CN109251679A - A kind of chemical mechanical polishing liquid - Google Patents
A kind of chemical mechanical polishing liquid Download PDFInfo
- Publication number
- CN109251679A CN109251679A CN201710570211.2A CN201710570211A CN109251679A CN 109251679 A CN109251679 A CN 109251679A CN 201710570211 A CN201710570211 A CN 201710570211A CN 109251679 A CN109251679 A CN 109251679A
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- China
- Prior art keywords
- chemical mechanical
- polishing
- mechanical polishing
- cerium oxide
- polishing liquid
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Classifications
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
Abstract
The present invention provides a kind of chemical mechanical polishing liquid, the chemical mechanical polishing liquid includes cerium oxide abrasives, oligosaccharide and pH adjusting agent.The present invention also provides a kind of application of chemical mechanical polishing liquid using above-mentioned formula in silica dioxide medium surface polishing.Using the chemical mechanical polishing liquid of above-mentioned formula, cerium oxide abrasives are significantly improved while being able to maintain low degree of imperfection to the polishing speed of silica dioxide medium material.
Description
Technical field
The present invention relates to chemical mechanical polishing liquid field more particularly to a kind of chemical mechanical polishing liquids containing oligosaccharide.
Background technique
Cerium oxide is a kind of important CMP polishing fluid abrasive material.Compared to traditional silica solution abrasive material, since cerium oxide is more efficient
Polishing characteristic, be widely used in the CMP polishing fluid of STI and LID.Currently, being used for the cerium oxide abrasives master of CMP planarization
Be divided into two kinds: one is traditional high-temperature roastings to synthesize cerium oxide powder, grinds by the cerium oxide that ball milling dispersion is prepared
Expect dispersion liquid；Another kind is the nano oxidized cerium abradant of colloidal sol type that hydrothermal synthesis is prepared.Two kinds of cerium oxide abrasives have not
Same polishing characteristic: the cerium oxide abrasives of conventional high-temperature roasting synthesis, which can pass through, adds pyridine carboxylic acid (picolinic acid)
Equal compounds improve it to the polishing speed of silica dioxide medium layer (see document: Carter et al., Electrochemical
And Solid-State Letter (vol 8 (8), page G218-G221, year 2005)；And for colloidal sol type cerium oxide
For, the addition of pyridine carboxylic acid cannot not only improve its polishing speed to silica dioxide medium layer, can inhibit cerium oxide instead
Polishing it is active (see case 1).Refer to different cerium oxide preparation methods to polishing activity and chemical compound to it in document
Difference is influenced (see document: Srinivasan et al., ECS Journal of Solid State Science and
Technology,4(11)P5029-P5039(2015))
However, technique fermentation proposes CMP planarization process as integrated circuit technique node is towards smaller szie development
Lower polishing defect requirement.Since the cerium oxide abrasives of conventional high-temperature roasting method synthesis are since particle is in multi-angular shape, CMP is thrown
Unavoidably generate Micro scratching in photoreduction process, therefore its CMP planarization requirement for being difficult to meet advanced process.And colloidal sol type cerium oxide is ground
Expect the granule-morphology with subcircular, there is good CMP planarization application prospect, more and more paid close attention to by people.Therefore,
It needs to provide a kind of using colloidal sol type cerium oxide as the chemical mechanical polishing liquid formula of abrasive material, had both been able to maintain existing colloidal sol type cerium oxide
The characteristic for the lower polishing defect that polishing fluid has, but the cerium oxide abrasives that can be realized the synthesis of conventional high-temperature roasting method have
High silica polishing speed.
Summary of the invention
In order to solve the problems, such as above-mentioned polishing speed, the present invention provides a kind of chemically mechanical polishings containing oligosaccharide
Liquid not only can ensure that with low polishing defect, but also can significantly improve to silica dioxide medium material using cerium oxide as abrasive material
The polishing speed of material.
The chemical mechanical polishing liquid includes cerium oxide abrasives, oligosaccharide and pH adjusting agent.
Preferably, the oligosaccharide is selected from glucan or beta-cyclodextrin.
Preferably, the cerium oxide abrasives include colloidal sol type cerium oxide.
Preferably, the partial size of the cerium oxide abrasives is 30nm-126nm.
Preferably, the concentration of the cerium oxide abrasives is mass percent 0.0.05wt%-2wt%.
Preferably, the molecular weight of the dextran molecule is 1500-70000, preferred molecular weight 20000.
Preferably, the concentration of the dextran molecule is 0.001wt%-1wt%, preferred concentration 0.02wt%.
Preferably, the pH value of the chemical mechanical polishing liquid is 3.5-5.5.
The invention also discloses a kind of application of chemical mechanical polishing liquid in silica dioxide medium surface polishing.
Compared with prior art, the positive effect of the present invention is that:
By adding dextran molecule in chemical mechanical polishing liquid, there can be low polishing defect, while can show again
It writes and improves cerium oxide abrasives to the polishing speed of TEOS.
The particle size that the present invention mentions is the same particle on the basis of Electronic Speculum, result and the light scattering of Electronic Speculum
(DLS) result is had any different, and see the table below:
| SEM (nanometer) | DLS (nanometer) |
| 25 | 83 |
| 45 | 110 |
| 60 | 163 |
Data are quoted from document: Pandija et al, " Effect of Ceria Size and Concentration in
Shallow Trench Isolation(STI)Chemical Mechanical Polishing(CMP)”in
International Conference on Planarization/CMP Technology·October 25–27,
2007Dresden,VDE VERLAG GMBH·Berlin-Offenbach
Specific embodiment
Below by specific embodiment, the advantages of the present invention are further explained, but protection scope of the present invention is not only limited to
In following embodiments.
Embodiment one
Table 1 is to add the chemical mechanical polishing liquid of pyridine carboxylic acid, ionic electrolyte and non-ionic electrolyte to dioxy
The influence of SiClx polishing speed.Wherein, the concentration of pyridine carboxylic acid is 0.01wt%-0.20wt%；Ionic electrolyte is respectively
Potassium nitrate (KNO3), potassium chloride (KCl), potassium acetate (KAc), tetramethyl ammonium acetate (TMAAc), tetramethyl butyric acid ammonium (TBAAc),
Concentration is 0.10wt%；Non-ionic electrolyte is respectively benzotriazole (BTA), triazole (TAZ), polyethylene glycol (PEG), second
Glycol (Ethylene glycol), mannitol (Mannitol), sorbierite (Sorbitol) and sucrose (Sucrose) and Portugal are poly-
Sugar.Corresponding colloidal sol type cerium oxide concentration is 1wt%, average grain diameter 60nm, with potassium hydroxide (KOH) or nitric acid (HNO3) adjust
Save pH to 4.5.Light liquid polishing performance is evaluated by the polish removal rate of corresponding TEOS blank wafer, selects Mirra polishing
Board carries out polishing test, and corresponding polishing condition includes: IC1010 polishing pad, chassis and rubbing head revolving speed be respectively 93rpm and
87rpm, pressure 3psi, polishing flow velocity are 150mL/min, and polishing time is 60 seconds.Comparative example corresponds to TEOS polishing speed
Rate is
Table 1 adds influence of the different component to TEOS polishing speed
As shown in table 1, by comparative example 1-6 it is found that the addition of pyridine carboxylic acid is active to the polishing of colloidal sol type cerium oxide
Influence increases with the increase of its concentration.Compared with blank embodiment, when the concentration of the pyridine carboxylic acid of addition is
When 0.2wt%, TEOS polishing speed decline 50% is corresponded to, only
In addition, by comparative example 7-11 it is found that the addition equally also throwing to colloidal sol type cerium oxide of ionic electrolyte
Optical speed produces significant inhibitory effect.In particular, when being added to potassium chloride (KCl) ionic electrolyte in polishing fluid, with
Blank embodiment is compared, and it is only to compare to implement that polishing fluid, which is inhibited by 54%, TEOS polishing speed to TEOS polishing speed,
The 46% of example.
By comparative example 1, comparative example 12-23 and embodiment it is found that the addition of non-ionic electrolyte is to colloidal sol
The polishing speed of cerium oxide can also generate certain inhibitory effect, but it influences to be much smaller than ionic electrolyte.However, exception
It is that dextran molecule but can further promote the polishing speed of colloidal sol cerium oxide as non-electrolyte.When being added in polishing fluid
After the dextran molecule of 0.01wt%, colloidal sol type cerium oxide increases 3% to the polishing speed of TEOS.
Embodiment two
Table 2 is that adjusting dextran molecule additive amount and molecular weight are advanced optimized on what colloidal sol cerium oxide polishing speed influenced
Research.By adjusting the additive amount and molecular weight of glucan in formula system, glucan has been advanced optimized to colloidal sol cerium oxide
The winding level of polishing speed.Polishing fluid polishing performance is evaluated by the polish removal rate of corresponding TEOS blank wafer, is selected
Polishing test is carried out with Mirra polishing machine platform, corresponding polishing condition includes: IC1010 polishing pad, chassis and rubbing head revolving speed point
Not Wei 93rpm and 87rpm, pressure 3psi, polishing flow velocity be 150mL/min, polishing time be 60 seconds.Table 3 is thrown to be prepared
The recipe ingredient of light liquid, corresponding colloidal sol type cerium oxide concentration is 1wt%, average grain diameter 60nm, with potassium hydroxide (KOH) or nitre
Acid (HNO3) pH to 4.5 is adjusted, the recipe ingredient for being not added with ionic electrolyte corresponds to TEOS polishing speed and is
Influence of the additive amount and molecular weight of 2 glucan of table to colloidal sol cerium oxide polishing speed
As shown in table 2, by comparative example and embodiment 1-4 it is found that when the dextran molecule amount of addition is identical (divides
When son amount is 20000), it is continuously increased the additive amount of glucan, content increases to 0.1wt% from 0.005wt%.Work as glucan
Content when being 0.02wt%, polishing fluid is the 118% of comparative example to the polishing speed highest of TEOS at this time.
By comparative example, embodiment 2 and embodiment 5-8 are it is found that when the dextran molecule content of addition is 0.02wt%
When, the molecular weight of glucan is adjusted in the range of 1500-70000, the polishing speed of colloidal sol cerium oxide is carried out further excellent
Change.When the molecular weight of glucan is 20000, the polishing fluid pair
The polishing speed highest of TEOS is the 118% of comparative example.
Embodiment three
Table 3 is that the identical molecular weight of polishing fluid addition containing various concentration, the colloidal sol cerium oxide abrasives of different-grain diameter is identical dense
What the dextran molecule colloidal sol cerium oxide polishing speed of degree influenced advanced optimizes research.In scheme, polishing fluid polishing performance is logical
The polish removal rate of corresponding TEOS blank wafer is crossed to evaluate, Mirra polishing machine platform is selected to carry out polishing test, corresponding polishing
Condition includes: IC1010 polishing pad, and chassis and rubbing head revolving speed are respectively 93rpm and 87rpm, and pressure 3psi polishes flow velocity
For 150mL/min, polishing time 60s.Selection concentration is 1wt% respectively and average grain diameter is 60nm, and concentration is 1wt% and puts down
Equal partial size is 90 nanometers and concentration is 0.25wt% and 126 nanometers of average grain diameter of three groups of colloidal sol cerium oxide abrasives are used as evaluation pair
As adding 0.02wt% glucan (molecular weight 20000).
Influence of 3 dextran molecule of table to the colloidal sol type cerium oxide polishing speed of different-grain diameter size, different content
As shown in Table 3, dextran molecule has a versatility to the improvement of colloidal sol type cerium oxide polishing speed, and not only office
It is limited to the colloidal sol cerium oxide abrasives with fixed average grain diameter and content.When the pH value of polishing fluid is 3.5-5.5, colloidal sol type oxidation
The average grain diameter of cerium abradant is 60-126nm, and when content is 0.05-2.00wt%, it is poly- that a certain amount of Portugal is added into polishing fluid
Glycan molecule can significantly improve colloidal sol type cerium oxide to the polishing speed of silica.Wherein, putting down when cerium oxide sol abrasive material
Equal partial size is 126nm, when content is 0.25wt%, adds the dextran molecule that molecular weight is 20000 and concentration is 0.02wt%
Afterwards, polishing fluid improves 52% compared with the polishing fluid for being not added with dextran molecule to the grinding rate of silica.
Example IV
Glucan is further illustrated to the improvement performance of cerium oxide polishing speed, research compares different polish pressure conditions
Improvement of the lower glucan to reply cerium oxide polishing speed.In the present solution, Mirra polishing machine platform is selected to carry out polishing test, it is right
Answering polishing condition includes: IC1010 polishing pad, and chassis and rubbing head revolving speed are respectively 93rpm and 87rpm, pressure 1.5psi,
2psi, 3psi, 4psi and 5psi, polishing flow velocity are 150mL/min, polishing time 60s.Choosing partial size is 60 nanometers molten
Glue cerium oxide abrasives are 200ppm as evaluation object, the additive amount of glycan (molecular weight 20000).With potassium hydroxide (KOH)
Or nitric acid (HNO3) adjust pH to 4.5.As a result it is listed in table 4.
Influence evaluation of 4 glucan of table to various concentration colloidal sol type cerium oxide polishing speed
Table 4 the result shows that, no matter under what polish pressure condition and cerium oxide abrasives concentration, added in polishing fluid
Glucan is all significantly increased to the polishing speed of silica (TEOS), and the degree of raising is from 5% to 50%.In embodiment 3,
When cerium oxide abrasives are 1.5%, under the conditions of polish pressure is 4psi, 0.02% glucan, throwing of the polishing fluid to TEOS are added
Optical speed can improve 50% compared with comparative example 3.
In conclusion compared to the addition of pyridine carboxylic acid, ionic electrolyte and other non-ionic electrolyte, when with
It, not only will not be to the polishing speed of cerium oxide abrasives after cerium oxide is adds dextran molecule in the chemical mechanical polishing liquid of abrasive material
Inhibiting effect is generated, its polishing speed to silica can be improved instead.To the content and molecular weight of the dextran molecule
Selection advanced optimized, it is known that, be 20000 and glucan that content is 0.02wt% when adding molecular weight in polishing fluid
When, cerium oxide abrasives silica may be implemented the polishing speed optimized.In addition, provided by the present invention be with cerium oxide
The polishing fluid of abrasive material has versatility to the cerium oxide of different average grain diameters, different content.It is being 30- containing average grain diameter
126nm, and a certain amount of dextran molecule is added in polishing fluid of the content for the cerium oxide abrasives of 0.05-2.00wt%, it can
Significantly improve its grinding rate to silica.Chemical mechanical polishing liquid provided by the present invention as a result, is with cerium oxide
Abrasive material can be applied to significantly improve polishing of the cerium oxide abrasives to silica dioxide medium material after adding dextran molecule
Rate provides a kind of scheme of optimization for the polishing speed problem of cerium oxide abrasives.
It should be noted that the embodiment of the present invention has preferable implementation, and not the present invention is made any type of
Limitation, any one skilled in the art change or are modified to possibly also with the technology contents of the disclosure above equivalent effective
Embodiment, as long as without departing from the content of technical solution of the present invention, it is to the above embodiments according to the technical essence of the invention
Any modification or equivalent variations and modification, all of which are still within the scope of the technical scheme of the invention.
Claims (12)
1. a kind of chemical mechanical polishing liquid, which is characterized in that include cerium oxide abrasives, oligosaccharide and pH adjusting agent.
2. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the oligosaccharide is selected from dextran molecule or β-
Cyclodextrin.
3. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the oligosaccharide is dextran molecule.
4. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the cerium oxide abrasives are aoxidized comprising colloidal sol type
Cerium.
5. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the partial size of the cerium oxide abrasives is 30nm-
126nm。
6. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the concentration of the cerium oxide abrasives is quality hundred
Divide and compares 0.05%-2wt%.
7. chemical mechanical polishing liquid as claimed in claim 3, which is characterized in that the molecular weight of the dextran molecule is
1500-70000。
8. chemical mechanical polishing liquid as claimed in claim 7, which is characterized in that the molecular weight of the dextran molecule is
20000。
9. chemical mechanical polishing liquid as claimed in claim 3, which is characterized in that the concentration of the dextran molecule is
0.001%-1wt%.
10. chemical mechanical polishing liquid as claimed in claim 9, which is characterized in that the concentration of the dextran molecule is
0.02wt%.
11. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the pH value of the chemical mechanical polishing liquid is
3.5-5.5。
12. a kind of if the described in any item chemical mechanical polishing liquids of claim 1-11 are in silica dioxide medium surface polishing
Using.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710570211.2A CN109251679A (en) | 2017-07-13 | 2017-07-13 | A kind of chemical mechanical polishing liquid |
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| CN201710570211.2A CN109251679A (en) | 2017-07-13 | 2017-07-13 | A kind of chemical mechanical polishing liquid |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101457127A (en) * | 2007-12-14 | 2009-06-17 | 安集微电子（上海）有限公司 | Chemico-mechanical polishing liquid |
| CN102757081A (en) * | 2012-07-25 | 2012-10-31 | 西安交通大学 | Synthesis method of cerium oxide hydrosol dispersed by PVA (Polyvinyl Alcohol) |
| CN102952466A (en) * | 2011-08-24 | 2013-03-06 | 安集微电子（上海）有限公司 | Chemical-mechanical polishing liquid |
| KR101524625B1 (en) * | 2013-12-13 | 2015-06-03 | 주식회사 케이씨텍 | Cmp slurry composition having automatic polishing stop function |
| CN105802506A (en) * | 2014-12-29 | 2016-07-27 | 安集微电子（上海）有限公司 | Chemico-mechanical polishing solution |
-
2017
- 2017-07-13 CN CN201710570211.2A patent/CN109251679A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101457127A (en) * | 2007-12-14 | 2009-06-17 | 安集微电子（上海）有限公司 | Chemico-mechanical polishing liquid |
| CN102952466A (en) * | 2011-08-24 | 2013-03-06 | 安集微电子（上海）有限公司 | Chemical-mechanical polishing liquid |
| CN102757081A (en) * | 2012-07-25 | 2012-10-31 | 西安交通大学 | Synthesis method of cerium oxide hydrosol dispersed by PVA (Polyvinyl Alcohol) |
| KR101524625B1 (en) * | 2013-12-13 | 2015-06-03 | 주식회사 케이씨텍 | Cmp slurry composition having automatic polishing stop function |
| CN105802506A (en) * | 2014-12-29 | 2016-07-27 | 安集微电子（上海）有限公司 | Chemico-mechanical polishing solution |
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