CN104556060B - A kind of wire nano silicon dioxide sol and preparation method thereof - Google Patents
A kind of wire nano silicon dioxide sol and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to CMP technique polishing field, particularly relate to a kind of linear silicon dioxide gel and preparation method thereof.The present invention provides a kind of wire silicon dioxide gel, and including liquid medium and sol particle, described sol particle is wire silica dioxide granule.This product provides the benefit that: by elite acid solution and processing method, forms wire silicon dioxide gel.Owing to silica colloid particle is wire, its single spherical particle of towing area ratio on chip to significantly increase, so polishing speed can be improved.Simultaneously as wire silica dioxide granule self has certain pliability, the damage to chip is also less compared with calcined silica.Use the wire nanometer silicon dioxide particle of the present invention as CMP abrasive grains, polishing speed can be effectively improved and reduce surface damage.
Description
Technical field
The present invention relates to CMP technique 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 the requirement that consumer is the highest to properties of product, semiconductor device is transported
Line speed is increasingly faster, and memory capacity is more and more higher, and chip feature sizes and integrated level are created all along Intel
The Moore's Law that beginning people G.Moore proposes develops rapidly.Order about processing technique towards higher electric current density, higher clock
Frequency and the transfer of more interconnection layer.Due to reducing of device size, the reduction of optical lithography equipment depth of focus, it is desirable to wafer surface
The flatness of acceptable resolution reaches nanoscale.For solving this problem, it is possible to the chemical machinery realizing global planarizartion is thrown
Light (Chemical Mechanical Polishing, CMP) technology, becomes one of important critical process of semiconductor manufacturing at one stroke.CMP
Technology is during carrying out, and polishing pad and wafer relatively rotate, and polishing fluid flows between, reaches the overall situation with this flat
The purpose of smoothization.
Since 1980s IBM introduces CMP technique, CMP application in semiconductor fabrication is more and more extensive.?
In many application of CMP, silicon oxide dielectric material polishes always in occupation of critically important position.Consult according to market in 2010
Inquiry company Linx investigates display, and silicon oxide dielectric material polishing about occupies the market share more than 20%.Because of oxidation siliceous hard,
(only react with HF and highly basic) in chemical inertness, main based on machinery removal in polishing, semiconductor factory generally uses
Silica membrane is polished by the silicon dioxide polishing solution of 20wt% even more high concentration, the high polish pressure of 4-6psi, but
It is only capable of reaching the removal rate of about 100nm/min.Therefore, polishing fluid how is optimized to reduce polishing fluid concentration, machinery pressure
Power, thus reduce polishing fluid cost and energy consumption while reaching to improve silicon oxide removal rate, it is constantly subjected to quasiconductor circle and is paid close attention to.
For accelerating silicon oxide removal rate, a lot of research worker are made that a lot of good try.As far back as nineteen ninety, L.M Cook
His article (Lee M.Cook.J.Non-Cryst.Solids, 120,152-171,1990.) refer to use catechol to promote
Enter agent, the coordination between product (orthosilicic acid) can be removed by catechol and silicon oxide and accelerate the polishing of silicon oxide；And
In patent CN 101463226, An Ji Microtronics A/S Song Wei is red et al. claims the heterocyclic compound used containing 1-4 nitrogen-atoms
Thing and derivant, silicon oxide removal rate can be brought up to about 90nm/min by 40nm/min.In An Ji Microtronics A/S
Another patent (CN 101638557) in, Chen Guodong et al. is disclosed in polishing fluid and uses carbon atom number is the polynary carboxylic of 2-8
Acid (salt) and a replacement organic phospho acid (salt) increase auxiliary agent as speed, it is possible to promote the polishing of silicon oxide.With Soluble tartar. it is
Example, their data display silicon oxide removal rate can be further increased to 310nm/min by 270nm/min.
Above patent all by adding various chelating agen in polishing fluid, accelerator improves polishing speed, the problem of do so exists
Easily stick in chip die in these chemical substances, make troubles to follow-up cleaning.People begin look for additive relatively
Few polishing fluid, wherein abrasive grains is that the polishing fluid of calcined silica (fumed silica) is remarkably improved polishing speed,
Because silicon dioxide is after calcined crystallization, hardness significantly rises, and strengthens with the mechanism of wafer.But, its shortcoming is also
Significant: exactly because calcined silica hardness is too big, easily leaving the scratch defects of unrepairable on wafer, this is can not
Tolerance.
How high polishing speed is combined with low surface defect, low stain, be the main side of CMP planarization liquid research from now on
To.
Summary of the invention
The present invention is to overcome deficiency of the prior art, it is provided that a kind of wire silicon dioxide gel and preparation method thereof, prepares
Sol particle be wire, a length of 100～200nm, coefficient of friction is big, and polishing efficiency is high.Empirical tests, uses the present invention's
Polishing speed can be promoted more than 20% by Ludox, and the rarer cut of polished silicon wafer produces simultaneously.
For achieving the above object, first aspect present invention provides a kind of wire silicon dioxide gel to the present invention, including liquid medium and
Sol particle, described sol particle is wire silica dioxide granule.
Described wire silicon dioxide gel, is characterized in that: the scanned electron microscopic observation of described silica colloidal particles is obvious line
Shape, a length of 100～200nm, distribution is more uniformly (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 tetraethyl orthosilicate (TEOS) as silicon source, it is mixed in proportion with alcohols solvent；
2) in the solution that step 1 prepares, add acid solution to mix；
3) by step 2 gained solution under room temperature, normal pressure continuously stirred 1～3h, and ageing 24～72h is sealed；
4) dispersion of step 3 gained solution centrifugal being cleaned, centrifugal speed is 2000～10000rpm, and centrifugation time is 15～60min；
5) step 4 gained solution being skimmed supernatant, bottom turbid solution mixes with the ultra-pure water of supernatant equivalent, ultrasonic
20～60min；
6) step 5 gained solution is repeated step 4, step 5, until remaining organic carbon content is at below 1000ppm in solution,
PH value is 6.5～7.5；
7) adding alkaline stabiliser regulation pH in step 6 gained solution is 8.5～10.5, prepares linear silicon dioxide gel.
Preferably, step 1) in, tetraethyl orthosilicate is 1:30～1:80 with the volume ratio of alcohols solvent.More preferably 1:50.
Preferably, step 1) in, described alcohols solvent is selected from any one in liquid single methanol kind solvent.It is furthermore preferred that institute
State any one in methanol, ethanol, single propanol, n-butyl alcohol or n-amyl alcohol of alcohols solvent.Most preferably, described alcohols
Solvent is dehydrated alcohol.
Preferably, step 2) in, acid solution is hydrochloric acid, sulphuric acid, nitric acid, formic acid, acetic acid, and citric acid, in oxalic acid
One or both.
Preferably, step 2) in, acid solution pH is 4～6.It is furthermore preferred that acid solution pH is 5～6.
Preferably, step 2) in, acid solution and step 1 gained liquor capacity are than for 1:50～1:100.It is furthermore preferred that it is acid
Solution and step 1 gained liquor capacity are than for 1:70～1:80.
Preferably, step 3) in, mixing 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 inorganic base or organic base.It is furthermore preferred that alkaline stabiliser is hydroxide
Sodium, potassium hydroxide, ammonia, any one or the combination of two kinds in triethylamine.
Third aspect present invention provides described linear silicon dioxide gel purposes in CMP planarization field.
Preferably, described purposes is particularly as follows: described linear silicon dioxide gel purposes in preparing polishing agent.
Fourth aspect present invention provides a kind of polishing agent, containing foregoing linear silicon dioxide gel in described polishing agent.
In polishing agent, described linear silicon dioxide gel, as abrasive grains, produces mechanism and removes by parabolic.Polishing is not
Same material can have different polishing agent formula, but the wire silicon dioxide gel that described polishing agent can use the present invention does
Abrasive grains.
This product provides the benefit that: this product provides the benefit that: by elite acid solution and processing method, forms line
Shape silicon dioxide gel.Owing to silica colloid particle is wire, its single spherical particle of towing area ratio on chip
Significantly increase, so polishing speed can be improved.Simultaneously as wire silica dioxide granule self has certain pliability,
Damage to chip is also less compared with calcined silica.Use the wire nanometer silicon dioxide particle of the present invention as CMP grinding
Grain, can be effectively improved 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.
Detailed description of the invention
Below by way of specific instantiation, embodiments of the present invention being described, those skilled in the art can be by disclosed by this specification
Content understand other advantages and effect of the present invention easily.The present invention can also be added by the most different detailed description of the invention
To implement or application, the every details in this specification can also be based on different viewpoints and application, in the essence without departing from the present invention
Various modification or change is carried out under god.
It should be clear that the conventional equipment in the not concrete process equipment indicated or device all use this area in the following example or device；
All force value and scope are all referring to absolute pressure.
In addition, it is to be understood that the one or more method steps mentioned in the present invention do not repel before and after described combination step all right
There is additive method step or additive method step can also be inserted, except as otherwise noted between these steps specifically mentioned；
Should also be understood that the combination annexation between the one or more equipment/devices mentioned in the present invention is not repelled to set in described combination
Other equipment/devices can also be there are before and after standby/device or can also be inserted it between these two equipment/devices specifically mentioned
His equipment/device, except as otherwise noted.And, except as otherwise noted, the numbering of various method steps only differentiates various method steps
Convenient tool, rather than for limit various method steps ordering or limit the enforceable scope of the present invention, its relativeness
It is altered or modified, in the case of without essence change technology contents, when being also considered as the enforceable category of the present invention.
In the present invention, each embodiment all uses TEOS 2000nm oxidized silicon chip to be polished 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 composition is as follows:
Colloidal silica particles content: 5wt%；
Particle diameter: 120nm；
Salinity: nothing；
Chelating agen；Nothing；
PH:10.0 (potassium hydroxide tune)；
Remaining is 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, prepare wire silicon dioxide gel, comprise the steps:
1) using tetraethyl orthosilicate (TEOS) as silicon source, it is mixed with dehydrated alcohol 1:50 by volume；
2) in the solution that step 1 prepares, add hydrochloric acid solution to mix, regulate pH=6；
3) by step 2 gained solution under room temperature, normal pressure continuously stirred 1～1.5h, and ageing 24～48h is sealed；
4) dispersion of step 3 gained solution centrifugal being cleaned, centrifugal speed is 6500rpm, and centrifugation time is 15min；
5) step 4 gained solution being skimmed supernatant, bottom turbid solution mixes with the ultra-pure water of supernatant equivalent, ultrasonic
40～60min；
6) step 5 gained solution is repeated step 4, step 5 more than three times, until remaining organic carbon content is at 1000ppm in solution
Hereinafter, pH value is 6.5～7.5；
7) adding potassium hydroxide regulation pH in step 6 gained solution is 10.0, prepares linear silicon dioxide gel.
The scanned electron microscopic observation of linear silica sol particles of above-mentioned acquisition in the most linear, a length of 100～200nm, point
Cloth is more uniformly (as shown in Figure 1).
Polishing fluid composition is as follows:
Linear silicon dioxide gel (colloidal silica particles) content: 5wt%；
Particle diameter: 120nm；(length direction)
Salinity: nothing；
Chelating agen；Nothing；
PH:10.0 (potassium hydroxide tune)；
Remaining is deionized water；
The results are shown in Table 1.
Table 1
Comparative example, it can be seen that polishing fluid disclosed by the invention, because of its abrasive grains have uniqueness shape linear,
It is greatly improved silica membrane removal rate.
Meanwhile, it is to be noted that only have 5% to the polishing fluid solid content used, it is significantly less than commercial polishing fluid solid content (20%), throws
Optical speed is the most considerable.
It addition, this polishing fluid is in addition to pH adjusting agent, there is no any chelating agen, accelerator, effectively reduce chip list
The contamination in face, provides conveniently to subsequent cleaning processes.
In sum, the present invention effectively overcomes various shortcoming of the prior art and has high industrial utilization.
The principle of above-described embodiment only illustrative present invention and effect thereof, not for limiting the present invention.Any it is familiar with this skill
Above-described embodiment all can be modified under the spirit and the scope of the present invention or change by the personage of art.Therefore, such as
All that in art, tool usually intellectual is completed under without departing from disclosed spirit and technological thought etc.
Effect is modified or changes, and must be contained by the claim of the present invention.
Claims (10)
1. a wire silicon dioxide gel, including liquid medium and sol particle, described sol particle is wire silica dioxide granule；
The preparation method of described wire silicon dioxide gel, comprises the steps:
1) using tetraethyl orthosilicate (TEOS) as silicon source, it is mixed in proportion with alcohols solvent；
2) in the solution that step 1 prepares, add acid solution to mix；Acid solution pH is 4～6；
3) by step 2 gained solution under room temperature, normal pressure continuously stirred 1～3h, and ageing 24～72h is sealed；
4) dispersion of step 3 gained solution centrifugal being cleaned, centrifugal speed is 2000～10000rpm, and centrifugation time is 15～60min；
5) step 4 gained solution being skimmed supernatant, bottom turbid solution mixes with the ultra-pure water of supernatant equivalent, ultrasonic
20～60min；
6) step 5 gained solution is repeated step 4, step 5, until remaining organic carbon content is at below 1000ppm in solution,
PH value is 6.5～7.5；
7) adding alkaline stabiliser regulation pH in step 6 gained solution is 8.5～10.5, prepares linear silicon dioxide gel.
2. wire silicon dioxide gel as claimed in claim 1, it is characterised in that the scanned Electronic Speculum of described silica colloidal particles
Observe in the most linear, a length of 100～200nm；Liquid medium is water, and pH is 8～10.
3. wire silicon dioxide gel as claimed in claim 1, it is characterised in that described sol particle is the line of length 150nm
Shape silica dioxide granule.
4. the preparation method of the wire silicon dioxide gel as described in claim 1-3 any claim, comprises the steps:
1) using tetraethyl orthosilicate (TEOS) as silicon source, it is mixed in proportion with alcohols solvent；
2) in the solution that step 1 prepares, add acid solution to mix；Acid solution pH is 4～6；
3) by step 2 gained solution under room temperature, normal pressure continuously stirred 1～3h, and ageing 24～72h is sealed；
4) dispersion of step 3 gained solution centrifugal being cleaned, centrifugal speed is 2000～10000rpm, and centrifugation time is 15～60min；
5) step 4 gained solution being skimmed supernatant, bottom turbid solution mixes with the ultra-pure water of supernatant equivalent, ultrasonic
20～60min；
6) step 5 gained solution is repeated step 4, step 5, until remaining organic carbon content is at below 1000ppm in solution,
PH value is 6.5～7.5；
7) adding alkaline stabiliser regulation pH in step 6 gained solution is 8.5～10.5, prepares linear silicon dioxide gel.
Method the most according to claim 4, it is characterised in that step 1) in, tetraethyl orthosilicate and the volume ratio of alcohols solvent
For 1:30～1:80.
Method the most according to claim 4, it is characterised in that step 2) in, acid solution is hydrochloric acid, sulphuric acid, nitric acid,
Formic acid, acetic acid, citric acid, one or both in oxalic acid.
Method the most according to claim 4, it is characterised in that step 7) in, alkaline stabiliser is inorganic base or organic base.
8. the purposes in CMP planarization field of the linear silicon dioxide gel as described in claim 1-3 any claim.
Purposes the most according to claim 8, it is characterised in that described purposes is specially described linear silicon dioxide gel in preparation
Purposes in polishing agent.
10. a polishing agent, it is characterised in that containing the line as described in claim 1-3 any claim in described polishing agent
Shape silicon dioxide gel.
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| CN106010297B (en) | 2016-06-20 | 2018-07-31 | 上海新安纳电子科技有限公司 | A kind of preparation method of alumina polishing solution |
| CN107541145B (en) * | 2017-09-20 | 2019-12-10 | 无锡市恒利弘实业有限公司 | Green environment-friendly polishing silica sol and preparation method 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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| US6062952A (en) * | 1997-06-05 | 2000-05-16 | Robinson; Karl M. | Planarization process with abrasive polishing slurry that is selective to a planarized surface |
| CN102372273A (en) * | 2011-08-23 | 2012-03-14 | 南通海迅天恒纳米科技有限公司 | Silica sol with double grain diameters and preparation method thereof |
| CN102390838A (en) * | 2011-08-22 | 2012-03-28 | 天津晶岭电子材料科技有限公司 | Preparation method of non-spherical silica sol |
| CN103484024A (en) * | 2013-09-13 | 2014-01-01 | 上海新安纳电子科技有限公司 | Chemico-mechanical polishing liquid for silicon dioxide dielectric materials and preparing method thereof |
| CN103896287A (en) * | 2012-12-28 | 2014-07-02 | 上海新安纳电子科技有限公司 | Non-spherical silicon dioxide sol and preparation method thereof |
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2014
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6062952A (en) * | 1997-06-05 | 2000-05-16 | Robinson; Karl M. | Planarization process with abrasive polishing slurry that is selective to a planarized surface |
| CN102390838A (en) * | 2011-08-22 | 2012-03-28 | 天津晶岭电子材料科技有限公司 | Preparation method of non-spherical silica sol |
| CN102372273A (en) * | 2011-08-23 | 2012-03-14 | 南通海迅天恒纳米科技有限公司 | Silica sol with double grain diameters and preparation method thereof |
| CN103896287A (en) * | 2012-12-28 | 2014-07-02 | 上海新安纳电子科技有限公司 | Non-spherical silicon dioxide sol and preparation method thereof |
| CN103484024A (en) * | 2013-09-13 | 2014-01-01 | 上海新安纳电子科技有限公司 | Chemico-mechanical polishing liquid for silicon dioxide dielectric materials and preparing method thereof |
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