CN104263249B - A kind of processing method of Ludox - Google Patents
A kind of processing method of Ludox Download PDFInfo
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- CN104263249B CN104263249B CN201410505730.7A CN201410505730A CN104263249B CN 104263249 B CN104263249 B CN 104263249B CN 201410505730 A CN201410505730 A CN 201410505730A CN 104263249 B CN104263249 B CN 104263249B
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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 relates to the processing method of a kind of Ludox, belong to microelectronics auxiliary material and Ultra-precision Turning Technology field.The method comprises the following steps: be mixed to get strong acid and strong base hybrid resin after strongly acidic cation-exchange and strong basic type anion-exchange resin are respectively regenerated process；Ordinary silicon colloidal sol and strong acid and strong base hybrid resin are put together, and controls temperature and be stirred to mix homogeneously；Above-mentioned whipping process adds azole compounds and Organic Acid and Base.The present invention overcomes ordinary silicon colloidal sol shortcoming in CMP planarization uses in prior art, promote its operation strategies in CMP planarization, make conventional Ludox all stable existence within the scope of pH 1-12 after treatment, and can keep particle stabilized in CMP planarization process, keep the stability of temperature in polishing process, it is thus achieved that uniform outer surface.
Description
Technical field
The invention belongs to microelectronics auxiliary material and Ultra-precision Turning Technology field, particularly to a kind of processing method to ordinary silicon colloidal sol.
Background technology
Chemically mechanical polishing (Chemicalmechanicalplanarization, CMP) technology in the nineties early stage be directed initially into semiconductor wafers operation, from the interlayer dielectrics such as oxide-film, it is generalized to polymerization silicon electrode, the tungsten plug (W-Plug) of conducting, STI (element separation), and in the high-performance with device draws the thin copper film Technology simultaneously introduced, have become as now one of key technology.It is also the technology being uniquely capable of global planarizartion that chemically mechanical polishing has proven to the best at present.Chemically mechanical polishing is the process of chemical reaction, mechanical friction, hydrodynamic comprehensive function, combination by the abrasive action of nanometer particle Yu the chemical attack effect of polishing fluid, make polished surface of the work smooth, thus obtaining the smooth planar surface that other plane machining means are extremely difficult to.
In CMP process, polishing fluid is the key factor affecting global planarization.Abrasive used by CMP, mainly has three kinds, respectively silicon dioxide, ceria and aluminium oxide.Alumina particle is relatively big, and Mohs' hardness is high, often scratches processed device surface, and is difficult to clean after polishing.Ceria hardness is moderate, but its resource-constrained, it is difficult to realize industrialization polishing.Silicon dioxide gel is silica dioxide granule suspension dispersion liquid in water, abrasive silica hardness is moderate, viscosity is little, be readily cleaned, environmentally safe, and silicon dioxide gel has heat-resisting, wear-resisting, chemically stable and high adsorption, it is considered as be main component in polished semiconductor liquid, is consumptive material indispensable in microelectronics industry.The factors such as its silicon dioxide size, consistency, dispersion directly affect speed and the quality of finish of chemically mechanical polishing, patent about its preparation and application aspect is more, such as CN1155514A, CN101121520B, CN101495409B, CN101177273A, CN101240068A, CN101475180A etc..
Find out from ordinary silicon colloidal sol in the experimental result (such as Fig. 1) of different pH value range internal stabilities, it it is metastable region when pH is 0～4, ordinary silicon colloidal sol can preserve a period of time under this state, it it is gelation district when pH is 4～7, ordinary silicon colloidal sol in this case can gel, can not stably depositing, when pH is 7～10.5, ordinary silicon colloidal sol still keeps micelle shape, can stably deposit.When particularly pH value is 2 or about 9, gelation time is the longest, namely ordinary silicon colloidal sol is respectively arranged with a stable region in acid and basic region, can stably deposit in this two region.
The pH value of polishing fluid determines the environment of polishing, drastically influence the formation of workpiece to be machined surface film, reduction and the decomposition that surface is produced is thrown in notable impact by hydration, and in polishing fluid, the suspension degree of abrasive material is also affected by the impact of pH value simultaneously.It is because neutral pH value causes that the suspension of abrasive material declines that such as SiOC, Cu and other metal materials are difficult to reach the excellent surface state of high damage smooth, low under the effect of pH neutral polishing fluid, adds the roughness on surface." Ludox pH value in this and polishing fluid has close relationship, improve Ludox and just naturally improve the pH value of polishing fluid, improve the Optimality of polishing fluid "
Polymerization is a maximum shortcoming of Ludox abrasive material, it is easy to form gel in polishing fluid, and therefore in the process of configuration polishing fluid, the control of solution ph is very strict, because the pH value of polishing fluid is to affect the most important reason of silicic acid polymerization.If SiO2 abrasive material condenses in polishing fluid, the repeatability of polishing velocity can there be is harmful effect, metal surface can be made simultaneously to produce scratch.
Frictional heat between abrasive material and wafer in CMP process, even if having water to exist, chip local also can become big and local heating because the friction of abrasive material gel.Experiments show that local temperature raises and cause that elastic deformation increases, thus polishing speed increases.At the temperature that local is too high, chemical reaction rate is high, and chemical attack is serious, causes that surface uniformity is poor.Additionally, due to the local temperature chemical reaction velocity caused out of control increases, make mechanism and chemical action can not reach rational equilibrium point, cause uneven polishing clearance.If chemical reaction velocity removes speed more than machinery, can cause the circuit on wafer of removing not exclusively or cause to wafer that the situation of depression occurs；Whereas if the speed that the speed of chemical reaction is removed lower than machinery, under the effect of abrasive particle, can cause and produce to scratch to the circuit on wafer.
Summary of the invention
The present invention is directed to the defect that prior art exists, it is proposed to a kind of processing method to Ludox.The present invention overcomes ordinary silicon colloidal sol shortcoming in CMP planarization uses in prior art, promote its operation strategies in CMP planarization, make conventional Ludox all stable existence within the scope of pH1-12 after treatment, and can keep particle stabilized in CMP planarization process, keep the stability of temperature in polishing process, it is thus achieved that uniform outer surface.
The processing method of a kind of Ludox of the present invention, it is characterised in that comprise the following steps:
(1) strong acid and strong base hybrid resin it is mixed to get after strongly acidic cation-exchange and strong basic type anion-exchange resin being respectively regenerated process；
(2) ordinary silicon colloidal sol and strong acid and strong base hybrid resin are put together, be stirred to mix homogeneously；
(3) in above-mentioned whipping process, azole compounds and Organic Acid and Base are added.
Whipping process temperature controllable in above-mentioned steps of the present invention (2) is 0～60 DEG C of better effects if；In described strong acid and strong base hybrid resin, strongly acidic cation-exchange and strong basic type anion-exchange resin volume ratio are (0.1～10): 1；The mass ratio of strong acid and strong base hybrid resin and ordinary silicon colloidal sol is 1:(1～100).
The silicon dioxide of described ordinary silicon colloidal sol is 1～40wt%, and silicon dioxide particle diameter is 1～300nm.
Described processing procedure can carry out in the container with cooling, heating and stirring.
Described azole compounds is nitrogenous azole compounds, there are a nitrogen azoles, ribavirin or triazole, one nitrogen azoles, 1,3-ribavirin, 1,2-ribavirin, imidazoles, 1,2,4-triazole, 3-amino triazole-5-carboxylic acid, 3-amino-1, one or more in 2,4-triazoles, 5-methyl tetrazole, 5-phenyl tetrazole, 5-aminotetrazole, described azole compounds addition is in Ludox the 0.05%～10% of silicon dioxide quality.
Described organic acid is one or more in glycine, Soviet Union amino acid, silk amino acid, proline, alanine, acetic acid, malonic acid, succinic acid, tartaric acid, oxalic acid, lactic acid, malic acid, hydroxyacetic acid, citric acid, benzoic acid, salicylic acid, aspartic acid, acrylic acid, poly, poly-aspartate, polyacrylic acid, polymethylacrylic acid, and described organic acid addition is in Ludox the 0.5～25% of silicon dioxide quality.
Described alkali is one or more in Tetramethylammonium hydroxide, ammonia, methyl amine, dimethyl amine, Trimethylamine, ethylamine, diethylamide, triethylamine, isopropanolamine, aminopropanol, tetraethyl amine, ethanolamine, trientine, hydroxyethylethylene diamine, hexamethylene diamine, diethylenetriamines, trien, Piperazine anhydrous, anthalazine, and described alkali addition is in Ludox the 0.5～20% of silicon dioxide quality.
The pH of described polishing fluid is 1-12.
The solution that the processing method of a kind of Ludox of the present invention obtains, it is possible to for the chemically mechanical polishing of electron trade, quasiconductor, hard disk, compound crystal or precision optics.
According to the required final pH reached, the Organic Acid and Base amount added can being adjusted, the Ludox after adjustment can remain stable for, and stable phase is more than 1 year.
Advantages of the present invention is mainly reflected in:
Ordinary silicon colloidal sol after the inventive method processes can realize pH stablizing within the scope of 1-12, and namely the silica dioxide granule in Ludox can keep suspension stability, reduces polymerization and condense phenomenon in polishing process.And can need pH is adjusted according to utilization, improve Ludox in the CMP industry scope of application；
In the inventive method processing procedure, azole compounds can act on Ludox surface, forms adsorption layer, the local temperature caused due to Ludox reunion can be prevented further too high, improve polishing material uniformity.
Step of the present invention is simple, and the time is short, and efficiency is high, can be used for industrialization and produces continuously.
Accompanying drawing explanation
Fig. 1 is the graph of a relation of ordinary silicon collosol stability and pH value.
Detailed description of the invention
The following examples can make those skilled in the art be more completely understood by the present invention, but does not limit the present invention in any way.
In embodiment, the Regeneration Treatment of strongly acidic cation-exchange and strong basic type anion-exchange resin is respectively adopted following methods:
(1) Regeneration Treatment of strongly acidic cation-exchange: the H2SO4 or the concentration that adopt concentration to be 1～8wt% are the HCl of 4～8wt%, strongly acidic cation-exchange is carried out Regeneration Treatment, regenerated liquid volume is 2～5 times of strong acid type cationic resin volume, regenerated liquid flow rate is 1～10m/h, uses water forward drip washing after entering acid, and being washed to resin pH is 3～7, after drip washing, inflation makes resin mix, and air pressure is 3～5kg/cm2, and the time is 10～30min；
(2) Regeneration Treatment of strong basic type anion-exchange resin: strong basic type anion-exchange resin is carried out Regeneration Treatment by the NaOH adopting concentration to be 2～5wt%, regenerated liquid volume is 2～6 times of strong base anion resin volume, regenerated liquid flow rate is 1～10m/h, enter after alkali with the reverse drip washing of water, washing with water to resin pH is 7～9, and after drip washing, inflation makes resin mix, air pressure is 3～5kg/cm2, and the time is 10～30min；
The regeneration treating method of above cation and anion exchange resin is a kind of general method, under the premise without departing from the technology of the present invention principle, it is also possible to make corresponding adjustment and improvement, and these adjust and improve and also should be regarded as protection scope of the present invention.
Embodiment 1
In ordinary silicon colloidal sol, dioxide-containing silica is 20%, and particle diameter is 20nm.Process step is as follows:
(1) strongly acidic cation-exchange and strong basic type anion-exchange resin are respectively regenerated process；
(2) strongly acidic cation-exchange regenerated and strong basic type anion-exchange resin 10:1 by volume are mixed to get strong acid and strong base hybrid resin, and load in the container with cooling, heating and stirring；
(3) being joined by ordinary silicon colloidal sol in the container equipped with strong acid and strong base hybrid resin, controlling Ludox temperature is 30 DEG C, and the weight ratio of strong acid and strong base hybrid resin and Ludox is 1:30；
(4) agitating device in container is opened, stirring, make ordinary silicon colloidal sol mix homogeneously with strong acid and strong base hybrid resin；
(5) carrying out adding a nitrogen azoles in process in step (4), addition is in Ludox the 5% of silicon dioxide quality；Adding hydroxyacetic acid after stirring 15min, addition is in Ludox the 1% of silicon dioxide quality；Being stirred for after 15min and add hydroxyethylethylene diamine, addition is in Ludox the 2% of silicon dioxide quality.
After process, the pH of Ludox is 7.5.
Embodiment 2-7 and comparative example 1-2
Embodiment 2-7 and comparative example 1-2 carries out with reference to the step of embodiment 1, changes corresponding treatment conditions, listed by table specific as follows.
In the present invention, the ordinary silicon colloidal sol of definition refers to, has the following Ludox in different pH value range internal stability situations.Being metastable region when pH is 0～4, Ludox can preserve a period of time under this state, is gelation district when pH is 4～7, and Ludox in this case can gel, it is impossible to stably depositing, when pH is 7～10.5, Ludox still keeps micelle shape, can stably deposit.When particularly pH value is 2 or about 9, gelation time is the longest, namely Ludox is respectively arranged with a stable region in acid and basic region, can stably deposit in this two region.It is above public definition method as well known to those skilled in the art.
Ludox is applicable to the performance verification of chemically mechanical polishing:
With the IC1000-XY/SUBAIV20 type composite polishing pad of Rodel company, polish testing machine by CETRCP4, at polish pressure 1.5psi, polishing speed of related movement 1m/s, Ludox flow 70mL/min, be polished test, polishing time 20 minutes.By measuring the change of temperature before and after 2 inches of copper facing wafer polishings and combining the change of Ludox mean diameter before and after polishing and evaluate the suitability in chemically mechanical polishing of the Ludox after process.The temperature change value in the system for detecting temperature record polishing process that testing machine carries is polished with CETRCP4, by Ludox mean diameter before and after the detection polishing of Malvern NANOS laser particle analyzer, and calculate after polishing the ratio of Ludox mean diameter before Ludox mean diameter and polishing, in the more big explanation polishing process of ratio, silica dioxide granule is reunited more serious, and Ludox polishing stable is also more poor.
Claims (1)
1. the processing method of a Ludox, it is characterised in that comprise the following steps:
(1) strongly acidic cation-exchange and strong basic type anion-exchange resin are respectively regenerated process；
(2) strongly acidic cation-exchange regenerated and strong basic type anion-exchange resin are mixed to get strong acid and strong base hybrid resin by volume at 10: 1, and load in the container with cooling, heating and stirring；
(3) being joined by ordinary silicon colloidal sol in the container equipped with strong acid and strong base hybrid resin, controlling Ludox temperature is 30 DEG C, and the weight ratio of strong acid and strong base hybrid resin and Ludox is 1: 30；
(4) agitating device in container is opened, stirring, make ordinary silicon colloidal sol mix homogeneously with strong acid and strong base hybrid resin；
(5) carrying out adding a nitrogen azoles in process in step (4), addition is in Ludox the 5% of silicon dioxide quality；Adding hydroxyacetic acid after stirring 15min, addition is in Ludox the 1% of silicon dioxide quality；Being stirred for after 15min and add hydroxyethylethylene diamine, addition is in Ludox the 2% of silicon dioxide quality；
In ordinary silicon colloidal sol, dioxide-containing silica is 20%, and particle diameter is 20nm；
After process, the pH of Ludox is 7.5.
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| CN106883769A (en) * | 2017-04-17 | 2017-06-23 | 黄美香 | A kind of Ludox polishing fluid |
| CN111186840B (en) * | 2020-01-17 | 2022-09-23 | 山东百特新材料有限公司 | Method for improving sphericity of silica sol particles |
| CN113004804B (en) * | 2021-03-01 | 2022-04-19 | 深圳清华大学研究院 | Polishing solution for edge of large-size silicon wafer, preparation method of polishing solution and polishing method |
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| WO2001013417A1 (en) * | 1999-08-17 | 2001-02-22 | Hitachi Chemical Company, Ltd. | Polishing compound for chemimechanical polishing and method for polishing substrate |
| CN1572017A (en) * | 2001-10-26 | 2005-01-26 | 旭硝子株式会社 | Polishing compound, method for production thereof, and polishing method |
| CN101475180A (en) * | 2009-01-16 | 2009-07-08 | 清华大学 | Purification method of ultra-pure silicon dioxide sol |
| CN102037094A (en) * | 2008-05-23 | 2011-04-27 | 卡伯特微电子公司 | Stable, high rate silicon slurry |
| CN102390837A (en) * | 2011-08-03 | 2012-03-28 | 南通海迅天恒纳米科技有限公司 | Preparation method of nonspherical nanometer-scale silica sol |
| CN102583406A (en) * | 2012-01-19 | 2012-07-18 | 深圳市力合材料有限公司 | Purifying method for high-purity silica sol |
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- 2014-09-26 CN CN201410505730.7A patent/CN104263249B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001013417A1 (en) * | 1999-08-17 | 2001-02-22 | Hitachi Chemical Company, Ltd. | Polishing compound for chemimechanical polishing and method for polishing substrate |
| CN1572017A (en) * | 2001-10-26 | 2005-01-26 | 旭硝子株式会社 | Polishing compound, method for production thereof, and polishing method |
| CN102037094A (en) * | 2008-05-23 | 2011-04-27 | 卡伯特微电子公司 | Stable, high rate silicon slurry |
| CN101475180A (en) * | 2009-01-16 | 2009-07-08 | 清华大学 | Purification method of ultra-pure silicon dioxide sol |
| CN102390837A (en) * | 2011-08-03 | 2012-03-28 | 南通海迅天恒纳米科技有限公司 | Preparation method of nonspherical nanometer-scale silica sol |
| CN102583406A (en) * | 2012-01-19 | 2012-07-18 | 深圳市力合材料有限公司 | Purifying method for high-purity silica sol |
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