CN102344761A - Preparation method of cerium-doped silica sol - Google Patents
Preparation method of cerium-doped silica sol Download PDFInfo
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- CN102344761A CN102344761A CN2011102204438A CN201110220443A CN102344761A CN 102344761 A CN102344761 A CN 102344761A CN 2011102204438 A CN2011102204438 A CN 2011102204438A CN 201110220443 A CN201110220443 A CN 201110220443A CN 102344761 A CN102344761 A CN 102344761A
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Abstract
The invention provides a preparation method of cerium-doped silica sol, which comprises the following steps: 1) using silica sol with different particle sizes obtained by an ion exchange method as a seed, adding a certain amount of an alkali catalyst for controlling the seed with pH value of 9-10, heating to the temperature of 60-90 DEG C; 2) dissolving a certain amount of ammonium ceric nitrate to an ammonium ceric nitrate aqueous solution by adding pure water for standby; 3) heating by using water-bath, heating the seed in a step 1) while stirring to the temperate of 60-90 DEG C, adding a certain amount of silicon powder, adding a certain amount of silicon powder and a certain amount of the ammonium ceric nitrate aqueous solution in a step 2) every 30-45 minutes; 4) repeatedly adding for 5-10 times according to a charging mode in a step 3); 5) continuously stirring and reacting for 1-2 hours after the charging is finished. The invention has the following technical effects: 1, the growth period is short, the technology is simple, and the method of the invention can be used in grinding and polishing of a CMP technology rough polishing process; 2, the method is beneficial to the equipment cost reduction and safe production; 3, the method enables higher removal rate to the medium materials during the polishing process.
Description
Technical field
The present invention relates to a kind of preparation method of metallic cerium doping silicon dioxide colloidal sol, belong to microelectronics chemistry mechanical polishing or planarization field.
Background technology
Along with the development of microelectronics,, need to adopt chemically machinery polished (CMP) or flatening process for the surface that makes semiconductor substrate materials and integrated circuit (IC) chip reaches the planeness of nano level even atom level towards device miniaturization, structure multiple stratification.
Chemically machinery polished realizes the quick global planarization of material surface by the synergy of chemical corrosion and mechanical grinding.In CMP (Chemical Mechanical Polishing) process, polishing fluid is being brought into play the dual function of chemical corrosion and mechanical grinding.Polishing fluid comprises abrasive, soluble chemical material and water medium three parts, and wherein abrasive provides the mechanical grinding effect, and the soluble chemical material is used for the corrosion material surface, and water medium is that polishing fluid provides good flowability.As the abrasive of performance mechanical effect, its abrasive species, particle size, pattern and solid content are determining the polishing speed and the quality of finish of polishing fluid to a great extent.
There am polishing speed phenomenon on the low side in we by present prepared ion exchange method silicon sol, are further to improve polishing speed, must try every possible means to improve the hardness of silicon dioxide granule.There is relevant report to show that mainly there are two trend in cerium modified silicon sol: (1) is nuclear with the silicon oxide, forms nucleocapsid structure at its surface parcel cerium oxide; (2) in the process of silicon sol nucleation, add cerium ion, form the adulterated silicon sol of cerium.At present, more relatively for the research of cerium oxide parcel silicon oxide formation nucleocapsid structure both at home and abroad, its conclusion all is decided to be this structure can improve polishing speed.Research for the modification of cerium doped silicon oxide is less, and mainly with headed by the people such as M.S.Tsai, other investigators' conclusion is consistent with it mostly.In addition, the somebody carries out physical mixed to cerium oxide and silicon oxide, as behind the polishing fluid abrasive material to the influence of polishing speed, its conclusion is for can improve polishing speed.The investigator is more and more higher for the attention rate of cerium oxide in silicon wafer polishing.
Find that in read documents cerium oxide wraps up and cerium mixes, and formed colloidal solid is not regular ball-type, this mainly is because cerium oxide compares easy and crystalline, the uniform one deck shell structure of very difficult formation in the process of parcel silicon-dioxide; In the adulterated process of cerium, cerium combines with chemical bond with silicon-dioxide and forms the Si-O-Ce structure, but the Si-O key is different with Ce-O length, and therefore the colloidal solid that forms is irregular.The electronegativity of Si is bigger than Ce, so the electron density around the Si atom increases the shielding effect increase; Simultaneously, also increase, changed former SiO through after the modification with electron density around the O atom of Si bonding
2The electron binding energy power of micelle might make micelle more tight.
There are some researches show that abroad non-spherical colloidal silica abrasive material is taked sliding friction at polishing process, its frictional coefficient can improve polishing speed greater than the rolling resistance of ball-type silicon sol.SiO
2/ CeO
2The nucleocapsid structure of particle can reduce particle to be impacted " firmly " on surface, reaches " flexible polishing " effect, thereby reduces surfaceness, alleviate microdefects such as polishing cut and pit.Variation has taken place because of its structure in the silicon sol after cerium modified, therefore aspect the raising polishing speed certain feasibility is being arranged.
Above-mentioned test method all is to utilize ion exchange method prepared, and utilizes on the basis that ion exchange method and silica flour hydrolysis method combine, and carries out metal-dopedly again, does not see relevant report at present as yet.
Summary of the invention
The objective of the invention is for solving silicon dioxide gel abrasive hardness problem of smaller in microelectronic industry polishing usefulness; In the process that does not change original preparation silicon sol, carry out metal-doped experiment; Obtain the higher abrasive silica of hardness; And then the polishing speed of raising abrasive material; Satisfy the surface quality requirement of electron trade, a kind of preparation method of cerium doping silicon dioxide colloidal sol is provided aluminium nitride chip.
The preparation method of cerium doping silicon dioxide colloidal sol of the present invention may further comprise the steps:
1) the different-grain diameter silicon sol that obtains with ion exchange method is as crystal seed, and seed concentration is 1.5-2wt%, adds a certain amount of alkaline catalysts and makes the pH value of crystal seed be controlled in the 9-10, intensification 60-90 ℃;
2) a certain amount of ceric ammonium nitrate is added pure water and be dissolved into the ceric ammonium nitrate aqueous solution, subsequent use;
3) utilize heating in water bath, the crystal seed in the step 1) followed to stir be warming up to 60-90 ℃, begin to add a certain amount of silica flour, after this every silica flour and a certain amount of step 2 that adds certain quantity once at a distance from 30-45min) in the ceric ammonium nitrate aqueous solution for preparing;
4), repeat to add 5-10 time according to the feed way of step 3);
5) behind reinforced the finishing, continue stirring reaction 1-2h.
Preferably,
The silicon sol of the different-grain diameter that said ion exchange method obtains, its particle diameter are 30-130nm.
Said alkaline catalysts is the 2-5wt%NaOH aqueous solution.
Each ceric ammonium nitrate consumption that adds is each 0.2-1% that adds the silica flour quality.
The particle diameter of said silica flour is 200 orders.
The activation temperature of said silica flour is controlled at 60 ℃, and in water-bath, activates.
The concentration of the said ceric ammonium nitrate aqueous solution is 10-50wt%.
The present invention has following technique effect:
1, the present invention adopts the silica flour hydrolysis method, through the reinforced proportioning in the reaction process, material concentration, reaction solution PH, temperature of reaction are carried out technology controlling and process, changes the add-on of cerium, directly prepares the higher silicon sol of different-grain diameter hardness.Growth cycle of the present invention is short, technology is simple.The silicon sol of preparation can be applied to the grinding and polishing that the CMP technology is slightly thrown process.
2, the present invention carries out under normal pressure and lesser temps, and is very useful with safety in production to reducing equipment cost.
3, than the silicon sol of traditional silica flour hydrolysis method preparation, cerium is entrained in the polishing process has higher removal speed to dielectric material; The smooth finish and the Flatness of polishing back crystal column surface can satisfy processing requirement.
Embodiment
Embodiment 1
The preparation method of the cerium doping silicon dioxide colloidal sol of present embodiment may further comprise the steps:
1) the 20nm silicon sol 20g that obtains with ion exchange method is as crystal seed, and thin up is to 500g.Add 4gNaOH, make the crystal seed pH value in the 9-10 scope, intensification 60-90 ℃;
2) the 1.5g ceric ammonium nitrate is added the 3g pure water and be dissolved into the ceric ammonium nitrate aqueous solution, subsequent use;
3) follow stirring to be warming up to 60-90 ℃ the crystal seed in (1) step, begin to add the 20g silica flour, the ceric ammonium nitrate aqueous solution that after this every separated 30min adding 10g silica flour 5g 5wt%NaOH and 0.2g (2) prepared in the step;
4) according to this order feed way of (3) step, repeat to add 10 times;
5) behind reinforced the finishing, continue stirring reaction 1h; Reaction finishes;
Experimental result: after polishing, speed is not mixed cerium than same particle size and is improved 20%
Embodiment 2
The preparation method of the cerium doping silicon dioxide colloidal sol of present embodiment may further comprise the steps:
1) the 20nm silicon sol 20g that obtains with ion exchange method is as crystal seed, and thin up is to 500g.Add 4gNaOH, make the crystal seed pH value in the 9-10 scope, intensification 60-90 ℃;
2) the 1.5g ceric ammonium nitrate is added the 3g pure water and be dissolved into the ceric ammonium nitrate aqueous solution, subsequent use;
3) follow stirring to be warming up to 60-90 ℃ the crystal seed in (1) step, begin to add the 20g silica flour, the ceric ammonium nitrate aqueous solution that after this every separated 30min adding 10g silica flour 5g 5wt%NaOH and 0.3g (2) prepared in the step;
4) according to this order feed way of (3) step, repeat to add 10 times;
5) behind reinforced the finishing, continue stirring reaction 1h; Reaction finishes;
Experimental result: after polishing, speed is not mixed cerium than same particle size and is improved 18%
Embodiment 3
The preparation method of the cerium doping silicon dioxide colloidal sol of present embodiment may further comprise the steps:
1) the 20nm silicon sol 20g that obtains with ion exchange method is as crystal seed, and thin up is to 500g.Add 4gNaOH, make the crystal seed pH value in the 9-10 scope, intensification 60-90 ℃;
2) the 1.5g ceric ammonium nitrate is added the 3g pure water and be dissolved into the ceric ammonium nitrate aqueous solution, subsequent use;
3) follow stirring to be warming up to 60-90 ℃ the crystal seed in (1) step, begin to add the 20g silica flour, the ceric ammonium nitrate aqueous solution that after this every separated 30min adding 10g silica flour 5g 5wt%NaOH and 0.1g (2) prepared in the step;
4) according to this order feed way of (3) step, repeat to add 10 times;
5) behind reinforced the finishing, continue stirring reaction 1h; Reaction finishes;
Experimental result: after polishing, speed is not mixed cerium than same particle size and is improved 15%
The above; It only is preferred embodiment of the present invention; Be not that the present invention is done any pro forma restriction, every foundation technical spirit of the present invention all still belongs in the scope of technical scheme of the present invention any simple modification, equivalent variations and modification that above embodiment did.
Claims (7)
1. the preparation method of cerium doping silicon dioxide colloidal sol is characterized in that, may further comprise the steps:
1) the different-grain diameter silicon sol that obtains with ion exchange method is as crystal seed, and seed concentration is 1.5-2wt%, adds a certain amount of alkaline catalysts and makes the pH value of crystal seed be controlled in the 9-10, intensification 60-90 ℃;
2) a certain amount of ceric ammonium nitrate is added pure water and be dissolved into the ceric ammonium nitrate aqueous solution, subsequent use;
3) utilize heating in water bath, the crystal seed in the step 1) followed to stir be warming up to 60-90 ℃, begin to add a certain amount of silica flour, after this every silica flour and a certain amount of step 2 that adds certain quantity once at a distance from 30-45min) in the ceric ammonium nitrate aqueous solution for preparing;
4), repeat to add 5-10 time according to the feed way of step 3);
5) behind reinforced the finishing, continue stirring reaction 1-2h.
2. the preparation method of cerium doping silicon dioxide colloidal sol according to claim 1 is characterized in that, the silicon sol of the different-grain diameter that said ion exchange method obtains, its particle diameter are 30-130nm.
3. the preparation method of cerium doping silicon dioxide colloidal sol according to claim 1 is characterized in that, said alkaline catalysts is the 2-5wt%NaOH aqueous solution.
4. the preparation method of cerium doping silicon dioxide colloidal sol according to claim 1 is characterized in that, adds the ceric ammonium nitrate consumption at every turn and is each 0.2-1% that adds the silica flour quality.
5. the preparation method of cerium doping silicon dioxide colloidal sol according to claim 1 is characterized in that, the particle diameter of said silica flour is 200 orders.
6. the preparation method of cerium doping silicon dioxide colloidal sol according to claim 1 is characterized in that the activation temperature of said silica flour is controlled at 60 ℃, and in water-bath, activates.
7. the preparation method of cerium doping silicon dioxide colloidal sol according to claim 1 is characterized in that, the concentration of the said ceric ammonium nitrate aqueous solution is 10-50wt%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104745146A (en) * | 2015-03-23 | 2015-07-01 | 江苏天恒纳米科技股份有限公司 | Nano-composite abrasive particle sol containing cerium-doped silicon dioxide, polishing agent and preparation method thereof |
| WO2016150176A1 (en) * | 2015-03-23 | 2016-09-29 | 江苏天恒纳米科技有限公司 | Cobalt-containing doped silicon dioxide nano-composite abrasive grain sol, polishing solution and preparation method thereof |
| CN106867449A (en) * | 2016-12-30 | 2017-06-20 | 上海映智研磨材料有限公司 | A kind of silica Compostie abrasive particles and its production and use |
| CN110437744A (en) * | 2019-08-19 | 2019-11-12 | 福建华清电子材料科技有限公司 | A kind of preparation method of the polishing fluid for aluminium nitride chip polishing |
| CN111269695A (en) * | 2020-02-29 | 2020-06-12 | 上海大学 | Peanut-shaped silicon oxide abrasive particles and preparation method and application thereof |
| CN111320178A (en) * | 2020-03-02 | 2020-06-23 | 正大能源材料(大连)有限公司 | Metal modified silica sol for synthesizing SAPO-34 molecular sieve and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104745146A (en) * | 2015-03-23 | 2015-07-01 | 江苏天恒纳米科技股份有限公司 | Nano-composite abrasive particle sol containing cerium-doped silicon dioxide, polishing agent and preparation method thereof |
| WO2016150176A1 (en) * | 2015-03-23 | 2016-09-29 | 江苏天恒纳米科技有限公司 | Cobalt-containing doped silicon dioxide nano-composite abrasive grain sol, polishing solution and preparation method thereof |
| CN106867449A (en) * | 2016-12-30 | 2017-06-20 | 上海映智研磨材料有限公司 | A kind of silica Compostie abrasive particles and its production and use |
| CN110437744A (en) * | 2019-08-19 | 2019-11-12 | 福建华清电子材料科技有限公司 | A kind of preparation method of the polishing fluid for aluminium nitride chip polishing |
| CN111269695A (en) * | 2020-02-29 | 2020-06-12 | 上海大学 | Peanut-shaped silicon oxide abrasive particles and preparation method and application thereof |
| CN111320178A (en) * | 2020-03-02 | 2020-06-23 | 正大能源材料(大连)有限公司 | Metal modified silica sol for synthesizing SAPO-34 molecular sieve and preparation method thereof |
| CN111320178B (en) * | 2020-03-02 | 2021-08-27 | 正大能源材料(大连)有限公司 | Metal modified silica sol for synthesizing SAPO-34 molecular sieve and preparation method thereof |
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Application publication date: 20120208 |