CN1935927A - Cerium oxide abrasive and method of polishing substrates - Google Patents
Cerium oxide abrasive and method of polishing substrates Download PDFInfo
- Publication number
- CN1935927A CN1935927A CNA2006101425095A CN200610142509A CN1935927A CN 1935927 A CN1935927 A CN 1935927A CN A2006101425095 A CNA2006101425095 A CN A2006101425095A CN 200610142509 A CN200610142509 A CN 200610142509A CN 1935927 A CN1935927 A CN 1935927A
- Authority
- CN
- China
- Prior art keywords
- cerium oxide
- particle
- slurry
- nanometers
- particle diameter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 118
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000000758 substrate Substances 0.000 title description 38
- 238000007517 polishing process Methods 0.000 title 1
- 239000002245 particle Substances 0.000 claims abstract description 215
- 239000002002 slurry Substances 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims description 36
- 239000008187 granular material Substances 0.000 claims description 35
- 239000000843 powder Substances 0.000 claims description 32
- 238000009826 distribution Methods 0.000 claims description 20
- 238000003556 assay Methods 0.000 claims 1
- 239000011164 primary particle Substances 0.000 abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 238000000227 grinding Methods 0.000 description 75
- 239000010410 layer Substances 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 25
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 25
- 238000010298 pulverizing process Methods 0.000 description 25
- 239000004065 semiconductor Substances 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 21
- 238000000576 coating method Methods 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 19
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 231100000241 scar Toxicity 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 13
- 239000011802 pulverized particle Substances 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 239000012528 membrane Substances 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 238000004438 BET method Methods 0.000 description 5
- 241000403354 Microplus Species 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002050 diffraction method Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000001413 cellular effect Effects 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- -1 vitriol Chemical compound 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 238000006748 scratching Methods 0.000 description 3
- 230000002393 scratching effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000013011 mating Effects 0.000 description 2
- 238000003701 mechanical milling Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000000452 restraining effect Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 1
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229940044927 ceric oxide Drugs 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- WDQNFBWXPGTMRL-UHFFFAOYSA-L cerium(4+) oxygen(2-) carbonate Chemical compound C([O-])([O-])=O.[O-2].[Ce+4] WDQNFBWXPGTMRL-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GRPQBOKWXNIQMF-UHFFFAOYSA-N indium(3+) oxygen(2-) tin(4+) Chemical class [Sn+4].[O-2].[In+3] GRPQBOKWXNIQMF-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004313 potentiometry Methods 0.000 description 1
- 230000003405 preventing effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000005328 spin glass Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
A cerium oxide abrasive for abrading surfaces of an SiO2 insulating film or the like film without causing defects and at high speeds. The abrasive includes a slurry obtained by dispersing, in a medium, the cerium oxide particles having diameters of primary particles of from 10 to 600 nm, a median value of 30 to 250 nm, a median value of particle diameters of 150 to 600 nm, and a maximum diameter of not larger than 3000 nm.
Description
The present invention relates to the Ginding process of cerium oxide abrasive and substrate.
In the manufacturing process of semiconductor device, the abrasive that generally uses colloidal silica system is as the cmp agent so that the SiO of methods such as plasma CVD (chemical vapour deposition), low pressure chemical vapor deposition formation traditionally
2Inorganic insulation retes such as insulating film carry out leveling.The manufacture method of colloidal silica based abrasive is, utilizes method such as thermolysis silicon tetrachloride to make silica dioxide granule grow up, utilize the basic solution of alkali-free metals such as ammoniacal liquor to adjust the pH value.Yet the technical problem of this abrasive is that the grinding rate of inorganic insulating membrane is insufficient, must use low grinding rate when reality is used this abrasive.
On the one hand, can use cerium oxide abrasive to carry out the surface grinding of photomask with glass.It is low that cerium oxide particle and silica dioxide granule, alumina particle etc. are compared hardness, thereby be difficult to scratch lapped face, grinds so can be used for polishing.In addition, well-known, cerium oxide is a kind of strong oxidizer, so have chemical activity.Effectively utilize this advantage, can be cerium oxide aptly as insulating film cmp agent.But, be used for the inorganic insulating membrane grinding if the photomask glass surface is ground the cerium oxide abrasive former state of using, then because its primary granule particle diameter is big, so can cause macroscopic grinding scar on the insulating film surface.
The invention provides and a kind ofly can not scratch SiO
2Insulating films etc. are by the cerium oxide abrasive that grinds under the high grinding rate of abrasive surface and the Ginding process of substrate.
According to cerium oxide abrasive of the present invention, contain the handlebar cerium oxide particle and be scattered in slurry in the medium, wherein the primary granule particle diameter median of this cerium oxide particle is that 30～250 nanometers, grain diameter median are 150～600 nanometers.
In addition, according to cerium oxide abrasive of the present invention, can contain the handlebar cerium oxide particle and be scattered in slurry in the medium, wherein the primary granule particle diameter median of this cerium oxide particle is that 100～250 nanometers, grain diameter median are 150～350 nanometers.
In the above-mentioned cerium oxide particle, preferably the maximum particle diameter of primary granule is below 600 nanometers, and the particle diameter of primary granule is preferably 10～600 nanometers.
In addition, according to cerium oxide abrasive of the present invention, the cerium oxide particle that can contain handlebar primary granule particle diameter median and be 30～70 nanometers, grain diameter median and be 250～600 nanometers is scattered in the slurry in the medium.
In the above-mentioned cerium oxide particle, preferably the primary granule particle diameter is 10～100 nanometers.
In cerium oxide abrasive of the present invention, preferably the maximum particle diameter of cerium oxide particle is below 3000 nanometers.
Medium can make water, and uses at least a dispersion agent that is selected from the family that is made up of for example water soluble organic polymer, water soluble anionic surfactant, water soluble nonionic surfactant and water-soluble amine, is preferably ammonium polyacrylate.
The cerium oxide that cerium oxide particle preferably uses cerous carbonate to obtain through burning till.
Utilize cerium oxide abrasive of the present invention, can grind the substrate of the defineds such as semi-conductor chip that for example are formed with silicon dioxide film.
Usually, the compound of ceriums such as cerium oxide carbonate, vitriol, oxalate obtains through burning till.SiO by formation such as TEOS-CVD methods
2Insulating film, though cerium oxide primary granule particle diameter is big more and crystallization deformation few more be that crystallinity is good more, may carry out high grinding rate more and grind, have and easily cause the tendency of grinding scar.Therefore, used cerium oxide particle among the present invention is made not improving under the crystallinity.In addition, because cerium oxide particle of the present invention is used for the grinding of semi-conductor chip, so preferably the content of basic metal and halogen is limited in below the 1ppm.
Abrasive purity height of the present invention, below 1ppm, Al content is below 10ppm respectively for the content of Na, K, Si, Mg, Ca, Zr, Ti, Ni, Cr, Fe.
Among the present invention, the preparation method of cerium oxide particle can use sintering method.But,, preferably do not improve crystalline easy fired as far as possible for the particle that makes preparation does not cause the grinding scar.Because the oxidizing temperature of cerium compound is 300 ℃, so firing temperature is preferably more than 600 ℃ below 900 ℃.
Preferably, cerous carbonate was burnt till in oxidizing atmospheres such as oxygen 5～300 minutes under the temperature below 900 ℃ more than 600 ℃.
Can utilize dry ground such as jet mill, stir method that mill (PVC-ズ ミ Le) isothermal method pulverizes and pulverize cerium oxide after burning till.In 527～532 pages of for example " chemical industry collection of thesis " the 6th volumes No. 5 (1980), have illustrated for jet mill.Find,, can take place to pulverize remaining if utilize dry ground method such as jet mill to pulverize cerium oxide after burning till.
According to ceria slurry of the present invention, be contain with good grounds method for preparing cerium oxide particle the aqueous solution or obtain by the cerium oxide particle, water and the composition that dispersion agent constituted in case of necessity that reclaim from this aqueous solution by disperseing.Wherein, though for the concentration of cerium oxide particle without limits, handle easily from suspension liquid, its concentration is preferably in 0.1～10% weight percentage ranges.In addition, dispersion agent is the dispersion agent of metal ion class not, its example has acrylate copolymer and ammonium salt thereof, methacrylate polymer and ammonium salt thereof, water soluble organic polymer classes such as polyvinyl alcohol, water soluble anionic surfactants such as ammonium lauryl sulfate, polyethylene oxide Zetesol AP, water soluble nonionic surfactants such as polyethylene oxide lauryl ether, poly-Tego-stearate, water-soluble amine such as Monoethanolamine MEA BASF, diethanolamine, or the like.
Especially, ammonium polyacrylate is preferably the ammonium polyacrylate of weight-average molecular weight 5000～20000.The addition of these dispersion agents, according to particulate dispersiveness and preventing property of sedimentation etc. in the slurry, corresponding to the cerium oxide particle of 100 weight parts, preferably at 0.01 weight part in the scope of 5 weight parts.In order to improve its dispersion effect, dispersion agent preferably when dispersion treatment and particle join in the dispersion machine simultaneously.
These cerium oxide particles are distributed to method in the water, can also use homogenizer, ultrasonic dispersing machine, ball mill etc. the dispersion treatment except being undertaken by common stirrer.Especially, for discrete particles is a cerium oxide particle below 1 micron, preferably use wet type dispersion machines such as ball mill, vibromill, planetary ball mill, medium stirring mill.In addition, under the situation that will improve slurry alkalescence, can be when dispersion treatment or handle the back and add the not alkaline matter of metal ion such as ammoniacal liquor.
Though cerium oxide abrasive of the present invention can former state use above-mentioned slurry, can add N in above-mentioned slurry, N-diethylethanolamine, N, additive such as N-dimethylethanolamine, N-aminoethyl ethanolamine and as abrasive.
The median that constitutes the primary granule particle diameter that is scattered in cerium oxide particle in the slurry of the present invention is 30～250 nanometers, and the median of the particle diameter of dispersed particles (pulp particle) is 150～600 nanometers.
If the primary particle particle diameter median of cerium oxide particle less than 150 nanometers, then can not be ground SiO by high grinding rate less than 30 nanometers or pulp particle particle diameter median
2Insulating film by abrasive surface.If the median of primary particle particle diameter, then can cause SiO greater than 600 nanometers greater than 250 nanometers or pulp particle particle diameter median
2Insulating film is by the scuffing of abrasive surface.
In addition, preferably the median of the primary particle particle diameter of cerium oxide particle is that 100～250 nanometers, grain diameter median are 150～350 nanometers.If they are less than the above-mentioned lower limit of median separately, then grinding rate diminishes; If greater than the upper limit separately, then easily scratch.
In the above-mentioned cerium oxide particle, preferably below 600 nanometers, the primary particle particle diameter is preferably 10～600 nanometers to the maximum particle diameter of primary particle.If primary particle greater than the higher limit of 600 nanometers, then easily scratches; If it is less than 10 nanometers, then grinding rate diminishes.
In addition, preferably the median of the primary particle particle diameter of cerium oxide particle is 30～70 nanometers, and the median of pulp particle particle diameter is 250～600 nanometers.If they are less than the above-mentioned lower limit of median separately, then grinding rate diminishes; If they then easily scratch greater than separately the upper limit.
In the above-mentioned cerium oxide particle, the primary particle particle diameter is preferably 10～100 nanometers.If primary particle is less than 10 nanometers, then grinding rate diminishes; If it greater than the higher limit of 100 nanometers, then easily scratches.
In the cerium oxide abrasive of the present invention, the maximum particle diameter of cerium oxide particle is preferably below 3000 nanometers.If the maximum particle diameter of cerium oxide particle greater than 3000 nanometers, then easily scratches.
By inference, burn till to contain in the cerium oxide particle after cerium oxide is pulverized by dry ground methods such as jet mills and pulverize remnants, this pulverizing residual particles is different with the coacervate that primary particle is reunited again, their stress when grinding has produced the destructive active face, it is believed that this active face helps do not scratching SiO
2Being ground under the high grinding rate of abrasive surface of insulating film.
Can contain the following pulverizing residual particles of 3000 nanometers in the slurry of the present invention.
Among the present invention, measure the primary particle particle diameter by scanning electron microscope (for example S-900 type of (strain) Hitachi manufacturing).Measure particle diameter by laser diffractometry (for example, the Master Sizer microplus that MalvernInstruments company makes, specific refractory power: 1.9285, light source: He-Ne laser absorbs O) as the cerium oxide particle of pulp particle.
Constitute the length-to-diameter ratio that is scattered in the primary particle of cerium oxide particle in the slurry of the present invention and be preferably 1～2, median is 1.3.Measure the length-to-diameter ratio of primary particle by scanning electron microscope (for example S-900 type of (strain) Hitachi manufacturing).
Being scattered in cerium oxide particle in the slurry of the present invention can use the Y value of structural parameter of its expression isotropy miniature deformation that records by the analysis of powder X-ray ray Rietvelt (リ-ト ベ Le ト) method (RIETAN-94) at the cerium oxide particle below 0.70 more than 0.01.By using this cerium oxide particle, can under not scratching, grind by lapped face and high grinding rate with crystallization deformation.
The specific surface area that is scattered in the cerium oxide particle in the slurry of the present invention is preferably 7～45m
2/ g.Specific surface area is less than 7m
2Can scratch by lapped face easily during/g, specific surface area is greater than 45m
2The slack-off tendency of grinding rate is arranged during/g.The specific surface area of cerium oxide particle is identical with the specific surface area of dispersive cerium oxide particle in the slurry.
In the slurry of the present invention the zeta current potential of cerium oxide particle be preferably-100mV is above-below the 10mV.Can make cerium oxide particle that good dispersiveness is arranged like this, and can under not scratching, grind by lapped face and high grinding rate.
The median size that is scattered in the cerium oxide particle in the slurry of the present invention is set in below above 400 nanometers of 200 nanometers, and the halfwidth of size-grade distribution is set in below 300 nanometers.
PH value of slurry of the present invention is preferably more than 7 below 10, more preferably more than 8 below 9.
Re-use after placing more than 7 days more preferably more than 30 days down at 5～55 ℃ if put into container such as polyethylene after the slurry adjustment, then scratch and tail off.
Slurry excellent dispersion of the present invention, settling velocity is slow, puts into the cylinder of the high 1m of diameter 10cm, places 2 hours, no matter how high position change rate of concentration is all less than 10%.
Can use the preparation method of the inorganic insulating membrane of cerium oxide abrasive of the present invention, low pressure chemical vapor deposition method, plasma CVD method etc. are for example arranged.Form SiO by the low pressure chemical vapor deposition method
2Use silane: SiH during insulating film
4As the Si source, use oxygen: O
2As oxygen source.By making this SiH
4-O
2Carry out under the low temperature of the oxidizing reaction of system below about 400 ℃ and obtain inorganic insulating membrane.In order to reach leveling, when Doping Phosphorus (P), preferably use SiH by high temperature reflux
4-O
2-PH
3It is reactant gases.The advantage of plasma CVD method is just can carry out the chemical reaction that must high temperature carries out at low temperature under common thermal equilibrium.The production method of plasma body for example has capacity mating type and induces two kinds of mating types.Reactant gases has and for example uses SiH
4As Si source, N
2O is as the SiH of oxygen source
4-N
2O is gas and uses the TEOS-O of tetraethoxysilane (TEOS) as the Si source
2Be gas (TEOS-plasma CVD method).Preferably in 250 ℃～400 ℃ scopes, reaction pressure is preferably in 67～400Pa scope for substrate temperature.Like this, SiO of the present invention
2Can be doped with elements such as phosphorus, boron in the insulating film.
The substrate of defined can use semiconductor substrate promptly form circuit element and wiring pattern stage semiconductor substrate, form on the semiconductor substrate of semiconductor substrate etc. in circuit element stage and be formed with SiO
2The substrate of insulating film layer.By using above-mentioned cerium oxide abrasive to grind this SiO that on semiconductor substrate, forms
2Insulating film layer can be eliminated SiO
2Insulating film layer surface uneven makes whole semiconductor substrate surface become even curface.Wherein, milling apparatus can use general milling apparatus, promptly contains the anchor clamps that keep semiconductor substrate and adheres to the platform (be equipped with can change revolution motor etc.) of abrasive cloth (pad pad).Abrasive cloth can use general non-woven fabrics, polyurathamc, porous fluoropolymer resin etc., and it is had no particular limits.In addition, preferably be processed with the ditch that can accumulate slurry on the abrasive cloth.For grinding condition without limits, but the speed of rotation of platform is preferably the following slow speed of revolution of 100rpm so that semi-conductor can not fly out, and is applied to pressure on the semiconductor substrate preferably at 1kg/cm
2Below so that do not produce scuffing after grinding.During grinding, utilize pump etc. that slurry is supplied on the abrasive cloth continuously.For its feed rate without limits, but the abrasive cloth surface preferably always covered by slurry.
After semiconductor substrate after preferably grinding being finished was fully cleaned in flowing water, use rotatory drier etc. stroked attached to the water droplet on the semiconductor substrate and makes its drying.At leveling SiO so
2On the insulating film layer, form the 2nd layer aluminum wiring, forming SiO by aforesaid method once more between its distribution and on the distribution
2Insulating film uses above-mentioned cerium oxide abrasive to grind then, thereby eliminates the uneven of insulating film surface, makes whole semiconductor surface become burnishing surface.By this technology being repeated the number of times of defined, can make the semi-conductor of the required number of plies.
Cerium oxide abrasive of the present invention not only can be used to grind the SiO that forms on semiconductor substrate
2Insulating film, and can also be used to grind the SiO that forms on the wiring board of deciding distribution to some extent containing
2Insulating film, glass, inorganic insulating membranes such as silicon nitride, opticglass such as photomask, lens, prism, ITO inorganic conductive films such as (tin indium oxides), by optic integrated circuit, switching element, the light-guide wave path that glass and crystalline material constitute, the end face of fiber optics, optics such as scintillator monocrystalline, Solid State Laser monocrystalline, celadon laser LED (photodiode) corundum substrate, semiconductor monocrystals such as SiC, GaP, GaAS, glass substrate for disc, magnetic head etc.
The substrate of defined among the present invention comprises being formed with SiO like this
2The semiconductor substrate of insulating film is formed with SiO
2The wiring board of insulating film, glass, inorganic insulating membranes such as silicon nitride, opticglass such as photomask, lens, prism, inorganic conductive films such as ITO are by optic integrated circuit, switching element, the light-guide wave path that glass and crystalline material constitute, the end face of fiber optics, optics such as scintillator monocrystalline, Solid State Laser monocrystalline, celadon laser LED corundum substrate, semiconductor monocrystals such as SiC, GaP, GaAS, glass substrate for disc, magnetic head etc.
Cerium oxide particle is dispersed in the slurry in the medium and is arranged between the part of the insulating film layer on the defined substrate and forms responding layer by chemical reaction, by using cerium oxide particle that this responding layer machinery is removed, can at high grinding rate and not cause to grind under the scar and grind insulating film layer.
Use cerium oxide abrasive to carry out the surface grinding of photomask with glass.It is low that cerium oxide particle and silica dioxide granule, alumina particle etc. are compared hardness, thereby be difficult to scratch lapped face, grinds so can be used for polishing.In addition, well-known, cerium oxide is a kind of strong oxidizer, so have chemical activity.Effectively utilize this advantage, can be cerium oxide aptly as insulating film cmp agent.But, be used for polishing insulation film if the photomask glass surface is ground the cerium oxide abrasive former state of using, then owing to its particle crystallinity height, so can cause macroscopic grinding scar on the insulating film surface.
Determine crystalline factor that crystallite dimension and crystallization deformation are arranged.If crystallite dimension more than 1 micron, then causes the grinding scar easily when crystallite dimension is extremely big; Even crystallite dimension is very little in addition, if but use the particle that does not have crystallization deformation, also can cause the grinding scar sometimes.Yet some crystalline ceric oxide particle is too low, though can not cause the grinding scar, can not grind by high grinding rate.Thereby, cerium oxide particle is not caused grind scar and the high grinding rate grinding of energy, it must have suitable particle size range and deformation to a certain degree.The factor of decision grinding rate not only has above-mentioned particulate crystallinity, but also the chemical activity of cerium oxide is arranged.
Although can use the pellet hardness silica dioxide granule harder than cerium oxide particle, the grinding rate of silica slurry is than slow many of the grinding rate of ceria slurry.This explanation is with regard to the chemical factor of chemical mechanical milling method, and ceria slurry is strong.SiO
2The insulating film surface is electronegative in the solution more than the pH3 in hydrogen concentration.If use the ceria slurry of particle positively charged to grind, then forming with the cerium oxide is the inert coating of principal constituent.This inert coating can not be removed by washing, but utilizes strongly acidic solution such as nitric acid to remove.When utilizing acid to remove inert coating, insulating film layer is removed more than 1000 nanometers.The insulating film of being removed is the responding layer that generates when forming inert coating.In addition, even cerium oxide particle also can form inert coating when electronegative.Inert coating depends on the charged size of particulate to the sticking power of insulating film.For example, the inert coating that forms when big of electronegative absolute value can be by washing, scrub and remove.The formation degree that is inert coating and responding layer depends on the particulate electriferous state.The phenomenon of this formation inert coating does not observe, is the peculiar phenomenon of ceria slurry for silica slurry.This phenomenon is the factor that the high grinding rate of decision grinds.Cerium oxide particle eliminates this inert layer and responding layer.This phenomenon is the element of chemical mechanical milling method.If the particulate crystallinity is bad, then responding layer can not be removed and grinding rate is slack-off.On the contrary, can remove responding layer when the particle crystallinity is good easily, also can eliminate the responding layer that forms fast fast after removing responding layer, responding layer formation-particle grinds the result that order carries out, and makes it possible to high grinding rate and grinds.
The method of particle electriferous state has the zeta potentiometry in the research slurry.Concrete principle is, cerium oxide is put into the cell that both sides are provided with platinum electrode, applies voltage on two electrodes.By applying voltage, charged cerium oxide particle is to electrode one side shifting of oppositely charged.Obtain its translational speed, utilize the relational expression between well-known translational speed and the zeta current potential just can obtain particulate zeta current potential.In order to form inert coating and responding layer, the zeta current potential of ceria slurry preferably-more than the 100mV.But,, all do not reach and form firm inert coating and do not cause the optimum particulate that grinds scar to grind even when the electronegative but electric charge absolute value of particle positively charged and particle during less than 10mV.Thereby, the zeta current potential of slurry preferably-more than the 100mv-below the 10mv.
Utilization contains the abrasive that the handlebar cerium oxide particle is scattered in the slurry in the medium, thereby optionally grinds other film by forming inert coating so that not only grind the surface of certain a kind of specific film, can grind the form layers that is made of two or more different films on the substrate.
By forming inert coating so that not only grind the surface of certain a kind of specific film in the form layers that constitutes by two or more different films on the substrate, thereby the membrane portions that forms this inert coating as restraining mass (stopper), can be by optionally grinding other film smooth above-mentioned form layers.
The feature of this Ginding process is; on the surface of certain specific interlayer dielectric and interlayer flatted membrane; owing to formed the inert coating that constitutes by the resultant of reaction between abrasive particles or lapping liquid constituent and the film constituent, so almost do not carry out the grinding of this film.So-called inert coating be meant grinding rate than original by the slow upper layer of grinding film.Pictograph is being become such specific interlayer dielectric of this inert coating and interlayer flatted membrane are used to form under the situation of pattern of semi-conductor chip, by thereon the layer grind and form other interlayer film, can reach whole planarizations to lower membrane as restraining mass.
As by at the device that different films constitute more than 2 kinds that forms on this substrate, can be semiconductor substrate as substrate, organic SOG (spin-on glass spin glass) film and the SiO that forms by chemical vapour deposition and thermooxidizing etc.
2Film is as the form layers above it, SiO
2Film is as the film that forms inert coating, organic sog film as the selectivity grinding film.
So-called organic sog film, be meant for example organoalkoxysilane and alkylalkoxy silane are dissolved in organic solvents such as ethanol, by making its hydrolysis to wherein adding water and catalyzer, utilize whirl coating etc. that the coating solution of gained is coated on the substrate, make it to solidify the film that obtains by heat treated then.
In this insulating film, the insulating film that the C atomicity in bonded Si atomicity and the alkyl has following relation in the siloxanes in insulation preferably:
C atomicity/(Si atomicity+C atomicity) 〉=0.1
On smooth organic SOG insulating film layer, form CVD-SiO
2Film and as the 2nd layer aluminum wiring.Forming the CVD-SiO of lower floor between its distribution and on the distribution once more
2Film and organic sog film by using above-mentioned ceria slurry to grind, are eliminated the uneven of insulating film layer surface then, make whole semiconductor surface become burnishing surface.By this technology being repeated the number of times of defined, can make the semi-conductor of the required number of plies.Thereby forms in the technology as the structure of purpose at the film that forms that utilizes this Ginding process to grind to constitute by film more than 2 kinds, smooth by utilizing the selectivity grinding to carry out, can realize the simplification and the high precision int of technology.
Embodiment 1
(preparation 1 of cerium oxide particle)
2kg cerous carbonate hydrate is packed in the platinum container, under 800 ℃, in air, burnt till 2 hours, thereby obtain the yellow-white powder of about 1kg.Utilize X-ray diffraction method to carry out the evaluation of this powder phase, turn out to be cerium oxide.Burning till the powder particle particle diameter is 30～100 microns.The surface that utilizes scanning electron microscopic observation to burn till powder particle, observe cerium oxide the grain circle.Measure the particle diameter of the cerium oxide primary granule that is surrounded by the grain circle, the median that obtains its distribution is 190 nanometers, and maximum value is 500 nanometers.Carry out X-ray diffraction and accurately measure burning till powder, utilize Rietvelt method (RIETAN-94) to analyze its result, the value that obtains expressing the structural parameter X of primary granule particle diameter is 0.080, and the value of expressing the structural parameter Y of isotropy miniature deformation is 0.223.Utilize jet mill that the 1kg ceria oxide powder is carried out dry ground.Utilize the scanning electron microscopic observation pulverized particles, find except the small-particle identical with the primary granule grain size, also mixing has from 1 micron to 3 microns bigger pulverizing residual particles with from 0.5 micron to 1 micron pulverizing residual particles.Pulverizing residual particles is not the coacervate of primary granule.Pulverized particles is carried out X-ray diffraction accurately measure, utilize Rietvelt method (RIETAN-94) to analyze its result, the value that obtains expressing the structural parameter X of primary granule particle diameter is 0.085, and the value of expressing the structural parameter Y of isotropy miniature deformation is 0.264.As a result, do not change the primary granule particle diameter substantially by pulverizing.Make by pulverizing in addition and introduced deformation on the particle.And then, utilizing BET method measurement the specific area, the result is 10m
2/ g.
(preparation 2 of cerium oxide particle)
2kg cerous carbonate hydrate is packed in the platinum container, under 750 ℃, in air, burnt till 2 hours, thereby obtain the yellow-white powder of about 1kg.Utilize X-ray diffraction method to carry out the evaluation of this powder phase, turn out to be cerium oxide.Burning till the powder particle particle diameter is 30～100 microns.The surface that utilizes scanning electron microscopic observation to burn till powder particle, observe cerium oxide the grain circle.Measure the particle diameter of the cerium oxide primary granule that is surrounded by the grain circle, the median that obtains size distribution is 141 nanometers, and maximum value is 400 nanometers.Carry out X-ray diffraction and accurately measure burning till powder, utilize Rietvelt method (RIETAN-94) to analyze its result, the value that obtains expressing the structural parameter X of primary granule particle diameter is 0.101, and the value of expressing the structural parameter Y of isotropy miniature deformation is 0.223.Utilize jet mill that the 1kg ceria oxide powder is carried out dry ground.Utilize the scanning electron microscopic observation pulverized particles, find except the small-particle identical with the primary granule grain size, also mixing has from 1 micron to 3 microns bigger pulverizing residual particles with from 0.5 micron to 1 micron pulverizing residual particles.Pulverizing residual particles is not the coacervate of primary granule.Pulverized particles is carried out X-ray diffraction accurately measure, utilize Rietvelt method (RIETAN-94) to analyze its result, the value that obtains expressing the structural parameter X of primary granule particle diameter is 0.104, and the value of expressing the structural parameter Y of isotropy miniature deformation is 0.315.As a result, do not change the primary granule particle diameter substantially by pulverizing.Make by pulverizing in addition and introduced deformation on the particle.And then, utilizing BET method measurement the specific area, the result is 16m
2/ g.
(preparation of ceria slurry)
The cerium oxide particle of the above-mentioned preparation 1,2 of 1kg, 23g polyacrylic acid aqueous ammonium (40% weight percent) and 8977g deionized water mix, and carry out ultrasonic dispersing 10 minutes while stir.Utilize 1 micron filter to filter the slurry of gained, and then obtain the abrasive of 3% weight percent by adding deionized water again.PH value of slurry is 8.3.
By laser diffractometry (for example, the MasterSizer microplus that Malvern Instrument company makes, specific refractory power: 1.9285, light source: He-Ne laser, absorption O) size distribution of mensuration pulp particle finds that the median of size distribution is 200 nanometers.The particle of largest particle particle diameter more than 780 nanometers is 0% volume percent.
For the dispersiveness of studying slurry and the electric charge of pulp particle, measure the zeta current potential of slurry.Ceria slurry is put into the cell that both sides are provided with platinum electrode, on two electrodes, apply the voltage of 10V.By applying voltage, charged pulp particle is to electrode one side shifting of oppositely charged.Just can obtain particulate zeta current potential by obtaining its translational speed.The measurement result of zeta current potential confirms, and is all electronegative under every kind of situation, its value is respectively-50mV ,-63mV, so the absolute value of zeta current potential is big, the slurry favorable dispersity.
(grinding of insulating film layer)
The SiO that is formed with according to the preparation of TEOS-plasma CVD method
2The Si wafer of insulating film is positioned over attached in the anchor clamps on the sub master that keeps substrate installation usefulness, make abrasive surface put anchor clamps down on the platform that adheres to cellular polyurethane resin ground dish, and then loaded weight is 300g/cm so that make machine load
2
On one side above-mentioned ceria slurry (solids content: 3% weight percent) speed of dividing with 50ml/ drops on the platform, one side with the speed rotatable platform of 30rpm 2 minutes, carry out the grinding of insulating film.After the grinding, take off wafer from anchor clamps, fully clean with flowing water, utilize sono-cleaner further to clean 20 minutes then.After cleaning, utilize rotatory drier to remove water droplet on the wafer, in 120 ℃ drying machine dry 10 minutes.
Utilize light interference type determining film thickness device to measure the Thickness Variation of grinding front and back, found that,
Eliminate the insulating film of 600 nanometers, 580 nanometers (grinding rate is respectively: 300 nm/min, 290 nm/min) respectively by this grinding, along entire wafer surface uniform film thickness.In addition, use observation by light microscope insulating film surface, do not find tangible scar.
Embodiment 2
(preparation of cerium oxide particle)
2kg cerous carbonate hydrate is packed in the platinum container, under 700 ℃, in air, burnt till 2 hours, thereby obtain the yellow-white powder of about 1kg.Utilize X-ray diffraction method to carry out the evaluation of this powder phase, turn out to be cerium oxide.Burning till the powder particle particle diameter is 30～100 microns.The surface that utilizes scanning electron microscopic observation to burn till powder particle, observe cerium oxide the grain circle.Measure the particle diameter of the cerium oxide primary particle that is surrounded by the grain circle, the median that obtains size distribution is 50 nanometers, and maximum value is 100 nanometers.Carry out X-ray diffraction and accurately measure burning till powder, utilize Rietvelt method (RIETAN-94) to analyze its result, the value that obtains expressing the structural parameter X of primary particle particle diameter is 0.300, and the value of expressing the structural parameter Y of isotropy miniature deformation is 0.350.
Utilize jet mill that the 1kg ceria oxide powder is carried out dry ground.Utilize the scanning electron microscopic observation pulverized particles, find except the small-particle identical with the primary particle grain size, also mixing has from 2 microns to 4 microns bigger pulverizing residual particles with from 0.5 micron to 1.2 microns pulverizing residual particles.Pulverizing residual particles is not the coacervate of primary particle.Pulverized particles is carried out X-ray diffraction accurately measure, utilize Rietvelt method (RIETAN-94) to analyze its result, the value that obtains expressing the structural parameter X of primary particle particle diameter is 0.302, and the value of expressing the structural parameter Y of isotropy miniature deformation is 0.412.As a result, do not change the primary particle particle diameter substantially by pulverizing.Make by pulverizing in addition and introduced deformation on the particle.And then, utilizing BET method measurement the specific area, the result is 40m
2/ g.
(preparation of ceria slurry)
The cerium oxide particle of the above-mentioned preparation of 1kg, 23g polyacrylic acid aqueous ammonium (40% weight percent) and 8977g deionized water mix, and carry out ultrasonic dispersing 10 minutes while stir.Utilize 2 micron filters to filter the slurry of gained, and then obtain the abrasive of 3% weight percent by adding deionized water again.PH value of slurry is 8.0.(determinator: Master Sizer microplus, specific refractory power: the 1.9285) size distribution of mensuration pulp particle, the median of discovery size distribution is 510 nanometers by laser diffractometry.The particle of largest particle particle diameter more than 1430 nanometers is 0% volume percent.
For the dispersiveness of studying slurry and the electric charge of pulp particle, measure the zeta current potential of slurry.Ceria slurry is put into the cell that both sides are provided with platinum electrode, on two electrodes, apply the voltage of 10V.By applying voltage, charged pulp particle is to electrode one side shifting of oppositely charged.Just can obtain particulate zeta current potential by obtaining its translational speed.The measurement result of zeta current potential confirms that pulp particle is electronegative, and the zeta potential value is-64mV, so its absolute value is big, and the slurry favorable dispersity.
(grinding of insulating film layer)
The SiO that is formed with according to the preparation of TEOS-plasma CVD method
2The Si wafer of insulating film is positioned over attached in the anchor clamps on the sub master that keeps substrate installation usefulness, make abrasive surface put anchor clamps down on the platform that adheres to cellular polyurethane resin ground dish, and then loaded weight is 300g/cm so that make machine load
2
On one side above-mentioned ceria slurry (solids content: 3% weight percent) speed of dividing with 35ml/ drops on the platform, one side with the speed rotatable platform of 30rpm 2 minutes, carry out the grinding of insulating film.After the grinding, take off wafer from anchor clamps, fully clean with flowing water, utilize sono-cleaner further to clean 20 minutes then.After cleaning, utilize rotatory drier to remove water droplet on the wafer, in 120 ℃ drying machine dry 10 minutes.Utilize the Thickness Variation of light interference type determining film thickness device before and after measure grinding, found that, by this grinding eliminate 740 nanometers (grinding rate is: insulating film 370 nm/min), along entire wafer surface uniform film thickness.In addition, use observation by light microscope insulating film surface, do not find tangible scar.
Embodiment 3
(preparation of cerium oxide particle)
2kg cerous carbonate hydrate is packed in the platinum container, under 800 ℃, in air, burnt till 2 hours, thereby obtain the yellow-white powder of about 1kg.Utilize X-ray diffraction method to carry out the evaluation of this powder phase, turn out to be cerium oxide.Burning till the powder particle particle diameter is 30～100 microns.The surface that utilizes scanning electron microscopic observation to burn till powder particle, observe cerium oxide the grain circle.Measure the particle diameter of the cerium oxide primary granule that is surrounded by the grain circle, the median that obtains its distribution is 190 nanometers, and maximum value is 500 nanometers.Carry out X-ray diffraction and accurately measure burning till powder, utilize Rietvelt method (RIETAN-94) to analyze its result, the value that obtains expressing the structural parameter X of primary particle particle diameter is 0.080, and the value of expressing the structural parameter Y of isotropy miniature deformation is 0.223.
Utilize to stir to grind the 1kg ceria oxide powder is carried out wet pulverization.Drying contains the liquid of pulverized particles, pulverizes dried particles with ball mill.By scanning electron microscopic observation, find that pulverized particles is the particle identical with the primary particle grain size, do not find big pulverizing residual particles.Pulverized particles is carried out X-ray diffraction accurately measure, utilize Rietvelt method (RIETAN-94) to analyze its result, the value that obtains expressing the structural parameter X of primary particle particle diameter is 0.085, and the value of expressing the structural parameter Y of isotropy miniature deformation is 0.300.As a result, do not change the primary particle particle diameter substantially by pulverizing.Make by pulverizing in addition and introduced deformation on the particle.And then, utilizing BET method measurement the specific area, the result is 10m
2/ g.
(preparation of ceria slurry)
The cerium oxide particle of the above-mentioned preparation of 1kg, 23g polyacrylic acid aqueous ammonium (40% weight percent) and 8977g deionized water mix, and carry out ultrasonic dispersing 10 minutes while stir.Utilize 1 micron filter to filter the slurry of gained, and then obtain the abrasive of 3% weight percent by adding deionized water again.PH value of slurry is 8.3.(determinator: Master Sizer microplus, specific refractory power: the 1.9285) size distribution of mensuration pulp particle, the median of discovery size distribution is 290 nanometers by laser diffractometry.The particle of largest particle particle diameter more than 780 nanometers is 0% volume percent.
For the dispersiveness of studying slurry and the electric charge of pulp particle, measure the zeta current potential of slurry.Ceria slurry is put into the cell that both sides are provided with platinum electrode, on two electrodes, apply the voltage of 10V.By applying voltage, charged pulp particle is to electrode one side shifting of oppositely charged.Just can obtain particulate zeta current potential by obtaining its translational speed.The measurement result of zeta current potential confirms that pulp particle is electronegative, and the zeta potential value is-50mV, so its absolute value is big, and the slurry favorable dispersity.
(grinding of insulating film layer)
The SiO that is formed with according to the preparation of TEOS-plasma CVD method
2The Si wafer of insulating film is positioned over attached in the anchor clamps on the sub master that keeps substrate installation usefulness, make abrasive surface put anchor clamps down on the platform that adheres to cellular polyurethane resin ground dish, and then loaded weight is 300g/cm so that make machine load
2On one side above-mentioned ceria slurry (solids content: 3% weight percent) speed of dividing with 35ml/ drops on the platform, one side with the speed rotatable platform of 30rpm 2 minutes, carry out the grinding of insulating film.
After the grinding, take off wafer from anchor clamps, fully clean with flowing water, utilize sono-cleaner further to clean 20 minutes then.After cleaning, utilize rotatory drier to remove water droplet on the wafer, in 120 ℃ drying machine dry 10 minutes.Utilize the Thickness Variation of light interference type determining film thickness device before and after measure grinding, found that, by this grinding eliminate 560 nanometers (grinding rate is: insulating film 280 nm/min), along entire wafer surface uniform film thickness.In addition, use observation by light microscope insulating film surface, do not find tangible scar.
Embodiment 4
(preparation of cerium oxide particle)
2kg cerous carbonate hydrate is packed in the platinum container, under 700 ℃, in air, burnt till 2 hours, thereby obtain the yellow-white powder of about 1kg.Utilize X-ray diffraction method to carry out the evaluation of this powder phase, turn out to be cerium oxide.Burning till the powder particle particle diameter is 30～100 microns.The surface that utilizes scanning electron microscopic observation to burn till powder particle, observe cerium oxide the grain circle.Measure the particle diameter of the cerium oxide primary granule that is surrounded by the grain circle, the median that obtains its distribution is 50 nanometers, and maximum value is 100 nanometers.Carry out X-ray diffraction and accurately measure burning till powder, utilize Rietvelt method (RIETAN-94) to analyze its result, the value that obtains expressing the structural parameter X of primary granule particle diameter is 0.300, and the value of expressing the structural parameter Y of isotropy miniature deformation is 0.350.
Utilize to stir to grind the 1kg ceria oxide powder is carried out wet pulverization.Drying contains the solution of pulverized particles, pulverizes dried particles with ball mill.Utilize the scanning electron microscopic observation pulverized particles, discovery is the particle identical with the primary granule grain size, does not find big pulverizing residual particles.Pulverized particles is carried out X-ray diffraction accurately measure, utilize Rietvelt method (RIETAN-94) to analyze its result, the value that obtains expressing the structural parameter X of primary granule particle diameter is 0.302, and the value of expressing the structural parameter Y of isotropy miniature deformation is 0.450.As a result, do not change the primary granule particle diameter substantially by pulverizing.Make by pulverizing in addition and introduced deformation on the particle.And then, utilizing BET method measurement the specific area, the result is 40m
2/ g.
(preparation of ceria slurry)
The cerium oxide particle of the above-mentioned preparation of 1kg, 23g polyacrylic acid aqueous ammonium (40% weight percent) and 8977g deionized water mix, and carry out ultrasonic dispersing 10 minutes while stir.Utilize 1 micron filter to filter the slurry of gained, and then obtain the abrasive of 3% weight percent by adding deionized water again.PH value of slurry is 8.5.(determinator: Master Sizer microplus, specific refractory power: the 1.9285) size distribution of mensuration pulp particle, the median of discovery size distribution is 290 nanometers by laser diffractometry.The particle of largest particle particle diameter more than 780 nanometers is 0% volume percent.
For the dispersiveness of studying slurry and the electric charge of pulp particle, measure the zeta current potential of slurry.Ceria slurry is put into the cell that both sides are provided with platinum electrode, on two electrodes, apply the voltage of 10V.By applying voltage, charged pulp particle is to electrode one side shifting of oppositely charged.Just can obtain particulate zeta current potential by obtaining its translational speed.The measurement result of zeta current potential confirms that pulp particle is electronegative, and the zeta potential value is-65mV, so its absolute value is big, and the slurry favorable dispersity.
(grinding of insulating film layer)
The SiO that is formed with according to the preparation of TEOS-plasma CVD method
2The Si wafer of insulating film is positioned over attached in the anchor clamps on the sub master that keeps substrate installation usefulness, make abrasive surface put anchor clamps down on the platform that adheres to cellular polyurethane resin ground dish, and then loaded weight is 300g/cm so that make machine load
2On one side above-mentioned ceria slurry (solids content: 3% weight percent) speed of dividing with 35ml/ drops on the platform, one side with the speed rotatable platform of 30rpm 2 minutes, carry out the grinding of insulating film.
After the grinding, take off wafer from anchor clamps, fully clean with flowing water, utilize sono-cleaner further to clean 20 minutes then.After cleaning, utilize rotatory drier to remove water droplet on the wafer, in 120 ℃ drying machine dry 10 minutes.Utilize the Thickness Variation of light interference type determining film thickness device before and after measure grinding, found that, by this grinding eliminate 400 nanometers (grinding rate is: insulating film 200 nm/min), along entire wafer surface uniform film thickness.In addition, use observation by light microscope insulating film surface, do not find tangible scar.
Comparative example
With embodiment similarly, for the SiO that is formed with according to TEOS-CVD method preparation
2The Si wafer of insulating film utilizes silica slurry to grind.The pH of this slurry is 10.3, SiO
2Granule content is 12.5% weight percent.Grinding condition is identical with embodiment.As a result, though scratch and be to grind evenly, only eliminate 150 nanometers (grinding rate: insulating film layer 75 nm/min) by 2 minutes grindings through grinding not cause.
As mentioned above, SiO can not scratched according to abrasive of the present invention
2Insulating films etc. are ground under the high grinding rate of abrasive surface, are applicable to the substrate of defineds such as grinding semiconductor substrate especially.
Claims (3)
1. slurry, by in medium, disperseing cerium oxide particle to form, this cerium oxide particle by powder X-ray ray Rietvelt method with the structural parameter Y value of the isotropic miniature deformation of expression of RIETAN-94 assay determination at 0.01-0.70, cerium oxide particle particle diameter median in the slurry is the 150-600 nanometer, primary granule particle diameter median is the 30-250 nanometer, and the maximum particle diameter of the cerium oxide particle in the slurry is below 3000 nanometers.
2. slurry, by disperse primary granule particle diameter median in medium is that the cerium oxide particle of 30-250 nanometer forms, cerium oxide particle particle diameter median in the slurry is the 150-600 nanometer, the maximum particle diameter of the cerium oxide particle in the slurry is the following cerium oxide particles of 3000 nanometers, the cerium oxide particle in the slurry has-and the zeta current potential of 100mV--10mV.
3. slurry, by disperse primary granule particle diameter median in medium is that the cerium oxide particle of 30-250 nanometer forms, cerium oxide particle particle diameter median in the slurry is the 150-600 nanometer, the maximum particle diameter of the cerium oxide particle in the slurry is below 3000 nanometers, and the specific surface area of the cerium oxide particle in the slurry is 7m
2-45m
2/ g, median size is the 200-400 nanometer, the halfwidth of size-grade distribution is below 300 nanometers.
Applications Claiming Priority (34)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25878196A JPH10106993A (en) | 1996-09-30 | 1996-09-30 | Polishing method of substrate |
| JP1996-258775 | 1996-09-30 | ||
| JP1996-258766 | 1996-09-30 | ||
| JP1996259138 | 1996-09-30 | ||
| JP1996258768 | 1996-09-30 | ||
| JP8258768A JPH10102039A (en) | 1996-09-30 | 1996-09-30 | Cerium oxide abrasive and grinding of substrate |
| JP1996-258776 | 1996-09-30 | ||
| JP25877496 | 1996-09-30 | ||
| JP25877696 | 1996-09-30 | ||
| JP1996-258768 | 1996-09-30 | ||
| JP1996258775 | 1996-09-30 | ||
| JP1996-258770 | 1996-09-30 | ||
| JP1996-258781 | 1996-09-30 | ||
| JP8258767A JPH10102038A (en) | 1996-09-30 | 1996-09-30 | Cerium oxide abrasive and grinding of substrate |
| JP1996-258767 | 1996-09-30 | ||
| JP25913896A JPH10106982A (en) | 1996-09-30 | 1996-09-30 | Polishing method |
| JP25877596 | 1996-09-30 | ||
| JP08258766 | 1996-09-30 | ||
| JP1996258774 | 1996-09-30 | ||
| JP1996-258774 | 1996-09-30 | ||
| JP1996258781 | 1996-09-30 | ||
| JP1996-259138 | 1996-09-30 | ||
| JP1996258770 | 1996-09-30 | ||
| JP1996258776 | 1996-09-30 | ||
| JP1996258766 | 1996-09-30 | ||
| JP1996258767 | 1996-09-30 | ||
| JP25877096 | 1996-09-30 | ||
| JP1437197A JPH10154672A (en) | 1996-09-30 | 1997-01-28 | Cerium oxide abrasive material and polishing method of substrate |
| JP1997014371 | 1997-01-28 | ||
| JP1997-014371 | 1997-01-28 | ||
| JP1997112396 | 1997-04-30 | ||
| JP1997-112396 | 1997-04-30 | ||
| JP1997-207866 | 1997-08-01 | ||
| JP1997207866 | 1997-08-01 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB97199370XA Division CN1282226C (en) | 1996-09-30 | 1997-09-30 | Cerium oxide abrasive and method of abrading substrates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1935927A true CN1935927A (en) | 2007-03-28 |
| CN1935927B CN1935927B (en) | 2010-11-03 |
Family
ID=37953673
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006101425095A Expired - Lifetime CN1935927B (en) | 1996-09-30 | 1997-09-30 | Cerium oxide abrasive and method of polishing substrates |
| CN200810184455A Pending CN101649182A (en) | 1996-09-30 | 1997-09-30 | Cerium oxide abrasive and method of polishing substrates |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810184455A Pending CN101649182A (en) | 1996-09-30 | 1997-09-30 | Cerium oxide abrasive and method of polishing substrates |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH10154672A (en) |
| CN (2) | CN1935927B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102686360A (en) * | 2009-11-12 | 2012-09-19 | 日立化成工业株式会社 | CMP polishing liquid and polishing method using the same and fabricating method of semiconductor substrate |
| CN103370174A (en) * | 2010-12-31 | 2013-10-23 | 圣戈本陶瓷及塑料股份有限公司 | Abrasive particles having particular shapes and methods of forming such particles |
| CN103500706A (en) * | 2010-11-22 | 2014-01-08 | 日立化成株式会社 | Slurry, polishing liquid set, polishing liquid, method for polishing substrate, and substrate |
| US9881802B2 (en) | 2010-11-22 | 2018-01-30 | Hitachi Chemical Company, Ltd | Slurry, polishing liquid set, polishing liquid, method for polishing substrate, and substrate |
| US9932497B2 (en) | 2012-05-22 | 2018-04-03 | Hitachi Chemical Company, Ltd. | Slurry, polishing-solution set, polishing solution, substrate polishing method, and substrate |
| US9982177B2 (en) | 2010-03-12 | 2018-05-29 | Hitachi Chemical Company, Ltd | Slurry, polishing fluid set, polishing fluid, and substrate polishing method using same |
| US10196542B2 (en) | 2012-02-21 | 2019-02-05 | Hitachi Chemical Company, Ltd | Abrasive, abrasive set, and method for abrading substrate |
| US10549399B2 (en) | 2012-05-22 | 2020-02-04 | Hitachi Chemcial Company, Ltd. | Slurry, polishing-solution set, polishing solution, substrate polishing method, and substrate |
| US10557059B2 (en) | 2012-05-22 | 2020-02-11 | Hitachi Chemical Company, Ltd. | Slurry, polishing-solution set, polishing solution, substrate polishing method, and substrate |
| US10557058B2 (en) | 2012-02-21 | 2020-02-11 | Hitachi Chemical Company, Ltd. | Polishing agent, polishing agent set, and substrate polishing method |
| CN116355537A (en) * | 2023-04-04 | 2023-06-30 | 蘅东光通讯技术(深圳)股份有限公司 | Optical fiber polishing grinding liquid, preparation method and optical fiber polishing grinding process |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4501694B2 (en) * | 1998-12-25 | 2010-07-14 | 日立化成工業株式会社 | Additive for CMP abrasives |
| JP4604727B2 (en) * | 1998-12-25 | 2011-01-05 | 日立化成工業株式会社 | Additive for CMP abrasives |
| JP3957924B2 (en) | 1999-06-28 | 2007-08-15 | 株式会社東芝 | CMP polishing method |
| JP3525824B2 (en) * | 1999-09-17 | 2004-05-10 | 日立化成工業株式会社 | CMP polishing liquid |
| JP5017574B2 (en) * | 2001-05-25 | 2012-09-05 | エア プロダクツ アンド ケミカルズ インコーポレイテッド | Cerium oxide abrasive and method for producing substrate |
| CN1311009C (en) | 2001-11-15 | 2007-04-18 | 三星电子株式会社 | Additive compositon, slurry composition including the same, and method of polishing an object using the slurry composition |
| KR100475457B1 (en) * | 2001-11-15 | 2005-03-08 | 삼성전자주식회사 | An additive composition, a slurry composition including the additive composition, and a method for polishing an object using the slurry composition |
| KR100511943B1 (en) | 2003-05-22 | 2005-09-01 | 한화석유화학 주식회사 | Concentrate of fine cerium oxide particles for chemical mechanical polishing and preparing method thereof |
| JP4637464B2 (en) * | 2003-07-01 | 2011-02-23 | Ｊｓｒ株式会社 | Aqueous dispersion for chemical mechanical polishing |
| JP2005179421A (en) * | 2003-12-17 | 2005-07-07 | Nissan Chem Ind Ltd | Abrasive composition |
| EP1844122B1 (en) | 2004-12-29 | 2013-02-20 | LG Chem, Ltd. | Adjuvant for chemical mechanical polishing slurry |
| US20060213126A1 (en) * | 2005-03-28 | 2006-09-28 | Cho Yun J | Method for preparing a polishing slurry having high dispersion stability |
| KR100786948B1 (en) | 2005-12-08 | 2007-12-17 | 주식회사 엘지화학 | Adjuvant capable of controlling a polishing selectivity and chemical mechanical polishing slurry comprising the same |
| KR100786949B1 (en) | 2005-12-08 | 2007-12-17 | 주식회사 엘지화학 | Adjuvant capable of controlling a polishing selectivity and chemical mechanical polishing slurry comprising the same |
| KR100880107B1 (en) | 2006-01-25 | 2009-01-21 | 주식회사 엘지화학 | Cmp slurry and method for polishing semiconductor wafer using the same |
| JP5621854B2 (en) | 2010-11-22 | 2014-11-12 | 日立化成株式会社 | Abrasive grain manufacturing method, slurry manufacturing method, and polishing liquid manufacturing method |
| WO2020021680A1 (en) * | 2018-07-26 | 2020-01-30 | 日立化成株式会社 | Slurry and polishing method |
| CN110788698B (en) * | 2019-10-14 | 2020-11-06 | 上海交通大学 | Based on atomized CeO2Grinding method, system, medium and equipment with auxiliary axial feed |
| KR102261151B1 (en) * | 2020-02-27 | 2021-06-07 | 비드오리진(주) | Spherical inorganic particles having surface bump and method for preparing same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5527423A (en) * | 1994-10-06 | 1996-06-18 | Cabot Corporation | Chemical mechanical polishing slurry for metal layers |
-
1997
- 1997-01-28 JP JP1437197A patent/JPH10154672A/en active Pending
- 1997-09-30 CN CN2006101425095A patent/CN1935927B/en not_active Expired - Lifetime
- 1997-09-30 CN CN200810184455A patent/CN101649182A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102686360A (en) * | 2009-11-12 | 2012-09-19 | 日立化成工业株式会社 | CMP polishing liquid and polishing method using the same and fabricating method of semiconductor substrate |
| US9982177B2 (en) | 2010-03-12 | 2018-05-29 | Hitachi Chemical Company, Ltd | Slurry, polishing fluid set, polishing fluid, and substrate polishing method using same |
| US10703947B2 (en) | 2010-03-12 | 2020-07-07 | Hitachi Chemical Company, Ltd. | Slurry, polishing fluid set, polishing fluid, and substrate polishing method using same |
| US9988573B2 (en) | 2010-11-22 | 2018-06-05 | Hitachi Chemical Company, Ltd. | Slurry, polishing liquid set, polishing liquid, method for polishing substrate, and substrate |
| US9881802B2 (en) | 2010-11-22 | 2018-01-30 | Hitachi Chemical Company, Ltd | Slurry, polishing liquid set, polishing liquid, method for polishing substrate, and substrate |
| US9881801B2 (en) | 2010-11-22 | 2018-01-30 | Hitachi Chemical Company, Ltd. | Slurry, polishing liquid set, polishing liquid, method for polishing substrate, and substrate |
| CN103500706A (en) * | 2010-11-22 | 2014-01-08 | 日立化成株式会社 | Slurry, polishing liquid set, polishing liquid, method for polishing substrate, and substrate |
| US10825687B2 (en) | 2010-11-22 | 2020-11-03 | Hitachi Chemical Company, Ltd. | Slurry, polishing liquid set, polishing liquid, method for polishing substrate, and substrate |
| CN103370174B (en) * | 2010-12-31 | 2017-03-29 | 圣戈本陶瓷及塑料股份有限公司 | The forming method of the abrasive grains with given shape and such particle |
| CN103370174A (en) * | 2010-12-31 | 2013-10-23 | 圣戈本陶瓷及塑料股份有限公司 | Abrasive particles having particular shapes and methods of forming such particles |
| US10196542B2 (en) | 2012-02-21 | 2019-02-05 | Hitachi Chemical Company, Ltd | Abrasive, abrasive set, and method for abrading substrate |
| US10557058B2 (en) | 2012-02-21 | 2020-02-11 | Hitachi Chemical Company, Ltd. | Polishing agent, polishing agent set, and substrate polishing method |
| US9932497B2 (en) | 2012-05-22 | 2018-04-03 | Hitachi Chemical Company, Ltd. | Slurry, polishing-solution set, polishing solution, substrate polishing method, and substrate |
| US10549399B2 (en) | 2012-05-22 | 2020-02-04 | Hitachi Chemcial Company, Ltd. | Slurry, polishing-solution set, polishing solution, substrate polishing method, and substrate |
| US10557059B2 (en) | 2012-05-22 | 2020-02-11 | Hitachi Chemical Company, Ltd. | Slurry, polishing-solution set, polishing solution, substrate polishing method, and substrate |
| CN116355537A (en) * | 2023-04-04 | 2023-06-30 | 蘅东光通讯技术(深圳)股份有限公司 | Optical fiber polishing grinding liquid, preparation method and optical fiber polishing grinding process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101649182A (en) | 2010-02-17 |
| CN1935927B (en) | 2010-11-03 |
| JPH10154672A (en) | 1998-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1323124C (en) | Cerium oxide abrasive material and grinding method of base plate | |
| CN1935927B (en) | Cerium oxide abrasive and method of polishing substrates | |
| JP5023626B2 (en) | Polishing method of cerium oxide slurry and substrate | |
| JPH11181403A (en) | Cerium oxide abrasive and grinding of substrate | |
| JPH10106991A (en) | Cerium oxide abrasive powder, and polishing method of substrate | |
| KR100622519B1 (en) | A Cerium Oxide Particle | |
| JP2004289170A (en) | Cerium oxide polishing agent and method of polishing substrate | |
| JP4445820B2 (en) | Cerium oxide abrasive and substrate polishing method | |
| JP2006148158A (en) | Cerium oxide polishing material and substrate-polishing method | |
| JP2004282092A (en) | Cerium oxide abrasive and substrate polishing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20101103 |