CN101684393A - Chemical mechanical polishing sizing agent - Google Patents
Chemical mechanical polishing sizing agent Download PDFInfo
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- CN101684393A CN101684393A CN 200810200577 CN200810200577A CN101684393A CN 101684393 A CN101684393 A CN 101684393A CN 200810200577 CN200810200577 CN 200810200577 CN 200810200577 A CN200810200577 A CN 200810200577A CN 101684393 A CN101684393 A CN 101684393A
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Abstract
The invention discloses a chemical mechanical polishing sizing agent comprising oxidant containing two groups of oxidants, wherein one group is selected from one or a plurality of permanganate and soluble salt thereof, and the other group is selected from one or a plurality of nitric acid and soluble salt thereof. The chemical mechanical polishing sizing agent of the invention increases the absolute removal speed of metal by mutual action of oxidant permanganic acid radical and bitrate radical as well as abrasive particles, improves selection ratio of relative removal speed of dielectric, canlower metal pinhole corrosion, lowers dielectric corrosion produced in the metal planarization process, obviously lowers defects and improves product yield.
Description
Technical field
The present invention relates to a kind of polishing slurries, be specifically related to a kind of chemical mechanical polishing slurry.
Background technology
Planarization has become with photoetching and etching is of equal importance and one of complementary indispensable gordian technique in unicircuit (IC) manufacturing process.And chemically machinery polished (CMP) technology is effective, the most sophisticated planarization at present.Chemical-mechanical polishing system is the chemical-mechanical planarization technology that integrates technology such as cleaning, drying, online detection, end point determination, being integrated circuit (IC) to the product of miniaturization, multiple stratification, planarization, slimming development, is that unicircuit is enhanced productivity, reduced cost, the indispensable technology of wafer overall situation planarization.CMP is widely used in IC manufacturing field, and the polishing object comprises substrate, medium and interconnection material etc.Wherein metal CMP is the device and one of critical process of making that interconnects in the following chip manufacturing of 90 nanometers, is the research focus of inferior 90 nanometer era.Metallic copper, aluminium, tungsten are being applied to the interconnection on the integrated circuit (IC)-components more and more, must realize multilayer interconnection by chemically machinery polished, thereby the chemical mechanical polishing of metals liquid of developing a new generation allows industry pay close attention to always.
US3429080 discloses a kind of composition that contains oxygenant of potassium permanganate that comprises and has been used for silicon polishing.Yet at the CMP of metal, oxygenant commonly used mainly contains the salt of ferrous metal, iodate, hydrogen peroxide etc.1991, F.B.Kaufman etc. have reported that the Tripotassium iron hexacyanide is used for the CMP technology of tungsten (" Chemical Mechanical Polishing for Fabricating Patterned W MetalFeatures as Chip Interconnects ", Journal of the Electrochemical Society, Vol.138, No.11, November 1991).United States Patent (USP) 5527423,6008119,6284151 grades disclose the CMP method that Fe (NO3) 3, alumina system carry out tungsten.United States Patent (USP) 5980775,5958288,6068787 disclose with iron ion make catalyzer, hydrogen peroxide as oxidant carries out the tungsten CMP method.Above patent all need be used the compound (iron nitrate) of iron as catalyzer.The pin-hole corrosion of their polishing object is higher, and dielectric substrate erosion is also higher, and the product yield is low.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is exactly at existing chemical mechanical polishing slurry above shortcomings, and a kind of chemical mechanical polishing slurry is provided, and the pin-hole corrosion of the polishing object of this polishing slurries is lower, dielectric substrate erosion is lower, and the product yield is higher.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of chemical mechanical polishing slurry, include oxygenant, wherein, described oxygenant comprises two groups of oxygenants, wherein one group is to be selected from permanganic acid and the soluble salt thereof one or more, and another group is for being selected from nitric acid and the soluble salt thereof one or more.
In the chemical mechanical polishing slurry of the present invention, the oxygenant that contains comprises two groups of oxygenants, and wherein one group is selected from permanganic acid and soluble salt thereof, and another group is selected from nitric acid and soluble salt thereof.The soluble salt of described permanganic acid is preferable is selected from sodium permanganate, potassium permanganate and ammonium permanganate; The soluble salt of described nitric acid is preferable is selected from SODIUMNITRATE, saltpetre and ammonium nitrate.What the total concn of described oxygenant was preferable is weight percentage 0.02～5%, and better was 0.15～2% (above per-cent all refers to account for the total weight percent of whole chemical mechanical polishing slurry).Preferable, described first and second groups of oxygenate content ratios are 1: 49～49: 1, the content of wherein single group oxygenant is not less than weight percent 0.01%.MnO4 content is high more in this system, and the removal speed of metal is high more; Otherwise it is then low more.
Chemical mechanical polishing slurry provided by the invention can not contain abrasive grains, and it is applicable to the fixedly polishing pad of abrasive grains, and the so-called fixedly polishing pad of abrasive grains is fixed with abrasive grains above being meant polishing pad itself.According to the present invention, the preferable abrasive grains that can also contain in the described chemical mechanical polishing slurry, it is applicable to general polishing pad, i.e. the fixing polishing pad of abrasive grains not.Described abrasive grains can be the existing any abrasive grains in this area, as silicon oxide, and metal oxide or oxyhydroxide and polymer beads etc.Wherein preferable silica sol and metal oxide or the hydroxide sol of being selected from.In the colloidal grinding particle one or more.Described metal oxide or hydroxide sol preferable for being selected from ferric hydroxide sol, silver suboxide colloidal sol, cupric oxide colloidal sol, manganese oxide colloidal sol, vanadium oxide colloidal sol, chromic oxide colloidal sol, molybdenum oxide colloidal sol, cobalt oxide colloidal sol, nickel oxide colloidal sol, titanium oxide sol, vanadium oxide colloidal sol, alumina sol, one or more in cerium oxide sol and the tin oxide sol.Preferable optional of described polymer beads from polyethylene and tetrafluoroethylene.That the particle diameter of described abrasive grains is preferable is 20～500nm, more is 30～200nm.The concentration of described abrasive grains is preferable to be weight percentage 0.1～10%.
The used carrier of chemical mechanical polishing slurry of the present invention can be the conventional carrier of this area, and preferable is water, or the mixed solution of alcohol and water.Described alcohol such as ethanol, Virahol.What the ratio of alcohol and water was preferable is 1: 999～1: 4.The content of carrier is that the weight percent of supplying this polishing slurries is 100%.
Chemical mechanical polishing slurry of the present invention also can contain the conventional additives of this area, and as tensio-active agent, stablizer, inhibitor and sterilant etc. are with the further polishing performance that improves the surface.
What chemical mechanical polishing slurry pH value of the present invention was preferable is 1.0～12.0, and better is 1～4.Used pH regulator agent can be various acid and/or alkali, so that pH regulator to desirable value is got final product, and sulfuric acid preferably, nitric acid, phosphoric acid, ammoniacal liquor, potassium hydroxide, thanomin and/or trolamine or the like.
Polishing slurries of the present invention can prepare according to the ordinary method of this area, as being made by following method: with the mentioned component uniform mixing, adopt the pH regulator agent to adjust the pH value to desirable value then.Agents useful for same of the present invention and raw material are all commercially available to be got.
The present invention also provides the application of described chemical mechanical polishing slurry in chemically machinery polished.The polishing object of its particularly suitable is the metal that common manufacture of semiconductor uses, and comprises tungsten, copper, aluminium, tantalum or tantalum nitride, titanium or titanium nitride; Optimal polishing is to liking tungsten or copper.
Positive progressive effect of the present invention is: chemical mechanical polishing slurry 1 of the present invention) by oxygenant MnO4 and nitrate radical, increase the absolute removal speed of metal with the interaction of abrasive grains, reduce the metal needle pitting corrosion, defective is obviously descended, improve the product yield.2) improve relative removal rate selection ratio in the planarization process to dielectric substance; Can reduce the dielectric substrate erosion that produces in the metal planarization process, improve the product yield.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.
Embodiment 1～18
Table 1 is the chemical mechanical polishing slurry prescription of embodiment 1～18.Press listed component and content thereof in the table 1, add in the reactor and stir, adding deionized water, to be diluted to the weight percent of supplying this polishing slurries be 100%, uses pH regulator agent (20%KOH or rare HNO at last
3, select according to the needs of pH value) be adjusted to required pH value and continue to be stirred to uniform fluid, promptly obtained chemical mechanical polishing slurry in static 30 minutes.
The component and the content of table 1. embodiment 1～18 chemical mechanical polishing slurry
Further specify beneficial effect of the present invention below by effect embodiment.
Effect embodiment 1
Table 2 is prescriptions of contrast clean-out system 1 and clean-out system of the present invention 1～6.By listed component and content thereof in the table, add in the reactor and stir, add deionized water and be diluted to volume requiredly, use pH regulator agent (20%KOH or rare HNO at last
3, select according to the needs of pH value) be adjusted to required pH value and continue to be stirred to uniform fluid, promptly obtained chemical mechanical polishing slurry in static 30 minutes.
The component of table 2. polishing slurries and content (wt%)
With above-mentioned polishing slurries differing materials is polished respectively and (comprise tungsten (W) substrate, titanium nitride (TiN) substrate, silicon-dioxide (TEOS) substrate, polishing condition is identical, burnishing parameters is as follows: Logitech. polishing pad, downward pressure 3-5psi, rotary speed/rubbing head rotating speed=60/80rpm, polishing time 120s, chemical mechanical polishing slurry flow velocity 100mL/min.Polish results sees Table 3.
Polishing speed and the polishing effect of table 3. polishing slurries on different chips
As can be seen from Table 3, compare with the contrast polishing slurries, polishing slurries of the present invention has increased the absolute removal speed of metal, and the tungsten static etch rate significantly reduces simultaneously, thereby reduces tungsten pin-hole corrosion, and defective is obviously descended, and improves the product yield.2) improve relative removal rate selection ratio in the planarization process to dielectric substance; Can reduce the dielectric substrate erosion that produces in the metal planarization process, improve the product yield.
Claims (14)
1, a kind of chemical mechanical polishing slurry, comprise oxygenant and carrier, it is characterized in that described oxygenant comprises two groups of oxygenants, wherein one group is to be selected from permanganic acid and the soluble salt thereof one or more, and another group is for being selected from nitric acid and the soluble salt thereof one or more.
2, chemical mechanical polishing slurry according to claim 1 is characterized in that, the soluble salt of described permanganic acid is selected from sodium permanganate, potassium permanganate and ammonium permanganate; The soluble salt of described nitric acid is selected from SODIUMNITRATE, saltpetre and ammonium nitrate.
3, chemical mechanical polishing slurry according to claim 1 is characterized in that, the total concn of described oxygenant is weight percentage 0.02～5%.
4, chemical mechanical polishing slurry according to claim 3 is characterized in that, the total concn of described oxygenant is weight percentage 0.15～2%.
5, chemical mechanical polishing slurry according to claim 1 is characterized in that, described first and second groups of oxygenate content ratios are 1: 49～49: 1, the content 〉=weight percent 0.01% of wherein single group oxygenant.
6, chemical mechanical polishing slurry according to claim 1 is characterized in that, described chemical mechanical polishing slurry also comprises abrasive grains.
7, chemical mechanical polishing slurry according to claim 6 is characterized in that, described abrasive grains is for being selected from silica sol, one or more in polymer beads and metal oxide or the hydroxide sol.
8, chemical mechanical polishing slurry according to claim 7 is characterized in that, described metal oxide or hydroxide sol are for being selected from ferric hydroxide sol, silver suboxide colloidal sol, cupric oxide colloidal sol, manganese oxide colloidal sol, vanadium oxide colloidal sol, chromic oxide colloidal sol, molybdenum oxide colloidal sol, cobalt oxide colloidal sol, nickel oxide colloidal sol, titanium oxide sol, vanadium oxide colloidal sol, alumina sol, one or more in cerium oxide sol and the tin oxide sol.
9, chemical mechanical polishing slurry according to claim 6 is characterized in that, the particle diameter of described abrasive grains is 20～500nm.
10, chemical mechanical polishing slurry according to claim 9 is characterized in that, the particle diameter of described abrasive grains is 30～200nm.
11, chemical mechanical polishing slurry according to claim 6 is characterized in that, the concentration of described abrasive grains is weight percentage 0.1～10%.
12, chemical mechanical polishing slurry according to claim 1 is characterized in that, described carrier is a water, or the mixed solution of alcohol and water.
13, chemical mechanical polishing slurry according to claim 1 is characterized in that, described pH value is 1～12.
14, chemical mechanical polishing slurry according to claim 13 is characterized in that, described pH value is 1～4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810200577.1A CN101684393B (en) | 2008-09-26 | 2008-09-26 | Chemical mechanical polishing sizing agent |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200810200577.1A CN101684393B (en) | 2008-09-26 | 2008-09-26 | Chemical mechanical polishing sizing agent |
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| CN101684393A true CN101684393A (en) | 2010-03-31 |
| CN101684393B CN101684393B (en) | 2014-02-26 |
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| CN200810200577.1A Expired - Fee Related CN101684393B (en) | 2008-09-26 | 2008-09-26 | Chemical mechanical polishing sizing agent |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464944A (en) * | 2010-11-05 | 2012-05-23 | 安集微电子（上海）有限公司 | Chemical-mechanical polishing liquid and its application method |
| CN103890127A (en) * | 2011-10-13 | 2014-06-25 | 三井金属矿业株式会社 | Polishing slurry, and polishing method |
| CN104403570A (en) * | 2014-11-03 | 2015-03-11 | 中国科学院上海微系统与信息技术研究所 | Double oxidant-containing GST chemical mechanical polishing liquid and preparation method and use thereof |
| CN104650739A (en) * | 2013-11-22 | 2015-05-27 | 安集微电子（上海）有限公司 | Chemical-mechanical polishing solution for polishing silica substrates |
| WO2017138308A1 (en) * | 2016-02-09 | 2017-08-17 | 三井金属鉱業株式会社 | Polishing slurry and polishing material |
| CN114410226A (en) * | 2022-01-27 | 2022-04-29 | 中国科学院上海微系统与信息技术研究所 | Polishing solution and preparation method and application thereof |
| CN115975511A (en) * | 2023-02-02 | 2023-04-18 | 张家港安储科技有限公司 | Polishing solution for grinding silicon carbide substrate, polishing solution kit and grinding method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050045852A1 (en) * | 2003-08-29 | 2005-03-03 | Ameen Joseph G. | Particle-free polishing fluid for nickel-based coating planarization |
-
2008
- 2008-09-26 CN CN200810200577.1A patent/CN101684393B/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464944A (en) * | 2010-11-05 | 2012-05-23 | 安集微电子（上海）有限公司 | Chemical-mechanical polishing liquid and its application method |
| CN103890127A (en) * | 2011-10-13 | 2014-06-25 | 三井金属矿业株式会社 | Polishing slurry, and polishing method |
| CN103890127B (en) * | 2011-10-13 | 2015-09-09 | 三井金属矿业株式会社 | Abrasive slurry and Ginding process |
| CN104650739A (en) * | 2013-11-22 | 2015-05-27 | 安集微电子（上海）有限公司 | Chemical-mechanical polishing solution for polishing silica substrates |
| CN104403570A (en) * | 2014-11-03 | 2015-03-11 | 中国科学院上海微系统与信息技术研究所 | Double oxidant-containing GST chemical mechanical polishing liquid and preparation method and use thereof |
| WO2017138308A1 (en) * | 2016-02-09 | 2017-08-17 | 三井金属鉱業株式会社 | Polishing slurry and polishing material |
| JPWO2017138308A1 (en) * | 2016-02-09 | 2018-11-29 | 三井金属鉱業株式会社 | Abrasive slurry and abrasive |
| US11015086B2 (en) | 2016-02-09 | 2021-05-25 | Mitsui Mining & Smelting Co., Ltd. | Polishing slurry and polishing material |
| CN114410226A (en) * | 2022-01-27 | 2022-04-29 | 中国科学院上海微系统与信息技术研究所 | Polishing solution and preparation method and application thereof |
| CN115975511A (en) * | 2023-02-02 | 2023-04-18 | 张家港安储科技有限公司 | Polishing solution for grinding silicon carbide substrate, polishing solution kit and grinding method |
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| CN101684393B (en) | 2014-02-26 |
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