CN1370820A - Water-containing detergent composition used after chemical and mechanical flattening treatment - Google Patents
Water-containing detergent composition used after chemical and mechanical flattening treatment Download PDFInfo
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- CN1370820A CN1370820A CN 01104317 CN01104317A CN1370820A CN 1370820 A CN1370820 A CN 1370820A CN 01104317 CN01104317 CN 01104317 CN 01104317 A CN01104317 A CN 01104317A CN 1370820 A CN1370820 A CN 1370820A
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Abstract
The detergent composition has pH value of 2-6, and consists of organic acid 1-10 wt%, corrosion inhibitor 0.05-0.5 wt%, alcohol amine 0.01-2 wt%, and polyol compound 0.01-2 wt% and water (the balance). It is used to eliminate residual pollution on the surface of chemically and mechanically flattened silicon chip, such as grinding particle, metal complex and organic molecule without rusting metal wires.
Description
The invention relates in the semi-conductor subsequent technique,, remove the pollutent of the process for copper silicon wafer surface behind chemical-mechanical planarization effectively, be beneficial to the carrying out of technologies such as subsequent thin film deposition, little shadow with the liquid cleaning composition that particular chemical is formed.
About semiconductor element, now just towards littler live width, more the direction of high density of integration develops, when the unicircuit minimum feature is reduced to below 0.25 micron, resistance and the caused time lag of dielectric layer stray capacitance (RC delay) by plain conductor itself, become the main key that influences the element arithmetic speed, therefore in order to improve the arithmetic speed of element, this area has changed into and has adopted the copper plain conductor of low-k (lowk dielectric) to replace traditional aluminum-copper alloy lead at present.
The technology of chemical-mechanical planarization (Chemical mechanical planarization) is applied in the copper plain conductor technology, not only can overcome the problem that is difficult for being difficult to define pattern because of the copper metal etch, and after grinding is the plane of a universe planarization (global planrity), is easy to the carrying out of multi-layer conductor leads metallization processes.The principle of chemical-mechanical planarization is that the abrasive grains in the mat lapping liquid matches with chemical assistant, make wafer surface is produced mechanical wear, be able to by this uneven higher position in surface is removed speed because of pressurized produces height greatly, the smooth lower of air spots has because of pressurized is little and removes speed more slowly, and then reaches the purpose of universe planarization.
Cmp (Chemical Mechanical Polishing, in process of lapping CMP), a large amount of fine ground particle and chemical assistant in the lapping liquid, and the chip of being peeled off in the process of lapping may be attached to wafer surface.General wafer common pollutent after grinding is metal ion, organic compound or abrasive grains etc., if no effective cleaning program is removed above-mentioned pollutent, then will influence the carrying out of subsequent technique and the good rate and the reliability of reduction element, therefore after CMP ground, cleaning had become the gordian technique of successful Application CMP in semiconductor technology.
The cardinal principle of chemical-mechanical planarization afterwash technology is for brushing wafer surface micronic dust, etched wafer surface to remove the specific pollutent of upper layer metallic pollution and mat acid fluid dissolves etc. with polyvinyl alcohol (PVA) brush.
Often use the RCA method of cleaning behind the chemical-mechanical planarization, it uses a kind of liquid cleaning composition that is called SC-1, comprise 28% ammonium hydroxide, 30% hydrogen peroxide and deionized water (ratio is 1: 1: 5), with the organic and contaminant metal ions of removal wafer surface, and remove zone of oxidation post-etch residue etc.After SC-1 cleans, continue to use the SC-2 liquid cleaning composition, comprise 30% hydrogen peroxide, 37% hydrochloric acid and deionized water (ratio is 1: 1: 5), further handle to remove remaining metal pollutant.
Hydrogen peroxide in the aforesaid method its role is to make wafer surface to produce the zone of oxidation of protectiveness, is corroded by strong acid or highly basic in solution to avoid wafer.Will utilize hydrofluoric acid solution or steam this zone of oxidation could be removed but often still need after cleaning, in addition, hydrogen peroxide decomposes voluntarily in solution easily and causes effective concentration to reduce, and this is the shortcoming of RCA method of cleaning.
Gai Liang method has in the market, replaces hydrogen peroxide with nonionic surface active agent in liquid cleaning composition, and adjustment pH value is 8 to 10 (being disclosed for No. 5466389 as United States Patent (USP)).Or the matrix and the amphoterics that add water-based, non-metallic ion in cleaning liquor substitute hydrogen peroxide (as the 88698th announcement of TaiWan, China patent).Though the cleaning compositions that is disclosed in the above-mentioned patent can allow wafer obtain a smooth-flat-surface after clean, but this type of cleaning compositions can produce the problem that cleaning rear surface promoting agent was adsorbed or residued in wafer surface, though can use the ozone ultrapure water to remove organic residue at present, but need special equipment and step, increase the complicacy of technology in rain.
For in the semi-conductor subsequent technique, remove the pollutent of the process for copper silicon wafer surface behind chemical-mechanical planarization effectively, be beneficial to the carrying out of subsequent technique, the application's inventor, through broad research, discovery has the aqueous cleaning fluid composition of some special composition, can realize purpose of the present invention, and the result of gained is set forth among the present invention.
Main purpose of the present invention is to provide a kind of aqueous cleaning fluid composition that is used for chemical-mechanical planarization.
Another object of the present invention provides a kind of residue that can effectively remove behind the cmp, and can not corrode the aqueous cleaning fluid composition of wafer surface.
Liquid cleaning composition of the present invention, its pH value comprise organic acid, corrosion inhibitor, hydramine, many alcohol compounds and water between 2～6.
Fig. 1 is surface scan Electronic Speculum (FE-SEM) photo of wafer after polluting.
Fig. 2 is surface scan Electronic Speculum (FE-SEM) photo of wafer after cleaning compositions of the present invention cleans.
The invention relates to a kind of for the aqueous cleaning fluid composition behind the chemical-mechanical planarization, its pH value comprises corrosion inhibitor, the 0.01-2 % by weight hydramine of organic acid, the 0.01-0.5 % by weight of 1-10 % by weight, many alcohol compounds and the water of 0.01-2 % by weight between 2～6.
Aqueous cleaning fluid composition of the present invention is adjusted the pH value by nitric acid or ammoniacal liquor, and the pH value is preferably 2～3.5 between 2～6.
Organic acid used in the present invention, better oxalic acid or the citric acid of being selected from. Its content is 0.5～10 % by weight, is preferably 4～8 % by weight.
The corrosion inhibitor that the present invention invented is preferably triazole compounds (triazole compound), goodly is selected from benzotriazole (benzotriazole, BTA) or derivatives thereof, its content are 0.01～0.5 weight %.
Hydramine used in the present invention can be selected from and comprise thanomin, diethanolamine, trolamine and Propanolamine.Its consumption is 0.01～2 weight %, is preferably 0.1～1 weight %.
Many alcohol compounds used in the present invention can be selected from and comprise that ethylene glycol, 1, ammediol and glycol ether, its consumption are 0.01～2 weight %, are preferably 0.1～1 weight %.
The present invention makes an addition to the hydramine of trace and many alcohol compounds and contains in the organic acid solution, can not only remove the metal ion that is deposited on the wafer by mat organic acid sequestering action, also can remove pollutents such as residual abrasive grains and organic compound simultaneously.In addition, cleaning liquor of the present invention has good clean effect, only need at normal temperatures to wafer surface in addition suitably flushing get final product.In addition, because composition of the present invention only uses the organic solvent of minute quantity, so can reduce to minimum to the pollution of environment.
Following examples will the invention will be further described, by no means in order to limit the scope of the invention.The modifications and changes that any personnel that are familiar with this technology can reach easily all are covered by in the scope of the present invention.
Embodiment
Experimental procedure
(1) get commercially available process for copper lapping liquid ETERPOL-U6 and mix by 9: 1 with hydrogen peroxide, other adds the cupric nitrate of 72ppm, is mixed with contaminating fluid.
(2) the copper wafer is dipped in the contaminating fluid after 12 minutes, immerses 2-3 second in the deionized water again, take out afterwards and dry up with nitrogen.
(3) will pollute in the cleaning soln that sheet immerses preparation 30 seconds, and take out with nitrogen afterwards and dry up.
(4) wafer after will cleaning places and observes particle number under the surface scan Electronic Speculum (FE-SEM).
Embodiment 1
Preparation different solutions (as shown in table 1), and be 2 with the pH value that nitric acid or ammoniacal liquor are adjusted solution.
Use obtain solution to clean the wafer that pollutes, the effect of observing its clean wafers surface, the result is as shown in table 1:
Table 1
| Use solution | Wafer surface film residual particulates removal amount |
| Deionized water | ????0％ |
| 0.5 weight % oxalic acid aqueous solution | ????0％ |
| 0.5 weight % aqueous citric acid solution | ????0％ |
| 0.5 the weight % diethylenetriamine aqueous solution | ????3％ |
| 0.5 weight % ethylenediamine solution | ????0％ |
| 0.5 weight % aqueous glycol solution | ????80％ |
| 0.5 weight %1, the ammediol aqueous solution | ????70％ |
| 0.5 the weight % glycol ether aqueous solution | ????80％ |
By The above results as can be known, add micro-many alcohol compounds wafer is had cleaning effect.
Embodiment 2～4
Prepare solution as shown in table 2, and adjust the pH value with ammoniacal liquor.Use obtain solution to clean the wafer that pollutes, the effect of observing its clean wafers surface, the result is as shown in table 2:
Table 2
| Obtain solution | Wafer surface film residual particulates removal amount | |
| Embodiment 2 | 6 weight % citric acids, 0.05 weight %BTA, 0.7 weight % ethylene glycol, 0.3 weight % diethanolamine, pH=3.5. | 85% |
| Embodiment 3 | 4 weight % citric acids, 0.05 weight %BTA, 0.5 weight % diethanolamine, pH=3.5. | 50% |
| | 5 weight % oxalic acid, 0.05 weight %BTA, pH=4.5. | ????20％ |
By The above results as can be known, add the hydramine of trace and the ability that many alcohol compounds can significantly be promoted clean wafers.If only use the hydramine of trace or only use organic acid soln, clean wafer surface effectively then.
Below Shen Qing claim is in order to define Reasonable Protection scope of the present invention.Yet those skilled in the art also should belong to the row of Reasonable Protection scope of the present invention based on the accessible various conspicuous improvement of announcement of the present invention.
Claims (10)
1, a kind of aqueous cleaning fluid composition that is used for behind the chemical-mechanical planarization, its pH comprises between 2～6: (a) organic acid of 1-10 weight %; (b) corrosion inhibitor of 0.01-0.5 weight %; (c) hydramine of 0.01-2 weight %; (d) many alcohol compounds of 0.01-2 weight %; Reach (e) water.
2, composition as claimed in claim 1, wherein said pH value is between 2～3.5.
3, composition as claimed in claim 1, wherein said organic acid is to be selected from oxalic acid or citric acid.
4, composition as claimed in claim 1, wherein said organic acid consumption are 4～8 weight %.
5, composition as claimed in claim 1, wherein said corrosion inhibitor is a triazole compounds.
6, composition as claimed in claim 5, wherein triazole compounds is to be selected from the benzotriazole or derivatives thereof.
7, composition as claimed in claim 1, wherein said hydramine is to be selected from thanomin, diethanolamine, trolamine and Propanolamine.
8, composition as claimed in claim 1, wherein the consumption of said hydramine is 0.1～1 weight %.
9, composition as claimed in claim 1, wherein said many alcohol compounds are to be selected from ethylene glycol, 1, ammediol and glycol ether.
10, composition as claimed in claim 1, wherein the content of said many alcohol compounds is 0.1～1 weight %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011043172A CN1164724C (en) | 2001-02-23 | 2001-02-23 | Water-containing detergent composition used after chemical and mechanical flattening treatment |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011043172A CN1164724C (en) | 2001-02-23 | 2001-02-23 | Water-containing detergent composition used after chemical and mechanical flattening treatment |
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| Publication Number | Publication Date |
|---|---|
| CN1370820A true CN1370820A (en) | 2002-09-25 |
| CN1164724C CN1164724C (en) | 2004-09-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB011043172A Expired - Fee Related CN1164724C (en) | 2001-02-23 | 2001-02-23 | Water-containing detergent composition used after chemical and mechanical flattening treatment |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130877B (en) * | 2006-08-25 | 2011-12-07 | 安集微电子（上海）有限公司 | Metal anti-corrosion protection liquid used for semiconductor manufacture process |
| CN101130876B (en) * | 2006-08-25 | 2012-02-29 | 安集微电子（上海）有限公司 | Metal anti-corrosion rinsing liquid used for semiconductor manufacture process |
| CN105513961A (en) * | 2014-09-22 | 2016-04-20 | 中芯国际集成电路制造(上海)有限公司 | Chemical-mechanical polishing method |
| CN108998267A (en) * | 2018-08-29 | 2018-12-14 | 李少伟 | A kind of semiconductor devices corrosion inhibitor cleaning agent and preparation method |
-
2001
- 2001-02-23 CN CNB011043172A patent/CN1164724C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130877B (en) * | 2006-08-25 | 2011-12-07 | 安集微电子（上海）有限公司 | Metal anti-corrosion protection liquid used for semiconductor manufacture process |
| CN101130876B (en) * | 2006-08-25 | 2012-02-29 | 安集微电子（上海）有限公司 | Metal anti-corrosion rinsing liquid used for semiconductor manufacture process |
| CN105513961A (en) * | 2014-09-22 | 2016-04-20 | 中芯国际集成电路制造(上海)有限公司 | Chemical-mechanical polishing method |
| CN108998267A (en) * | 2018-08-29 | 2018-12-14 | 李少伟 | A kind of semiconductor devices corrosion inhibitor cleaning agent and preparation method |
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| Publication number | Publication date |
|---|---|
| CN1164724C (en) | 2004-09-01 |
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Owner name: CHANGXING DEVELOPMENT TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: CHANGXING CHEMICAL INDUSTRY CO LTD Effective date: 20060714 |
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