CN103897202A - Preparation method and application of polystyrene/silicon oxide core-shell nano compound abrasive - Google Patents
Preparation method and application of polystyrene/silicon oxide core-shell nano compound abrasive Download PDFInfo
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- CN103897202A CN103897202A CN201210586912.2A CN201210586912A CN103897202A CN 103897202 A CN103897202 A CN 103897202A CN 201210586912 A CN201210586912 A CN 201210586912A CN 103897202 A CN103897202 A CN 103897202A
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Abstract
The invention relates to a preparation method for forming a polystyrene/silicon oxide core-shell nano compound abrasive polishing solution with polystyrene nano particles as an inner core and silicon oxide as a shell layer and belongs to the technical field of preparation technology of precise polishing materials. The preparation method of the polystyrene/silicon oxide core-shell nano compound abrasive polishing solution comprises the following steps: (1) preparing polystyrene nano particles; (2) adding alcohol into PS colloid obtained in the step (1), stirring to obtain uniformly mixed liquid, then adding ammonia water with the dosage of 0.3-8wt%; finally adding TEOS (tetraethyl orthosilicate); stirring for 12-48 hours, so that the compound abrasive is obtained; (3) preparing the polystyrene/silicon oxide core-shell nano compound abrasive polishing solution by adopting the polystyrene/silicon oxide core-shell nano compound abrasive. The prepared polystyrene/silicon oxide core-shell nano compound abrasive has smooth surface and can serve as abrasive in a polishing solution.
Description
Technical field
The present invention relates to one using polystyrene nanoparticles as kernel, using silicon oxide as shell, form the preparation method of polystyrene/silicon oxide core-shell type nano compounded abrasive polishing fluid, belong to precise polishing materials fabricating technology field.
Background technology
At present, integrated circuit technology is towards future developments such as less characteristic dimension, silicon single crystal flake ever-larger diameters and integrated level densifications.Along with constantly the dwindling of device architecture, the increase gradually of the metal line number of plies, the nanometer of integrated circuit technology characteristic dimension, cause RC to postpone to increase, in order to reduce the problems such as signal delay, power consumption, the improper transmission of signal, therefore adopt copper wiring and surpass low-k dielectric materials, compare silica dioxide medium layer, copper and ultralow K dielectric material have more weak physical strength and hardness, therefore to integrated circuit technology, processing has proposed stern challenge, more and more higher to the requirement of working accuracy and surfaceness.
Chemically machinery polished (CMP) is current unique overall planarization techniques.Abrasive material is the important component part of polishing fluid, and the character of abrasive material self, if the pattern of abrasive material, particle diameter, size-grade distribution and hardness are the important factor in order that determines polishing planarization.At present, business-like main flow abrasive material has the abrasives such as aluminum oxide, cerium oxide, silicon oxide.Because the hardness of these three kinds of abrasive materials is large, in CMP (Chemical Mechanical Polishing) process, single abrasive material often can not obtain satisfied polishing performance, easily causes cut and defect.Therefore limited the surface flatness of polishing material.
Summary of the invention
The object of the invention is to overcome the defect that existing abrasive material exists, a kind of preparation method of novel polystyrene/silicon oxide core-shell type nano compounded abrasive polishing fluid and the application in chemically machinery polished thereof are provided.
First aspect present invention provides a kind of preparation method of polystyrene/silicon oxide core-shell type nano compounded abrasive, comprises the steps:
(1) preparation of polystyrene nanoparticles: styrene monomer is added to the water, add dispersion agent, stir and form uniform dispersion liquid, pass into nitrogen purge protective reaction system, add afterwards cationic initiator, under 60～80 ℃ of conditions, react and within 1～24 hour, can obtain cationic polystyrene colloid;
(2) in the PS colloid preparing in step 1, add alcohol, stir the liquid being uniformly mixed, add afterwards ammoniacal liquor, its consumption is 0.3～8wt%; Finally add TEOS; Stir and can obtain compounded abrasive in 12～48 hours;
(3) prepare polishing fluid by compounded abrasive: the alcohol that the compounded abrasive of step 2 gained is carried out to evaporative removal the inside, add afterwards a certain amount of water, the mass ratio of compounded abrasive and water is 1～10%, the amount that adds oxygenant is 0.5～5wt%, add again inhibiter 0.01～0.1wt%, finally add sequestrant 0.1～1wt%, stir and be polystyrene/monox nanometer compounded abrasive polishing fluid.
Preferably, in described step 1, the mode of stirring is mechanical stirring.
Preferably, in described step 1, described dispersion agent is selected from the one in polyvinyl pyrrolidone, poly N-vinyl pyrrolidone.
Preferably, in described step 2, the volume ratio of alcohol and PS colloid is 5:1～20:1.
Preferred, in described step 2, alcohol is selected from any in methyl alcohol, ethanol, Virahol.
Preferably, in described step 2, the rapid stirring that the mode of stirring is magnetic stirring apparatus.
Preferably, in described step 2, the aqueous solution that ammoniacal liquor is 28wt%.
Preferably, in described step 2, the amount of TEOS is determined according to needed silicon oxide shell thickness, is generally 0.1～3wt%.
Preferably, in described step 3, the method for evaporation is for adopting rotary evaporation.
Preferably, in described step 3, described oxygenant is hydrogen peroxide; Described inhibiter is benzotriazole; Described sequestrant is glycine.
Second aspect present invention provides the application of described polystyrene/silicon oxide core-shell type nano compounded abrasive in chemically machinery polished field.
Hud typed compounded abrasive of the present invention, is using polystyrene as kernel, and silicon oxide is as shell, and because silicon oxide surface contains a large amount of hydroxyls, surfactivity is high, and easily modification, has wetting ability, shows very good dispersiveness.The more important thing is that prepared compounded abrasive has smooth surface, is suitable as the abrasive material in polishing fluid.This hud typed compounded abrasive is in polishing process, due to its special structure and mechanical property, in polishing process, can there is to polish pressure the effect of a buffering from the effect of the elastic property of polystyrene core, reduce the excessive physical abuse that silicon oxide shell brings, thereby reduce cut and the damage of polishing material, finally obtain the glazed surface roughness of a sub-nanometer scale.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope image of the hud typed compounded abrasive of polystyrene/silicon oxide.
Fig. 2 is the surface topography map that before polishing, the atomic force microscope (AFM) of copper sheet records.
Fig. 3 is the copper sheet afm image after compounded abrasive polishing.
Fig. 4 is the afm image of the copper sheet after silica abrasive polishing.
Embodiment
Below, by specific specific examples explanation embodiments of the present invention, those skilled in the art can understand other advantages of the present invention and effect easily by the disclosed content of this specification sheets.The present invention can also be implemented or be applied by other different embodiment, and the every details in this specification sheets also can be based on different viewpoints and application, carries out various modifications or change not deviating under spirit of the present invention.
Notice, processing unit or device concrete not dated in the following example all adopt conventional equipment or the device in this area; All force value and scope all refer to absolute pressure.
In addition should be understood that one or more method stepss of mentioning in the present invention do not repel between the step that can also have additive method step or clearly mention at these before and after described combination step can also insert additive method step, except as otherwise noted; Will also be understood that, the relation that is connected between one or more equipment/devices of mentioning in the present invention is not repelled between two equipment/devices that can also have other equipment/devices or clearly mention at these before and after described clustered aggregates/device can also insert other equipment/devices, except as otherwise noted.And, except as otherwise noted, the numbering of various method steps is only for differentiating the convenient tool of various method steps, but not for limiting the ordering of various method steps or limiting the enforceable scope of the present invention, the change of its relativeness or adjustment, in the situation that changing technology contents without essence, when being also considered as the enforceable category of the present invention.
Embodiment 1: polishing fluid preparation process and step in the present embodiment are as described below:
(1) preparation of the hud typed compounded abrasive of polystyrene/silicon oxide: adopt two-step approach to prepare ganoid nano combined abrasive material.The first step adopts polymerization to prepare polystyrene nanoparticles, and the styrene monomer of getting 3mL adds in 300mL water, packs in the round-bottomed flask of 4 necks, and mechanical stirring forms homogeneous system, passes into N
2emptying, after ten minutes, the polyvinylpyrrolidone of 50mg (PVP K-30) is dissolved in 50mL water, pours into rapidly in reaction mixture, start to heat with shell type thermostatted, design temperature is 70 ℃, the speed of now accelerating to stir is to 300rpm, and the temperature of question response reaches 70 ℃, by the azo diisobutyl amidine hydrochloride (AIBA of 50mg, Aldrich company of the U.S.) solution that is dissolved in 50mL water pours in reaction system, heated and stirred 12 hours under 70 ℃ of conditions.After reaction finishes, be cooled to room temperature, can obtain PS colloid.Second step prepares the coated nano combined abrasive material of polystyrene core shell mould of silicon oxide under the condition of ammonia-catalyzed hydrolysis tetraethoxy, get the PS colloid that 10mL has prepared, pack in 250mL round-bottomed flask, add afterwards 70mL ethanol, the liquid being uniformly mixed under the rapid stirring of magnetic stirring apparatus, add afterwards the ammoniacal liquor (28%) of 2mL, finally drip 1mL TEOS with constant flow pump with the speed of 3mL/h, under normal temperature, stir and can obtain compounded abrasive in 24 hours.Fig. 1 is the TEM image of compounded abrasive.
(2) by PS/SiO
2hud typed compounded abrasive is mixed with polishing fluid: by prepared PS/SiO
2hud typed compounded abrasive colloid adopts Rotary Evaporators to isolate the ethanol of the inside, constantly adds deionized water in evaporative process.The mass ratio that finally regulates compounded abrasive and water is 2%, then adds the hydrogen peroxide of 1wt%, 1wt% glycine, and the BTA of 0.1wt%, is uniformly mixed.The add-on of each material, all using 100 grams of water as with reference to benchmark, has obtained PS/SiO so above
2hud typed compounded abrasive polishing fluid.
In order to contrast comparison, adopt the polishing fluid of monox nanometer particle as a comparison case.
Comparative example 1
The silicon oxide particle of large particle diameter (120nm) is added to the water, and the mass ratio of silicon oxide and water is 2%, adds the hydrogen peroxide of 1wt%, 1wt% glycine, and the BTA of 0.1wt%, is uniformly mixed.Obtain the polishing fluid of silica abrasive.
Polishing experiments
The polishing fluid that uses respectively embodiment 1 and comparative example 1, carries out polishing experiments to copper sheet under the following conditions.
Polishing condition
The CP-4 board of polishing machine: CETR.
Polishing material: the thick titanium nitride of sputter 20nm on the silicon chip of 3 inches, the thick seed crystal copper of sputter 50nm, finally electroplates the copper of 5 micron thickness afterwards.The AFM surface appearance feature of the copper sheet before polishing as shown in Figure 2.
Polishing pad: model IC1010(Tao Shi electronics), material is urethane.
Polish pressure 1psi.
Polishing pad rotating speed 60rpm.
Polished section rotating speed 60rpm.
Polishing fluid flow 100mL/min.
25 ℃ of temperature.
Polishing time: 5 minutes.
Polishing pad is repaired: under 2psi pressure, repair with the diamond reparation dish of 4 inches.
After polishing, washing and dry copper sheet, adopt AFM to measure the surface appearance feature of copper sheet.
The polishing effect of embodiment 1 and comparative example 1 is respectively referring to Fig. 3 and Fig. 4.
Visible in figure, adopt polystyrene/silicon oxide core-shell type nano compounded abrasive polishing fluid of the present invention to show lower surfaceness and cut than single silica abrasive in the CMP (Chemical Mechanical Polishing) process of copper.Can obtain smooth surface with the nano combined abradant polishing solution of PS/SiO2 of the present invention, meet the needs of unicircuit planarization.
In sum, the present invention has effectively overcome various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all can, under spirit of the present invention and category, modify or change above-described embodiment.Therefore, such as in affiliated technical field, have and conventionally know that the knowledgeable, not departing from all equivalence modifications that complete under disclosed spirit and technological thought or changing, must be contained by claim of the present invention.
Claims (9)
1. a preparation method for polystyrene/silicon oxide core-shell type nano compounded abrasive, comprises the steps:
(1) preparation of polystyrene nanoparticles: styrene monomer is added to the water, add dispersion agent, stir and form uniform dispersion liquid, pass into nitrogen purge protective reaction system, add afterwards cationic initiator, under 60～80 ℃ of conditions, react and within 1～24 hour, can obtain cationic polystyrene colloid;
(2) in the PS colloid preparing in step 1, add alcohol, stir the liquid being uniformly mixed, add afterwards ammoniacal liquor, its consumption is 0.3～8wt%; Finally add TEOS; Stir and can obtain compounded abrasive in 12～48 hours;
(3) prepare polishing fluid by compounded abrasive: the alcohol that the compounded abrasive of step 2 gained is carried out to evaporative removal the inside, add afterwards a certain amount of water, the mass ratio of compounded abrasive and water is 1～10%, the amount that adds oxygenant is 0.5～5wt%, add again inhibiter 0.01～0.1wt%, finally add sequestrant 0.1～1wt%, stir and be polystyrene/monox nanometer compounded abrasive polishing fluid.
2. the preparation method of a kind of polystyrene/silicon oxide core-shell type nano compounded abrasive as claimed in claim 1, is characterized in that, in described step 1, described dispersion agent is selected from the one in polyvinyl pyrrolidone, poly N-vinyl pyrrolidone.
3. the preparation method of a kind of polystyrene/silicon oxide core-shell type nano compounded abrasive as claimed in claim 1, is characterized in that, in described step 2, the volume ratio of alcohol and PS colloid is 5:1～20:1.
4. the preparation method of a kind of polystyrene/silicon oxide core-shell type nano compounded abrasive as claimed in claim 1, is characterized in that, in described step 2, alcohol is selected from any in methyl alcohol, ethanol, Virahol.
5. the preparation method of a kind of polystyrene/silicon oxide core-shell type nano compounded abrasive as claimed in claim 1, is characterized in that, in described step 2, and the aqueous solution that ammoniacal liquor is 28wt%.
6. the preparation method of a kind of polystyrene/silicon oxide core-shell type nano compounded abrasive as claimed in claim 1, is characterized in that, in described step 2, the amount of TEOS is determined according to needed silicon oxide shell thickness, is generally 0.1～3wt%.
7. the preparation method of a kind of polystyrene/silicon oxide core-shell type nano compounded abrasive as claimed in claim 1, is characterized in that, in described step 3, the method for evaporation is for adopting rotary evaporation.
8. the preparation method of a kind of polystyrene/silicon oxide core-shell type nano compounded abrasive as claimed in claim 1, is characterized in that, in described step 3, described oxygenant is hydrogen peroxide; Described inhibiter is benzotriazole; Described sequestrant is glycine.
9. polystyrene/silicon oxide core-shell type nano the compounded abrasive as described in claim as arbitrary in claim 1-8 is in the application in chemically machinery polished field.
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Cited By (6)
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| CN104149039A (en) * | 2014-07-09 | 2014-11-19 | 华侨大学 | Method for coating surface of ultrafine abrasive with monox |
| CN104448945A (en) * | 2014-11-06 | 2015-03-25 | 东华大学 | Method for preparing polystyrene coated SiO2 composite particles by using oil-water interface method |
| CN105778861A (en) * | 2014-12-24 | 2016-07-20 | 深圳富泰宏精密工业有限公司 | Elastic abrasive particle and manufacturing method thereof |
| CN109249018A (en) * | 2018-10-15 | 2019-01-22 | 华中科技大学 | A kind of self-assembling method of nanogold particle foam covering polystyrene microsphere |
| CN109880533A (en) * | 2019-03-26 | 2019-06-14 | 中南大学 | A kind of composite abrasive grain polishing solution and preparation method thereof |
| CN117050661A (en) * | 2023-06-21 | 2023-11-14 | 湖北兴福电子材料股份有限公司 | Green monocrystalline silicon coarse polishing solution |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104149039A (en) * | 2014-07-09 | 2014-11-19 | 华侨大学 | Method for coating surface of ultrafine abrasive with monox |
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| CN104448945A (en) * | 2014-11-06 | 2015-03-25 | 东华大学 | Method for preparing polystyrene coated SiO2 composite particles by using oil-water interface method |
| CN105778861A (en) * | 2014-12-24 | 2016-07-20 | 深圳富泰宏精密工业有限公司 | Elastic abrasive particle and manufacturing method thereof |
| CN109249018A (en) * | 2018-10-15 | 2019-01-22 | 华中科技大学 | A kind of self-assembling method of nanogold particle foam covering polystyrene microsphere |
| CN109249018B (en) * | 2018-10-15 | 2019-09-06 | 华中科技大学 | A kind of self-assembling method of nanogold particle foam covering polystyrene microsphere |
| CN109880533A (en) * | 2019-03-26 | 2019-06-14 | 中南大学 | A kind of composite abrasive grain polishing solution and preparation method thereof |
| CN109880533B (en) * | 2019-03-26 | 2020-07-17 | 中南大学 | Composite abrasive particle polishing solution and preparation method thereof |
| CN117050661A (en) * | 2023-06-21 | 2023-11-14 | 湖北兴福电子材料股份有限公司 | Green monocrystalline silicon coarse polishing solution |
| CN117050661B (en) * | 2023-06-21 | 2024-05-17 | 湖北兴福电子材料股份有限公司 | Green monocrystalline silicon coarse polishing solution |
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Application publication date: 20140702 |