CN103740281A - Polishing composition applicable to polishing on large-size silicon wafer and preparation method thereof - Google Patents
Polishing composition applicable to polishing on large-size silicon wafer and preparation method thereof Download PDFInfo
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- CN103740281A CN103740281A CN201310753521.XA CN201310753521A CN103740281A CN 103740281 A CN103740281 A CN 103740281A CN 201310753521 A CN201310753521 A CN 201310753521A CN 103740281 A CN103740281 A CN 103740281A
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Abstract
The invention relates to a polishing composition applicable to polishing on a large-size silicon wafer and a preparation method thereof, belonging to the field of chemical mechanical polishing (CMP). The composition comprises the following components: acidy silicon dioxide sol, a silica sol grain stabilizing agent, a heat absorbent, an alkali compound, a surfactant and the balance of deionized water, wherein the diameter of the large-size silicon wafer is 200-300mm. Due to stable mechanical function and chemical function of the composition, the phenomenon that the temperature is out of control in the polishing process is avoided, the large-size silicon wafer can be uniformly polished, and the large-size silicon wafer is rapid in polishing velocity, high in surface flatness and good in surface quality.
Description
Technical field
The present invention relates to chemically machinery polished (CMP) field, particularly a kind of polishing composition for the above silicon wafer polishing of 200mm.
Background technology
Semiconductor industry is the core of hyundai electronics industry, and the basis of semiconductor industry is silicon materials industry.Although there is various novel semiconductor material constantly to occur, more than 90% semiconducter device and circuit, especially super large-scale integration (ULSI) are to be all produced on the silicon single-crystal polishing plate of high-purity high-quality and epitaxial wafer.At present, super large-scale integration manufacturing technology has developed into below characteristic line breadth 0.1 μ m, the 300mm epoch.
Chemical Mechanical Polishing Technique is as current unique Technology that can be provided in global planarization on whole round silicon wafer, be widely applied to semiconductor integrated circuit field, silicon polished industry development has good prospect at home, present 12 inches of large diameter silicon monocrystal substrate slices have become the mainstream technology that IC manufactures, the 300mm FAB foundries that only inland of China is being built or planned to build has 8 lines, it is very large to the demand of polishing fluid, the unit manufacturing cost of large-sized silicon wafers increases, the height of its yield plays a key effect to cost, so the stable change of the optimization of technique and polishing fluid performance is abnormal crucial.From improving China's silicon industrial chain, promote silicon level of industrial technology, the angle consideration of Development Technology innovative product, technology and industry that 12 inches of levels of domestic researchdevelopment are silicon polished are very necessary.
Along with the further microminiaturization of characteristic line breadth, the degree of planarization of silicon chip surface to be had higher requirement, 200mm silicon chip can just can meet application requiring by silicon chip twin grinding and glossing.But to 300mm silicon chip, in application, to not only exigent overall planeness precision of the front of silicon chip, and require higher local planeness.Traditional is single-sided polishing to the CMP of base silicon material, but along with the development of super large-scale integration, single-sided polishing can not meet the requirement of less live width, therefore to being that the processing of 300mm silicon chip of the following technique of 0.13 μ m needs to carry out two-sided chemically machinery polished for live width, this is also the development trend of large-diameter silicon wafer processing.For example, meet the silicon chip of 65nm manufacture process requirement, front side of silicon wafer requires overall planeness (GBIR) to be less than 1 micron, and local planeness (SFQR) is less than 0.07 micron.
Polish temperature is an important parameter that affects silicon wafer polishing speed and quality.Along with the increase of polish temperature, the corresponding increase that the chemical reaction ability of polishing fluid will exponent function relation, also can cause the quick volatilization of polishing fluid simultaneously, will cause like this silicon chip surface seriously corroded, remove inhomogeneous, thereby quality of finish is declined.But the too low chemical reaction velocity that can make again of polish temperature reduces, and then makes mechanical effect be greater than chemical action, and silicon chip physical abuse is serious.
Polish pressure and polishing rotating speed are very large to polishing velocity and glazed surface quality influence, and along with the increase of polish pressure and polishing rotating speed, mechanical effect will strengthen conventionally, and polishing velocity also will increase.But use that too high polish pressure and rotating speed will cause that silicon wafer polishing speed is inhomogeneous, polish temperature raises and wayward, thereby make to occur that the probability scratching increases greatly, quality of finish declines.
US2008/0127573 discloses a kind of precise polished with formula for Silicon Wafer, comprising pH value conditioning agent, water-soluble thickener, tensio-active agent, the additives such as heterocyclic amine, the microscopic asperity that can significantly reduce the scattering imperfection of silicon chip surface local light, reduce greatly mist defect and silicon chip surface by being adjusted to partition ratio and abrasive size.But there is no the surface quality after effect and polishing clearance and the polishing in polishing process of the concentration of each composition in clear and definite polishing fluid, each composition.
The people such as Sasaki disclose a kind of silicon wafer polishing composition that contains silane coupler modified silicon sol (patent EP0371147B1, JP09324174); The clear rich people such as grade of He Seto discloses a kind of silicon wafer polishing composition (patent WO2004042812) that adds sequestrant; In patent US5876490 and US3922393, adopted the silicon-dioxide of cerium dioxide coating and aluminum oxide coating layer; Patent US4664679 has adopted the method for modifying that reduces colloid silica surface silicon alcohol groups.These processing have all obtained certain effect to the control of defect, but for the monocrystalline silicon buffing liquid of requirements at the higher level of new generation, above method also exists certain limitation.
Summary of the invention
The present invention is directed to the deficiency existing in present technology, a kind of polishing composition that is applicable to large size silicon wafer polishing and preparation method thereof is proposed, overcome traditional silicon wafer polishing fluid in polishing process because polish temperature raises and the not high difficult problem of parameter index such as the wayward surface imperfection causing is many, polishing velocity is inhomogeneous, overall planeness and local planeness.
A kind of composition that is applicable to large size silicon wafer polishing of the present invention, is characterized in that, its component and proportioning are:
Described large size silicon wafer diameter is 200mm～300mm.
The silicon-dioxide median size of described acid silicon dioxide sol is 5nm～500nm, and its particle specific surface area is 50m2/g～400m2/g; The pH of acidic silicasol is less than 6.
Described silica sol granule stablizer is the organic polymer that contains hydroxyl, ether, carboxyl and amide group, is one or more in polyethylene oxide (PEO), poly(propylene oxide) (PPO), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylamide (PAM).
Described heat absorbent is the salt of labile acidic cpd, acidic cpd.
Described acidic cpd has oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid and contains one or more in the potassium of carbonate, bicarbonate radical, inferior sulfate radical, bisulfite, nitrate radical, sodium, ammonium salt.
Described basic cpd comprises mineral alkali, organic bases.
Described mineral alkali is alkali metal hydroxide, one or more in potassium hydroxide or sodium hydroxide; Organic bases is in a kind of or several in ammonia, methylamine, dimethyl amine, Trimethylamine, ethylamine, diethylamide, triethylamine, α-amino isopropyl alcohol, aminopropanol, tetraethyl-amine, thanomin, diethyl triamine, trientine, hydroxyethylethylene diamine, hexamethylene-diamine, diethylenetriamine, Triethylenetetramine (TETA), Piperazine anhydrous, Uricida; Described mineral alkali and organic bases are used alone or as a mixture.
Described tensio-active agent is nonionogenic tenside.
Described nonionogenic tenside is one or more in fatty alcohol-polyoxyethylene ether (AEO), polyoxyethylene nonylphenol ether (NP-10), polyoxyethylene octylphenol ether (OP-10), polyoxyethylene polyoxypropylene segmented copolymer (EO-PO), polyvinylpyrrolidone (PVP).
A kind of preparation method for large size silicon wafer polishing composition of the present invention, is characterized in that, comprises the following steps:
To be scattered in water and the acid silicon dioxide sol of high-speed stirring and silica sol granule stablizer mix and blend 5～30 minutes;
Add wherein heat absorbent to stir 5～30 minutes, preparation temperature is controlled in 5～40 degree;
Add basic cpd to stir 5～30 minutes, preparation temperature is controlled in 5～40 degree again;
Add tensio-active agent to stir, after mixing, obtain polishing composition of the present invention.
The present composition is by stable mechanical effect and chemical action in composition, avoid especially temperature control phenomenon in polishing process, realize the uniform polish of large size silicon wafer, make the polishing speed of large size silicon wafer fast, surface finish is high, surface quality is good.
Accompanying drawing explanation
Fig. 1 is polishing composition components do match of the present invention polishing fluid laser particle size measurement figure before and after (embodiment 3) polishing when more excellent.
Fig. 2 is polishing composition components do match of the present invention polishing fluid laser particle size measurement figure before and after (embodiment 4) polishing when good.
Fig. 3 be in polishing composition of the present invention, use general silica colloidal sol 1, polishing fluid laser particle size measurement figure before and after (comparative example 2) polishing while not adding heat absorbent.
Fig. 4 be in polishing composition of the present invention, use general silica colloidal sol 2, polishing fluid laser particle size measurement figure before and after (comparative example 3) polishing while not adding heat absorbent.
Embodiment
Below by embodiment and comparative example, the invention will be further elaborated, certainly in no case should be construed as limiting the scope of the invention.
Concrete each component of adding and edge polishing result are as shown in subordinate list.Test with these edge polishing compositions, to 12 inches of silicon wafer P<100> type wafers as polishing object.
In embodiment, edge polishing technique is as follows:
Polishing machine: 20B-5P-4D(Speedfam Co., Ltd. manufactures)
Pressure: 10Mpa
Rotating speed: 30rpm
Polishing pad: SUBA800(Rodel, Inc.U.S.A manufactures)
Polishing fluid flow: 4L/ minute
Polishing time: 30 minutes
After polishing, wafer through cleaning, dry, silicon chip surface is detected with ADE AFS3220 surface geometry parameter detecting instrument, test silicon wafer GBIR after polishing, SFQR parameter and variation in thickness.According to the silicon wafer thickness before and after throwing, change and change into polish removal rate.
The each component of the present invention and effect are described in detail as follows:
Acid silicon dioxide sol
In the component of edge polishing composition of the present invention, abrasive material is silicon-dioxide, and what specifically adopt is that its particle specific surface area of median size 5nm～500nm is 50m2/g～400m2/g; The acidic silicasol that pH is less than 6.Silicon-dioxide carries out polishing as abrasive particle by mechanical effect effects on surface, and the mean particle size of silicon-dioxide refers to the mean particle size that data that light scattering method is surveyed obtain, and specific surface area refers to the specific surface area of determination of adsorption method.
Selected silicon sol is because specific grain surface is long-pending little, particle compactedness is high, in polishing process, be not subject to affected by high and fragmentation, can make the mechanical effect in polishing process keep stable, the scuffing that can avoid the out-of-shape particle causing due to grain breakage to cause simultaneously.
Silica sol granule stablizer
In polishing large size silicon wafer process; for further improving the stability of polishing particles; when using this acidic silicasol; also add wherein silica sol granule stablizer, silica sol granule stablizer forms absorption with silica sphere under acidic conditions, forms one deck particle protective layer; make polishing particles not only be not easy fragmentation; and be not easy to reunite, can keep the stability of polishing particles, further guaranteed that the mechanical effect when polishing large size silicon wafer is stable.
Described silica sol granule stablizer is the organic polymer that contains hydroxyl, ether, carboxyl and amide group, is one or more in polyethylene oxide (PEO), poly(propylene oxide) (PPO), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylamide (PAM).
Heat absorbent
In the present invention, heat absorbent can be taken away the waste heat of the generation in polishing process, make polish temperature keep stable, make in polishing chemical action keep stable, the silicon chip surface seriously corroded avoiding causing due to temperature control, remove non-uniform phenomenon, improve planeness after polishing.
Described heat absorbent is the salt of labile acidic cpd and acidic cpd, and specifically can be contained in acidic cpd of the present invention has oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid and contain carbonate, bicarbonate radical, inferior sulfate radical, bisulfite, the potassium of nitrate radical, sodium, ammonium salt.In the present invention, heat absorbent can be the mixture of above-claimed cpd.
Basic cpd
Basic cpd is the main etching reagent that guarantees silicon wafer polishing speed, and its contamination will affect the chemical reaction ability of polishing fluid, affects the temperature control in polishing process simultaneously.
In the present invention, basic cpd comprises mineral alkali and organic bases.Mineral alkali is alkali metal hydroxide, potassium hydroxide or sodium hydroxide.Organic bases is ammonia, methylamine, dimethyl amine, Trimethylamine, tetramethyl-ammonium, ethylamine, diethylamide, triethylamine, α-amino isopropyl alcohol, aminopropanol, tetraethyl-amine, quadrol, thanomin, diethyl triamine, trientine, hydroxyethylethylene diamine, hexamethylene-diamine, Piperazine anhydrous, Uricida, and neutral and alkali compound of the present invention can be the mixture of above-mentioned basic cpd.
Tensio-active agent
Described tensio-active agent is nonionogenic tenside.Nonionogenic tenside is one or more in fatty alcohol-polyoxyethylene ether (AEO), polyoxyethylene nonylphenol ether (NP-10), polyoxyethylene octylphenol ether (OP-10), polyoxyethylene polyoxypropylene segmented copolymer (EO-PO), polyvinylpyrrolidone (PVP).
Tensio-active agent can further improve granule stability in this composition, plays effect wetting and that further stop particle to adsorb in polishing process.
Polishing composition preparation method of the present invention, comprises the following steps:
To be scattered in water and the acid silicon dioxide sol of high-speed stirring mixes with silica sol granule stablizer, can stir and play a role and stable system, pH are controlled at below 6 to component for 5～30 minutes;
Add wherein heat absorbent, can stir and play a role and stable system, pH are controlled at below 5 to component for 5～30 minutes, preparation temperature is controlled in 5～40 degree;
Add basic cpd again, can stir and play a role and make stable system to component for 5～30 minutes, pH is controlled at 10-12, and preparation temperature is controlled in 5～40 degree;
Add tensio-active agent, after being uniformly mixed, obtain polishing composition of the present invention.
The each component of subordinate list and edge polishing result
In addition, those skilled in the art can also do other and change in spirit of the present invention, and the variation that these do according to spirit of the present invention, all should be included in the present invention's scope required for protection.
Claims (10)
1. a composition that is applicable to large size silicon wafer polishing, is characterized in that, its component and proportioning are:
Described large size silicon wafer diameter is 200mm～300mm.
2. composition according to claim 1, is characterized in that, the silicon-dioxide median size of described acid silicon dioxide sol is 5nm～500nm, and its particle specific surface area is 50m2/g～400m2/g; The pH of acidic silicasol is less than 6.
3. composition according to claim 1, it is characterized in that, described silica sol granule stablizer is the organic polymer that contains hydroxyl, ether, carboxyl and amide group, is one or more in polyethylene oxide (PEO), poly(propylene oxide) (PPO), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylamide (PAM).
4. composition according to claim 1, is characterized in that, described heat absorbent is the salt of labile acidic cpd, acidic cpd.
5. composition according to claim 4, it is characterized in that, described acidic cpd has oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid and contains one or more in the potassium of carbonate, bicarbonate radical, inferior sulfate radical, bisulfite, nitrate radical, sodium, ammonium salt.
6. composition according to claim 1, is characterized in that, described basic cpd comprises mineral alkali, organic bases.
7. composition according to claim 6, is characterized in that, described mineral alkali is alkali metal hydroxide, one or more in potassium hydroxide or sodium hydroxide; Organic bases is in a kind of or several in ammonia, methylamine, dimethyl amine, Trimethylamine, ethylamine, diethylamide, triethylamine, α-amino isopropyl alcohol, aminopropanol, tetraethyl-amine, thanomin, diethyl triamine, trientine, hydroxyethylethylene diamine, hexamethylene-diamine, diethylenetriamine, Triethylenetetramine (TETA), Piperazine anhydrous, Uricida; Described mineral alkali and organic bases are used alone or as a mixture.
8. composition according to claim 1, is characterized in that, described tensio-active agent is nonionogenic tenside.
9. composition according to claim 8, it is characterized in that, described nonionogenic tenside is one or more in fatty alcohol-polyoxyethylene ether (AEO), polyoxyethylene nonylphenol ether (NP-10), polyoxyethylene octylphenol ether (OP-10), polyoxyethylene polyoxypropylene segmented copolymer (EO-PO), polyvinylpyrrolidone (PVP).
10. for a preparation method for large size silicon wafer polishing composition, it is characterized in that, comprise the following steps:
To be scattered in water and the acid silicon dioxide sol of high-speed stirring and silica sol granule stablizer mix and blend 5～30 minutes;
Add wherein heat absorbent to stir 5～30 minutes, preparation temperature is controlled in 5～40 degree;
Add basic cpd to stir 5～30 minutes, preparation temperature is controlled in 5～40 degree again;
Add tensio-active agent to stir, after mixing, obtain polishing composition of the present invention.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530987A (en) * | 2014-12-10 | 2015-04-22 | 深圳市力合材料有限公司 | Composition for finishing polish of silicon wafer and preparation method of composition |
| CN104827592A (en) * | 2015-04-22 | 2015-08-12 | 苏州爱彼光电材料有限公司 | Processing method of large-sized sapphire substrate slice |
| CN109111857A (en) * | 2018-09-06 | 2019-01-01 | 北京保利世达科技有限公司 | A kind of polishing fluid and its purposes for polishing 2.5D zirconia ceramics plate |
| CN111378972A (en) * | 2018-12-29 | 2020-07-07 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
| TWI807853B (en) * | 2021-07-08 | 2023-07-01 | 南韓商榮昌化工股份有限公司 | Slurry composition for final polishing a silicone wafer for reducing the number of surface defects and haze and final polishing method using the same |
| WO2023181929A1 (en) * | 2022-03-23 | 2023-09-28 | 株式会社フジミインコーポレーテッド | Polishing composition |
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| CN109111857A (en) * | 2018-09-06 | 2019-01-01 | 北京保利世达科技有限公司 | A kind of polishing fluid and its purposes for polishing 2.5D zirconia ceramics plate |
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| TWI807853B (en) * | 2021-07-08 | 2023-07-01 | 南韓商榮昌化工股份有限公司 | Slurry composition for final polishing a silicone wafer for reducing the number of surface defects and haze and final polishing method using the same |
| WO2023181929A1 (en) * | 2022-03-23 | 2023-09-28 | 株式会社フジミインコーポレーテッド | Polishing composition |
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