CN104556060A - Linear nano silica sol and preparation method thereof - Google Patents
Linear nano silica sol and preparation method thereof Download PDFInfo
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- CN104556060A CN104556060A CN201410854330.7A CN201410854330A CN104556060A CN 104556060 A CN104556060 A CN 104556060A CN 201410854330 A CN201410854330 A CN 201410854330A CN 104556060 A CN104556060 A CN 104556060A
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Abstract
The invention relates to the technical field of CMP, in particular to linear silica sol and a preparation method thereof. The invention provides the linear silica sol which includes a liquid medium and sol particles, wherein the sol particles are linear silica particles. The benefit provided the invention is that the linear silica sol is formed through a specially selected acidic solution and a processing method; because the silica sol particles are linear, and the drag area on a chip is significantly increased compared with that of a single spherical particle, the polishing rate is improved; and in addition, since the linear silica particles has a certain degree of flexibility, the damage to the chip is much smaller than fumed silica. By using the linear nano silica particles provided by the invention as CMP abrasive particles, the polishing rate is improved effectively, and surface damages are reduced.
Description
Technical field
The present invention relates to CMP technology polishing field, particularly relate to a kind of wire nano silicon dioxide sol and preparation method thereof.
Background technology
For meeting huge semi-conductor market demand and tackling human consumer's requirement more and more higher to product performance, semiconducter device travelling speed is more and more faster, storage capacity is also more and more higher, and chip feature sizes and integrated level are always along the Moore's Law develop rapidly that Intel originator G.Moore proposes.Order about complete processing towards higher current density, higher clock requency and more interconnection layer transfer.Due to reducing of device size, the reduction of optical lithography equipment depth of focus, requires that the planeness of the acceptable resolving power of wafer surface reaches nano level.For addressing this problem, chemically machinery polished (Chemical Mechanical Polishing, the CMP) technology of global planarizartion can be realized, becoming one of important critical process of semiconductor manufacturing at one stroke.CMP technology is in implementation process, and polishing pad and wafer relatively rotate, and polishing fluid flows between, reaches the object of global planarizartion with this.
Since 1980s IBM introduces CMP technology, the application of CMP in semiconductor fabrication is more and more extensive.In many application of CMP, silicon oxide dielectric material polishing is always in occupation of very important position.Investigate display according to market consultation company Linx in 2010, silicon oxide dielectric material polishing about occupies the market share more than 20%.Because of be oxidized siliceous hard, (only react with HF and highly basic) in unreactiveness, in polishing mainly based on machinery removal, in semiconductor factory, the high polish pressure of employing the 20wt% even silicon dioxide polishing solution of greater concn, 4-6psi carries out polishing to silica membrane usually, but also only can reach the removal speed of about 100nm/min.Therefore, how to optimize polishing fluid to reduce polishing fluid concentration, mechanical pressure, thus reach reduction polishing fluid cost and energy consumption while raising silicon oxide removes speed, be subject to semi-conductor circle always and pay close attention to.
Remove speed for accelerating silicon oxide, a lot of researchist has made a lot of good try.As far back as nineteen ninety, L.M Cook is at his article (Lee M.Cook.J.Non-Cryst.Solids, 120,152-171,1990.) refer in and use pyrocatechol promotor, accelerate the polishing of silicon oxide by the coordination of removing between product (orthosilicic acid) of pyrocatechol and silicon oxide; And in patent CN 101463226, the red people of grade of An Ji Microtronics A/S Song Wei claims the heterogeneous ring compound and derivative that use containing 1-4 nitrogen-atoms, silicon oxide removes speed can bring up to about 90nm/min by 40nm/min.In another section of patent (CN 101638557) of An Ji Microtronics A/S, the people such as Chen Guodong are disclosed in polishing fluid the polycarboxylic acid (salt) that uses carbon atom number to be 2-8 and and replace organic phospho acid (salt) and increase auxiliary agent as speed, also can the polishing of accelerating oxidation silicon.For soluble tartrate, their data presentation silicon oxide is removed speed and can be brought up to 310nm/min further by 270nm/min.
Above patent all by adding various sequestrant in polishing fluid, promotor improves polishing speed, the problem done like this is that these chemical substances easily stick in chip die, makes troubles to follow-up cleaning.People start to find the less polishing fluid of additive, wherein abrasive grains is that the polishing fluid of calcined silica (fumed silica) can significantly improve polishing speed, because silicon-dioxide is after calcined crystallization, hardness significantly rises, and strengthens with the mechanical effect of wafer.But its shortcoming is also significant: exactly because calcined silica hardness is too large, easily leave the scratch defects of unrepairable on wafer, this is flagrant.
How high polishing speed and low surface defect, low stain to be combined, be the Main way of CMP polishing fluid research from now on.
Summary of the invention
The present invention is to overcome deficiency of the prior art, provides a kind of wire silicon dioxide gel and preparation method thereof, and obtained sol particle is wire, and length is 100 ~ 200nm, and frictional coefficient is large, and polishing efficiency is high.Empirical tests, uses silicon sol of the present invention polishing speed can be promoted more than 20%, and the rarer cut of polished section produces simultaneously.
For achieving the above object, first aspect present invention provides a kind of wire silicon dioxide gel, comprises liquid medium and sol particle in the present invention, and described sol particle is wire silica dioxide granule.
Described wire silicon dioxide gel, is characterized in that: described silica colloidal particles is through scanning electron microscopic observation in obviously linear, and length is 100 ~ 200nm, and distribution comparatively evenly (Fig. 1).Liquid medium is water, and pH is 8 ~ 10.
Preferably, described sol particle is the wire silica dioxide granule of length 150nm.
Second aspect present invention provides the preparation method of described wire silicon dioxide gel, comprises the steps:
1) using tetraethoxy (TEOS) as silicon source, itself and alcoholic solvent are mixed in proportion;
2) in the solution that step 1 is obtained, add acidic solution to mix;
3) by step 2 gained solution Keep agitation 1 ~ 3h under normal temperature, normal pressure, and ageing 24 ~ 72h is sealed;
4) by step 3 gained solution centrifugal dispersion cleaning, centrifugal speed is 2000 ~ 10000rpm, and centrifugation time is 15 ~ 60min;
5) step 4 gained solution is skimmed supernatant liquor, bottom turbid solution mixes with the ultrapure water of supernatant liquor equivalent, ultrasonic 20 ~ 60min;
6) by step 5 gained solution repeating step 4, step 5, until remaining organic carbon content is at below 1000ppm in solution, pH value is 6.5 ~ 7.5;
7) in step 6 gained solution, add alkaline stabiliser regulates pH to be 8.5 ~ 10.5, obtained linear silicon dioxide gel.
Preferably, step 1) in, the volume ratio of tetraethoxy and alcoholic solvent is 1:30 ~ 1:80.Be more preferably 1:50.
Preferably, step 1) in, described alcoholic solvent be selected from liquid single methanol kind solvent any one.Preferred, described alcoholic solvent be selected from methyl alcohol, ethanol, single propyl alcohol, n-butyl alcohol or Pentyl alcohol any one.Most preferred, described alcoholic solvent is dehydrated alcohol.
Preferably, step 2) in, acidic solution is hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, citric acid, one or both in oxalic acid.
Preferably, step 2) in, acidic solution pH is 4 ~ 6.Preferred, acidic solution pH is 5 ~ 6.
Preferably, step 2) in, acidic solution and step 1 gained liquor capacity are than being 1:50 ~ 1:100.Preferred, acidic solution and step 1 gained liquor capacity are than being 1:70 ~ 1:80.
Preferably, step 3) in, churning time is 1 ~ 1.5h, and digestion time is 24 ~ 48h.
Preferably, step 4) in, centrifugal speed is 3000 ~ 6500rpm, and centrifugation time is 15 ~ 35min.
Preferably, step 5) in, ultrasonic time is 40 ~ 60min.
Preferably, step 7) in, pH is 9.5 ~ 10.0.
Preferably, step 7) in, alkaline stabiliser is mineral alkali or organic bases.Preferred, alkaline stabiliser is sodium hydroxide, potassium hydroxide, ammoniacal liquor, the combination of any one or two kinds in triethylamine.
Third aspect present invention provides the purposes of described linear silicon dioxide gel in CMP polishing field.
Preferably, described purposes is specially: described linear silicon dioxide gel is preparing the purposes in rumbling compound.
Fourth aspect present invention provides a kind of rumbling compound, containing foregoing linear silicon dioxide gel in described rumbling compound.
In rumbling compound, described linear silicon dioxide gel, as abrasive grains, produces mechanical effect and removes polished object.The different material of polishing can have different rumbling compound formulas, but described rumbling compound can adopt wire silicon dioxide gel of the present invention to do abrasive grains.
The beneficial effect of this product is: the beneficial effect of this product is: by elite acidic solution and treatment process, forms wire silicon dioxide gel.Because silica colloid particle is wire, its single spherical particle of towing area ratio on chip will enlarge markedly, so can improve polishing speed.Meanwhile, because wire silica dioxide granule self has certain pliability, also less compared with calcined silica to the damage of chip.Use wire nanometer silicon dioxide particle of the present invention as CMP abrasive grains, effectively can improve polishing speed and reduce surface damage.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the wire silicon dioxide gel that the embodiment of the present invention prepares.
Embodiment
Below by way of specific specific examples, embodiments of the present invention are described, those skilled in the art the content disclosed by this specification sheets can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this specification sheets also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Notice, in the following example, the concrete processing unit that indicates or device all adopt conventional equipment in this area or device; All force value and scope all refer to absolute pressure.
In addition should be understood that the one or more method stepss mentioned in the present invention do not repel and can also to there is additive method step or can also insert additive method step before and after described combination step between these steps clearly mentioned, except as otherwise noted; Will also be understood that, the relation that is connected between the one or more equipment/devices mentioned in the present invention is not repelled and can also to be there are other equipment/devices or can also insert other equipment/devices before and after described clustered aggregates/device between these two equipment/devices clearly mentioned, except as otherwise noted.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not be ordering or the enforceable scope of restriction the present invention of restriction various method steps, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the present invention.
In the present invention, each embodiment all adopts TEOS 2000nm oxidized silicon chip to carry out polishing test, and its concrete grammar is as follows:
Instrument: CMP tester (CETR CP-4), Park XE150AFM
Condition: pressure (Down Force): 4psi
Polishing pad rotating speed (Pad Speed): 80rpm
Rubbing head rotating speed (Carrier Speed): 80rpm
Temperature: room temperature
Polishing fluid flow velocity (Feed Rate): 100ml/min
Polishing time: 4min
Roughness concentration scope is 2.5 × 2.5 μm
Embodiment 1 ordinary silicon colloidal sol polishing experiments
Polishing fluid is composed as follows:
Colloidal silica particles content: 5wt%;
Particle diameter: 120nm;
Salinity: nothing;
Sequestrant; Nothing;
PH:10.0 (potassium hydroxide tune);
All the other are deionized water;
The results are shown in Table 1.
Embodiment 2 uses the linear silicon dioxide gel prepared by the present invention to do polishing experiments
First, preparation wire silicon dioxide gel, comprises the steps:
1) using tetraethoxy (TEOS) as silicon source, by its with dehydrated alcohol by volume 1:50 mix;
2) in the solution that step 1 is obtained, add hydrochloric acid soln to mix, regulate pH=6;
3) by step 2 gained solution Keep agitation 1 ~ 1.5h under normal temperature, normal pressure, and ageing 24 ~ 48h is sealed;
4) by step 3 gained solution centrifugal dispersion cleaning, centrifugal speed is 6500rpm, and centrifugation time is 15min;
5) step 4 gained solution is skimmed supernatant liquor, bottom turbid solution mixes with the ultrapure water of supernatant liquor equivalent, ultrasonic 40 ~ 60min;
6) by step 5 gained solution repeating step 4, step 5 more than three times, until remaining organic carbon content is at below 1000ppm in solution, pH value is 6.5 ~ 7.5;
7) in step 6 gained solution, add potassium hydroxide regulates pH to be 10.0, obtained linear silicon dioxide gel.
The linear silica sol particles of above-mentioned acquisition is through scanning electron microscopic observation in obviously linear, and length is 100 ~ 200nm, and distribution comparatively evenly (as shown in Figure 1).
Polishing fluid is composed as follows:
Linear silicon dioxide gel (colloidal silica particles) content: 5wt%;
Particle diameter: 120nm; (length direction)
Salinity: nothing;
Sequestrant; Nothing;
PH:10.0 (potassium hydroxide tune);
All the other are deionized water;
The results are shown in Table 1.
Table 1
Comparative example, can find out, polishing fluid disclosed by the invention, because its abrasive grains has unique shape---linear, and greatly can improve silica membrane and remove speed.
Meanwhile, notice that used polishing fluid solid content only has 5%, be significantly less than commercial polishing fluid solid content (20%), polishing speed is but still considerable.
In addition, this polishing fluid, except pH adjusting agent, without any sequestrant, promotor, effectively reduces the contamination of chip surface, provides conveniently to subsequent cleaning processes.
In sum, the present invention effectively overcomes 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 without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (10)
1. a wire silicon dioxide gel, comprises liquid medium and sol particle, and described sol particle is wire silica dioxide granule.
2. wire silicon dioxide gel as claimed in claim 1, is characterized in that, described silica colloidal particles is through scanning electron microscopic observation in obviously linear, and length is 100 ~ 200nm; Liquid medium is water, and pH is 8 ~ 10.
3. wire silicon dioxide gel as claimed in claim 1, it is characterized in that, described sol particle is the wire silica dioxide granule of length 150nm.
4. the preparation method of the wire silicon dioxide gel as described in claim as arbitrary in claim 1-3, comprises the steps:
1) using tetraethoxy (TEOS) as silicon source, itself and alcoholic solvent are mixed in proportion;
2) in the solution that step 1 is obtained, add acidic solution to mix;
3) by step 2 gained solution Keep agitation 1 ~ 3h under normal temperature, normal pressure, and ageing 24 ~ 72h is sealed;
4) by step 3 gained solution centrifugal dispersion cleaning, centrifugal speed is 2000 ~ 10000rpm, and centrifugation time is 15 ~ 60min;
5) step 4 gained solution is skimmed supernatant liquor, bottom turbid solution mixes with the ultrapure water of supernatant liquor equivalent, ultrasonic 20 ~ 60min;
6) by step 5 gained solution repeating step 4, step 5, until remaining organic carbon content is at below 1000ppm in solution, pH value is 6.5 ~ 7.5;
7) in step 6 gained solution, add alkaline stabiliser regulates pH to be 8.5 ~ 10.5, obtained linear silicon dioxide gel.
5. method according to claim 4, is characterized in that, step 1) in, the volume ratio of tetraethoxy and alcoholic solvent is 1:30 ~ 1:80.
6. method according to claim 4, is characterized in that, step 2) in, acidic solution is hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, citric acid, one or both in oxalic acid.
7. method according to claim 4, is characterized in that, step 7) in, alkaline stabiliser is mineral alkali or organic bases.
8. the purposes of linear silicon dioxide gel in CMP polishing field as described in claim as arbitrary in claim 1-3.
9. purposes according to claim 8, is characterized in that, described purposes is specially described linear silicon dioxide gel and is preparing the purposes in rumbling compound.
10. a rumbling compound, is characterized in that, containing, for example the linear silicon dioxide gel described in the arbitrary claim of claim 1-3 in described rumbling compound.
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| CN106010297A (en) * | 2016-06-20 | 2016-10-12 | 上海新安纳电子科技有限公司 | Preparation method of aluminum oxide polishing solution |
| CN107541145A (en) * | 2017-09-20 | 2018-01-05 | 无锡市恒利弘实业有限公司 | A kind of green polishing Ludox and preparation method thereof |
| CN112480868A (en) * | 2020-11-10 | 2021-03-12 | 上海大学 | Rod-shaped carbon-coated silicon oxide abrasive particle, preparation method and application thereof |
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| CN112480868A (en) * | 2020-11-10 | 2021-03-12 | 上海大学 | Rod-shaped carbon-coated silicon oxide abrasive particle, preparation method and application thereof |
| CN112480868B (en) * | 2020-11-10 | 2022-07-12 | 上海大学 | Rod-shaped carbon-coated silicon oxide abrasive particle, preparation method and application thereof |
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