CN108410424A - The preparation method and application of lanthanide series metal doping cerium dioxide nano-abrasive - Google Patents
The preparation method and application of lanthanide series metal doping cerium dioxide nano-abrasive Download PDFInfo
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- CN108410424A CN108410424A CN201810440980.5A CN201810440980A CN108410424A CN 108410424 A CN108410424 A CN 108410424A CN 201810440980 A CN201810440980 A CN 201810440980A CN 108410424 A CN108410424 A CN 108410424A
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1436—Composite particles, e.g. coated particles
- C09K3/1445—Composite particles, e.g. coated particles the coating consisting exclusively of metals
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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
Abstract
The invention discloses the preparation method and application of lanthanide series metal doping cerium dioxide nano-abrasive, wherein preparation method includes：(1) water absorption rate of cerium dioxide nano powder is measured；(2) lanthanide metal nitrate solution is prepared, and incipient impregnation, ageing, drying, roasting and grinding are carried out to the cerium dioxide nano powder, to obtain the cerium dioxide nano abrasive grain of the lanthanide series metal doping.The cerium dioxide nano abrasive grain of lanthanide element doping not only can effectively be prepared using this method, and dielectric material is chemically-mechanicapolish polished using the cerium dioxide nano abrasive grain that the lanthanide element adulterates, higher material removal rate and surface of polished quality can be realized under low abrasive grain content, especially dielectric material can be made to have both higher polishing speed and surface quality under alkaline condition, to realize ideal chemically mechanical polishing effect.
Description
Technical field
The invention belongs to Material Fields, specifically, the present invention relates to lanthanide series metal doping cerium dioxide nano-abrasives
Preparation method and application.
Background technology
Ceria (CeO2) abrasive grain due to being chosen to remove characteristic with controllable dissimilar materials, is widely used in integrating
The CMP process of circuit media material.Compared to traditional silica (SiO2) and aluminium oxide (Al2O3) etc. mills
Grain, CeO2The maximum feature of abrasive grain is that have mechanical grinding effect and chemical reactivity simultaneously.CeO2It is arranged with fluorite type atom
Row, surface have Ce3+, and can be with Ce4+It mutually converts.CeO2The Ce on surface3+CeO can be improved2With dielectric material surface water
The interaction between layer is closed, it is specific to act on by taking the chemically mechanical polishing of SiO2 media as an example to significantly improve polishing speed
Principle is：Ce3+It can be with SiO2- the Si-OH on surface reacts, and forms Ce-O-Si keys.The intensity of Ce-O-Si keys is more than Si-
The intensity of O-Si keys, then surface layer SiO2With Si (OH)4Form enter in polishing fluid, it is real under chemistry and mechanical double action
Existing material removal.
However, CeO2Dispersing characteristic of the abrasive grain in water base polishing fluid be undesirable, is easy to generate in crystal column surface after polishing
Cut.CeO is improved at present2The main method of the CMP properties of abrasive grain be surface be modified, with improve charging characteristic and
Stability in solution, as patent CN106590442A is reported CeO2Powder be added silane based coupling agents compound with it is organic molten
To improve its stability in polishing slurries in the mixed solution of liquid, although the method for organo-functional group grafting can be to a certain degree
Upper improvement CeO2Dispersing characteristic in polishing fluid, but cannot be guaranteed the removal rate of dielectric material；Element doping is to CeO2Into
The modified preferable mode of row, but pure CeO2Defect of both having：Sintering affects the original construction of fluorite, stores the energy of oxygen
Power weakens significantly；Oxygen defect is few, and oxygen ion transport ability is weak.The doping of many types metal can accelerate Ce4+It is converted into Ce3 +.Patent CN101970347A reports use the bulk phase-doped CeO of metallic element yttrium2Particle can reduce the induction in polishing process
Ratio of defects.The bulk phase-doped CeO of metallic element2There is preferable application prospect in photocatalysis field, but since preparation process is easy to break
Bad CeO2Intrinsic crystal structure, thus be difficult to keep CeO2The good characteristic of abrasive grain, in CMP art by certain
Limitation.
According to the above analysis, we are desirable to the mode of lanthanide series metal surface doping, are not changing intrinsic crystal
On the basis of structure, CeO is improved2CMP properties (such as material removal rate, surface quality).It is mixed by adjusting
Miscellaneous technological parameter (such as doping method, element species, load capacity, calcination temperature) obtains while having higher chemical reaction
The CeO of active and preferable dispersing morphology2Abrasive grain.
Invention content
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, the present invention
One purpose is to propose the preparation method and application of lanthanide series metal doping cerium dioxide nano-abrasive.Not only may be used using this method
The cerium dioxide nano abrasive grain of lanthanide element doping is effectively prepared, and utilize lanthanide element doping
Cerium dioxide nano abrasive grain chemically-mechanicapolish polishes dielectric material, can realize that higher material is gone under low abrasive grain content
Removal rates and surface of polished quality, especially can make dielectric material have both higher polishing speed and surface matter under alkaline condition
Amount, to realize ideal chemically mechanical polishing effect.
According to the first aspect of the invention, the present invention proposes a kind of cerium dioxide nano abrasive grain of lanthanide series metal doping
Preparation method, including：
(1) water absorption rate of cerium dioxide nano powder is measured；
(2) lanthanide metal nitrate solution is prepared, and incipient impregnation, old is carried out to the cerium dioxide nano powder
Change, drying, roast and grind, to obtain the cerium dioxide nano abrasive grain of the lanthanide series metal doping.
The preparation method of the cerium dioxide nano abrasive grain of lanthanide series metal doping according to the above embodiment of the present invention, not only may be used
So that lanthanide element successfully loads on cerium dioxide nano powder, and consolidating for ceria ontology will not be substantially change
There are crystal structure and the excellent physical properties as abrasive grain, moreover it is possible to effectively improve the ceria after doping lanthanide element and receive
The trivalent cerium Ce of rice abrasive particle surface3+Content, and then significantly improve CeO2With the phase interaction between dielectric material surface hydration layer
With to significantly improve polishing speed, in addition, inventor also found, lanthanide series metal is adulterated simultaneously into cerium dioxide nano abrasive grain
The particle size of original cerium dioxide nano abrasive grain will not be changed.Use the preparation method of the above embodiment of the present invention not as a result,
The cerium dioxide nano abrasive grain of lanthanide element doping only can effectively be prepared, and mixed using the lanthanide element
Miscellaneous cerium dioxide nano abrasive grain can also chemically-mechanicapolish polish dielectric material under low abrasive grain content, and dielectric material is made to exist
Higher material removal rate and surface of polished quality may be implemented in polishing process, especially dielectric material can be made in alkaline item
Higher polishing speed and surface quality are had both under part, are prepared in sub- 10nm technology nodes integrated circuit fin formula field effect transistor
There is boundless application prospect in technique.
In addition, the preparation method of the cerium dioxide nano abrasive grain of lanthanide series metal doping according to the above embodiment of the present invention is also
There can be following additional technical characteristic：
In some embodiments of the invention, the lanthanide metal nitrate is selected from lanthanum nitrate hexahydrate, five hydration nitre
At least one of sour ytterbium and six nitric hydrate neodymiums.Thus, it is possible to keep at least one of lanthanide element lanthanum, neodymium and ytterbium negative
It is downloaded on cerium dioxide nano powder.
In some embodiments of the invention, the lanthanide series metal loaded in the cerium dioxide nano abrasive grain be selected from lanthanum,
At least one of neodymium and ytterbium.
In some embodiments of the invention, the load capacity of the lanthanide series metal is 1-10wt%.Thus, it is possible to further
Improve the trivalent cerium Ce of cerium dioxide nano abrasive particle surface3+Content, and then significantly improve CeO2With dielectric material surface hydration
Interaction between layer, to significantly improve the rate and surface quality that are chemically-mechanicapolish polished to dielectric material.
In some embodiments of the invention, the primary particle size of the cerium dioxide nano powder is not more than 50nm, purity
It is 99.95%.The excellent physical properties that not only ceria ontology can be kept intrinsic as a result, moreover it is possible to further increase preparation
The trivalent cerium Ce of the cerium dioxide nano abrasive particle surface of obtained lanthanide element doping3+Content, and then significantly improve
CeO2With the interaction between dielectric material surface hydration layer, to significantly improve polishing speed.
In some embodiments of the invention, a concentration of 0.23mol/L- of the lanthanide metal nitrate solution
2.9mol/L.Thus, it is possible to make the lanthanide element being finally prepared adulterate cerium dioxide nano abrasive grain in group of the lanthanides gold
The load capacity of category reaches 1-10wt%, to significantly improve the rate chemically-mechanicapolish polished to dielectric material and surface matter
Amount.
In some embodiments of the invention, in step (2), the ageing is that progress 12-24h is complete in confined conditions
At.The stability that lanthanide element loads on cerium dioxide nano abrasive grain can be not only further increased as a result, moreover it is possible to be had
Effect avoids the trivalent cerium Ce of cerium dioxide nano abrasive particle surface3+It is oxidized to Ce in air4+, and then influence finally to be prepared into
To lanthanide element doping characteristic of the cerium dioxide nano abrasive grain in chemically mechanical polishing.
In some embodiments of the invention, in step (2), the temperature of the drying is 100-150 DEG C.Thus, it is possible to
Further increase Drying Rates.
In some embodiments of the invention, in step (2), the roasting be after completing the drying, with 1-10 DEG C/
The heating rate of min is warming up to 400-600 DEG C and maintains 1-5h.The efficiency of calcination process can be not only significantly improved as a result,
The stability of the cerium dioxide nano abrasive grain for the lanthanide element doping being finally prepared can also be further increased and changed
Learn the characteristic in mechanical polishing.
According to the second aspect of the invention, the invention also provides a kind of cmp method, in this method, to
The preparation method that the cerium dioxide nano abrasive grain adulterated using the lanthanide series metal of the above embodiment of the present invention is added in polishing fluid is obtained
The cerium dioxide nano abrasive grain for the lanthanide series metal doping arrived.
Cmp method according to the above embodiment of the present invention, by the way that lanthanide series metal doping is added into polishing fluid
Cerium dioxide nano abrasive grain, dielectric material can be chemically-mechanicapolish polished under low abrasive grain content, and make dielectric material
Higher material removal rate and surface of polished quality are realized in polishing process, can especially make dielectric material in alkaline condition
Under have both higher polishing speed and surface quality, sub- 10nm technology nodes integrated circuit fin formula field effect transistor prepare work
There is boundless application prospect in skill.
In some embodiments of the invention, the addition of the lanthanide series metal doping cerium dioxide nano-abrasive is not more than
1wt%.Thus, it is possible to be chemically-mechanicapolish polished to dielectric material under low abrasive grain content, and realize higher material removal
Rate and surface of polished quality.
In some embodiments of the invention, the dielectric material of chemically mechanical polishing is silica, silicon nitride or carbonization
Silicon.Thus, it is possible to which the dielectric material after polishing is enable more preferably to be applied to integrated circuit.
Specific implementation mode
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, it is intended to for explaining this
Invention, and be not considered as limiting the invention.
According to the first aspect of the invention, the present invention proposes a kind of cerium dioxide nano abrasive grain of lanthanide series metal doping
Preparation method, including：
(1) water absorption rate of cerium dioxide nano powder is measured；(2) lanthanide metal nitrate solution is prepared, and to titanium dioxide
Cerium nano-powder carries out incipient impregnation, ageing, drying, roasting and grinding, to obtain the ceria of lanthanide series metal doping
Nano-abrasive.
The preparation method of the cerium dioxide nano abrasive grain of lanthanide series metal doping according to the above embodiment of the present invention, not only may be used
So that lanthanide element successfully loads on cerium dioxide nano powder, and consolidating for ceria ontology will not be substantially change
There are crystal structure and the excellent physical properties as abrasive grain, moreover it is possible to effectively improve the ceria after doping lanthanide element and receive
The trivalent cerium Ce of rice abrasive particle surface3+Content, and then significantly improve CeO2With the phase interaction between dielectric material surface hydration layer
With to significantly improve polishing speed, in addition, inventor also found, lanthanide series metal is adulterated simultaneously into cerium dioxide nano abrasive grain
The particle size of original cerium dioxide nano abrasive grain will not be changed.Use the preparation method of the above embodiment of the present invention not as a result,
The cerium dioxide nano abrasive grain of lanthanide element doping only can effectively be prepared, and mixed using the lanthanide element
Miscellaneous cerium dioxide nano abrasive grain can also chemically-mechanicapolish polish dielectric material under low abrasive grain content, and dielectric material is made to exist
Higher material removal rate and surface of polished quality may be implemented in polishing process, especially dielectric material can be made in alkaline item
Higher polishing speed and surface quality are had both under part, are prepared in sub- 10nm technology nodes integrated circuit fin formula field effect transistor
There is boundless application prospect in technique.
The preparation method of the cerium dioxide nano abrasive grain of the lanthanide series metal of the above embodiment of the present invention doping is carried out below
Detailed description.
According to a particular embodiment of the invention, lanthanide metal nitrate can be selected from La (NO3)3·6H2O (purity
99.99%), five nitric hydrate ytterbium Yb (NO3)3·5H2O (purity 99.9%) and six nitric hydrate neodymium Nd (NO3)3·6H2O is (pure
At least one of 99.9%), the lanthanide series metal loaded in cerium dioxide nano abrasive grain can be selected from lanthanum (La), neodymium (Nd) to degree
At least one of with ytterbium (Yb).Not only at least one of lanthanide element lanthanum, neodymium and ytterbium can be made successfully to bear as a result,
It is downloaded on cerium dioxide nano powder, and the intrinsic crystal structure of ceria ontology will not be substantially change and as abrasive grain
Excellent physical properties, moreover it is possible to improve the trivalent cerium Ce of the cerium dioxide nano abrasive particle surface after doping lanthanide element3+Contain
Amount, and then significantly improve CeO2With the interaction between dielectric material surface hydration layer, to significantly improve to dielectric material
The rate and surface quality chemically-mechanicapolish polished.
According to a particular embodiment of the invention, in the cerium dioxide nano abrasive grain of lanthanide series metal doping, lanthanide series metal is born
Carrying capacity can be 1-10wt%.Inventor has found that the load capacity by controlling lanthanide series metal is 1-10wt%, not only will not be apparent
Change the intrinsic crystal structure of ceria ontology and the excellent physical properties as abrasive grain, moreover it is possible to further increase doping group of the lanthanides
The trivalent cerium Ce of cerium dioxide nano abrasive particle surface after metallic element3+Content, and then significantly improve CeO2With dielectric material
Interaction between surface hydration layer, to significantly improve the rate chemically-mechanicapolish polished to dielectric material and surface matter
Amount.
According to a particular embodiment of the invention, in the cerium dioxide nano abrasive grain of lanthanide series metal doping, lanthanide series metal is born
Carrying capacity can be 1-5wt%.Thus, it is possible to it is substantially reduced the roughness on dielectric material surface after polishing, and further increasing
Learn the rate of mechanical polishing.
According to a particular embodiment of the invention, the primary particle size of cerium dioxide nano powder can be not more than 50nm, purity
Can be 99.95%.When adulterating lanthanide element into cerium dioxide nano powder as a result, titanium dioxide can be not only kept
The intrinsic excellent physical properties of cerium ontology, moreover it is possible to which the ceria for further increasing the lanthanide element doping being prepared is received
The trivalent cerium Ce of rice abrasive particle surface3+Content, and then significantly improve CeO2With the phase interaction between dielectric material surface hydration layer
With to significantly improve the rate and surface quality that are chemically-mechanicapolish polished to dielectric material.
According to a particular embodiment of the invention, the concentration of lanthanide metal nitrate solution can be 0.23mol/L-
2.9mol/L.Thus, it is possible to make the lanthanide element being finally prepared adulterate cerium dioxide nano abrasive grain in group of the lanthanides gold
The load capacity of category reaches 1-10wt%, to significantly improve the rate chemically-mechanicapolish polished to dielectric material and surface matter
Amount.
According to a particular embodiment of the invention, in step (2), ageing is progress 12-24h completions in confined conditions.By
This, can not only further increase the stability that lanthanide element loads on cerium dioxide nano abrasive grain, moreover it is possible to effectively keep away
Exempt from the trivalent cerium Ce of cerium dioxide nano abrasive particle surface3+It is oxidized to Ce in air4+, and then influence finally to be prepared
Characteristic of the cerium dioxide nano abrasive grain of lanthanide element doping in chemically mechanical polishing.
According to a particular embodiment of the invention, in step (2), the temperature of drying can be 100-150 DEG C.Thus, it is possible to
Further increase Drying Rates.
According to a particular embodiment of the invention, in step (2), roasting can be after completing to dry, with 1-10 DEG C/min's
Heating rate is warming up to 400-600 DEG C and maintains 1-5h.The efficiency of calcination process can be not only significantly improved as a result, moreover it is possible into
One step improves the stability of the cerium dioxide nano abrasive grain for the lanthanide element doping being finally prepared and in chemical machinery
Characteristic in polishing.
According to the second aspect of the invention, the invention also provides a kind of cmp method, in this method, to
The preparation method that the cerium dioxide nano abrasive grain adulterated using the lanthanide series metal of the above embodiment of the present invention is added in polishing fluid is obtained
The cerium dioxide nano abrasive grain for the lanthanide series metal doping arrived.
Cmp method according to the above embodiment of the present invention, by the way that lanthanide series metal doping is added into polishing fluid
Cerium dioxide nano abrasive grain, dielectric material can be chemically-mechanicapolish polished under low abrasive grain content, and make dielectric material
Higher material removal rate and surface of polished quality are realized in polishing process, can especially make dielectric material in alkaline condition
Under have both higher polishing speed and surface quality, sub- 10nm technology nodes integrated circuit fin formula field effect transistor prepare work
There is boundless application prospect in skill.
According to a particular embodiment of the invention, the cerium dioxide nano abrasive grain of lanthanide series metal doping is added into polishing fluid
Method is：A certain amount of abrasive grain is added in deionized water, ultrasonic disperse 20min, polishing fluid pH value is adjusted using KOH/HCl,
Polishing fluid is persistently stirred in CMP process using magnetic stirring apparatus.
According to a particular embodiment of the invention, the addition of lanthanide series metal doping cerium dioxide nano-abrasive is not in polishing fluid
More than 1wt%.Inventor's discovery, property of the cerium dioxide nano abrasive grain that lanthanide series metal adulterates in CMP process
Traditional silica abrasive grain, but also the trivalent cerium Ce on its surface can be not only better than3+Content be also apparently higher than pure ceria
Nano-abrasive can significantly improve CeO2With the interaction between dielectric material surface hydration layer, lanthanide series metal is utilized as a result,
The cerium dioxide nano abrasive grain of doping can chemically-mechanicapolish polish dielectric material under low abrasive grain content, and realize higher
Material removal rate and surface of polished quality；Further, inventor also found, when lanthanide series metal doping two in polishing fluid
The addition of cerium oxide nano abrasive grain is remarkably improved the speed chemically-mechanicapolish polished to dielectric material when being not more than 1wt%
Rate and surface quality.
According to a particular embodiment of the invention, chemical machinery is carried out using the cerium dioxide nano abrasive grain of lanthanide series metal doping
The dielectric material of polishing can be silica, silicon nitride or silicon carbide, thus, it is possible to significantly improve CMP process
Middle dielectric material removal rate and surface of polished quality enable the dielectric material after polishing to be more preferably applied to integrated circuit.
According to a particular embodiment of the invention, chemical machinery is carried out using the cerium dioxide nano abrasive grain of lanthanide series metal doping
Polishing preferably carries out under alkaline condition, thus, it is possible to make to have both higher polishing in dielectric material CMP process
Rate and surface quality.
Implementation below by way of specific embodiment the present invention will be described in detail scheme and possessed advantageous effect, but cannot be right
The present invention can practical range form any restriction.The person skilled in the art in the field is according to the content of aforementioned present invention to this hair
The bright nonessential modifications and adaptations of some made, still fall within protection scope of the present invention.
Conventional method：
(1) method of cerium dioxide nano abrasive grain for preparing lanthanide series metal doping is：Measure cerium dioxide nano powder
Water absorption rate；Lanthanide metal nitrate solution is prepared, and incipient impregnation, ageing, drying, roasting are carried out to cerium dioxide nano powder
It burns and grinds, to obtain the cerium dioxide nano abrasive grain of lanthanide series metal doping.
(2) it is by the method that polishing fluid is added in abrasive grain：A certain amount of abrasive grain is added in deionized water, ultrasonic disperse
20min adjusts polishing fluid pH value using KOH/HCl, and polishing fluid is continued in CMP process using magnetic stirring apparatus
Stirring (3) cmp method is：Dielectric material (being polished material) is prepared by chemical vapour deposition technique two inches
Silica wafers, using Universal-150 polishing machines, using Politex polishing pads, polish pressure 1-4psi, rubbing head/
Polishing disk rotating speed 100/100rpm polishes flow quantity 100mL/min, polishing time 1.5min.
Embodiment 1
Doping abrasive grain A-1 is prepared using equi-volume impregnating：Doped chemical lanthanum La, load capacity 1%, digestion time 12h dry
Dry 100 DEG C of temperature, 400 DEG C of calcination temperature, 5 DEG C/min of heating rate.
CMP process A-1-5 is：Content of the A-1 abrasive grains in polishing fluid is 0.25%, and polish pressure is
2psi, polishing fluid pH are 5.
CMP process A-1-9.5 is：Content of the A-1 abrasive grains in polishing fluid is 0.25%, and polish pressure is
2psi, polishing fluid pH are 9.5.
Embodiment 2
Doping abrasive grain A-5 is prepared using equi-volume impregnating：Doped chemical lanthanum La, load capacity 5%, digestion time 12h dry
Dry 100 DEG C of temperature, 400 DEG C of calcination temperature, 5 DEG C/min of heating rate.
CMP process A-5-5 is：Content of the A-5 abrasive grains in polishing fluid is 0.25%, and polish pressure is
2psi, polishing fluid pH are 5.
CMP process A-5-9.5 is：Content of the A-5 abrasive grains in polishing fluid is 0.25%, and polish pressure is
2psi, polishing fluid pH are 9.5.
Embodiment 3
Doping abrasive grain B-1 is prepared using equi-volume impregnating：Determination of Neodymium Doped Nd, load capacity 1%, digestion time 12h dry
Dry 100 DEG C of temperature, 400 DEG C of calcination temperature, 5 DEG C/min of heating rate.
CMP process B-1-5 is：Content of the B-1 abrasive grains in polishing fluid is 0.25%, and polish pressure is
2psi, polishing fluid pH are 5.
CMP process B-1-9.5 is：Content of the B-1 abrasive grains in polishing fluid is 0.25%, and polish pressure is
2psi, polishing fluid pH are 9.5.
Embodiment 4
Doping abrasive grain B-5 is prepared using equi-volume impregnating：Determination of Neodymium Doped Nd, load capacity 5%, digestion time 12h dry
Dry 100 DEG C of temperature, 400 DEG C of calcination temperature, 5 DEG C/min of heating rate.
CMP process B-5-5 is：Content of the B-5 abrasive grains in polishing fluid is 0.25%, and polish pressure is
2psi, polishing fluid pH are 5.
CMP process B-5-9.5 is：Content of the B-5 abrasive grains in polishing fluid is 0.25%, and polish pressure is
2psi, polishing fluid pH are 9.5.
Embodiment 5
Doping abrasive grain C-1 is prepared using equi-volume impregnating：Doped chemical ytterbium Yb, load capacity 1%, digestion time 12h dry
Dry 100 DEG C of temperature, 400 DEG C of calcination temperature, 5 DEG C/min of heating rate.
CMP process C-1-5 is：Content of the C-1 abrasive grains in polishing fluid is 0.25%, and polish pressure is
2psi, polishing fluid pH are 5.
CMP process C-1-9.5 is：Content of the B-5 abrasive grains in polishing fluid is 0.25%, and polish pressure is
2psi, polishing fluid pH are 9.5.
Embodiment 6
Doping abrasive grain C-5 is prepared using equi-volume impregnating：Doped chemical ytterbium Yb, load capacity 5%, digestion time 12h dry
Dry 100 DEG C of temperature, 400 DEG C of calcination temperature, 5 DEG C/min of heating rate.
CMP process C-5-5 is：Content of the C-5 abrasive grains in polishing fluid is 0.25%, and polish pressure is
2psi, polishing fluid pH are 5.
CMP process C-5-9.5 is：Content of the C-5 abrasive grains in polishing fluid is 0.25%, and polish pressure is
2psi, polishing fluid pH are 9.5.
Comparative example 1
Pure nano ceric oxide abrasive grain D.
CMP process D-5 is：Content of the D abrasive grains in polishing fluid is 0.25%, polish pressure 2psi, is thrown
Light liquid pH is 5.
Comparative example 2
Pure nano ceric oxide abrasive grain D.
CMP process D-9.5 is：Content of the D abrasive grains in polishing fluid be 0.25%, polish pressure 2psi,
Polishing fluid pH is 9.5.
Comparative example 3
Commercial ceria abrasive particles E.
CMP process E-5 is：Content of the E abrasive grains in polishing fluid is 0.25%, polish pressure 2psi, is thrown
Light liquid pH is 5.
Comparative example 4
Commercial ceria abrasive particles E.
CMP process E-9.5 is：Content of the E abrasive grains in polishing fluid be 0.25%, polish pressure 2psi,
Polishing fluid pH is 9.5.
Characterizing method：
(1) x-ray photoelectron spectroscopy is used to calculate Ce in prepared abrasive grain3+Content；
(2) size of abrasive grain primary particle size prepared by scanning electron microscopy measurement is used；
(3) material removal rate that sample is polished in CMP process is measured using film thickness measuring instrument；
(4) three-dimensional surface profile instrument is used to measure sample surfaces roughness Sa after polishing.
Wherein, the key property of abrasive grain is shown in Table 1, and CMP process the results are shown in Table 2.
The key property of 1 embodiment abrasive grain of table
| Product | A-1 | B-1 | C-1 | A-5 | B-5 | C-5 | D | E |
| Ce3+Content | 0.335 | 0.341 | 0.343 | 0.359 | 0.361 | 0.363 | 0.322 | |
| Primary particle size (nm) | 19.3 | 19.2 | 19.5 | 18.8 | 19.4 | 19.7 | 19.8 | 80.6 |
The main result of 2 embodiment CMP process of table
Conclusion：
From table 1 it follows that in the cerium dioxide nano abrasive grain of lanthanide series metal doping, Ce3+Content be apparently higher than it is pure
And cerium oxide abrasive grain, and adulterate the particle size that process does not change former cerium dioxide nano abrasive grain.
From Table 2, it can be seen that (1) under alkaline condition, uses lanthanide series metal compared with pure ceria abrasive particles nanometer
The cerium dioxide nano abrasive grain of doping can significantly improve the chemical-mechanical polishing rate of dielectric material；(2) with commercial titanium dioxide
Cerium abrasive grain is compared, and the cerium dioxide nano abrasive grain adulterated using lanthanide series metal can be substantially reduced the surface of dielectric material after polishing
Roughness obtains better surface quality.The cerium dioxide nano abrasive grain of the lanthanide series metal doping prepared as a result, using the present invention
It is more suitable for the polishing process of integrated circuit dielectric material.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be any
It can be combined in any suitable manner in a or multiple embodiments or example.In addition, without conflicting with each other, the technology of this field
The feature of different embodiments or examples described in this specification and different embodiments or examples can be combined by personnel
And combination.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (10)
1. a kind of preparation method of the cerium dioxide nano abrasive grain of lanthanide series metal doping, which is characterized in that including：
(1) water absorption rate of cerium dioxide nano powder is measured；
(2) lanthanide metal nitrate solution is prepared, and incipient impregnation, ageing, baking are carried out to the cerium dioxide nano powder
Dry, roasting and grinding, to obtain the cerium dioxide nano abrasive grain of the lanthanide series metal doping.
2. preparation method according to claim 1, which is characterized in that the lanthanide metal nitrate is selected from six hydration nitre
At least one of sour lanthanum, five nitric hydrate ytterbiums and six nitric hydrate neodymiums.
3. preparation method according to claim 2, which is characterized in that the group of the lanthanides loaded in the cerium dioxide nano abrasive grain
Metal is selected from least one of lanthanum, neodymium and ytterbium.
4. preparation method according to claim 3, which is characterized in that the load capacity of the lanthanide series metal is 1-10wt%.
5. preparation method according to claim 1, which is characterized in that the primary particle size of the cerium dioxide nano powder is not
More than 50nm, purity 99.95%.
6. preparation method according to claim 1, which is characterized in that the lanthanide metal nitrate solution it is a concentration of
0.23mol/L-2.9mol/L。
7. preparation method according to claim 1, which is characterized in that in step (2), the ageing is in confined conditions
12-24h completions are carried out,
Optionally, the temperature of the drying is 100-150 DEG C,
Optionally, the roasting is to be warming up to 400-600 DEG C simultaneously after completing the drying with the heating rate of 1-10 DEG C/min
Maintain 1-5h.
8. a kind of cmp method, which is characterized in that be added into polishing fluid using any one of claim 1-7 institute
The cerium dioxide nano abrasive grain for the lanthanide series metal doping that the preparation method stated obtains.
9. polishing method according to claim 8, which is characterized in that the lanthanide series metal doping cerium dioxide nano-abrasive
Addition be not more than 1wt%.
10. polishing method according to claim 8, which is characterized in that dielectric material is silica, silicon nitride or carbonization
Silicon.
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