CN101475791B - Preparation and use of cerium oxide / silicon oxide compound abrasive - Google Patents
Preparation and use of cerium oxide / silicon oxide compound abrasive Download PDFInfo
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- CN101475791B CN101475791B CN200910028189A CN200910028189A CN101475791B CN 101475791 B CN101475791 B CN 101475791B CN 200910028189 A CN200910028189 A CN 200910028189A CN 200910028189 A CN200910028189 A CN 200910028189A CN 101475791 B CN101475791 B CN 101475791B
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- 238000005498 polishing Methods 0.000 claims abstract description 72
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 150000000703 Cerium Chemical class 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract 10
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 60
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 49
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 47
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 46
- 238000002360 preparation method Methods 0.000 claims description 22
- 229910052684 Cerium Inorganic materials 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 13
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- -1 cerium ions Chemical class 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000004005 microsphere Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims 1
- 229960000935 dehydrated alcohol Drugs 0.000 claims 1
- 239000012153 distilled water Substances 0.000 claims 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims 1
- 238000001556 precipitation Methods 0.000 abstract description 10
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000003082 abrasive agent Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 238000011160 research Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 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
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 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 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001550 time effect Effects 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
The invention relates to a method for preparing a ceria/monox compounded abrasive, and application of the compounded abrasive. The method uses monodisperse spherical monox as a kernel of a coating type compounded abrasive, hexamethylenetetramine (HMT) as a precipitator and cerium salt as a raw material, and adopts an even precipitation method process to synthesize the ceria/monox compounded abrasive. Through the optimization of process parameters, such as the use amount ratio of monox master particles to the cerium salt, the molar ratio of the HMT to the cerium salt, and reaction and calcination temperature, the method controls the covering amount, the shape and the distribution state of ceria particles on the surface of the monox, thereby preparing the ceria/monox compounded abrasive of which the nanometer-level ceria particles evenly cover on the surface of the monox and which has good monodispersity; the method does not need complex equipment; and the needed chemical materials have less varieties, cheap prices and good experiment repeatability. The ceria/monox compounded abrasive is prepared into polishing slurry for chemical mechanical polishing of a gallium arsenide chip so as to obtain the polishing surface with the roughness in sub-nanometer magnitude and further improve polishing speed, reduce polishing pass and improve efficiency.
Description
Technical field
The invention belongs to field of preparation of ultrafine compound powder, the preparation method of special monodisperse spherical cerium oxide/silicon oxide cladded type compounded abrasive, and the purposes in Ultraprecise polished.
Background technology
Along with the raising with integrated level that reduces of VLSI device feature size, require must reach nano level as the roughness of substrate material surface, this just has higher requirement to the quality of finish of substrate material.(Chemical-mechanical polishing is a kind of important processing means that obtains super-smooth surface CMP), and almost is unique technology that can realize global planarization in chemically machinery polished.Gallium arsenide (GaAs) is a kind of important III-V group iii v compound semiconductor material, and GaAs material hardness low (Mohs' hardness is 4.5), fragility big, be prone to cleavage, what this made the GaAs wafer is processed into the main difficult problem of GaAs unicircuit in making.
CeO
2It is one of abrasive material that uses among the CMP; Be widely used in the chemically machinery polished of precision glass polishing and ULSI silica dioxide medium layer; Show that the glazed surface roughness is low, the polishing efficiency advantages of higher; But subject matter is to be difficult to form stable dispersion system, and the dispersiveness of slurry is stablized relatively poor.Abrasive material is brought into play important role as polishing medium in the Super-smooth Surface Polishing material removal process, the character of abrasive material self greatly influences the glazed surface quality.In order to overcome the shortcoming of single abrasive material, the research of compounded abrasive becomes the focus in the CMP field gradually.Compounded abrasive most typical application in CMP is that employing flame combustion process such as Wang Zhonglin prepare TiO
2Doping spherical CeO
2Powder, and be successfully applied to the chemically machinery polished of silicon wafer, through using this spherical TiO
2Doped Ce O
2Powder is as abrasive material; Can be so that polishing speed improves 50%, surface imperfection reduces by 80% (Xiangdong Feng; Dean C.Sayle, Zhong Lin Wang, et al.Converting Ceria Polyhedral Nanoparticles into Single-Crystal Nanospheres [J] .Science; 2006,312:1504-1508.).
Lee is that precipitation agent adopts liquid-phase precipitation method at silicon oxide surface coating cerium oxide particle with ammoniacal liquor; Find that this compounded abrasive is to the polishing performance of silica dioxide medium layer (the Seung-Ho Lee that is improved; Zhenyu Lu, S.V.Babu, et al.Chemical mechanical polishing of thermal oxide films using silicaparticles coated with ceria [J] .Materrials Research Society; 2002,17 (10): 2744-2749).Xiao Baoqi etc. are that precipitation agent adopts homogeneous precipitation method to prepare cerium oxide/silica abrasive to be used for the optical digital disk glass substrate with urea, obtained roughness and be 0.971nm glazed surface (Xiao Baoqi, Lei Hong. nanometer SiO
2/ CeO
2The preparation of Compostie abrasive particles and polishing characteristic research [J] thereof. the tribology journal; 2008 the 2nd phases); Lei Hong etc. and at this point art applications the patent (preparation method of alumina/silica Compostie abrasive particles; Application number: 200610026974.2); In addition Lei Hong etc. also just with traditional abrasives such as ultra-fine alumina, silicon oxide and zirconium white be kernel, with the hydrophilic macromolecule chain segment compounds or to contain polarity organo-functional group compound be the preparation of the abrasive of shell, applied for patent (application number: 200510023377.X).Chai Mingxia etc. are raw material with cerous carbonate, basic zirconium chloride and ammoniacal liquor, adopt mechanical solid state reaction method to prepare submicron-grade superfine SiO
2-CeO
2Composite oxides, and (Feng Xiaoping waits .SiO for Chai Mingxia, Hu Jiandong to be used for the chemically machinery polished of opticglass
2-CeO
2The preparation of composite oxides and polishing performance [J]. Chinese Journal of Inorganic Chemistry, 2007 the 4th phases).Song also is that precipitation agent adopts liquid-phase precipitation method to prepare cladded type cerium oxide/silica powder with sodium hydroxide; Studied the dispersiveness of coated powder; Variation has taken place in the zeta current potential of this cladded type composite granule of presentation of results; Dispersiveness also be improved (Xiaolan Song, Nan Jiang, Synthesis of CeO
2-coatedSiO
2Nanoparticle and dispersion stability of its suspension [J] .Materials Chemistry, 2008,110 (1): 128-135).But above-mentioned is the prepared cerium oxide/silica powder of precipitation agent with ammoniacal liquor or sodium hydroxide, and cerium oxide particle is even inadequately in the coating of silicon oxide surface, can not satisfy Ultraprecise polished requirement.
At present, generally using among the GaAs wafer CMP is SiO
2Abrasive material, but subject matter is SiO
2The polishing speed of abrasive material is low excessively, in practical application, often in the needs polishing slurries, adds oxygenant and waits and improve polishing speed, therefore makes the complex chemical composition of polishing slurries; Perhaps adopt the method that increases the polishing passage, increases polishing time, therefore make polishing efficiency low.Chen Yang and Chen Zhigang etc. use ultra-fine CeO
2The abrasive polishing gallium arsenide wafer has obtained glazed surface (Chen Yang, the Li Xiazhang of roughness Ra value for 0.740nm; Chen Zhigang, etc. nanometer abrasive is to the polishing research [J] of GaAs wafer. Solid State Electronics research and progress, 2006 the 4th phases); And at this point art applications patent (application number: 200510041507.2); But what should technology pass through is two step glossings, and total polishing time is 60 minutes, and polishing efficiency is on the low side.
Summary of the invention
The objective of the invention is the shortcoming for existing gallium arsenide polish abrasive, the preparation method and the purposes of a kind of monodisperse spherical cerium oxide/silicon oxide cladded type compounded abrasive is provided, the kernel of prepared compounded abrasive is a silicon oxide, and coating layer is a cerium oxide.This coated type cerium oxide can further improve polishing speed satisfying on the basis that obtains the glazed surface quality, reduces the polishing passage, raises the efficiency.
The present invention is with the kernel of monodisperse sphere conformal silicon oxide as the cladded type compounded abrasive, and is precipitation agent with vulkacit H (HMT), and cerium salt is raw material, adopts sluggish precipitation technology to synthesize.Through optimizing the amount ratio of silicon oxide coatingparticles and cerium salt; The mol ratio of HMT and cerium salt; Processing parameters such as reaction and calcining temperature come covering amount, pattern and the distribution of controlled oxidation cerium particle at silicon oxide surface, thereby have prepared the cerium oxide that nano level cerium oxide particle evenly coats at silicon oxide surface, monodispersity is good/silicon oxide compounded abrasive.And it is mixed with the chemically machinery polished that polishing slurries is used for gallium arsenide wafer, obtained the glazed surface of roughness in inferior nanometer scale.
Concrete preparation process of the present invention is: take by weighing a certain amount of particle diameter and be dispersed in the deionized water at single silicon oxide microsphere that disperses of 200～250nm; And the adding mass fraction is the dispersion agent (calculating with the quality of dispersion agent and the mass ratio of silicon oxide microsphere) of 10wt%; In silicon oxide suspension-s, add a certain amount of cerium salt again; Stir with magnetic stirrer; Wherein the mass concentration scope of silicon oxide suspension-s is 0.5～5wt%, and the concentration range of cerium ion is 0.01mol/l～0.5mol/l.Add a certain amount of vulkacit H again, stir, wherein the molar concentration rate of vulkacit H and cerium salt is between 2: 1～20: 1.Under the condition of induction stirring, place 70～90 ℃ water-bath to react 1～5h the reaction soln of preparation; With throw out spinning, washing (zero(ppm) water is given a baby a bath on the third day after its birth and is washed one time all over, absolute ethyl alcohol); Place 70 ℃ of air dry oven oven dry again, grind; Through 300～600 ℃ of calcining 0.5～4h, can obtain cerium oxide/silicon oxide cladded type compounded abrasive again.
Said cerium salt is cerous nitrate, and the mass concentration scope of silicon oxide suspension-s is 0.5～2wt%, and the concentration range of cerium ion is between 0.05mol/l～0.5mol/l, and calcining temperature is between 400～500 ℃, and calcination time effect between 1～2h is better.
Wherein, cerium salt can also be in cerous nitrate, cerous sulfate and the Cerium II Chloride any, and dispersion agent is any among X 2073, Sodium hexametaphosphate 99 and the PEG400.
Prepared cerium oxide/silicon oxide compounded abrasive is mixed with polishing slurries; Its mass concentration scope is at 0.5wt～5wt%; The mass concentration of oxygenant (ydrogen peroxide 50) is 5～15%; With ammoniacal liquor the pH value of polishing slurries is transferred to 8～10, use the high precision polishing machine under the processing condition (polish pressure is 25min as 5N, lower wall rotating speed as 200r/min, polishing time) of certain polishing, gallium arsenide wafer to be polished.
Prepared composite abrasive material of the present invention is spherical in shape, and its particle diameter is about 200～250nm, and monodispersity is good, and the kernel of this coated type cerium oxide is a silicon oxide, and coating layer is the cerium oxide particle of particle diameter at 10～20nm.Through finishing and the surface-treated of cerium oxide particle, thereby improved the zeta current potential absolute value of coated type cerium oxide in liquid phase water solution, and then improved its dispersiveness silicon oxide.In addition, the structure of the special coating of this cerium oxide/silicon oxide compounded abrasive also helps and reduces the polishing passage, improves polishing efficiency, improves the glazed surface quality.
The present invention adopts comparatively simple chemical technology to prepare and coats evenly, the coated type cerium oxide of good dispersivity, need not complex apparatus, and required chemical feedstocks kind is few, low price, experiment favorable repeatability.Spherical in shape owing to the prepared composite abrasive material simultaneously, and surperficial clad nano level cerium oxide particle, the Ultraprecise polished of gallium arsenide wafer had than obvious superiority, show as high polishing clearance and glazed surface roughness with inferior nanometer scale.
Description of drawings
Fig. 1 is the transmission electron microscope photo in the 500nm scale scope
Fig. 2 is the transmission electron microscope photo in the 200nm scale scope
Fig. 3 is the transmission electron microscope photo in the 100nm scale scope
Fig. 4 is the transmission electron microscope photo in the 100nm scale scope
Fig. 5 is the XRD spectra of coated type cerium oxide
Embodiment
The present invention makes further detailed description below in conjunction with embodiment:
Embodiment 1: take by weighing silicon oxide microsphere 1g and be distributed in the 50ml deionized water, the X 2073 that adds 0.1g is again strengthened dispersion as dispersion agent through ultrasonic and mechanical stirring.Take by weighing the 1.263g cerous nitrate again and be dissolved in the 50ml deionized water, add the vulkacit H of 3g again, and electric mixer stirs.Two kinds of reaction solns are mixed, stir, and wherein the mass concentration of silicon oxide suspension-s is 1wt%, and cerium ion concentration is 0.02mol/l, and the molar concentration rate of vulkacit H and cerous nitrate is 10: 1.Under the condition of induction stirring, place 80 ℃ water-bath to react 2h the reaction soln of preparation; With throw out spinning, washing (zero(ppm) water is given a baby a bath on the third day after its birth and is washed one time all over, absolute ethyl alcohol); Place 70 ℃ of air dry oven oven dry again, grind; Through 500 ℃ of calcining 1h, can obtain cerium oxide/silicon oxide cladded type compounded abrasive again.Characterize with the phase structure of XRD diffractometer, and prepare the particle diameter and the pattern of sample with transmission electron microscope (TEM) observation post to the sample of gained.
Press transmission electron microscope photo such as Fig. 1, Fig. 2, Fig. 3 and shown in Figure 4 of the prepared coated type cerium oxide sample of the processing parameter of embodiment 1; Wherein Fig. 1 is the transmission electron microscope photo in the 500nm scale scope; Fig. 2 is the transmission electron microscope photo in the 200nm scale scope; Fig. 3 is the transmission electron microscope photo in the 100nm scale scope, and Fig. 4 is the transmission electron microscope photo in the 50nm scale scope.Therefrom can find out; Prepared coated type cerium oxide is spherical in shape, and its particle diameter is about 200～250nm, and monodispersity is fine; Cerium oxide nanoparticles is even, complete is coated on silicon oxide core surface, the wherein about 5～10nm of the particle diameter of cerium oxide particle.Relatively collection of illustrative plates is as shown in Figure 5 for the XRD of this coated type cerium oxide and pure silica and pure zirconia cerium.Can find out, in the coating of preparation the characteristic diffraction peak of tangible cerium oxide has appearred in the XRD figure spectrum of silicon oxide of nano-cerium oxide, explain to have formed cerium oxide after reacting.The characteristic diffraction peak of simultaneous oxidation silicon relatively very a little less than, possibly be since cerium oxide particle the complete coating of silicon oxide is caused.
To use deionized water to be mixed with mass concentration by the prepared cerium oxide of the processing parameter of embodiment 1/silicon oxide compounded abrasive and be 2wt%; The mass concentration of oxygenant (ydrogen peroxide 50) is 10% polishing slurries; With ammoniacal liquor the pH value of polishing slurries is transferred to 9, use the high precision polishing machine that gallium arsenide wafer (100) is polished.Under certain polishing technological conditions (polish pressure is that 5N, lower wall rotating speed are that 200r/min, polishing time are 25min); Test result shows that the surface roughness Ra value of polishing back gallium arsenide wafer is 0.591nm; With thickness difference (getting ten point measurement MVs) the exosyndrome material clearance of gallium arsenide wafer before and after the polishing, reach 1640nm/min through measuring polishing speed.
At present domestic document about the gallium arsenide wafer polishing is still rare, and documents (nanometer abrasive is to the polishing research [J] of GaAs wafer. Solid State Electronics research and progress, 2006 the 4th phases; Nano Ce O
2Particulate preparation and chemically machinery polished performance study [J] thereof. the tribology journal; The first phase in 2007) can know; Chen Yang, Li Xiazhang etc. use fine cerium oxide abrasive polishing gallium arsenide wafer; After two step polishings (total time of pre-polish(ing) and finishing polish is 60 minutes), the roughness Ra value of gallium arsenide wafer glazed surface is 0.740nm.And the prepared cerium oxide/silicon oxide compounded abrasive of processing parameter of use embodiment 1; Just can directly the gallium arsenide abrasive sheet be thrown to minute surface through polishing (polishing time is 25 minutes) together; The surface roughness Ra value of polishing gallium arsenide wafer is 0.591nm, reaches 1640nm/min through measuring polishing speed.Show that more than the cerium oxide of this clad structure/silicon oxide compounded abrasive shows stronger polishing advantage, on the basis of satisfying the glazed surface quality, has improved polishing efficiency.
Embodiment 2: the step of present embodiment and the foregoing description 1 is basic identical, and difference is: the mass concentration of silicon oxide suspension-s is 0.5wt%, and cerium ion concentration is 0.01mol/l in the solution, and the molar concentration rate of vulkacit H and cerous nitrate is 5: 1.Place 70 ℃ water-bath to react 1h the reaction soln of preparation, the presoma that again institute's spinning is obtained is calcined 0.5h through 300 ℃.
To be mixed with the polishing slurries that mass concentration is 0.5wt% by the prepared cerium oxide of the processing parameter of embodiment 2/silicon oxide compounded abrasive; The mass concentration of oxygenant (ydrogen peroxide 50) is 15%; With ammoniacal liquor the pH value of polishing slurries is transferred to 10; Use the high precision polishing machine that gallium arsenide wafer (100) is polished, concrete glossing parameter is the same.
Embodiment 3: the step of present embodiment and the foregoing description 1 is basic identical, and difference is: the mass concentration of silicon oxide suspension-s is 5wt%, and cerium ion concentration is 0.5mol/l in the solution, and the molar concentration rate of vulkacit H and cerous nitrate is 20: 1.Place 90 ℃ water-bath to react 5h the reaction soln of preparation, the presoma that again institute's spinning is obtained is calcined 4h through 600 ℃.
To be mixed with the polishing slurries that mass concentration is 5wt% by the prepared cerium oxide of the processing parameter of embodiment 3/silicon oxide compounded abrasive; The mass concentration of oxygenant (ydrogen peroxide 50) is 5%; With ammoniacal liquor the pH value of polishing slurries is transferred to 8; Use the high precision polishing machine that gallium arsenide wafer (100) is polished, concrete glossing parameter is the same.
Embodiment 4: the step of present embodiment and the foregoing description 1 is basic identical; Difference is: changing cerium salt is cerous sulfate; The change dispersion agent is a Sodium hexametaphosphate 99; The mass concentration of silicon oxide suspension-s is 2wt%, and cerium ion concentration is 0.2mol/l in the solution, and the molar concentration rate of vulkacit H and cerous nitrate is 20: 1.Place 80 ℃ water-bath to react 2h the reaction soln of preparation, the presoma that again institute's spinning is obtained is calcined 2h through 400 ℃.
To be mixed with the polishing slurries that mass concentration is 3wt% by the prepared cerium oxide of the processing parameter of embodiment 4/silicon oxide compounded abrasive; The mass concentration of oxygenant (ydrogen peroxide 50) is 12%; With ammoniacal liquor the pH value of polishing slurries is transferred to 9.5; Use the high precision polishing machine that gallium arsenide wafer (100) is polished, concrete glossing parameter is the same.
Embodiment 5: the step of present embodiment and the foregoing description 1 is basic identical; Difference is: changing cerium salt is that Cerium II Chloride change dispersion agent is PEG400; The mass concentration of silicon oxide suspension-s is 1wt%; Cerium ion concentration is 0.2mol/l in the solution, and the molar concentration rate of vulkacit H and cerous nitrate is 15: 1.Place 80 ℃ water-bath to react 2h the reaction soln of preparation, the presoma that again institute's spinning is obtained is calcined 2h through 500 ℃.
Polishing slurries composition and glossing parameter are with embodiment 1.
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