CN108250976A - A kind of chemical mechanical polishing liquid - Google Patents
A kind of chemical mechanical polishing liquid Download PDFInfo
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- CN108250976A CN108250976A CN201611231361.2A CN201611231361A CN108250976A CN 108250976 A CN108250976 A CN 108250976A CN 201611231361 A CN201611231361 A CN 201611231361A CN 108250976 A CN108250976 A CN 108250976A
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- China
- Prior art keywords
- mechanical polishing
- chemical mechanical
- polishing liquid
- polishing
- sulfate
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- C—CHEMISTRY; METALLURGY
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
One aspect of the present invention provides a kind of chemical mechanical polishing liquid, and it includes water, the negatively charged abrasive grains in surface can generate the compound of silver ion, can generate the compound of sulfate ion, peroxide.The present invention significantly improves the stability of polishing fluid, further improves polishing stable degree, improves polishing efficiency, reduce polishing cost by changing the charge of abrasive grains silica surface.
Description
Technical field
The present invention relates to chemical mechanical polishing liquid field more particularly to a kind of chemically mechanical polishings for polishing metal tungsten
Liquid.
Background technology
With the continuous development of semiconductor technology and being continuously increased for large scale integrated circuit interconnection layer, conductive layer and
The planarization of insulating medium layer becomes particularly critical, wherein, the chemical machine initiated the eighties in twentieth century by IBM Corporation
Tool polishing (CMP) technology is considered as the most efficient method of current global planarizartion.Chemically mechanical polishing (CMP) be it is a kind of by
Chemical action, mechanism and both effects are combined and realize the technology of planarization；It is usually by one with polishing
The grinding table of pad and a grinding head composition for being used to carry chip.Wherein grinding head fixes chip, then by chip just
Face pressure is on polishing pad, when being chemically-mechanicapolish polished, grinding head on polishing pad linear movement or along with grinding table
The same direction of motion rotation；At the same time, the slurries containing grinding agent are dripped on polishing pad, and because centrifugal action is laid in
On polishing pad.Chip surface realizes global planarizartion under double action mechanically and chemically.
To chemical metal layer mechanical polishing (CMP) main mechanism be considered as：Oxidant first by oxidation on metal surface into
Film is the grinding agent of representative by this layer of oxidation film mechanical removal using silica and aluminium oxide, generates new metal surface；It generates
New metal surface continue to be aoxidized, both effect collaborations carry out.
As the tungsten of one of chemically mechanical polishing (CMP) object, at higher current densities, anti-electron transfer capabilities
By force, and good Ohmic contact can be formed with silicon, so can be as contact hole and the filling metal of interlayer hole and diffusion resistance
Barrier.
The chemically mechanical polishing (CMP) of tungsten at present, there are many method, such as：The potassium ferricyanide of the reports such as F.B.Kaufman is used
In method (" Chemical Mechanical Polishing for Fabricating of tungsten CMP
Patterned W Metal Features as Chip Interconnects ", Journal of the Electro
Society, Vol.138, No.11,1991 years November of chemical), a kind of disclosed in United States Patent (USP) US5340370 be used for tungsten
The formula of size of (CMP) is chemically-mechanicapolish polished, wherein containing the potassium ferricyanide and silica abrasive, is contained simultaneously as pH buffer
Acetate.Since the potassium ferricyanide is under ultraviolet light or solar radiation and in acid medium, the hydrogen cyanogen of severe toxicity can be decomposited
Acid, thus limit it and be widely used.
Chemical metal layer machine polishing liquor, United States Patent (USP) US006008119A are disclosed disclosed in United States Patent (USP) US5527423
Method of polishing semiconductor wafer and United States Patent (USP) US6284151 disclosed in tungsten CMP slurry etc. use Fe
(NO3)3/ alumina system mechanically polishes (CMP) for tungsten.The polishing body ties up to static etch rate (static etch
Rate) aspect has advantage, but since using aluminium oxide, as grinding agent, product defects (defect) aspect exists significantly not
Foot.The ferric nitrate of high concentration causes the pH value of polishing fluid in highly acid simultaneously, severe corrosion equipment, meanwhile, generate iron rust, pollution
Polishing pad.In addition to this, the iron ion of high concentration is as moveable metal ion, and seriously reduce semiconductor components and devices can
By property.
Metal CMP polishing composition is used as catalyst, hydrogen peroxide using ferric nitrate disclosed in United States Patent (USP) US5958288
It is used as oxidant, carries out tungsten CMP, it should be noted that in that patent, it is noted that a variety of transition metal elements,
It is confirmed in experiment and significantly effectively there was only ferro element, therefore the actual implementation effect and range of the invention are very limited.Though this method
The dosage of ferric nitrate is so considerably reduced, but Fenton reactions occur between hydrogen peroxide since iron ion still has,
Hydrogen peroxide can rapid and tempestuously decomposition failure, therefore the polishing fluid there are stability it is poor the problem of.
United States Patent (USP) US5980775 discloses rubbing paste disclosed in metal CMP polishing slurries and United States Patent (USP) US6068787
Material adds in organic acid and makees stabilizer, improve the decomposition rate of hydrogen peroxide, still on the basis of United States Patent (USP) US5958288
Hydrogen peroxide decomposition rate is still higher, and hydrogen peroxide concentration can reduce by more than 10% in usual two weeks, and polishing velocity is caused to decline,
The gradual decomposition failure of polishing fluid.
Due to tungsten in the system of iron and hydrogen peroxide static corrosion speed quickly, directly influence the yield of production, thus
Need the static corrosion inhibitor of further addition tungsten.As included inhibitor of tungsten etching disclosed in Chinese patent CN1326199C
Polishing composition and the disclosed polishing compositions for including inhibitor of tungsten etching of CN1966594A, are catalyzed in hydrogen peroxide and iron
The erosion inhibitor of tungsten is added in the system of agent, inhibits the corrosion of tungsten.
Wolfram polishing liquid, the cycles of concentration of the prior art be not high, because after improving cycles of concentration, the stability of formula can be substantially
Decline, be in particular in abrasive particles increase, sedimentation, lose original polishing performance.In order to make tungsten in semiconductor technology
Preferably application, people continuously attempt to the improvement of new polishing fluid.
Invention content
To solve the above problems, the present invention provides a kind of chemical mechanical polishing liquid, the polishing fluid is by changing abrasive grains
The charge of silica surface significantly improves the stability of polishing fluid, further improves polishing stable degree, improves polishing effect
Rate reduces polishing cost.
Specifically, one aspect of the present invention is to provide a kind of chemically mechanical polishing polishing fluid, and it includes water, surface are negatively charged
The grinding agent of lotus, the compound that silver ion can be generated, the compound that sulfate ion can be generated, peroxide.
Wherein, preferably, the abrasive grains are at pH value 2~4 (including 2 and 4), surface band 30mv to 70mv is born
The silica of charge.
Preferably, a concentration of 0.1~20wt% of the abrasive grains；Preferably, a concentration of the 0.5 of the abrasive grains
~6wt%.
Preferably, the negative electrical charge on the abrasive grains surface can be by silica and containing carboxyl or sulfonic silane
It is obtained after coupling agent treatment.Preferably, the negative electrical charge on the abrasive grains surface can be by containing sulfonic silane coupling agent
It is obtained after processing.
Preferably, the compound that can generate silver ion is silver sulfate, silver nitrate, silver fluoride and/or silver perchlorate
It is one or more in soluble silver salt.
Preferably, a concentration of 0.001%~0.2wt% of the compound that silver ion can be generated.
Preferably, the compound that can generate sulfate ion is sulfate.Preferably, it is described can generate sulfate radical from
The compound of son is one or more in nonmetallic sulfate.Preferably, the nonmetallic sulfate is ammonium sulfate.
Preferably, the compound concentration that can generate sulfate ion is 0.1%~0.3wt%.
Preferably, the peroxide is hydrogen peroxide.
Preferably, the peroxide concentrations are 0.1~5wt%；Preferably, the peroxide concentrations for 1~
2wt%.
Preferably, the pH of the chemical mechanical polishing liquid is 2~4.
In addition, further include pH adjusting agent in the polishing fluid.
Another aspect of the present invention is to provide a kind of above-mentioned chemical mechanical polishing liquid answering in the polishing of tungsten
With.
Specific embodiment
Selected raw material is all commercially available in the present embodiment, and all components are dissolved and are uniformly mixed, and quality is supplied with water
Percentage is to 100%.It is adjusted with pH adjusting agent to desired pH, it is as follows to obtain specific embodiment.
1 comparative example of table and embodiment, which are matched, is when embodied result
The polishing fluid prepared in above-described embodiment 1~8 and comparative example is carried out to the chemically mechanical polishing of tungsten respectively, and will be thrown
Light effect is compared.
Polishing condition：Polishing machine platform is Mirra, IC1010 polishing pads, grinding pressure 3psi, polishing fluid rate of addition
100ml/ minutes.
It is comparative example and the proportioning of embodiment and its specific implementation result in table 1.Wherein, comparative example 1 shows only to grind
In the presence of agent and hydrogen peroxide, the polishing velocity of tungsten is very low；Comparative example 2 shows in the presence of iron ion and hydrogen peroxide are common, tungsten
Polishing velocity can be obviously improved, but grinding agent (silica) is unstable, and average grain diameter increases by 5 nanometers in 3 days；3 table of comparative example
It is bright, in the presence of iron ion and hydrogen peroxide are common, by the surface charge of abrasive silica to dropping to -30mv, grinding agent
Stability is obviously improved, and average grain diameter wants 100 talentes to increase by 5 nanometers；Comparative example 4 shows：It can be generated with the system of silver ion
The take-off speed of tungsten quickly, significant advantage are that polishing velocity is stablized, 21 talent's attenuation 10%.(iron-containing system is to decay for 3 days
10%).Shortcoming is that grinding agent (silica) stability is bad, and average grain diameter increases by 5 nanometers in 3 days.
And the embodiment of the present invention 1 shows：In argentiferous system, by the surface charge of abrasive silica to drop to-
30mv, grinding agent stability are obviously improved, and average grain diameter wants 110 talentes to increase by 5 nanometers.Polishing velocity and attenuation are still relatively steady
It is fixed；Embodiment 2-8 shows：In argentiferous system, change the surface charge of silica, silica concentration, silver ion it is dense
The concentration of concentration hydrogen peroxide etc. of degree, sulfate radical can obtain satisfied tungsten removal speed, the silica that greatly improves
The rate of decay of stability and polishing velocity.
In conclusion the chemical mechanical polishing liquid of the present invention is shown by changing the charge of abrasive grains silica surface
The stability for improving polishing fluid is write, the stability of polishing is further improved, improves polishing efficiency, reduce and be polished to
This.
Specific embodiments of the present invention are described in detail above, but it is intended only as example, it is of the invention and unlimited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
It substitutes also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should be contained within the scope of the invention.
Claims (15)
1. a kind of chemical mechanical polishing liquid, comprising water, the electronegative abrasive grains in surface can generate the compound of silver ion, energy
Generate the compound and peroxide of sulfate ion.
2. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the abrasive grains are in 2~4 range of pH value
When surface with 30mv to the silica of 70mv negative electrical charges.
3. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the abrasive grains content for 0.1~
20wt%.
4. the chemical mechanical polishing liquid as described in claim 1 or 3, which is characterized in that the abrasive grains content for 0.5~
6wt%.
5. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the compound that can generate silver ion is sulphur
Sour silver, silver nitrate, silver fluoride and/or silver perchlorate soluble silver salt.
6. the chemical mechanical polishing liquid as described in claim 1 or 5, which is characterized in that the compound that silver ion can be generated
Content is 0.001%~0.2wt%.
7. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the compound that sulfate ion can be generated
For sulfate.
8. the chemical mechanical polishing liquid as described in claim 1 or 7, which is characterized in that the sulfate is nonmetallic sulfate.
9. chemical mechanical polishing liquid as claimed in claim 8, which is characterized in that the nonmetallic sulfate is ammonium sulfate.
10. the chemical mechanical polishing liquid as described in claim 1 or 7, which is characterized in that the ammonium sulphate content is 0.1%
~0.3wt%.
11. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the peroxide is hydrogen peroxide.
12. the chemical mechanical polishing liquid as described in claim 1 or 11, which is characterized in that the peroxide content for 0.1~
5wt%.
13. chemical mechanical polishing liquid as claimed in claim 12, which is characterized in that the peroxide content for 1~
2wt%.
14. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the chemical mechanical polishing liquid also includes
PH adjusting agent.
15. the chemical mechanical polishing liquid as described in claim 1 or 14, which is characterized in that the chemical mechanical polishing liquid
PH value is 2~4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611231361.2A CN108250976A (en) | 2016-12-28 | 2016-12-28 | A kind of chemical mechanical polishing liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611231361.2A CN108250976A (en) | 2016-12-28 | 2016-12-28 | A kind of chemical mechanical polishing liquid |
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| Publication Number | Publication Date |
|---|---|
| CN108250976A true CN108250976A (en) | 2018-07-06 |
Family
ID=62720000
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611231361.2A Pending CN108250976A (en) | 2016-12-28 | 2016-12-28 | A kind of chemical mechanical polishing liquid |
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| CN (1) | CN108250976A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110820048A (en) * | 2019-11-28 | 2020-02-21 | 南京纳鑫新材料有限公司 | Metal ion-assisted non-nitric acid polishing method |
| CN111378374A (en) * | 2018-12-28 | 2020-07-07 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing solution |
| CN111378973A (en) * | 2018-12-28 | 2020-07-07 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing solution and application thereof |
-
2016
- 2016-12-28 CN CN201611231361.2A patent/CN108250976A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111378374A (en) * | 2018-12-28 | 2020-07-07 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing solution |
| CN111378973A (en) * | 2018-12-28 | 2020-07-07 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing solution and application thereof |
| CN111378374B (en) * | 2018-12-28 | 2022-05-13 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing solution |
| CN110820048A (en) * | 2019-11-28 | 2020-02-21 | 南京纳鑫新材料有限公司 | Metal ion-assisted non-nitric acid polishing method |
| CN110820048B (en) * | 2019-11-28 | 2021-01-01 | 南京纳鑫新材料有限公司 | Metal ion-assisted non-nitric acid polishing method |
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Application publication date: 20180706 |