CN106928855A - A kind of acidic chemical machine polishing liquor - Google Patents
A kind of acidic chemical machine polishing liquor Download PDFInfo
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- CN106928855A CN106928855A CN201511019748.7A CN201511019748A CN106928855A CN 106928855 A CN106928855 A CN 106928855A CN 201511019748 A CN201511019748 A CN 201511019748A CN 106928855 A CN106928855 A CN 106928855A
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- acidic chemical
- machine polishing
- chemical machine
- polishing
- liquors
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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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- Organic Chemistry (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
The present invention relates to a kind of acidic chemical machine polishing liquor, it contains：Silicon-containing compound, abrasive grains, azole compounds, acid, polyvinylpyrrolidone and its salt, oxidant and water.The pH value of the acid CMP planarization liquid is 36.The polishing fluid can be under acidity polishing environment, meet polishing speed and selection ratio during barrier polishing to various materials to require, while having very strong correction ability to the defect of semiconductor device surface, fast planarization can be realized, operating efficiency is improved, production cost is reduced.
Description
Technical field
The present invention relates to a kind of chemical mechanical polishing liquid, more particularly to a kind of acidic chemical machine polishing liquor.
Background technology
With continuing to develop for semiconductor technology, the device size of integrated circuit constantly reduces, the cloth of integrated circuit
The line number of plies is more and more, and then demand higher is proposed to the performance of wiring metal, and metallic copper is because with than aluminium
Lower resistivity and there is high impedance to electromigration, be widely used in interconnection line.But copper can be dissolved in dielectric material
Material, so in the Wiring technique of integrated circuit, in order to prevent copper to be dissolved in dielectric material, it is necessary in copper and dielectric
Need to cover one layer of diffusion impervious layer between material, conventional barrier material includes tantalum, tantalum nitride, titanium, nitrogen
Change titanium etc..
In semiconductor fabrication process, it usually needs entered glossing, the planarization of device surface is realized.But,
Due to increasing for the wiring number of plies, the planarization to each layer of integrated circuit proposes requirement higher.By
IBM Corporation twentieth century eighties pioneering chemically mechanical polishing (CMP) technology be considered as complete at present
The most efficient method of office's planarization.Chemically mechanical polishing (CMP) is a kind of by chemical action, machinery work
With and both act on be combined and realize planarization technology.The CMP of copper is generally divided into two steps,
A kind of polishing fluid of the first step quickly removes the copper metal that barrier layer covers above, and the polishing fluid generally has very high
Copper polishing speed and the polishing speed on low barrier layer, so as to the unnecessary copper of quick removal barrier layer surface,
Then stop over the barrier layer；Second step removes barrier layer and a small amount of dielectric layer with a kind of barrier polishing solution.
By removing selection ratios different between barrier layer, dielectric layer and copper, the planarization of integrated circuit is realized.
In the CMP fields of semiconductor, conventional chemical mechanical polishing liquid is mainly divided to acid and two kinds of alkalescence.Relate to
And the patent of acid polishing slurry has a lot, such as CN1312845A patents disclose a kind of acid in the patent
Property barrier polishing solution, its surfactant for containing metal abrasives and a large amount of macromoleculars, but the polishing fluid exist
Polished surface is damaged, and is to the with serious pollution acidic materials of equipment corrosion；The barrier polishing solution of alkalescence, than
Such as：Patent CN101302405A, it discloses a kind of alkali barrier polishing fluid, it contains polyvinyl pyrrole
Pyrrolidone and imines, carbonate, inhibitor, complexing agent；But it can produce substantial amounts of foam in polishing process,
Polishing fluid is weighed in the skewness of polishing pad and polished surface, and influence the stability of polishing fluid；It is and for example special
Sharp CN1400266, which disclose a kind of chemically mechanical polishing containing amine and nonionic surfactant
Liquid.But the polishing fluid is in polishing to the surface losses on barrier layer than more serious.As fully visible, alkaline slurry
Stability is relatively good, but exists without suitable oxidant, and easily caused in polishing process surface cloud point and
The slight problem for scratching.Acid Slurry shows certain advantage in this respect.It can be dense in abrasive grains
Polishing speed higher is reached in the case of spending relatively low.But the size of abrasive grain can be with depositing in Acid Slurry
The extension of storage time, the effect of chemical constituent in slurry and gradually grow up, when particle diameter be more than 120 nanometers after,
The phenomenons such as sedimentation layering occur, quality of finish is had a strong impact on, product failure is caused.So control abrasive particle
Grow up, increase the service life be Acid Slurry be eager solve problem.
Chemical mechanical polishing liquid contains abrasive grains, and major part is using nano silicon dioxide sol as abrasive material
Grain.In polishing fluid, also usually need to add some polymer come in the viscosity and polishing process that adjust polishing fluid
Frictional force, but add this kind of polymer to cause abrasive grains, especially electronegative grind in acid polishing slurry
The coalescence of abrasive particle.Stability on silicon dioxide gel has many document reports.But closed in CMP fields
Increase in abrasive grain particle diameter is suppressed, the document for extending chemical mechanical polishing liquid stability has not been reported.
The content of the invention
To solve the above problems, the present invention provides a kind of chemically mechanical polishing for meeting barrier polishing stage demand
Liquid, it has barrier layer (Ta/TaN) removal rate high, is suitable for cover closing material in different polishing process
(TEOS), the removal rate of Ni metal and selection ratio are required, and can quickly correct semiconductor device surface
Existing defect, pollutant residual is few after polishing, and self stability is high.Meanwhile, the invention can also be used for
The polishing on TSV barrier layers.
The invention discloses a kind of acidic chemical machine polishing liquor, the polishing fluid includes abrasive grains, siliceous organic
Compound, azole compounds, organic/inorganic acid, polyvinylpyrrolidone and its salt, oxidant and water.
Wherein, described abrasive grains are selected from SiO2、Al2O3、ZrO2、SiC、CeO2、TiO2And Si3N4
In one or more, preferably SiO2；The content of the abrasive grains is preferably 1~15wt%, more preferably
It is 1~10wt%；The particle diameter of described abrasive grains is 20~100nm.
Wherein, described silicon-containing organic compound can be represented with following formulas：
Formula：
Herein, R is unhydrolyzable substitution base, usually alkyl, containing 1-50 carbon atom, with 1-10
Individual carbon atom is preferred, and 3-7 carbon atom is optimal；Carbon atom on the Long carbon chain can also continue to by oxygen, nitrogen,
Other atoms continuation such as sulphur, phosphine, halogen, silicon replaces；A, B are same or different hydrolyzable substitution
Base or hydroxyl；C can be the alkyl substituent of hydrolyzable groups or hydroxyl, or non-hydrolysable；D
It is the organo-functional group being connected on R；A, B and C are typically chloro, methoxyl group, ethyoxyl, methoxy
Base oxethyl, acetoxyl group, hydroxyl etc., generation silanol (Si (OH) when these groups are hydrolyzed3), and with nothing
Machine material is combined, and forms siloxanes.D be vinyl, amino, epoxy radicals, propylene acidic group, acryloxy,
Sulfydryl or urea groups etc., these reactive groups can with organic substance reaction and it is in connection.The siliceous organic compound
Thing is preferably selected from APTES (trade name KH-550), γ-(2,3- glycidoxies)
Propyl trimethoxy silicane (trade name KH-560), γ-(methacryloxypropyl) propyl trimethoxy silicane (business
Name of an article KH-570), gamma-mercaptopropyltriethoxysilane (trade name KH-580), N- (β-aminoethyl)-γ-
Aminopropyltriethoxy dimethoxysilane (trade name KH-602), γ-aminoethylaminopropyl trimethoxy silane (business
Name of an article KH-792), one or more in γ-aminopropyltriethoxy diethoxy silane (trade name KH-902).
The content of described silicon-containing organic compound is preferably 0.01~1wt%, more preferably 0.01~0.5wt%.
Wherein, described azole compounds are preferably selected from BTA, methyl benzotriazazole, 5- phenyl
Tetrazole, mercaptophenyl tetrazole, benzimidazole, aphthotriazoles, 5- aminotetrazoles, 1,2,4- triazoles,
The triazole of 3- amino -1,2,4, the triazole of 4- amino -1,2,4,3,5- diaminostilbenes, 2,4 triazoles, 2- sulfydryls-benzene
And thiazole.The content of described azole compounds is preferably 0.001~1wt%, more preferably 0.01~0.5wt%.
Wherein, described organic/inorganic acid preferably selected from acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid,
One or more in citric acid, adipic acid, tartaric acid, phosphoric acid, boric acid.Described organic/inorganic acid
Content is preferably 0.001~2wt%, more preferably 0.001~0.5wt%.
Wherein, the molecular weight of described polyvinylpyrrolidone is preferably 1000~1000000, more preferably
1000~500000.The content of described polyvinylpyrrolidone is preferably 0.005~0.5wt%.
Wherein, described oxidant is preferably selected from hydrogen peroxide, Peracetic acid, potassium peroxydisulfate, ammonium persulfate
In one or more.The content of described oxidant is preferably 0.01~5wt%, more preferably 0.1~1wt%.
Wherein, the pH value of described chemical mechanical polishing liquid is 3.0-6.0, more preferably 4.0-6.0.
Wherein, described chemical mechanical polishing liquid can also be comprising other this areas such as pH adjusting agent and bactericide
Typical additives.
It is of the invention actively to have technical effect that：
1) may be such that polishing fluid has excellent silicon dioxide etc. dielectric layer by adding silicon-containing organic compound
The removal rate on the barrier layer such as removal rate and tantalum；
2) polishing fluid of the invention can reduce the removal rate of ultra-low dielectric materials ULK simultaneously；
3) there is provided a kind of polishing fluid formula of stable under acidic conditions, its can abrasive grains solid content compared with
In the case of low (2~10wt%), alkalescence polishing liquid abrasive grains content ability between 30-50wt% is reached
The grinding rate for reaching.
4) chemical mechanical polishing liquid of the invention can be prepared into concentrated product, be easy to storage with transport.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but do not limited the present invention to this described
Scope of embodiments among.
Chemical mechanical polishing liquid of the invention can be prepared as follows：Other components in addition to oxidant are pressed
Ratio is well mixed, with pH adjusting agent (such as KOH or HNO3) pH value of the regulation required for, use
Preceding oxidizer, and total amount is supplemented to 100% with water, it is well mixed.
Agents useful for same of the present invention and raw material are commercially available.
Table 1 contrasts the formula of polishing fluid 1 and polishing fluid of the invention 1~15
It should be noted that siliceous organic matter selected in the present invention is not limited in used in the form
It is several, also including corresponding silicon-containing organic compound that atomic number of alkyl carbon is 1,2,8,9,10.
Effect example 1
Using contrast polishing fluid and polishing fluid of the invention 1~15 according to following conditions to copper (Cu), tantalum (Ta),
Silica (TEOS) is polished.Polishing condition：Polishing machine platform is 8 " Mirra boards, polishing pad is
Fujibo pad, lower pressure is 1.5psi, and rotating speed is polishing disk/rubbing head=93/87rpm, and polishing flow velocity is
150ml/min, polishing time is 1min.
Table 2 contrasts polishing fluid 1 and polishing fluid of the present invention 1~15 goes to copper (Cu), tantalum (Ta), silica (TEOS)
The comparison result of removal rates and correction ability
From table 2, compared with polishing fluid 1 is contrasted, polishing fluid of the invention can obtain stop higher
The removal rate of layer Ta and silica (TEOS).Embodiment 1-15 shows by adjusting grinding agent, containing
The usage amount of silicon organic matter, azole compounds, organic/inorganic acid, polyvinylpyrrolidone and oxidant, can
To adjust suitable polishing selection ratio.Compared with polishing fluid 2 is contrasted, this application provides under a kind of acid condition
The polishing fluid formula of stabilization, it can reach in the case of abrasive grains solid content is relatively low (1%~10%)
The grinding rate that alkalescence polishing liquid abrasive grains content can be only achieved between 30%-50%.
In addition, contrasted by embodiment 1-15 and comparative example 1 find, polishing fluid of the invention to the wide line area and
The defect correction of fine line district is significantly improved, can be in the blemish surface of short time correction semiconductor devices, so as to realize
Planarization.
It should be appreciated that wt% of the present invention refers to weight/mass percentage composition.
Specific embodiment of the invention has been described in detail above, but it is intended only as example, and the present invention is simultaneously
It is not restricted to particular embodiments described above.To those skilled in the art, it is any that the present invention is carried out
Equivalent modifications and substitute also all among scope of the invention.Therefore, spirit of the invention and model are not being departed from
Enclose lower made impartial conversion and change, all should be contained within the scope of the invention.
Claims (26)
1. a kind of acidic chemical machine polishing liquor, comprising abrasive grains, silicon-containing organic compound, azole compounds, organic/inorganic acid, polyvinylpyrrolidone and its salt, oxidant and water.
2. acidic chemical machine polishing liquor as claimed in claim 1, it is characterised in that the abrasive grains are selected from SiO2、Al2O3、ZrO2、SiC、CeO2、TiO2And Si3N4In one or more.
3. acidic chemical machine polishing liquor as claimed in claim 2, it is characterised in that the abrasive grains are SiO2。
4. acidic chemical machine polishing liquor as claimed in claim 1, it is characterised in that the content of the abrasive grains is 1~15wt%.
5. acidic chemical machine polishing liquor as claimed in claim 4, it is characterised in that the content of the abrasive grains is 1~10wt%.
6. acidic chemical machine polishing liquor as claimed in claim 1, it is characterised in that the particle diameter of the abrasive grains is 20~100nm.
7. acidic chemical machine polishing liquor as claimed in claim 1, it is characterised in that the silicon-containing organic compound has following formulas：
Wherein, R is unhydrolyzable substitution base, and A, B are same or different hydrolyzable substitution base or hydroxyl；C is hydrolyzable groups or hydroxyl, or non-hydrolysable alkyl substituent；D is the organo-functional group being connected on R, selected from vinyl, amino, epoxy radicals, acrylic, acryloxy, sulfydryl or urea groups.
8. acidic chemical machine polishing liquor as claimed in claim 7, it is characterised in that the R in the formula of the silicon-containing organic compound is alkyl, wherein containing 1-10 carbon atom.
9. acidic chemical machine polishing liquor as claimed in claim 8, it is characterized in that, R in the formula of the silicon-containing organic compound is alkyl, wherein being replaced by oxygen, nitrogen, sulphur, phosphine, halogen or silicon atom containing the carbon atom on 3-7 carbon atom, and the alkyl carbon chain；A, B and C are respectively selected from chloro, methoxyl group, ethyoxyl, methoxy ethoxy, acetoxyl group or hydroxyl.
10. chemical mechanical polishing liquid as claimed in claim 1, it is characterized in that, the silicon-containing organic compound is selected from APTES (trade name KH-550), γ-(2, 3- glycidoxies) propyl trimethoxy silicane (trade name KH-560), γ-(methacryloxypropyl) propyl trimethoxy silicane (trade name KH-570), gamma-mercaptopropyltriethoxysilane (trade name KH-580), N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane (trade name KH-602), one or more in γ-aminoethylaminopropyl trimethoxy silane (trade name KH-792) and/or γ-aminopropyltriethoxy diethoxy silane (trade name KH-902).
11. acidic chemical machine polishing liquors as claimed in claim 1, it is characterised in that the content of described silicon-containing organic compound is 0.01~1wt%.
12. acidic chemical machine polishing liquors as claimed in claim 11, it is characterised in that the content of the silicon-containing organic compound is 0.01~0.5wt%.
13. acidic chemical machine polishing liquors as claimed in claim 1, characterized in that, the azole compounds are selected from BTA, methyl benzotriazazole, 5- phenyl tetrazole, mercaptophenyl tetrazole, benzimidazole, aphthotriazoles, 5- aminotetrazoles, 1,2,4- triazoles, 3- amino -1,2,4 triazoles, 4- amino -1,2,4 triazoles, 3,5- diaminostilbenes, 2,4 triazoles and/or 2- Mercapto-benzothiazoles.
14. acidic chemical machine polishing liquors as claimed in claim 1, it is characterised in that the content of the azole compounds is 0.001~1wt%.
15. acidic chemical machine polishing liquors as claimed in claim 14, it is characterised in that the content of the azole compounds is 0.01~0.5wt%.
16. acidic chemical machine polishing liquors as claimed in claim 1, it is characterised in that the organic/inorganic acid is selected from one or more in acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, citric acid, adipic acid, tartaric acid, phosphoric acid, boric acid.
17. acidic chemical machine polishing liquors as claimed in claim 1, it is characterised in that the content of the organic/inorganic acid is 0.001~2wt%.
18. acidic chemical machine polishing liquors as claimed in claim 17, it is characterised in that the content of the organic/inorganic acid is 0.001~0.5wt%.
19. acidic chemical machine polishing liquors as claimed in claim 1, it is characterised in that the molecular weight of the polyvinylpyrrolidone is 1000~1000000.
20. acidic chemical machine polishing liquors as claimed in claim 19, it is characterised in that the molecular weight of the polyvinylpyrrolidone is 1000~500000.
21. acidic chemical machine polishing liquors as claimed in claim 1, it is characterised in that the content of the polyvinylpyrrolidone is：0.005~0.5wt%.
22. acidic chemical machine polishing liquors as claimed in claim 1, it is characterised in that the oxidant is selected from one or more in following middle hydrogen peroxide, Peracetic acid, potassium peroxydisulfate, ammonium persulfate.
23. acidic chemical machine polishing liquors as claimed in claim 1, it is characterised in that the content of the oxidant is 0.01~5wt%.
24. acidic chemical machine polishing liquors as claimed in claim 23, it is characterised in that the content of the oxidant is 0.1~1wt%.
25. acidic chemical machine polishing liquors as claimed in claim 1, it is characterised in that the pH value of the chemical mechanical polishing liquid is 3.0-6.0.
26. acidic chemical machine polishing liquors as claimed in claim 25, it is characterised in that the pH value of the chemical mechanical polishing liquid is 4.0-6.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511019748.7A CN106928855A (en) | 2015-12-30 | 2015-12-30 | A kind of acidic chemical machine polishing liquor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511019748.7A CN106928855A (en) | 2015-12-30 | 2015-12-30 | A kind of acidic chemical machine polishing liquor |
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| CN106928855A true CN106928855A (en) | 2017-07-07 |
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| CN201511019748.7A Pending CN106928855A (en) | 2015-12-30 | 2015-12-30 | A kind of acidic chemical machine polishing liquor |
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Address after: 201201 Pudong New Area East Road, No. 5001 Jinqiao Export Processing Zone (South) T6-9 floor, the bottom of the Applicant after: Anji microelectronic technology (Shanghai) Limited by Share Ltd Address before: 201201 Pudong New Area East Road, No. 5001 Jinqiao Export Processing Zone (South) T6-9 floor, the bottom of the Applicant before: Anji Microelectronics (Shanghai) Co., Ltd. |
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| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170707 |
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| WD01 | Invention patent application deemed withdrawn after publication |