CN107384220B - A kind of polishing silica solution and preparation method thereof for LED Sapphire Substrate - Google Patents
A kind of polishing silica solution and preparation method thereof for LED Sapphire Substrate Download PDFInfo
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- CN107384220B CN107384220B CN201710854292.9A CN201710854292A CN107384220B CN 107384220 B CN107384220 B CN 107384220B CN 201710854292 A CN201710854292 A CN 201710854292A CN 107384220 B CN107384220 B CN 107384220B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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Abstract
The present invention provides a kind of polishing silica solution for LED Sapphire Substrate, the silica solution includes silica source ethyl orthosilicate, surfactant polyethylene list octyl phenyl ether, cosurfactant 4- methyl -2- amylalcohol, organic solvent hexamethylene, pH adjusting agent potassium tert-butoxide, metal ion chelation agent ethylenediamine tetra-acetic acid, surplus are deionized water.The size of the silicon oxide particle wherein obtained is between 10-20nm, under room temperature, viscosity≤10mm of silica solution2/ s, pH value 10.5-12.5,1.1 ~ 1.2g/cm of specific gravity3.The silica solution service life is long, and the shelf-life is greater than 1.5 years, and polishing efficiency is high, and hydroxyl utilization rate is high.
Description
Technical field
The present invention relates to the technical field of LED Sapphire Substrate polishing, in particular to a kind of polishing silica solution and its preparation
Method.
Background technique
With the rapid development of photoelectric technology, the increasingly increase of LED photovoltaic product material demand, current there are many substrates
Material can be used for GaN wafer LED, but really can be also fewer at present for realizing commercialized substrate material, general to only have
Two kinds, i.e. sapphire and SiC, there is presently no the third substrates to be used for commercially producing for the LED of GaN.SiC be it is a kind of very
Important substrate material, compared with sapphire, SiC belongs to low-resistance material, can make electrode, the heat of lattice constant and material
The coefficient of expansion with GaN material more closely, and it is easy to dissolve, and itself has blue light emitting characteristic, but SiC material also has
Its disadvantage, mainly its thermal expansion coefficient differ larger with GaN, are easy to cause the crackle of epitaxial gan layers, are not suitable for largely making
With price is relatively expensive.Sapphire Substrate is that current use is desirably also a kind of substrate material the most universal.
Sapphire crystal (α-A12O3) it is a kind of high temperature resistant, wear-resistant, anticorrosive and wide transmission region high-quality smooth function
Material, it has hexagonal closs packing type identical with III group-III nitride, is by physics, mechanically and chemically characteristic three unique combination
Excellent material.In optical communication field, sapphire crystal is not only used as short wavelength's active device, also serves as the passive device of polarised light
Part is in microelectronic field, and sapphire can be used as the substrate of new generation of semiconductor substrate S OI (on insulating layer), since sapphire is excellent
Good barrier effect can reduce the capacity effect of transistor, and arithmetic speed can become faster, and power consumption becomes lower.In light
Electronic field, sapphire crystal are the preferred substrate materials for manufacturing GaN light emitting diode (LED).It grows on a sapphire substrate
Before film, scuffing, pit, the stressed zone etc. generated when removal slice is first had to, surface roughness is then reduced.Surface
Roughness is bigger, and the dangling bonds on surface are more, easier absorption other impurities, and has poor lattice with film above
Match.Traditional purely mechanic polishing is that the surface for being polished material is constantly ground with polishing powder, is easy to produce deeper scuffing.And
CMP(chemically mechanical polishing) it is that chemical reactant is got rid of by mechanism, improves material in the environment of chemical action
The removal rate of material, while also obtaining good configuration of surface.
Currently used CMP is silicon oxide silicon colloidal sol, it is a kind of hard and crisp ceramic material, and chemical mobility of the surface is very
It is low.SiO2The hydrosol is electric double layer structure, and outer-shell electron shows negative electrical charge, the colloid SiO prepared by coacervation2Particle surface is rich
Containing silicone hydroxyl, research, which also found, has been also enriched in silicone hydroxyl inside the silica solution using coacervation preparation, exactly this feature, so that
The SiO of coacervation preparation2Colloid viscosity is small, and hardness is moderate, and no corner angle will not generate scuffing in CMP.
However, the silica sol of country's patent report but has the following problems at present: (1) particle size is excessive, such as
CN106966399A by using the big partial size silica solution of silica that the crystal seed of the silica of 10nm prepares 105nm-120nm, though
The concentration of silica is higher on right ordinary meaning, and size is bigger, is more conducive to the raising of polishing speed, but undeniably,
In the identical situation of silicone content, the hydroxy number of large-sized silica solution silicon face is far below the hydroxyl on the silica solution surface of small particle
Radix, and hydroxy number is most important in silica solution polishing process, secondly the preparation method of the invention is the oxygen of simple growth
SiClx, since the growth course of silica is complicated, and mechanism is still not clear, and in actual production, is difficult to prepare size uniformity
Silica solution, the polishing stable being unfavorable for during CMP.
A kind of sapphire polishing composition disclosed in CN106700942A and preparation method thereof, this method passes through in silica solution
The glucide of middle addition 0.1~5%, which can effectively inhibit the generation of etch pit, and be able to maintain that polishing
Rate is constant, but the polishing silica solution ignores a particularly important factor, the i.e. stability of silica solution and shelf-life, leads to
The shelf-life of normal commercially available silica solution is half a year or more, when glucide is added in silica solution, it is easy to breed bacterium and true
Bacterium, the final pH value for reducing silica solution, seriously affects the polishing efficiency of silica solution or directly results in scrap of the product.In addition, other
Patent report in silica solution add grease there is also the above problems with the silica solution that improves its polishing effect.
CN106978088A discloses a kind of preparation method of silica solution polishing fluid, includes in the silica solution of this method preparation
The silica solution and partial size that partial size is 100-120nm, solid content is 43%-45% are 20-30nm, solid content is 43%-45%'s
Silica solution, and applicant claims that the silica solution polishing rate of double sizes is higher, but it is actually really not so, this is because throwing
In photoreduction process, big silica dioxide granule and the touch opportunity on sapphire substrate surface are more, and reaction possibility is bigger, because
And it is increasing, until reaching the two solid-solid reaction equilibrium state, and small particle is reacted with increasing for number is polished
A possibility that it is smaller and smaller, thus partial size is basically unchanged, i.e., big particle is increasing, and more and more irregular, small particle
It is unable to fully always utilize, is finally unfavorable for the raising of polishing efficiency.
Summary of the invention
For above-mentioned one or more problems existing in the prior art, the present invention provides a kind of for LED sapphire lining
The polishing silica solution at bottom, the silica sol particle size in the polishing silica solution is uniform, and polishing effect is stablized, after polishing
Particle size is without deformation, and silicon oxide particle hardness is moderate, and without being crushed in polishing process, no scuffing, so that treated, indigo plant is precious
Stone surface is smooth, and roughness is low；Service life is long, and the shelf-life is greater than 1.5 years；Polishing efficiency is high, and hydroxyl utilization rate is high.
The present invention provides a kind of polishing silica solution for LED Sapphire Substrate, and the silica solution includes:
Silica source: ethyl orthosilicate, 5 ~ 40wt.%；
Surfactant: Value 3608,1 ~ 15wt.%；
Cosurfactant: 4- methyl -2- amylalcohol, 1 ~ 1.5wt.%；
Organic solvent: hexamethylene, 5 ~ 7wt.%；
PH adjusting agent: potassium tert-butoxide；
Metal ion chelation agent: ethylenediamine tetra-acetic acid, 3 ~ 5wt.%,
Surplus is deionized water, wherein the size of the silicon oxide particle obtained is between 10-20nm, under room temperature, silica solution
Viscosity≤10mm2/ s, pH value 10.5-12.5,1.1 ~ 1.2g/cm of specific gravity3。
The group of the silica solution, which is grouped as, may also comprise:
Silica source: ethyl orthosilicate, 20wt.%；
Surfactant: Value 3608；
Cosurfactant: 4- methyl -2- amylalcohol, 1.25wt.%；
Organic solvent: hexamethylene, 5wt.%；
PH adjusting agent: potassium tert-butoxide；
Metal ion chelation agent: ethylenediamine tetra-acetic acid, 4wt.%,
Surplus is deionized water, and wherein deionized water/Value 3608 molar ratio is 23, the oxygen of acquisition
The size of silicon carbide particle is about 17nm, pH value 12.0,1.17 ~ 1.19g/cm of specific gravity2, viscosity 7.8mm2/s。
The present invention also provides a kind of preparation methods of polishing silica solution for LED Sapphire Substrate, and steps are as follows: first
Successively into reaction kettle be added Value 3608 surfactant, 4- methyl -2- amylalcohol cosurfactant and
The mixing of hexamethylene organic solvent, room temperature, 10 ~ 20min of magnetic agitation are added a certain amount of deionized water, continue magnetic agitation 30 ~
40min obtains uniform and stable W/O emulsion, ethylenediamine tetra-acetic acid metal ion-chelant is then sequentially added into emulsion
Agent, ethyl orthosilicate silica source and deionized water, stirring are slowly added to appropriate potassium tert-butoxide and adjust pH value be 10.5-12.5,
It continuously stirs 4 ~ 5 hours, obtains uniform and stable, viscosity≤10mm2/ s, silica solution of the silica size in 10-20nm, appearance
It is creamy white.
The reaction kettle of the silica solution is vinyon bucket, which can be used directly, or use deionized water
It is used after 1-2 times of dilution.
Beneficial effect
Polishing silica solution of the present invention for LED Sapphire Substrate has following beneficial technical effect:
(1) silica sol particle size is uniform, and polishing effect is stablized, and particle size is without deformation after polishing；
(2) silicon oxide particle hardness is moderate, without broken, no scuffing in polishing process, so that treated sapphire surface
Smooth, roughness is low；
(3) service life is long, and the shelf-life is greater than 1.5 years；
(4) polishing efficiency is high, and hydroxyl utilization rate is high.
Detailed description of the invention
Attached drawing 1 is the TEM figure of not used silica sol granule prepared by the present invention.
Attached drawing 2 is the TEM figure to the silica sol granule after sapphire polishing.
Specific embodiment
The present invention is described in more detail below by embodiment.
Embodiment 1
A kind of polishing silica solution for LED Sapphire Substrate, the silica solution include:
Silica source: ethyl orthosilicate, 5wt.%；
Surfactant: Value 3608,1wt.%；
Cosurfactant: 4- methyl -2- amylalcohol, 1wt.%；
Organic solvent: hexamethylene, 5wt.%；
PH adjusting agent: potassium tert-butoxide；
Metal ion chelation agent: ethylenediamine tetra-acetic acid, 3wt.%；
Surplus is deionized water.
A kind of preparation method of the polishing silica solution for LED Sapphire Substrate, steps are as follows: first successively to reaction kettle
Middle addition Value 3608 surfactant, 4- methyl -2- amylalcohol cosurfactant and hexamethylene are organic molten
A certain amount of deionized water is added in agent mixing, room temperature, 10 ~ 20min of magnetic agitation, continues 30 ~ 40min of magnetic agitation, obtains equal
Even stable W/O emulsion, then sequentially adds ethylenediamine tetra-acetic acid metal ion chelation agent, ethyl orthosilicate into emulsion
Silica source and deionized water, stirring are slowly added to appropriate potassium tert-butoxide and adjust pH value be 10.5-12.5, it is small to continuously stir 4 ~ 5
When, uniform and stable silica solution is obtained, appearance is creamy white.
The reaction kettle of the silica solution is vinyon bucket, and the polishing silica solution can be used directly, or use deionization
Water uses after diluting 1-2 times.
Embodiment 2
A kind of polishing silica solution for LED Sapphire Substrate, the silica solution include:
Silica source: ethyl orthosilicate, 20wt.%；
Surfactant: Value 3608；
Cosurfactant: 4- methyl -2- amylalcohol, 1.25wt.%；
Organic solvent: hexamethylene, 5wt.%；
PH regulator: potassium tert-butoxide；
Metal ion chelation agent: ethylenediamine tetra-acetic acid, 4wt.%；
Surplus is deionized water, and wherein deionized water/Value 3608 molar ratio is 23, the oxygen of acquisition
The size of silicon carbide particle is between 10-20nm, pH value 12.0, polishing speed 306nm/min, and stability is greater than 1.5 years, milky white
Color, roughness 0.7nm, 1.17 ~ 1.19g/cm of specific gravity2, viscosity 7.8mm2/s。
Embodiment 3
A kind of polishing silica solution for LED Sapphire Substrate, the silica solution include:
Silica source: ethyl orthosilicate, 40wt.%；
Surfactant: Value 3608,15wt.%；
Cosurfactant: 4- methyl -2- amylalcohol, 1.5wt.%；
Organic solvent: hexamethylene, 7wt.%；
PH adjusting agent: potassium tert-butoxide；
Metal ion chelation agent: ethylenediamine tetra-acetic acid, 5wt.%；
Surplus is deionized water.
Particle size test:
Value 3608 surfactant, 4- methyl -2- amylalcohol is kept to help surface-active in preparation process
Agent, hexamethylene organic solvent, ethylenediamine tetra-acetic acid metal ion chelation agent, ethyl orthosilicate silica source, potassium tert-butoxide are always
Measure, different amounts of deionized water is added thereto, continuously stirs 4 ~ 5 hours, stand 48 hours, obtain different sizes, uniformly
Stable silicon oxide particle colloidal sol lotion.
Table 1
| Deionized water/Value 3608 (molar ratio) | It is tested using TEM, counts 100 particle mean sizes |
| 5 | 103nm |
| 10 | 72nm |
| 15 | 34nm |
| 23 | 17nm |
Show that silica solution is 10-20nm in the TEM figure of the not used silica sol granule of attached drawing 1, it is molten using silicon of the invention
After glue polishes sapphire, silica sol granule is grown up to 40-50nm, the particle after polishing can be intuitive to see very much in attached drawing 2
For partial size than significantly increasing before polishing, the silica dioxide granule before polishing is spherical in shape, and the granular size after polishing is uniform, does not occur
Change in shape does not see clast substantially without elliposoidal, can determine whether that silicon oxide particle is not affected by abrasion and is crushed accordingly, therefore particle
The increased part of partial size stems purely from Al2O3The solid-phase compound of generation.
The polishing speed and stability test of silica solution in embodiment 2
By upper table it can be concluded that, the polishing silica solution using silica sol granule having a size of 10-20nm, although polishing speed
Not as good as large-sized silica solution, but its sapphire roughness of polishing obtained is best, and under same concentrations, short grained
The hydroxyl on its surface of silica solution is richer, is more advantageous to the usage amount for reducing silica solution, and the polishing effect of little particle silica solution
Stablize, particle size is without deformation after polishing, and silicon oxide particle hardness is moderate, without broken, no scuffing, polishing silicon in polishing process
The service life of sol solutions is long, and the shelf-life is greater than 1.5 years.
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and
Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and
Modification, all should be contained within the scope of the invention.
Claims (4)
1. a kind of preparation method of LED Sapphire Substrate polishing silica solution, which is characterized in that be successively added first into reaction kettle
Value 3608 surfactant, 4- methyl -2- amylalcohol cosurfactant and the mixing of hexamethylene organic solvent,
A certain amount of deionized water is added in room temperature, 10 ~ 20min of magnetic agitation, continues 30 ~ 40min of magnetic agitation, obtains uniform and stable
W/O emulsion, ethylenediamine tetra-acetic acid metal ion chelation agent, ethyl orthosilicate silica are then sequentially added into emulsion
Source and deionized water, stirring are slowly added to appropriate potassium tert-butoxide and adjust pH value be 10.5-12.5, continuously stir 4 ~ 5 hours, obtain
The silica solution obtained, appearance are creamy white, and ingredient includes:
Silica source: ethyl orthosilicate, 5 ~ 40wt.%；
Surfactant: Value 3608；
Cosurfactant: 4- methyl -2- amylalcohol, 1 ~ 1.5wt.%；
Organic solvent: hexamethylene, 5 ~ 7wt.%；
PH adjusting agent: potassium tert-butoxide；
Metal ion chelation agent: ethylenediamine tetra-acetic acid, 3 ~ 5wt.%；
Surplus is deionized water, and the molar ratio of the deionized water and Value 3608 is 23, wherein obtain
The size of silicon oxide particle is between 10-20nm, under room temperature, viscosity≤10mm of silica solution2/ s, pH value 10.5-12.5, than
Weigh 1.1 ~ 1.2g/cm3。
2. a kind of preparation method of LED Sapphire Substrate polishing silica solution as described in claim 1, it is characterised in that the silicon
Colloidal sol includes:
Silica source: ethyl orthosilicate, 20wt.%；
Surfactant: Value 3608；
Cosurfactant: 4- methyl -2- amylalcohol, 1.25wt.%；
Organic solvent: hexamethylene, 5wt.%；
PH adjusting agent: potassium tert-butoxide；
Metal ion chelation agent: ethylenediamine tetra-acetic acid, 4wt.%,
Surplus is that the molar ratio of deionized water, wherein deionized water and Value 3608 is 23, the oxidation of acquisition
The size of silicon particle is 17nm, pH value 12.0,1.17 ~ 1.19g/cm of specific gravity2, viscosity 7.8mm2/s。
3. a kind of preparation method of LED Sapphire Substrate polishing silica solution as described in claim 1-2 any one, feature
The reaction kettle for being the silica solution is vinyon bucket.
4. a kind of silicon that the polishing silica solution preparation method of the LED Sapphire Substrate as described in claim 1-2 any one obtains
The application of colloidal sol, which is characterized in that the polishing silica solution can be used directly, or use after diluting 1-2 times with deionized water.
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| CN112680113A (en) * | 2020-12-29 | 2021-04-20 | 北京航天赛德科技发展有限公司 | Composition for sapphire double-sided polishing and preparation method and application thereof |
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| JP2005048125A (en) * | 2003-07-31 | 2005-02-24 | Hitachi Chem Co Ltd | Cmp abrasive, polishing method, and production method for semiconductor device |
| US7037175B1 (en) * | 2004-10-19 | 2006-05-02 | Cabot Microelectronics Corporation | Method of sharpening cutting edges |
| CN101225281B (en) * | 2007-12-17 | 2012-02-22 | 河南省联合磨料磨具有限公司 | Polishing film and method for making same |
| CN102585705B (en) * | 2011-12-21 | 2014-02-05 | 上海新安纳电子科技有限公司 | CMP (chemical mechanical polishing) liquid with high polishing rate for sapphire supporting base and application thereof |
| TWI535835B (en) * | 2015-02-05 | 2016-06-01 | 盟智科技股份有限公司 | Chemical mechanical polishing slurry |
| CN107011804A (en) * | 2016-01-28 | 2017-08-04 | 浙江晶圣美纳米科技有限公司 | A kind of sapphire chemical mechanical polishing liquid |
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