acidic degreasing agent for copper electroplating and preparation method thereof |
-
2012
- 2012-12-19 CN CN201210556881.6A patent/CN103881848A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104330959A (en) * | 2014-10-25 | 2015-02-04 | 江阴市化学试剂厂有限公司 | Preparation method of photoresist stripping liquid |
| CN104388953A (en) * | 2014-10-30 | 2015-03-04 | 青岛昌安达药业有限公司 | Metal cleaning agent |
| CN109576090A (en) * | 2018-12-13 | 2019-04-05 | 中国科学院上海光学精密机械研究所 | Leftover cleaning agent and preparation method thereof after the chemically mechanical polishing of oxide optical element |
| CN110387549A (en) * | 2019-07-17 | 2019-10-29 | 武汉钢铁有限公司 | Inhibit the additive and method of coil of strip pickling rear surface residual ferrous powder |
| CN112064050A (en) * | 2020-09-18 | 2020-12-11 | 广州三孚新材料科技股份有限公司 | Acidic degreasing agent for copper electroplating and preparation method thereof |
| CN112064050B (en) * | 2020-09-18 | 2021-09-24 | 广州三孚新材料科技股份有限公司 | Acidic degreasing agent for copper electroplating and preparation method thereof |
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Application publication date: 20140625 |