CN101525751A - Creatine compound used as corrosion inhibitor - Google Patents
Creatine compound used as corrosion inhibitor Download PDFInfo
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- CN101525751A CN101525751A CN200810008014A CN200810008014A CN101525751A CN 101525751 A CN101525751 A CN 101525751A CN 200810008014 A CN200810008014 A CN 200810008014A CN 200810008014 A CN200810008014 A CN 200810008014A CN 101525751 A CN101525751 A CN 101525751A
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- corrosion inhibitor
- musculamine
- acid
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- creatine compound
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Abstract
The invention relates to a creatine compound used as a corrosion inhibitor. The creatine compound which is taken as the corrosion inhibitor is creatine and a salt compound thereof. The corrosion inhibitor can be used as a chemical mechanical polishing composition, and can form a protective film on the surface of a processing object during chemical mechanical polishing so as to prevent the processing object from corrosion. In addition, the creatine compound can overcome the defect that residuals are formed on the surface of the processing object due to the use of the prior corrosion inhibitor (such as benzotriazole, BTA). A chemical formula which can best display the characteristics of the corrosion inhibitor is shown.
Description
Technical field
The relevant a kind of musculamine as corrosion inhibitor of the present invention is sour or creatine compound used, purpose is providing a kind of corrosion inhibitor that is used for the cmp constituent, can improve the inhibition corrosive power of processing object, and can object surface is residual a residue grinding.
Background technology
The rapid increase of and the lead number of plies more and more little along with the critical size (Critical Dimension) of electronic package, resistance time lag (RC Time Delay) will have a strong impact on the operating speed of integrated circuit.In order to improve,, replace Al-alloy metal so select the low and high copper conductor material of anti-electronic migration destructiveness of resistivity along with the metal inline line width is dwindled time lag and the electronic migration integrity problem that is caused.Yet,, must change and adopt another kind (Damascene) mode of inlaying and form the copper plain conductor because the copper metal has and be difficult for etched characteristic.
Inlay (Damascene) mode processing procedure and be different from tradition elder generation definition metal pattern is filled out ditch again with dielectric layer metallization process, its method is earlier after etching the groove of metal wire on the smooth dielectric, again metal level is inserted, at last unnecessary metal is removed, had the flat structures of damascene in dielectric layer and obtain one.Inserted processing procedure has the following advantages compared with traditional metallization process: (1) can make substrate surface keep smooth at any time; (2) can get rid of the shortcoming that dielectric materials in the conventional process is difficult for inserting the plain conductor gap: (3) can solve the problem, the particularly etching of copper metal that the metallic substance etching is difficult for.
In addition, for contact hole structure in the processing procedure that overcomes traditional interconnect needs to make respectively with wire pattern, make the shortcoming that whole fabrication steps is extremely complicated, develop in addition at present and a kind of dual damascene (dual damascene) processing procedure, its making processes is to carry out selective etch twice, after respectively lead dielectric substance (line dielectric) and interlayer dielectric substance (via dielectric) erosion being opened, once finish the barrier layer of metal level and connector, and once conducting metal is inserted interlayer hole and interconnect groove, reach the effect of simplifying fabrication steps.In recent years, be the development of matable assembly size downsizing and the demand that improves assembly operation speed, have the copper metal of low resistance constant and high electron mobility impedance, be used to material gradually, replace aluminum metal processing procedure technology in the past as the metal interconnect.The inserted interconnect technology of copper metal not only can reach the downsizing of interconnect and can reduce the RC time lag, has also solved the problem that the metallic copper etching is difficult for simultaneously, has therefore become the main development trend of multiple now interconnect.
No matter be singly to inlay or the copper wiring of dual damascene, after the filling of finishing the copper metal, all need to carry out the planarization processing procedure, with metal removal unnecessary on the dielectric layer.At present, reach this purpose by the cmp processing procedure usually.Usually with copper-cmp processing procedure, be divided into two steps.Fs removes most copper with grinding rate faster, to increase the unit quantum of output.Subordinate phase is used and is avoided the copper in the groove is caused excessive abrasive phenomenon then with the worn remaining a little copper of slower grinding rate.Usually, the copper of two-stage grinds processing procedure, needs to change the different grinding composites of forming, and grinds demand with the copper that meets different steps.
Generally speaking; the cmp of metal level (copper) all carries out (different under alkaline condition with dielectric layer) under about about 4 the acid range of pH value; and the cmp constituent can add small amounts agent (as hydrogen peroxide) usually, to improve grinding rate.Yet; because the copper metal corroded and very easily oxidation easily, and copper can't can form the self-protection zone of oxidation as aluminium, therefore after grinding under such condition; final copper conductor usually is subjected to the corrosive situation, thereby badly influences the quality of interconnect.
For addressing the above problem, prior art is to add a corrosion inhibitor in process of lapping, as benzotriazole (1H-benzotriazole; BTA), to avoid copper metal or its alloy under acidic medium, to be corroded.Yet, grinding later, this benzotriazole can have residue in processing object (chip) remained on surface, and this residue is not easy to be removed by clean-out systems such as deionized waters, makes this processing object (chip) surface be formed uneven surface by residue, and influences the successive process of this processing object (chip).
Summary of the invention
Main purpose of the present invention is promptly providing a kind of corrosion inhibitor that is used for the cmp constituent, can improve the inhibition corrosive power of processing object, and can not grind the residual corrosion inhibitor that residue is arranged of object surface.
Take off purpose on reaching, be musculamine acid and salt compounds thereof as the creatine compound used of corrosion inhibitor among the present invention, this corrosion inhibitor is used for the cmp constituent, can when cmp, form layer protecting film in the surface in processing object, to avoid processing object to be corroded, also can improve to practise and utilize corrosion inhibitor (benzotriazole for example; BTA), can form the disappearance of residue in the processing object surface.
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 creatine compound used as corrosion inhibitor; 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 cmp constituent; can when cmp, form layer protecting film in the surface in processing object; to avoid processing object to be corroded; can improve the inhibition corrosive power of processing object; this cmp constituent also further includes except corrosion inhibitor: abrasive particle, oxygenant, accelerator, inhibitor and solvent.
The example of this abrasive particle comprises, but the non-silicon-dioxide that is limited to calcination; The silicon dioxide gel that forms from water glass or potassium silicate hydrolysis or silane hydrolyzate and condensation; The aluminium dioxide of precipitation or calcination; The titanium dioxide of precipitation or calcination; Macromolecular material; And metal oxide and macromolecular material mixture (hybrid).The preferably is a silicon dioxide gel.If the abrasive particle consumption is low excessively, be unfavorable for mechanical mill, can't reach desired grinding clearance; On the other hand, if the too high effect of then can acceleration mechanical grinding of abrasive particle consumption, increase the clearance of barrier layer and insulating oxide, also be easy to generate the grinding defective of surface abrasion.In a specific examples, this silicon sol accounts for constituent gross weight 0.01 to 30 weight %, preferable 0.1 to the 15 weight % that accounts for.
With regard to the cmp constituent that grinds the copper layer, preferable use hydrogen peroxide is as oxygenant.Usually, this oxygenant accounts for 0.25 to 5 weight % of constituent gross weight, preferable 0.5 to the 3 weight % that accounts for.
The example that is used for the accelerator of this cmp constituent comprises, but non-citric acid, oxalic acid, tartrate, histidine, Beta Alanine or the glycine of being limited to.This accelerator is used to promote metal to be ground, for example the dissolving of copper.Improve the accelerator addition in the grinding composite, help to promote the grinding clearance of metal level, be applicable to that the metal level of fs grinds.Yet, improve the accelerator addition in the grinding composite, also can increase static etched speed simultaneously, be unfavorable for the trickle polishing of subordinate phase.In a specific examples, this accelerator accounts for 0.01 to 10 weight % of constituent gross weight, preferable 0.1 to the 5 weight % that accounts for, better 0.3 to the 3 weight % that accounts for.
The corrosion inhibitor of this cmp constituent and inhibitor, grind at height under the condition of clearance, effectively suppress static etch rate, to be applicable to the grinding and polishing processing procedure of fs and subordinate phase, corrosion inhibitor of the present invention 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-be 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，CAS97-78-9)
N-anilide musculamine acid (N-acyl sarcosine), cocounut oil anilide musculamine acid (cocoyl sarcosine), oily vinegar musculamine acid (oleoyl sarcosine), stearic vinegar musculamine acid (stearoyl sarcosine), the cool vinegar musculamine of Ji Rou Beans 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-Lauroyl Sarcosinate) for example.
Formula three
【CH
3(CH
2)
10CON(CH
3)CH
2COONa，CAS 137-16-6】
Generally speaking, this corrosion inhibitor accounts for 0.0005 to 1% of constituent gross weight, preferable 0.001 to 0.5% of the constituent gross weight that accounts for, better 0.005 to 0.1% of the constituent gross weight that accounts for.
The example of this inhibitor comprises, but the non-imidazolines that is limited to; Triazole class compounds and derivative thereof, for example 1,2,4-triazole, 3-amido-1,2,4-triazole, 3-nitro-1,2,4-triazole, 3-amido-1H-1,2,4-triazole-5-carboxylic acid, 1-H-benzotriazole or 5-methyl isophthalic acid, 2,3-benzotriazole.Generally speaking, this inhibitor accounts for 0.0001 to 1% of constituent gross weight, preferable 0.005 to 0.8% of the constituent gross weight that accounts for, better 0.01 to 0.5% of the constituent gross weight that accounts for.
Constituent of the present invention can make water as solvent, and preferable use deionized water is as the solvent of this grinding composite.
Below further specify characteristics of the present invention and effect by particular specific embodiment, but non-ly be used to limit category of the present invention.
Embodiment one
Listed according to table one, use comprises silicon dioxide gel abrasive particle, Beta Alanine, the hydrogen peroxide, 1 of the about 90nm of median size, 2,4-triazole (inhibitor), cocounut oil anilide musculamine acid sodium (corrosion inhibitor) and solvent are that the ground slurry constituent control sample of water is tested.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)
Table one
Grinding test is to carry out according to following condition, grind clearance (Removal Rate, RR) and the mean value result of etch-rate (Etch Rate) be embedded in table two.
Grinder station: Mirra polisher (Applied Materials)
Type of wafer: 8 o'clock cover copper film wafer (Ramco Co)
Grind overdraft: 2psig
Platform rotating speed: 90rpm
Carrier rotating speed: 85rpm
Grinding pad: IC 1010 (Rohm and Haas)
Grind slurry flow velocity: 200ml/min.
Table two
According to table two result as can be known, in this reference examples 1 and the reference examples 2, the copper grinding clearance of reference examples 1 and etch-rate are greater than reference examples 2, and in reference examples 3 and the reference examples 4, the copper of reference examples 3 grinding clearance and etch-rate are greater than reference examples 4, and the result as can be known thus, if use cocounut oil anilide musculamine acid sodium as corrosion inhibitor, can significantly reduce copper and grind clearance and etch-rate,, can avoid processing object to be corroded effectively so this corrosion inhibitor can provide preferable inhibition corrosive power.
Embodiment two
Listed according to table three, reference examples 5 is used silicon dioxide gel abrasive particle, hydrogen peroxide, potassium hydroxide, the benzotriazole (corrosion inhibitor) that comprises the about 90nm of median size, reference examples 6 is then used the silicon dioxide gel abrasive particle that comprises the about 90nm of median size, hydrogen peroxide, potassium hydroxide, cocounut oil anilide musculamine acid sodium (corrosion inhibitor) and the solvent ground slurry constituent as water, be that control sample is tested under 11 the environment in the pH value.
| Oxygenant (hydrogen peroxide) (wt%) | Abrasive particle (silicon dioxide gel) (wt %) | BTAppm | Corrosion inhibitor ppm | KOH (wt％) | pH | |
| Reference examples 5 | 0.5 | 30.0 | 50 | 0 | 0.1 | 11 |
| Reference examples 6 | 0.5 | 30.0 | 0 | 50 | 0.1 | 11 |
Table three
Grinding test carries out according to following condition, and (Removal Rate, mean value result RR) is embedded in table four to grind clearance.
Grinder station: Applied Material Mirra Polisher, (San Jose, CA)
Type of wafer: 8 o'clock cover copper, TEOS, tantalum films wafer
Grind overdraft: 2psig
Platform rotating speed: 70rpm
Carrier rotating speed: 65rpm
Grinding pad: IC 1010 (Rohm and Haas)
Grind slurry flow velocity: 200ml/min.
| Ox grinds clearance (A/min) | Cu grinds clearance (A/min) | Ta grinds clearance (A/min) | |
| Reference examples 5 | 1244 | 657 | 633 |
| Reference examples 6 | 1223 | 556 | 601 |
Table four
According to table four result as can be known, the copper of this reference examples 5 grinds clearance and tantalum (Ta) grinds clearance greater than reference examples 6, the result as can be known thus, if use cocounut oil anilide musculamine acid sodium as corrosion inhibitor, can significantly reduce the grinding clearance of copper and tantalum (Ta), so can provide preferable inhibition corrosive power (compared to benzotriazole as corrosion inhibitor) with cocounut oil anilide musculamine acid sodium as corrosion inhibitor, can avoid processing object to be corroded effectively.
By the various embodiments described above as can be known, the present invention utilizes creatine compound used (as musculamine acid and salt compounds thereof) as the corrosion inhibitor in the cmp constituent, utilizes benzotriazole (1H-benzotriazole with habit; BTA) compare as corrosion inhibitor, have preferable inhibition corrosive power, can avoid processing object to be corroded, and also can be in grinding the residual situation generation that residue is arranged of object surface.
Technology contents of the present invention and technical characterstic 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 (12)
1, a kind of creatine compound used as corrosion inhibitor, this corrosion inhibitor is used for the cmp constituent, and wherein, this corrosion inhibitor is musculamine acid and salt compounds or its composition.
2, creatine compound used as corrosion inhibitor according to claim 1, wherein this musculamine acid and salt compounds thereof comprise, but non-musculamine acid, the acid of N-anilide musculamine, the acid of bay vinegar musculamine, the acid of cocounut oil anilide musculamine, the acid of oily vinegar musculamine, the acid of stearic vinegar musculamine, the cool vinegar musculamine acid of Ji Rou Beans or its lithium salts, sodium salt, sylvite or amine salt or its composition of being limited to.
3, creatine compound used as corrosion inhibitor according to claim 1, wherein this musculamine acid and salt compounds thereof can be musculamine acid, the chemical formula of this musculamine acid is suc as formula one:
Formula one
(CH
3NHCH
2COOH，CAS＝107-97-1)。
4, creatine compound used as corrosion inhibitor according to claim 1, wherein this musculamine acid and salt compounds thereof can be the acid of bay vinegar musculamine, the chemical formula of this bay vinegar musculamine acid is suc as formula two:
Formula two
(C
15H
29NO
3，CAS 97-78-9)。
5, creatine compound used as corrosion inhibitor according to claim 1, wherein this musculamine acid and salt compounds thereof can be bay vinegar musculamine acid sodium-salt, the chemical formula of this bay vinegar musculamine acid sodium-salt is suc as formula three:
Formula three
【CH
3(CH
2)
10CON(CH
3)CH
2COONa，CAS 137-16-6】。
6, creatine compound used as corrosion inhibitor according to claim 1, wherein this musculamine acid and salt compounds thereof can be cocounut oil anilide musculamine acid sodium, the chemical formula of this cocounut oil anilide musculamine acid sodium is suc as formula four:
Formula four.
7, creatine compound used as corrosion inhibitor according to claim 1, wherein this cmp constituent further includes: abrasive particle, oxygenant, accelerator, inhibitor and solvent.
8, as creatine compound used as corrosion inhibitor as described in the claim 7, wherein this abrasive particle can be silicon dioxide gel, and this abrasive particle accounts for 0.01 to 30% of constituent gross weight.
9, as creatine compound used as corrosion inhibitor as described in the claim 7, wherein this accelerator accounts for 0.01 to 5% of constituent gross weight.
10, as creatine compound used as corrosion inhibitor as described in the claim 7, wherein this inhibitor is selected from imidazolines, and cohort that triazole class compounds constituted.
11, as creatine compound used as corrosion inhibitor as described in the claim 7, wherein this inhibitor accounts for 0.0001 to 1% of constituent gross weight.
12, as creatine compound used as corrosion inhibitor as described in the claim 7, wherein this corrosion inhibitor accounts for 0.0001 to 1% of constituent gross weight.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100080142A CN101525751B (en) | 2008-03-03 | 2008-03-03 | Chemical mechanical grinding composition |
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|---|---|---|---|
| CN2008100080142A CN101525751B (en) | 2008-03-03 | 2008-03-03 | Chemical mechanical grinding composition |
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|---|---|---|---|
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| CN101525751B CN101525751B (en) | 2012-05-30 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304716A (en) * | 2011-08-30 | 2012-01-04 | 吴江市精工铝字制造厂 | Corrosion inhibitor |
| CN104762627A (en) * | 2015-04-03 | 2015-07-08 | 上海依科绿色工程有限公司 | High-performance, closed and environment-friendly carbon steel corrosion inhibitor and preparation and application thereof |
| US11339310B2 (en) | 2017-03-22 | 2022-05-24 | Fujimi Incorporated | Polishing composition |
-
2008
- 2008-03-03 CN CN2008100080142A patent/CN101525751B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304716A (en) * | 2011-08-30 | 2012-01-04 | 吴江市精工铝字制造厂 | Corrosion inhibitor |
| CN104762627A (en) * | 2015-04-03 | 2015-07-08 | 上海依科绿色工程有限公司 | High-performance, closed and environment-friendly carbon steel corrosion inhibitor and preparation and application thereof |
| CN104762627B (en) * | 2015-04-03 | 2017-07-18 | 上海依科绿色工程有限公司 | A kind of high-performance closed environment-friendly type carbon steel corrosion inhibitor and its preparation and application |
| US11339310B2 (en) | 2017-03-22 | 2022-05-24 | Fujimi Incorporated | Polishing composition |
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| Publication number | Publication date |
|---|---|
| CN101525751B (en) | 2012-05-30 |
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