CN104745082A - Chemical mechanical polishing liquid and polishing method - Google Patents
Chemical mechanical polishing liquid and polishing method Download PDFInfo
- Publication number
- CN104745082A CN104745082A CN201310726697.6A CN201310726697A CN104745082A CN 104745082 A CN104745082 A CN 104745082A CN 201310726697 A CN201310726697 A CN 201310726697A CN 104745082 A CN104745082 A CN 104745082A
- Authority
- CN
- China
- Prior art keywords
- apply
- brand
- trade
- name
- ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
The invention relates to application of a chemical mechanical polishing liquid in increasing silicon dioxide / silicon nitride selectivity ratio. The chemical mechanical polishing liquid contains abrasive particles, an organic compound containing silicon, electrolyte ions with ionic strength greater than or equal to 0.1mol / Kg, and a nitrogen-containing compound. The organic compound containing silicon has the following formula, wherein R is a non-hydrolyzable substituent, D is an organic functional group connected to R, and can react with organic substances for combination, A and B are same or different hydrolyzable substituents or hydroxyl, and C is a hydrolyzable group or hydroxyl, or a non-hydrolyzable alkyl substituent.
Description
Technical field
The present invention relates to a kind of chemical mechanical polishing liquid and finishing method.
Background technology
Manufacture normally integrated hundreds of millions of active part (comprising NMOS and PMOS) on silicon substrate material of COMS chip, and then design logic function and the analog functuion of various circuit realiration complexity.Guarantee the electric isolation between different components, insulating material will be adopted to be isolated, shallow-trench isolation (STI) is exactly the industrial method forming isolated area between active part.This partition method, be at Grown layer of silicon dioxide layer, and then deposit one deck silicon nitride film, the typical thickness of the two is respectively 10-20nm and 50-100nm, then carries out gluing, exposure and development.
Wherein remove silicon-dioxide fast by cmp planarization metallization processes and stop at above silicon nitride, this just requires that its polishing fluid will have the removal speed of higher high density plasma silicon-dioxide (HDP), and high silicon-dioxide is to the polishing Selection radio of silicon nitride (HDP/Si3N4), usually 10 are greater than, and the butterfly depression in different densities region can not differ 200 dusts, smooth surface is clean, and particulate pollutant and defect etc. are all less than processing requirement index.
The widespread use of current chip factory be cerium dioxide polishing fluid, relevant technical patent is also a lot, such polishing fluid polishing velocity of such as US Patent No. 7109117B2, US7364600B2 is fast, high to the selection and comparison of silicon nitride, be comparatively ripe industrialization product, but polishing fluid easily produce deposition layering, higher to online equipment requirements, expensive in addition, under the background of global chip industry consumption reduction synergy, reducing costs also is one of the requirement of polishing fluid.
Also there is a problem in the method that above-mentioned patent is mentioned, under high ionic strength, such as, add a large amount of potassium ion (>0.1mol/Kg), the median size of abrasive grains can increase gradually, and polishing fluid is unstable, is easy to sedimentation, layering.So must use in very short time after manufacture, like this produce and client terminal use on be difficult to operate.
At present, chemical mechanical polishing liquid (CMP) abrasive grains used adopts silicon-dioxide usually, comprises silicon sol (colloidal silica) and aerosil (fumed silica).They itself are solids, but in aqueous can be dispersed, and not sedimentation even can keep the permanent stability of 1 to 3 year.
The stability (not sedimentation) of abrasive grains in aqueous phase can explain with double electrode layer theory-because each particle surface is with identical electric charge, and they repel mutually, can not produce cohesion.According to Stern model, colloid ion, when moving, the face of cutting can produce Zeta electric potential.Zeta electric potential is an important indicator of colloidal stability, because the stable of colloid is closely-related with interparticle electrostatic repulsion forces.The reduction of Zeta electric potential can make electrostatic repulsion forces reduce, and causes interparticle van der Waals magnetism to be dominant, thus causes gathering and the sedimentation of colloid.The height of ionic strength is the important factor affecting Zeta electric potential.
The stability of colloid, except the impact by zeta electromotive force, is also permitted multifactorial impact by other.Such as, by the impact of temperature, at relatively high temperatures, the random thermal motion aggravation of particle, the probability of collision mutually increases, and can accelerate cohesion; Such as, affect by pH value, than indifferent equilibrium under strong basicity, strong acidic condition, its neutral and alkali is the most stable, and pH value 4-7 interval is least stable; Such as, by the impact of kinds of surfactants, some surfactivity can play the effect of dispersion agent, improve stability, and some tensio-active agent can reduce nanoparticle surface charge, reduces Coulomb repulsion, Accelerated subsidence.In tensio-active agent, usual aniorfic surfactant is conducive to the stability of nano particle, and cationic surfactant easily reduces stability; Again such as, relevant with the molecular weight of additive, oversize polymkeric substance long-chain is wound around nano particle sometimes, increases the viscosity of dispersion liquid, accelerates particle aggregation.Therefore, the stability of silicon sol is subject to the impact of many factors.
United States Patent (USP) 60142706 and United States Patent (USP) 09609882 disclose polishing fluid containing silane coupling agent and finishing method.Wherein silane coupling agent plays the polishing velocity changing multiple material and the effect improving surfaceness.These two sections of patents do not find: when high ionic strength (>0.1mol/Kg), and silane coupling agent can play effect, the stable nanoparticles of antagonism high ionic strength.Because usually when containing very high ionic strength (such as containing being greater than >0.2mol/Kg potassium ion), the electrostatic double layer of silica sol granule can significantly be compressed, electrostatic repulsion forces reduces, and forms rapidly gel, precipitation.
Summary of the invention
The invention provides a kind of chemical mechanical polishing liquid for shallow-trench isolation, at least containing a kind of silica-based abrasive material, siliceous organic compound, guarantee in whole system containing ionogen positively charged ion, a kind of nitrogenous compound of particle intensity being more than or equal to 0.1mol/Kg.
The present invention relates to a kind of chemical mechanical polishing liquid and improve the application in silicon dioxide/silicon nitride Selection radio, chemical mechanical polishing liquid comprises abrasive grains, siliceous organic compound, is more than or equal to the electrolyte ion of the ionic strength of 0.1mol/Kg, and nitrogenous compound
This siliceous organic compound can represent with following general formula:
General formula:
In above formula, R is unhydrolyzable substituting group, and D is the organo-functional group be connected on R, and these reactive groups can react with organic substance and combine.A, B are identical or different hydrolyzable substituting group or hydroxyl, and C can be hydrolysable group or hydroxyl, also can be the alkyl substituents of non-hydrolysable.Say further, R is alkyl normally, such as the alkyl of 1-50 carbon atom, more preferably, is the alkyl of 1-20 carbon atom, best, is the alkyl of 2-10 carbon atom.And it will be appreciated by persons skilled in the art that the carbon atom in R substituent can also continue to be continued to replace by other atoms such as oxygen, nitrogen, sulphur, phosphine, halogen, silicon.D can be amino, urea groups, sulfydryl, epoxy group(ing), acrylic, vinyl, acryloxy etc.A, B and C be chloro, methoxyl group, oxyethyl group, methoxy ethoxy, acetoxyl group, hydroxyl etc. normally, generates silanol (Si (OH) during the hydrolysis of these groups
3), and be combined with inorganic substance, form siloxanes.
Representational siliceous organic compound is silane coupling agent, such as following structure:
APTES (trade(brand)name KH-550)
γ-(2,3-glycidoxy) propyl trimethoxy silicane (trade(brand)name KH-560)
γ-(methacryloxypropyl) propyl trimethoxy silicane (trade(brand)name KH-570)
Gamma-mercaptopropyltriethoxysilane (trade(brand)name KH-580)
γ-mercaptopropyl trimethoxysilane (trade(brand)name KH-590)
N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane (trade(brand)name KH-602)
γ-aminoethylaminopropyl Trimethoxy silane (trade(brand)name KH-792)
γ-aminopropyltriethoxy diethoxy silane (trade(brand)name KH-902)
γ-divinyl triammonium base hydroxypropyl methyl dimethoxysilane (trade(brand)name KH-103)
This siliceous organic compound can be added in polishing fluid through number of ways, 1: abrasive grains is first and silicon-containing compound bonding (the particle surface modification be commonly called as, surface treatment) before preparing polishing fluid, is then joined in polishing fluid by the abrasive grains after surface modification.2: this siliceous organic compound when producing polishing fluid and abrasive grains and other components mix simultaneously.3: this siliceous organic compound can first complete hydrolysis or partial hydrolysis, generate Si-OH group, and then add in polishing fluid, Si-OH group and the particle surface complete bonding of Si-OH or moiety in polishing fluid.The variforms such as free, bonding, partial hydrolysis, complete hydrolysis may be there is in the siliceous organic compound that therefore the present invention adopts when polishing.
The present invention's nitrogenous compound used be preferably in polydimethyl two allyl ammonium chloride, 2-amino-2-methyl-1-propanol, glycidyltrimetiiylammonium ammonium chloride, Tetramethylammonium hydroxide, TBAH, ammonium lauryl sulfate, guanidine acetate, Guanidinium carbonate, phosphoguanidine, urea one or more; The content of described nitrogenous compound is preferably mass percent 0.01 ~ 1.5%, and better is 0.05 ~ 0.5%.
Described polishing composition can work under acid ph value or alkaline ph values.Preferably, the pH value of polishing composition is at 1-7.Within the scope of this, its pH value should be more than or equal to 2, and less than or equal to 6, most preferably pH value is 3-5.
Affiliated polishing composition also can comprise inorganic or organic pH value regulator, so that the pH value of polishing composition is down to acid ph value, or pH value is increased to alkaline ph values.Suitable inorganic pH value reduces agent and comprises such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid or comprise the combination that the above-mentioned inorganic pH value of at least one reduces agent.Suitable pH value growth promoter comprises following one: metal hydroxides, ammonium hydroxide or nitrogenous organic base or above-mentioned pH value increase the combination of agent.
In this polishing fluid, the concentration of siliceous organic compound is mass percent 0.001% ~ 1%, is preferably 0.01% ~ 0.5%.
In this polishing fluid, abrasive grains can be various conventional abrasive grains well known to those skilled in the art, preferably can be Silica abrasive particle, and abrasive grains concentration is mass percent 1% ~ 50%, is preferably 2% ~ 10%.Particle diameter is 20 ~ 200nm, is preferably 20 ~ 120nm.
In this polishing fluid, the electrolyte ion being more than or equal to the ionic strength of 0.1mol/Kg is metal ion and nonmetallic ion.The concentration of the electrolyte ion of the ionic strength of the described 0.1mol/Kg of being more than or equal to is 0.1mol/Kg-1mol/Kg.For example, can be potassium ion, ammonium ion, iron ion, TBuA ion.Preferably, electrolyte ion is potassium ion.
Positive progressive effect of the present invention is: polishing fluid has the removal speed that higher silicon-dioxide removes speed and lower silicon nitride under acid polishing environment, and can realize improving the stability of colloid under the ionogen positively charged ion of high strength by siliceous organic compound, and the Selection radio of silicon-dioxide to silicon nitride is controlled under the effect of suitable pH value with other additives, realize the planarization of shallow-trench isolation, and significantly reduce the cost of STI polishing fluid, improve production capacity.
Embodiment
Set forth advantage of the present invention further below by specific embodiment, but protection scope of the present invention is not only confined to following embodiment.
According to composition and the proportions polishing fluid thereof of embodiment each in table 1 and comparative example, mix, supply mass percent to 100% with water.With KOH, HNO
3or pH adjusting agent is adjusted to required pH value.Wherein polishing condition is: polishing machine platform is Mirra board, IC1000 polishing pad, 200mm Wafer, overdraft 3psi, polishing fluid rate of addition 150ml/ minute.
Comparative example 1 shows: under very high ionic strength, and the removal speed of silicon-dioxide only has 350A/min, and the removal speed of silicon nitride is 400A/min, and the Selection radio of silicon-dioxide to silicon nitride is only 0.9, and polishing fluid is unstable, rapid delaminating deposition.Comparative example 3 and comparative example 1 contrast and show: under very high ionic strength, add silane coupling agent, the removal speed of silicon-dioxide adds 120A/min, but the removal rate reduction of silicon nitride 220A/min, Selection radio brings up to 2.6, further, polishing fluid is very stable, and abrasive grains median size (particle mean size) does not increase.Comparative example 2 shows: add Tetramethylammonium hydroxide, the polishing velocity of silicon-dioxide can be made to increase 600A/min, and the removal rate reduction of silicon nitride 80A/min, Selection radio is only 2, and polishing fluid is unstable, rapid delaminating deposition.Embodiment 1 and comparative example 2 contrast and show: under Tetramethylammonium hydroxide exists, add silane coupling agent, the removal speed ratio of silicon-dioxide does not add Tetramethylammonium hydroxide and does not add silane coupling agent, add 1217A/min, this increasing amount is greater than silane coupling agent (120A/min) and both contribution sums of Tetramethylammonium hydroxide (600A/min), and the removal speed of silicon nitride reduces to 150A/min, Selection radio increases substantially 10, show: between silane coupling agent and Tetramethylammonium hydroxide and other nitrogenous compounds, there is synergy, silicon-dioxide is improved to the Selection radio of silicon nitride while can significantly improving the polishing velocity of silicon-dioxide.Comparative example 1 ~ 2 does not all add silane coupling agent, and polishing fluid is unstable.Embodiment 1 ~ 9, has silane coupling agent, and polishing fluid is more stable, and the removal speed of silicon-dioxide significantly promotes, and Selection radio improves simultaneously.
Embodiment 1 ~ 9, all shows, silane coupling agent has " effect of anti-high ionic strength ", and polishing fluid is highly stable.
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.
Claims (19)
1. a chemical mechanical polishing liquid is improving the application in silicon dioxide/silicon nitride Selection radio, it is characterized in that, described chemical mechanical polishing liquid comprises abrasive grains, siliceous organic compound, be more than or equal to the electrolyte ion of the ionic strength of 0.1mol/Kg, and nitrogenous compound, and described siliceous organic compound is following general formula
Wherein, R is unhydrolyzable substituting group, and D is the organo-functional group be connected on R, and it can react with organic substance and combine, A, and B is identical or different hydrolyzable substituting group or hydroxyl, and C is hydrolysable group or hydroxyl, or the alkyl substituent of non-hydrolysable.
2. apply as claimed in claim 1, it is characterized in that, described abrasive grains is Silica abrasive particle.
3. apply as claimed in claim 1, it is characterized in that, the concentration of described abrasive grains is mass percent 1% ~ 50%.
4. apply as claimed in claim 3, it is characterized in that, the concentration of described abrasive grains is mass percent 2% ~ 10%.
5. apply as claimed in claim 1, it is characterized in that, the particle diameter of described abrasive grains is 20 ~ 200nm.
6. apply as claimed in claim 5, it is characterized in that, the particle diameter of described abrasive grains is 20 ~ 120nm.
7. apply as claimed in claim 1, it is characterized in that, wherein R is alkyl, and the carbon atom on described alkyl carbon chain is continued to replace by oxygen, nitrogen, sulphur, phosphine, halogen, Siliciumatom; A, B and C are respectively chloro, methoxyl group, oxyethyl group, methoxy ethoxy, acetoxyl group or hydroxyl; D is amino, urea groups, sulfydryl, epoxy group(ing), acrylic, vinyl or acryloxy.
8. apply as claimed in claim 1, it is characterized in that, described siliceous organic compound is silane coupling agent.
9. apply as claimed in claim 8, it is characterized in that, described siliceous organic compound is APTES (trade(brand)name KH-550), γ-(2, 3-glycidoxy) propyl trimethoxy silicane (trade(brand)name KH-560), γ-(methacryloxypropyl) propyl trimethoxy silicane (trade(brand)name KH-570), gamma-mercaptopropyltriethoxysilane (trade(brand)name KH-580), γ-mercaptopropyl trimethoxysilane (trade(brand)name KH-590), N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane (trade(brand)name KH-602), γ-aminoethylaminopropyl Trimethoxy silane (trade(brand)name KH-792), γ-aminopropyltriethoxy diethoxy silane (trade(brand)name KH-902), one or more in γ-divinyl triammonium base hydroxypropyl methyl dimethoxysilane (trade(brand)name KH-103).
10. apply as claimed in claim 1, it is characterized in that, described in be more than or equal to the ionic strength of 0.1mol/Kg electrolyte ion be metal ion and nonmetallic ion.
11. apply as claimed in claim 10, it is characterized in that, described in be more than or equal to the ionic strength of 0.1mol/Kg electrolyte ion be potassium ion, ammonium ion, iron ion, one or more in TBuA ion.
12. apply as claimed in claim 1, it is characterized in that, described in be more than or equal to the electrolyte ion of the ionic strength of 0.1mol/Kg concentration be 0.1mol/Kg-1mol/Kg.
13. apply as claimed in claim 1, it is characterized in that, described nitrogenous compound is one or more in polydimethyl two allyl ammonium chloride, 2-amino-2-methyl-1-propanol, glycidyltrimetiiylammonium ammonium chloride, Tetramethylammonium hydroxide, TBAH, ammonium lauryl sulfate, guanidine acetate, Guanidinium carbonate, phosphoguanidine, urea.
14. apply as claimed in claim 1, it is characterized in that, the content of described nitrogenous compound is mass percent 0.01 ~ 1.5%.
15. apply as claimed in claim 14, it is characterized in that, the content of described nitrogenous compound is mass percent 0.05 ~ 0.5%.
16. apply as claimed in claim 1, it is characterized in that, the concentration of described siliceous organic compound is mass percent 0.001% ~ 1%.
17. apply as claimed in claim 16, it is characterized in that, the concentration of described siliceous organic compound is mass percent 0.01% ~ 0.5%.
18. apply as claimed in claim 1, it is characterized in that, the pH of described chemical mechanical polishing liquid is 1-7.
19. apply as claimed in claim 1, it is characterized in that, the pH of described chemical mechanical polishing liquid is 3-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310726697.6A CN104745082A (en) | 2013-12-25 | 2013-12-25 | Chemical mechanical polishing liquid and polishing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310726697.6A CN104745082A (en) | 2013-12-25 | 2013-12-25 | Chemical mechanical polishing liquid and polishing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104745082A true CN104745082A (en) | 2015-07-01 |
Family
ID=53585365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310726697.6A Pending CN104745082A (en) | 2013-12-25 | 2013-12-25 | Chemical mechanical polishing liquid and polishing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104745082A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111378379A (en) * | 2018-12-29 | 2020-07-07 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution and application thereof |
| CN112400005A (en) * | 2018-08-03 | 2021-02-23 | 霓达杜邦股份有限公司 | Polishing composition |
| US11560495B2 (en) | 2020-01-23 | 2023-01-24 | Samsung Sdi Co., Ltd. | CMP slurry composition for polishing tungsten pattern wafer and method of polishing tungsten pattern wafer using the same |
-
2013
- 2013-12-25 CN CN201310726697.6A patent/CN104745082A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112400005A (en) * | 2018-08-03 | 2021-02-23 | 霓达杜邦股份有限公司 | Polishing composition |
| CN111378379A (en) * | 2018-12-29 | 2020-07-07 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution and application thereof |
| CN111378379B (en) * | 2018-12-29 | 2022-08-05 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution and application thereof |
| US11560495B2 (en) | 2020-01-23 | 2023-01-24 | Samsung Sdi Co., Ltd. | CMP slurry composition for polishing tungsten pattern wafer and method of polishing tungsten pattern wafer using the same |
| TWI824226B (en) * | 2020-01-23 | 2023-12-01 | 南韓商三星Ｓｄｉ股份有限公司 | Cmp slurry composition and method of polishing tungsten pattern wafer using the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111363550A (en) | Selective etching liquid composition and preparation method and application thereof | |
| CN107207268A (en) | Modified colloidal sifica and its manufacture method and use its grinding agent | |
| JP6284443B2 (en) | Method for producing colloidal silica containing core-shell type silica particles | |
| CN103620747A (en) | Polishing composition | |
| CN108504288A (en) | Chemical mechanical planarization of films comprising elemental silicon | |
| CN104371553B (en) | A kind of chemical mechanical polishing liquid and application | |
| JP2014527298A5 (en) | ||
| JP3560484B2 (en) | Abrasive composition for polishing LSI devices and polishing method | |
| CN104745082A (en) | Chemical mechanical polishing liquid and polishing method | |
| TWI757349B (en) | Silica-based particles for polishing and abrasives | |
| CN104371549A (en) | Chemical mechanical polishing liquid for polishing low dielectric material | |
| CN104371550A (en) | Chemical mechanical polishing liquid for polishing silicon material | |
| CN106928856A (en) | A kind of acidic chemical machine polishing liquor | |
| CN102816530B (en) | A kind of chemical mechanical polishing liquid | |
| CN105802507A (en) | Chemico-mechanical polishing solution and application thereof | |
| CN101955732B (en) | A kind of chemical mechanical polishing liquid | |
| JP2020083736A (en) | Hollow silica particle and method for producing the same | |
| CN107686703A (en) | A kind of chemical mechanical polishing liquid | |
| CN102477260A (en) | Chemically mechanical polishing liquid | |
| JP2014130957A (en) | Polishing liquid composition for semiconductor substrate | |
| CN107686702A (en) | A kind of chemical mechanical polishing liquid for barrier layer planarization | |
| CN104745087A (en) | Chemical mechanical polishing solution and polishing method | |
| CN102464945A (en) | Chemically mechanical polishing solution | |
| CN104371551A (en) | Alkali barrier layer chemical mechanical polishing solution | |
| CN105802511A (en) | Chemical mechanical polishing liquid and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150701 |
|
| WD01 | Invention patent application deemed withdrawn after publication |