CN1889237A - Method for using special chelant for micro electronic - Google Patents
Method for using special chelant for micro electronic Download PDFInfo
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- CN1889237A CN1889237A CN 200610014908 CN200610014908A CN1889237A CN 1889237 A CN1889237 A CN 1889237A CN 200610014908 CN200610014908 CN 200610014908 CN 200610014908 A CN200610014908 A CN 200610014908A CN 1889237 A CN1889237 A CN 1889237A
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- metal ion
- micro electronic
- oxidant
- chelating agent
- hydrogen peroxide
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Abstract
The present invention provides micro-electronics special used chelating agent uses method for effectively removing metal ion on base material surface. It contains adding 0.1-3 per cent micro-electronics special chelating agent diethylenediamine tetraacetic acid tetrahydroxy ethyl ethylene diamine in usual polishing solution by volume, if polishing solution being basicity then polishing; if polishing solution being acidity then adding 1-5 per cent oxyful in above-mentioned polishing solution then polishing; putting above-mentioned polished section in purge tank and adding 0.1-3 per cent micro-electronics special chelating agent diethylenediamine tetraacetic acid tetrahydroxy ethyl ethylene diamine in cleaning agent by volume percentage, and 1-5 per cent oxyful, then to make cleaning. The present invention can oxidize metal atom existing chip surface to metal ion and fully chelating with chelating agent, thereby to obtain removing.
Description
Technical field
The present invention relates to microelectronic, in particular, relate to a kind of special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt are effectively removed metal ion in surperficial ultraprecise processing such as microelectronics polishing and cleaning using method.
Background technology
Development along with very lagre scale integrated circuit (VLSIC), integrated level improves constantly, the characteristic size of device constantly reduces, requirement to the surface of silicon cleanliness factor is also strict more, silicon chip cleans and causes people's great attention already in the importance of semi-conductor industry, the no more than 500/m of very lagre scale integrated circuit (VLSIC) technological requirement adsorbate on the substrate slice that provides
2* 0.12 μ m, metallic pollution is less than 1010atom/cm
2When heavy metal (mainly from cutter) is in the forbidden band central authorities of silicon crystal at its energy level, be called " deep-level impurity ", this moment, they played a part the complex centre in electronics and hole, cause that minority carrier life time descends greatly in the crystal, few son runs off and makes leakage current increase, and these beavy metal impurities especially at high temperature have very big diffusion coefficient in silicon, when silicon single crystal flake at high temperature adds man-hour repeatedly, metal impurities just are diffused into the substrate internal layer, in the IC preparation, its leakage current is increased, the PN junction soft breakdown, resistivity of material also can change.And these metal impurities are the precipitation of the fault location in crystal very easily, produces stress or make the PN junction distortion around precipitation, and also can produce deposition at the big local metal ion of stress.This often is to cause the PN junction leakage current to increase the main cause of soft breakdown.Therefore the use of chelating agent has become essentially, and chelating agent contains two or more atoms that duplet can be provided, and two or three other atoms of will being separated by between these atoms.These can provide the atom of duplet to become the chelate of five yuan or six-membered cyclic with complexing of metal ion.Thereby metal ion is no longer spread in silicon chip, in general, can provide the atom of duplet many more, the ring of formation is many more, and chelate is also just stable more, and metal ion is just difficult more to the silicon chip diffusion inside.At present, normally used chelating agent is that ethylenediamine tetra-acetic acid has five chelate rings, and it is unstable and be slightly soluble in water, though its disodium salt is water-soluble, and stable, but the introducing of sodium ion is bigger to microelectronic harm, therefore also should not use.
The shortcoming of existing chelating agent is mainly:
(1) unstable and be slightly soluble in water, as: ethylenediamine tetra-acetic acid.
(2) the water-soluble metal ion that but contains is as the disodium salt of ethylenediamine tetra-acetic acid.
(3) chelate ring is less.
(4) only be applicable to alkaline solution.
And, the effect of chelating agent need suitable service condition could with the abundant complexing of metal ion, reach the purpose of removing metal ion.Because chelating agent is with the metal ion generation complexing of wafer surface, and because the reduction of silicon, part metal ion is reduced into atom and is present in wafer surface, make the effect of chelating agent can not fully play effect, so its metal ion content can not be effectively reduced after the substrate surface processing.
Summary of the invention
The present invention is in order to overcome weak point of the prior art, to provide a kind of and can effectively remove metal ion, can realize in the present microelectronic industry requirement to the substrate surface metal ion, the using method of the special chelant for micro electronic of environmental protection simultaneously.
The present invention is achieved through the following technical solutions:
A kind of using method of special chelant for micro electronic is characterized in that, comprises the steps:
(1) abrasive disc is put into polishing machine, the special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt of the 0.1-3% of percentage adding by volume in polishing fluid commonly used, if polishing fluid is an alkalescence, then the finishing method according to routine polishes; If polishing fluid is acid, then in the above-mentioned polishing fluid that contains chelating agent, add the hydrogen peroxide of 1-5% or the oxidant that equates with the hydrogen peroxide oxidation effect, the finishing method according to routine polishes afterwards, obtains the polished silicon wafer of cleaning;
(2) above-mentioned polished silicon wafer is put into rinse bath, 3% special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt are foretold in percentage adding by volume 0. in cleaning agent, and by volume percentage adds the hydrogen peroxide of 1-5% or the oxidant that equates with the hydrogen peroxide oxidation effect, cleaning method according to routine cleans afterwards, obtains clean wafer.
Described oxidant is F
2, Cl
2, Br
2, O
2, O
3, the oxidant of metal ion not such as hydrogen peroxide.
The present invention has following technique effect:
Special chelant for micro electronic of the present invention is the FA/O chelating agent (two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt) that professor Liu Yuling of Hebei University of Technology once obtained invention award, it has the chelate ring more than 13, water-soluble, do not contain metal ion, can in wideer pH solution, use, and have certain non-oxidizability.The effect of chelating agent need suitable service condition could with the abundant complexing of metal ion, reach the purpose of removing metal ion.The metallic atom that is present in wafer surface can be oxidized to metal ion by method of the present invention,, thereby reach the purpose of removal with the abundant chelating of chelating agent.And environmental protection.
Action principle of the present invention:
Because the reduction of silicon, a part of metal ion is reduced into atom and is present in wafer surface, and in order to reach the purpose of removal, the approach that we solve is exactly to add proper amount of oxidant therein.And in alkali condition following time, the coefficient of stability of chelating agent itself is bigger, and because the existence of polishing conditions such as pressure and rotating speed, make the oxygen that itself contains in the polishing fluid just metallic atom wherein can be oxidized to metal ion, so under alkali condition, can in polishing fluid, not add oxidant and only add chelating agent.But under acid condition, because the coefficient of stability of chelating agent itself is smaller, even there is the existence of polishing conditions such as pressure and rotating speed metallic atom wherein can not be oxidized to metal ion, so will in the polishing fluid under the acid condition, add oxidant, metallic atom is oxidized to metal ion, increases the effect of chelating agent metal ion.And in ensuing cleaning owing to there is not the effect of external conditions such as pressure, no matter cleaning agent is alkalescence or acidity, the oxygen that itself contains all can not be converted into metal ion with metallic atom wherein, so must add oxidant when in cleaning agent, adding chelating agent, the metallic atom of wafer surface is oxidized to metal ion, increases the effect of chelating agent metal ion.Therefore, process above-mentioned two goes on foot the polishing of adding oxidants and chelating agent and cleans the back with regard to the metal ion in the substrate surface ultraprecise processing in the more effective removal microelectronic industry of energy.
Description of drawings
Fig. 1 is the chelating figure of special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt used in the present invention and metal ion.
Embodiment
The ligand of chelate is commonly referred to chelating agent, their major parts are organic compounds, chelating agent among the present invention is two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt, Fig. 1 is the chelating figure of special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt used in the present invention and metal ion, special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt used in the present invention have the atom that can " give " duplet more than 13, because it contains 13 above coordination atoms, therefore it can form 13 above chelate rings with metal ion, becomes the stable chelate of a class.Its energy and tens kinds of metallic elements carry out complexing and generate stable chelate, particularly in the aqueous solution, do not form the metal ion of complex compound with general ligand, as Li+, Na+, Ca2+, Mg2+ etc., also can be generated stable chelate, efficiently solve the problem of metal ion enrichment in the surperficial ultraprecise processing such as microelectronics cleaning and polishing by complexing.
Oxidant among the present invention is preferably selected the oxidant that does not contain metal ion for use, as hydrogen peroxide, F
2, Cl
2, Br
2, O
2, O
3, the oxidant of metal ion not such as hydrogen peroxide.If selection contains the consumption that the oxidant of metal ion need increase chelating agent, increased production cost.
Below in conjunction with specific embodiment to the detailed description of the invention.
Embodiment 1
Abrasive disc is put into polishing machine, the special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt of percentage adding by volume 0.1% in polishing fluid commonly used, polishing fluid is an alkalescence, and pH value is 13, and the finishing method according to routine polishes afterwards.
Again above-mentioned polished silicon wafer is put into rinse bath, the special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt of adding 0.1% in cleaning agent, and 1% hydrogen peroxide is as oxidant, and the cleaning method according to routine cleans afterwards, obtains clean wafer.
Embodiment 2
Abrasive disc is put into polishing machine, polishing fluid is acid, pH value is 1, the special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt of percentage adding by volume 3% in above-mentioned polishing fluid, with 1% hydrogen peroxide as oxidant, the finishing method according to routine polishes afterwards.
Again above-mentioned polished silicon wafer is put into rinse bath, the special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt of adding 3% in cleaning agent, and 3% hydrogen peroxide is as oxidant, and the cleaning method according to routine cleans afterwards, obtains clean wafer.
Embodiment 3
Abrasive disc is put into polishing machine, polishing fluid is acid, pH value is 3, the special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt of percentage adding by volume 1% in above-mentioned polishing fluid, with 2% hydrogen peroxide as oxidant, the finishing method according to routine polishes afterwards.
Again above-mentioned polished silicon wafer is put into rinse bath, the special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt of adding 1% in cleaning agent, and 5% hydrogen peroxide is as oxidant, and the cleaning method according to routine cleans afterwards, obtains clean wafer.
Embodiment 4
Abrasive disc is put into polishing machine, polishing fluid is acid, pH value is 4, the special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt of percentage adding by volume 1% in above-mentioned polishing fluid, with 2% hydrogen peroxide as oxidant, the finishing method according to routine polishes afterwards.
Again above-mentioned polished silicon wafer is put into rinse bath, the special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt of adding 1% in cleaning agent, and 2% hydrogen peroxide is as oxidant, and the cleaning method according to routine cleans afterwards, obtains clean wafer.
Embodiment 5
Abrasive disc is put into polishing machine, and polishing fluid is an alkalescence, and pH value is 11, the special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt of percentage adding by volume 1% in above-mentioned polishing fluid, and the finishing method according to routine polishes afterwards.
Again above-mentioned polished silicon wafer is put into rinse bath, in cleaning agent, add 1% special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt, and 1% Cl
2As oxidant, the cleaning method according to routine cleans afterwards, obtains clean wafer.
Embodiment 6
Abrasive disc is put into polishing machine, and polishing fluid is an alkalescence, and pH value is 10, the special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt of percentage adding by volume 1% in above-mentioned polishing fluid, and the finishing method according to routine polishes afterwards.
Again above-mentioned polished silicon wafer is put into rinse bath, in cleaning agent, add 1% special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt, and 1% F
2As oxidant, the cleaning method according to routine cleans afterwards, obtains clean wafer.
Embodiment 7
Abrasive disc is put into polishing machine, and polishing fluid is an alkalescence, and pH value is 10, the special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt of percentage adding by volume 1% in above-mentioned polishing fluid, and the finishing method according to routine polishes afterwards.
Again above-mentioned polished silicon wafer is put into rinse bath, in cleaning agent, add 1% special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt, and 0.5% O
2As oxidant, the cleaning method according to routine cleans afterwards, obtains clean wafer.
Embodiment 8
Abrasive disc is put into polishing machine, polishing fluid is acid, pH value is 6, the special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt of percentage adding by volume 1% in above-mentioned polishing fluid, with 5% hydrogen peroxide as oxidant, the finishing method according to routine polishes afterwards.
Again above-mentioned polished silicon wafer is put into rinse bath, in cleaning agent, add 1% special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt, and 0.25% O
3As oxidant, the cleaning method according to routine cleans afterwards, obtains clean wafer.
After adopting said method that substrate is polished and clean contour Precision Machining, carry out sampling Detection, generally based on the chromatogram detection, detect the back metal ion content and all can reach requirement, qualification rate reaches more than 99%.Adding the wafer surface metal ion of processing behind the chelating agent is 10
-9Individual/cm
2, and what do not add chelating agent is 2 * 10
-7Individual/cm
2, metal ion can effectively reduce 2 orders of magnitude.Adopt the chelating agent among the present invention, the big more effect that obtains of additive capacity is good more, but can increase corresponding cost.
Although the disclosed using method that relates to a kind of special chelant for micro electronic has been carried out special description with reference to embodiment, embodiment described above is illustrative and not restrictive, under the situation that does not break away from the spirit and scope of the present invention, all variations and modification are all within the scope of the present invention.
Claims (3)
1, a kind of using method of special chelant for micro electronic is characterized in that, comprises the steps:
(1) abrasive disc is put into polishing machine, the special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt of the 0.1-3% of percentage adding by volume in polishing fluid commonly used, if polishing fluid is an alkalescence, then the finishing method according to routine polishes; If polishing fluid is acid, then in the above-mentioned polishing fluid that contains chelating agent, add the hydrogen peroxide of 1-5% or the oxidant that equates with the hydrogen peroxide oxidation effect, the finishing method according to routine polishes afterwards, obtains the polished silicon wafer of cleaning;
(2) above-mentioned polished silicon wafer is put into rinse bath, the special chelant for micro electronic two ethylenediamine tetra-acetic acid tetrahydroxyethy-lethylenediamine salt of the 0.1-3% of percentage adding by volume in cleaning agent, and by volume percentage adds the hydrogen peroxide of 1-5% or the oxidant that equates with the hydrogen peroxide oxidation effect, cleaning method according to routine cleans afterwards, obtains clean wafer.
2, the using method of special chelant for micro electronic according to claim 1 is characterized in that, described oxidant is the oxidant of metal ion not.
3, the using method of special chelant for micro electronic according to claim 1 is characterized in that, described oxidant is F
2Or Cl
2Or Br
2Or O
2Or O
3Or hydrogen peroxide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100149083A CN100423202C (en) | 2006-07-25 | 2006-07-25 | Method for using special chelant for micro electronic |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100149083A CN100423202C (en) | 2006-07-25 | 2006-07-25 | Method for using special chelant for micro electronic |
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| Publication Number | Publication Date |
|---|---|
| CN1889237A true CN1889237A (en) | 2007-01-03 |
| CN100423202C CN100423202C (en) | 2008-10-01 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101892510A (en) * | 2010-07-21 | 2010-11-24 | 河北工业大学 | Cleaning method for removing surface metal impurities on polished silicon substrate material |
| CN103474330A (en) * | 2013-09-26 | 2013-12-25 | 如皋市易达电子有限责任公司 | Diode product cleaning process |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW467953B (en) * | 1998-11-12 | 2001-12-11 | Mitsubishi Gas Chemical Co | New detergent and cleaning method of using it |
| CN1236478C (en) * | 2001-08-03 | 2006-01-11 | 联华电子股份有限公司 | Cheminomechanical grinding method |
| CN1140599C (en) * | 2002-05-10 | 2004-03-03 | 河北工业大学 | Chemical and mechanical leveling polishing liquid for multilayer copper wire in large scale integrated circuit |
| CN1121060C (en) * | 2002-05-10 | 2003-09-10 | 河北工业大学 | Method for controlling adsorption state of particles adsorbed on surface of polished silicon substrate for integrated circuit |
| CN1137230C (en) * | 2002-05-10 | 2004-02-04 | 河北工业大学 | Chemimechanical overall planar polishing solution of copper and tantalum in super-large-scale integrated circuit multilayer copper wiring |
| JP4912592B2 (en) * | 2002-11-08 | 2012-04-11 | 株式会社フジミインコーポレーテッド | Polishing composition and method of using the same |
| JP2005056879A (en) * | 2003-08-01 | 2005-03-03 | Tosoh Corp | Solution and method for polishing cooper-based metal |
| US20050205835A1 (en) * | 2004-03-19 | 2005-09-22 | Tamboli Dnyanesh C | Alkaline post-chemical mechanical planarization cleaning compositions |
-
2006
- 2006-07-25 CN CNB2006100149083A patent/CN100423202C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101892510A (en) * | 2010-07-21 | 2010-11-24 | 河北工业大学 | Cleaning method for removing surface metal impurities on polished silicon substrate material |
| CN103474330A (en) * | 2013-09-26 | 2013-12-25 | 如皋市易达电子有限责任公司 | Diode product cleaning process |
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| CN100423202C (en) | 2008-10-01 |
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Granted publication date: 20081001 Termination date: 20180725 |