CN101525563B - Corrosion inhibitor for after polishing detergent - Google Patents
Corrosion inhibitor for after polishing detergent Download PDFInfo
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- CN101525563B CN101525563B CN2008100080138A CN200810008013A CN101525563B CN 101525563 B CN101525563 B CN 101525563B CN 2008100080138 A CN2008100080138 A CN 2008100080138A CN 200810008013 A CN200810008013 A CN 200810008013A CN 101525563 B CN101525563 B CN 101525563B
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Abstract
The invention relates to a corrosion inhibitor for an after polishing detergent. A creatine compound which is taken as the corrosion inhibitor is creatine and a salt compound thereof. The corrosion inhibitor is used in the after polishing detergent for chemical mechanical polishing, and can protect the surface of a processing object from corrosion when the after CMP (chemical mechanical polishing) cleaning is carried out. A chemical formula which can best display the characteristics of the corrosion inhibitor is shown.
Description
Technical field
The relevant a kind of corrosion inhibitor that is used for the back polishing detergent of the present invention, purpose can protect the processing object surface to avoid the corrosion inhibitor that is corroded when a kind of back cleaning that is used for cmp is provided.
Background technology
Chemically machinery polished or planarization (CMP) are technology that is used for the semiconductor fabrication process of planarization semiconductor subassembly or substrate top end surface.This semiconductor subassembly is generally by silicon-based wafer, and it has the active region that is formed in the wafer or on the wafer and is deposited in the etching line so that connect the connection wire of these active regions along wafer by metal (being generally copper or tungsten) formation.The excess copper that utilizes the CMP program to remove to be deposited on the semiconductor subassembly is so that planarization should the surface.The CMP program generally comprises under controlled condition against this semiconductor substrate of wet tumbling surface rotation.This chemical polishing agent comprises abrasive substance (as aluminum oxide or silicon-dioxide), and chemical assistant then can be pH value buffer reagent, oxygenant or interfacial agent etc.Certainly, CMP grinds object not simultaneously, and the abrasive substance of its required use is difference to some extent also.As the copper abrasive substance that uses in the copper CMP processing procedure is to add ammonium hydroxide and hydrofluoric acid (HF).In addition; because easy oxidation of copper-base and corrosion; therefore in the copper CMP processing procedure; often add the solution that contains triazole (triazole) and grind the copper pattern of wafer to protect quilt; and copper corrosion takes place when avoiding after grinding waiting for next processing procedure; for example in lapping liquid, add benzotriazole (benzotriazole is designated hereinafter simply as BTA) as copper corrosion inhibitor with protection copper film surface.
And after the grinding of wafer process, surface potential must residual a large amount of grinding powders and metal ion.Therefore, behind the CMP processing procedure, and then must carry out repeatedly surface cleaning processing procedure, to remove these particulates, metal ion, organism etc.The crystal column surface of industry removing at present particulate, metal ion, organism are large with wet chemistry washing out method (wet chemical cleaning) still, its be mixture with aqueous soda acid solvent and deionized water as chemical cleaning wafer surface, the wetting subsequently program of exsiccant again.
Yet, because the BTA as copper corrosion inhibitor in the copper CMP processing procedure has tackyness and is difficult for removal, therefore known cleaning step adds acid with alkaline chemical agent respectively to reduce the BTA stickiness, and cooperate the scouring method with aspire to cleaning other particulate, metal ion and the organic BTA that removes simultaneously, still the crystal column surface that utilizes known techniques to clean still has residual BTA.And because manufacturing process for cleaning only reduces the BTA stickiness by the chemical agent that adds behind the known copper CMP, BTA can't be removed fully, cause BTA to residue in crystal column surface, even cohere into piece, pollute at crystal column surface.This BTA that residues in crystal column surface can cause the not good problem of interface of the film and the copper of resistance value rising, heat effect and follow-up formation, making the wafer reliability descend, is organic contamination source common when wafer cleans behind the cmp so BTA has been confirmed to be.
Summary of the invention
Main purpose of the present invention is promptly providing a kind of corrosion inhibitor that the cleaning group is ground in the back that is used for; in this wafer behind the CMP processing procedure; can utilize this back to grind cleaning composition and carry out surface cleaning; with particulate, metal ion, organism and the residual BTA of removal crystal column surface, and can protect the processing object surface to avoid for example being given birth to electric current erosion or photoresponse erosion by eating properties, oxygenizement, the back cleaning burn into chemistry of cleaning soln.
Take off purpose on reaching; be musculamine acid and salt compounds thereof as the creatine compound used of corrosion inhibitor among the present invention; polishing detergent (post CMP cleanagent) after this corrosion inhibitor is used for can protect the processing object surface to avoid for example being given birth to electric current erosion or photoresponse erosion by eating properties, oxygenizement, the back cleaning burn into chemistry of cleaning soln.
Embodiment
Characteristics of the present invention can be consulted the detailed description of the graphic and embodiment of this case and obtained to be well understood to.
The present invention is used for the corrosion inhibitor of back polishing detergent; this corrosion inhibitor is creatine compound used or its mixtures such as musculamine acid and salt compounds thereof; and this corrosion inhibitor is used for the back polishing detergent; this corrosion inhibitor can be creatine compound used or its mixtures such as musculamine acid and salt compounds thereof equally, and it can protect the processing object surface to avoid for example being given birth to electric current erosion or photoresponse erosion by eating properties, oxygenizement, the back cleaning burn into chemistry of cleaning soln.
Though CMP is the planarization process object surface effectively, this program is stayed pollutent on the processing object surface, must use the back polishing detergent to remove this type of pollution residue.The purpose of its cleaning is to remove the left residue of CMP step and not etching metal, relict sediment or processing object applied significantly organic (for example for carbon) pollutent from the teeth outwards significantly from the surface of processing object.In addition, the corrosion that protection processing object surface avoids various different mechanisms is an ideal, and it is for example given birth to electrolytic corrosion or photoresponse corrosion by chemical milling, chemistry.The corrosion on this processing object surface can cause the metal depression and make the metal wire thinning.Acid clean solution is removing organic pollutant with in addition normally quite efficient in the misfit to remaining copper from the processing object surface.Therefore obtaining in moderate will be ideal for the effective cleaning agent to the low pH value.The acidic chemical typical case go up to use what be used for back CMP cleaning and scrubs case or ultrasound cleaning unit.
So this back polishing detergent can include acidic cpd and corrosion inhibitor, this acidic cpd can be citric acid, oxalic acid, phosphoric acid, amino trimethylammonium phosphoric acid, 1-hydroxy ethylene 1, the 1-bisphosphate, 2-phosphonic acids butane-1,2, the 4-tricarboxylic acid, Amino Trimethylene Phosphonic Acid, 1,4 propylhomoserin hexamethyl-(tetramethyl-) 1,4 phosphoric acid, 1,5 phosphoric acid-diethylenetriamine pentamethyl-, 1,5 phosphoric acid-hexamethyl ethene triamine pentamethyl-, propanedioic acid, lactic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, succsinic acid, hexanodioic acid, oxysuccinic acid, toxilic acid, tartrate, methylsulfonic acid, Phenylsulfonic acid, toluenesulphonic acids, Witco 1298 Soft Acid, ethylenediamine tetraacetic acid (EDTA), diethylene triamine pentacetic acid (DTPA), three glycines, N-(hydroxyethyl) ethylenediamine triacetic acid or its composition, and this corrosion inhibitor can be creatine compound used for musculamine acid and salt compounds thereof etc., the example of this musculamine acid and its esters comprises, but non-ly is limited to musculamine acid (sarcosine);
Formula one
(CH
3NHCH
2COOH，CAS＝107-97-1)
Bay vinegar musculamine acid (lauroyl sarcosine),
Formula two
(C
15H
29NO
3，CAS?97-78-9)
N-anilide musculamine acid (N-acyl sarcosine), cocounut oil anilide musculamine acid (cocoylsarcosine), oily vinegar musculamine acid (oleoyl sarcosine), stearic vinegar musculamine acid (stearoylsarcosine), and nutmeg vinegar musculamine acid (myristoyl sarcosine) or its lithium salts, sodium salt, sylvite or amine salt etc. or its mixture; Bay vinegar musculamine acid sodium-salt (Sodium n-LauroylSarcosinate) for example.
Formula three
【CH
3(CH
2)
10CON(CH
3)CH
2COONa，CAS?137-16-6】
Embodiment one
Listed according to table one, as to utilize reference examples 1 to 3 composition to form back polishing detergent carries out the back and grinds cleaner assay, and compares the wastage rate of crystal column surface copper in each reference examples.Wherein, the chemical formula of this cocounut oil anilide musculamine acid sodium is suc as formula four:
Formula four
(RCON(CH
3)CH
2COONa，CAS?61791-59-1)
| Citric acid (wt%) | Oxalic acid (wt%) | Bay vinegar musculamine acid ppm | Cocounut oil anilide musculamine acid ppm |
| Reference examples 1 | 0.2 | 0.2 | 0 | 0 |
| Reference examples 2 | 0.2 | 0.2 | 20 | 0 |
| Reference examples 3 | 0.2 | 0.2 | 0 | 20 |
Table one
It is to carry out according to following condition that cleaner assay is ground in the back, and wastage rate (copper loss) result who utilizes TXRF (full-reflection X-ray fluorescence spectra) to analyze copper is embedded in table two.
Type of wafer: 2 2000A are thick covers the copper wafer
Cleaning equipment: Ontrak post CMP brush box (Lam Research, CA USA)
Clean-out system flow velocity: 300ml/min
Scavenging period: 50 seconds
| Cu wastage rate (A/min) | |
| Reference examples 1 | 21.66 |
| Reference examples 2 | 16.47 |
| Reference examples 3 | 13.34 |
Table two
According to table two result as can be known, this reference examples 2 and 3 copper loss rate are less than reference examples 1, so be added with the loss that the back polishing detergent of musculamine acid of bay vinegar or the acid of cocounut oil anilide musculamine can effectively suppress copper.
Embodiment two
Listed according to table three, as to utilize reference examples 4 to 5 compositions to form back polishing detergent carries out back CMP cleaner assay, and compares the wastage rate of crystal column surface copper in each reference examples.
| Citric acid (wt%) | Witco 1298 Soft Acid (wt%) | Cocounut oil anilide musculamine acid sodium ppm | |
| Reference examples 4 | 0.25 | 0.0085 | 0 |
| Reference examples 5 | 0.25 | 0.0085 | 10 |
Table three
Back grinding cleaner assay is carried out according to following condition, and the mean value result who utilizes TXRF (full-reflection X-ray fluorescence spectra) to analyze the wastage rate (copper loss) of copper is embedded in table four.
Type of wafer: 2 2000A are thick covers the copper wafer
Cleaning unit: Ontrack post CMP brush box (Lam Research, CA USA)
Clean-out system flow velocity: 300ml/min
Scavenging period: 50 seconds
| Copper loss rate mean value A/min | |
| Reference examples 4 | 13.92 |
| Reference examples 5 | 11.71 |
Table four
According to table four result as can be known, the copper loss rate of this reference examples 5 is less than reference examples 4, so be added with the loss that the back polishing detergent of cocounut oil anilide musculamine acid sodium can effectively suppress copper.
By the foregoing description one, two as can be known; corrosion inhibitor in the back polishing detergent of conduct that the present invention utilizes creatine compound used (as musculamine acid and salt compounds thereof) can be protected the processing object surface for example to avoid eating properties, oxygenizement, back cleaning burn into chemistry by cleaning soln and be given birth to polishing detergent additive behind electric current erosion or the photoresponse erosive.
Technology contents of the present invention and technical characterstic the sixth of the twelve Earthly Branches disclose as above, yet the personage who is familiar with this technology still may do various replacement and the modifications that do not deviate from this case invention spirit based on announcement of the present invention.Therefore, protection scope of the present invention should be not limited to those disclosed embodiments, and should comprise various do not deviate from replacement of the present invention and modifications, and is contained by following claim.
Claims (11)
1. post-chemical mechanical polishing detergent constituent, it comprises creatine compound used or its salt, an acidic cpd, and wherein this creatine compound usedly has a following formula:
Wherein R is lauroyl, cocoyl, oleoyl, stearyl-Huo Rou Beans myristoyl.
2. post-chemical mechanical polishing detergent constituent according to claim 1, wherein this salt is selected from lithium salts, sodium salt, sylvite or ammonium salt.
3. post-chemical mechanical polishing detergent constituent according to claim 1, wherein this creatine compound used or its salt is the acid of lauroyl musculamine or its sodium salt.
4. post-chemical mechanical polishing detergent constituent according to claim 1, wherein this creatine compound used or its salt is the acid of cocounut oil acyl musculamine or its sodium salt.
5. post-chemical mechanical polishing detergent constituent according to claim 1, wherein this acidic cpd can be citric acid, oxalic acid, phosphoric acid, amino trimethylammonium phosphoric acid, 1-hydroxy ethylene 1, the 1-bisphosphate, 2-phosphonic acids butane-1,2, the 4-tricarboxylic acid, Amino Trimethylene Phosphonic Acid, 1,4 propylhomoserin hexamethyl-(tetramethyl-) 1,4 phosphoric acid, 1,5 phosphoric acid-diethylenetriamine pentamethyl-, 1,5 phosphoric acid-hexamethyl ethene triamine pentamethyl-, propanedioic acid, lactic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, succsinic acid, hexanodioic acid, oxysuccinic acid, toxilic acid, tartrate, methylsulfonic acid, Phenylsulfonic acid, toluenesulphonic acids, Witco 1298 Soft Acid, ethylenediamine tetraacetic acid (EDTA), diethylene triamine pentacetic acid (DTPA), three glycines, N-(hydroxyethyl) ethylenediamine triacetic acid or its composition.
6. a creatine compound used or its esters is as the application of the corrosion inhibitor in the post-chemical mechanical polishing detergent constituent, and wherein this creatine compound usedly has a following formula:
Wherein R is lauroyl, cocoyl, oleoyl, stearyl-Huo Rou Beans myristoyl.
7. application as described in wanting 6 as right, wherein this salt is selected from lithium salts, sodium salt, sylvite or ammonium salt.
8. as application as described in the claim 6, wherein this creatine compound used or its salt is the acid of lauroyl musculamine or its sodium salt.
9. as application as described in the claim 6, wherein this creatine compound used or its salt is the acid of cocounut oil acyl musculamine or its sodium salt.
10. as application as described in the claim 6, wherein this post-chemical mechanical polishing detergent constituent includes an acidic cpd in addition.
11. as application as described in the claim 10, wherein this acidic cpd is a citric acid, oxalic acid, phosphoric acid, amino trimethylammonium phosphoric acid, 1-hydroxy ethylene 1, the 1-bisphosphate, 2-phosphonic acids butane-1,2, the 4-tricarboxylic acid, Amino Trimethylene Phosphonic Acid, 1,4 propylhomoserin hexamethyl-(tetramethyl-) 1,4 phosphoric acid, 1,5 phosphoric acid-diethylenetriamine pentamethyl-, 1,5 phosphoric acid-hexamethyl ethene triamine pentamethyl-, propanedioic acid, lactic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, succsinic acid, hexanodioic acid, oxysuccinic acid, toxilic acid, tartrate, methylsulfonic acid, Phenylsulfonic acid, toluenesulphonic acids, Witco 1298 Soft Acid, ethylenediamine tetraacetic acid (EDTA), diethylene triamine pentacetic acid (DTPA), three glycines, N-(hydroxyethyl) ethylenediamine triacetic acid or its composition.
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| CN101525563B true CN101525563B (en) | 2011-04-13 |
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Families Citing this family (10)
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| CN101937687A (en) * | 2010-07-21 | 2011-01-05 | 河北工业大学 | Method for cleaning surface of indium phosphide substrate of computer hardware after chemical mechanical polishing (CMP) |
| JPWO2012073909A1 (en) * | 2010-11-29 | 2014-05-19 | 和光純薬工業株式会社 | Copper wiring substrate cleaning agent and copper wiring semiconductor substrate cleaning method |
| GB2486241A (en) | 2010-12-08 | 2012-06-13 | Rhodia Operations | A sulfosuccinate corrosion inhibitor |
| WO2014049016A1 (en) | 2012-09-27 | 2014-04-03 | Basf Se | Non-corrosive soft-magnetic powder |
| EP2783774A1 (en) | 2013-03-28 | 2014-10-01 | Basf Se | Non-corrosive soft-magnetic powder |
| US20160060584A1 (en) * | 2013-04-10 | 2016-03-03 | Wako Pure Chemical Industries, Ltd. | Cleaning agent for metal wiring substrate, and method for cleaning semiconductor substrate |
| US9944828B2 (en) | 2014-10-21 | 2018-04-17 | Cabot Microelectronics Corporation | Slurry for chemical mechanical polishing of cobalt |
| CN116288366A (en) | 2014-10-21 | 2023-06-23 | Cmc材料股份有限公司 | Corrosion inhibitors and related compositions and methods |
| US9688885B2 (en) | 2014-10-21 | 2017-06-27 | Cabot Microelectronics Corporation | Cobalt polishing accelerators |
| KR102525356B1 (en) | 2014-10-21 | 2023-04-25 | 씨엠씨 머티리얼즈, 인코포레이티드 | Cobalt dishing control agents |
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| US3787227A (en) * | 1972-06-29 | 1974-01-22 | Grace W R & Co | Rust preventative compositions |
| JP3397501B2 (en) * | 1994-07-12 | 2003-04-14 | 株式会社東芝 | Abrasive and polishing method |
| CN1735670A (en) * | 2003-01-03 | 2006-02-15 | 气体产品及化学制品公司 | Composition and method used for chemical mechanical planarization of metals |
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2008
- 2008-03-03 CN CN2008100080138A patent/CN101525563B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3787227A (en) * | 1972-06-29 | 1974-01-22 | Grace W R & Co | Rust preventative compositions |
| JP3397501B2 (en) * | 1994-07-12 | 2003-04-14 | 株式会社東芝 | Abrasive and polishing method |
| CN1735670A (en) * | 2003-01-03 | 2006-02-15 | 气体产品及化学制品公司 | Composition and method used for chemical mechanical planarization of metals |
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