CN101684393B - Chemical mechanical polishing sizing agent - Google Patents
Chemical mechanical polishing sizing agent Download PDFInfo
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- CN101684393B CN101684393B CN200810200577.1A CN200810200577A CN101684393B CN 101684393 B CN101684393 B CN 101684393B CN 200810200577 A CN200810200577 A CN 200810200577A CN 101684393 B CN101684393 B CN 101684393B
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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, can lower 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
In integrated circuit (IC) manufacturing process, planarization has become with photoetching and etching is of equal importance and one of complementary indispensable key technology.And chemico-mechanical polishing (CMP) technique be at present the most effectively, the most ripe planarization.Chemical-mechanical polishing system is the chemical-mechanical planarization technology that integrates the technology such as cleaning, dry, online detection, end point determination, being integrated circuit (IC) to the product of miniaturization, multiple stratification, planarization, slimming development, is that integrated circuit is enhanced productivity, reduced costs, the indispensable technology of wafer overall situation planarization.CMP is widely used in IC manufacture field, and polishing object comprises substrate, medium and interconnection material etc.Wherein metal CMP is device and one of critical process of manufacturing that interconnects in the following chip manufacturing of 90 nanometer, is the study hotspot of sub-90 nanometer era.Metallic copper, aluminium, tungsten is being applied to the interconnection in integrated circuit (IC)-components more and more, must realize multilayer interconnection by chemico-mechanical polishing, thereby develops chemical mechanical polishing of metals liquid of new generation and allow industry pay close attention to always.
US3429080 discloses a kind of composition containing oxidant that comprises potassium permanganate for silicon polishing.Yet for the CMP of metal, conventional oxidant mainly contains the salt of ferrous metal, iodate, hydrogen peroxide etc.1991, F.B.Kaufman etc. have reported CMP technology (the ＂ Chemical Mechanical Polishing for Fabricating Patterned W MetalFeatures as Chip Interconnects ＂ of the potassium ferricyanide for tungsten, Journal of the Electrochemical Society, Vol.138, No.11, November1991).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 catalyst, hydrogen peroxide as oxidant carries out tungsten CMP method.Above patent all needs to use the compound (ferric nitrate) of iron as catalyst.The pin-hole corrosion of their polishing object is higher, and dielectric substrate erosion is also higher, and product yield is low.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is exactly for 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 product yield is higher.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of chemical mechanical polishing slurry, include oxidant, wherein, described oxidant package is containing two groups of oxidants, wherein one group is to be selected from one or more in permanganic acid and soluble-salt thereof, and another group is for being selected from one or more in nitric acid and soluble-salt thereof.
In chemical mechanical polishing slurry of the present invention, the oxidant package containing is containing two groups of oxidants, 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 preferably selected from sodium permanganate, potassium permanganate and ammonium permanganate; The soluble-salt of described nitric acid is preferably selected from sodium nitrate, potassium nitrate and ammonium nitrate.The total concentration of described oxidant is preferably weight percentage 0.02～5%, and better was 0.15～2% (above percentage all refers to account for the total weight percent of whole chemical mechanical polishing slurry).Preferably, first and second groups of described oxygenate content ratios are 1:49～49:1, and wherein the content of single group oxidant is not less than percentage by weight 0.01%.In this system, MnO4 content is higher, and the removal speed of metal is higher; Otherwise lower.
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 refers to that polishing pad itself is fixed with abrasive grains above.According to the present invention, the abrasive grains that preferably can also contain in 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 silica, and metal oxide or hydroxide and polymer beads etc.Wherein preferably be selected from silica sol and metal oxide or hydroxide sol.One or more in colloidal grinding particle.Described metal oxide or hydroxide sol be preferably for being selected from ferric hydroxide sol, Sol silver oxide, cupric oxide colloidal sol, manganese oxide colloidal sol, vanadium oxide colloidal sol, chromium 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 tin oxide sol.Described polymer beads is preferably optional from polyethylene and polytetrafluoroethylene.The particle diameter of described abrasive grains is preferably 20～500nm, is more 30～200nm.The concentration of described abrasive grains is for being preferably weight percentage 0.1～10%.
Chemical mechanical polishing slurry of the present invention carrier used can be the conventional carrier of this area, is preferably water, or the mixed liquor of alcohol and water.Described alcohol is as ethanol, isopropyl alcohol.The ratio of alcohol and water is preferably 1:999～1:4.The content of carrier is that the percentage by weight 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 surfactant, stabilizer, inhibitor and bactericide etc., further to improve surperficial polishing performance.
Chemical mechanical polishing slurry pH value of the present invention is preferably 1.0～12.0, and better is 1～4.PH adjusting agent used can be various acid and/or alkali, so that pH is adjusted to desirable value, and sulfuric acid preferably, nitric acid, phosphoric acid, ammoniacal liquor, potassium hydroxide, monoethanolamine and/or triethanolamine etc.
Polishing slurries of the present invention can be prepared according to the conventional method of this area, as made by following method: mentioned component is evenly mixed, then adopt pH adjusting agent to adjust pH value to desirable value.Agents useful for same of the present invention and raw material be commercially available obtaining all.
The application of chemical mechanical polishing slurry described in the present invention also provides in chemico-mechanical polishing.The polishing object of its particularly suitable is the metal that common manufacture of semiconductor is used, 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 oxidant MnO4 and nitrate anion, increase the absolute removal speed of metal with the interaction of abrasive grains, reduce metal needle pitting corrosion, defect is obviously declined, improve product yield.2) in planarization process, improve the relative removal speed of dielectric medium is selected to ratio; Can reduce the dielectric substrate erosion producing in metal planarization process, improve product yield.
Embodiment
With embodiment, further illustrate the present invention below, but the present invention is not limited.The experimental technique of unreceipted actual conditions in the following example, conventionally according to normal condition, or the condition of advising according to manufacturer.
Embodiment 1～18
Table 1 is the chemical mechanical polishing slurry formula of embodiment 1～18.Press listed component and content thereof in table 1, add in reactor and stir, adding deionized water to be diluted to supply the percentage by weight of this polishing slurries is 100%, finally uses pH adjusting agent (20%KOH or rare HNO
3, according to the needs of pH value, select) be adjusted to required pH value and continue to be stirred to homogeneous (uniform) fluid, within static 30 minutes, obtain chemical mechanical polishing slurry.
Component and the content of table 1. embodiment 1～18 chemical mechanical polishing slurry
Below by effect embodiment, further illustrate beneficial effect of the present invention.
Effect embodiment 1
Table 2 is formulas of contrast cleaning agent 1 and cleaning agent of the present invention 1～6.By listed component and content thereof in table, add in reactor and stir, add deionized water to be diluted to volume required, finally use pH adjusting agent (20%KOH or rare HNO
3, according to the needs of pH value, select) be adjusted to required pH value and continue to be stirred to homogeneous (uniform) fluid, within static 30 minutes, obtain chemical mechanical polishing slurry.
The component of table 2. polishing slurries and content (wt%)
With above-mentioned polishing slurries, different materials is carried out to polishing 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 is in 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 contrast polishing slurries, polishing slurries of the present invention has increased the absolute removal speed of metal, and tungsten static etch rate significantly reduces simultaneously, thereby reduces tungsten pin-hole corrosion, and defect is obviously declined, and improves product yield.2) in planarization process, improve the relative removal speed of dielectric medium is selected to ratio; Can reduce the dielectric substrate erosion producing in metal planarization process, improve product yield.
Claims (11)
1. the chemical mechanical polishing slurry application in improving metallic copper or tungsten polishing speed, described chemical mechanical polishing liquid comprises oxidant and carrier, it is characterized in that, described oxidant package is containing two groups of oxidants, wherein one group is to be selected from one or more in permanganic acid and soluble-salt thereof, another group is for being selected from one or more in nitric acid and soluble-salt thereof, and described polishing slurries also comprises abrasive grains, and the pH value of described chemical mechanical polishing slurry is 1～4.
2. application 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 sodium nitrate, potassium nitrate and ammonium nitrate.
3. application according to claim 1, is characterized in that, the total concentration of described oxidant is weight percentage 0.02～5%.
4. application according to claim 3, is characterized in that, the total concentration of described oxidant is weight percentage 0.15～2%.
5. application according to claim 1, is characterized in that, first and second groups of described oxygenate content ratios are 1:49～49:1, wherein content >=the percentage by weight 0.01% of single group oxidant.
6. application according to claim 1, is characterized in that, described abrasive grains is for being selected from silica sol, one or more in polymer beads and metal oxide or hydroxide sol.
7. application according to claim 6, is characterized in that, described metal oxide or hydroxide sol are for being selected from ferric hydroxide sol, Sol silver oxide, cupric oxide colloidal sol, manganese oxide colloidal sol, vanadium oxide colloidal sol, chromium oxide colloidal sol, molybdenum oxide colloidal sol, cobalt oxide colloidal sol, nickel oxide colloidal sol, titanium oxide sol, alumina sol, one or more in cerium oxide sol and tin oxide sol.
8. application according to claim 1, is characterized in that, the particle diameter of described abrasive grains is 20～500nm.
9. application according to claim 8, is characterized in that, the particle diameter of described abrasive grains is 30～200nm.
10. application according to claim 1, is characterized in that, the concentration of described abrasive grains is weight percentage 0.1～10%.
11. application according to claim 1, is characterized in that, described carrier is water, or the mixed liquor of alcohol and water.
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 CN101684393A (en) | 2010-03-31 |
| CN101684393B true CN101684393B (en) | 2014-02-26 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464944B (en) * | 2010-11-05 | 2015-05-20 | 安集微电子（上海）有限公司 | Chemical-mechanical polishing liquid and its application method |
| CN103890127B (en) * | 2011-10-13 | 2015-09-09 | 三井金属矿业株式会社 | Abrasive slurry and grinding method |
| 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 |
| CN104403570B (en) * | 2014-11-03 | 2016-08-17 | 上海新安纳电子科技有限公司 | A kind of GST chemical mechanical polishing liquid comprising dual oxidants and its production and use |
| JP6768717B2 (en) * | 2016-02-09 | 2020-10-14 | 三井金属鉱業株式会社 | Polished slurry and abrasive |
| 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 | A kind of polishing liquid and its preparation method and application |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1598062A (en) * | 2003-08-29 | 2005-03-23 | Cmp罗姆和哈斯电子材料控股公司 | Particle-free polishing fluid for nickel-based coating planarization |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1598062A (en) * | 2003-08-29 | 2005-03-23 | Cmp罗姆和哈斯电子材料控股公司 | Particle-free polishing fluid for nickel-based coating planarization |
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