CN109312213A - Lapping liquid, chemical and mechanical grinding method - Google Patents
Lapping liquid, chemical and mechanical grinding method Download PDFInfo
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- CN109312213A CN109312213A CN201780034712.7A CN201780034712A CN109312213A CN 109312213 A CN109312213 A CN 109312213A CN 201780034712 A CN201780034712 A CN 201780034712A CN 109312213 A CN109312213 A CN 109312213A
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- China
- Prior art keywords
- lapping liquid
- acid
- grinding
- mass
- concentration
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
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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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- 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
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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
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
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- 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
Abstract
The issue of the present invention is to provide a kind of to be not likely to produce the lapping liquid and chemical and mechanical grinding method of defect in the case where being used in CMP on being ground body.Lapping liquid of the invention is the lapping liquid being used in chemical mechanical grinding, and in the lapping liquid, containing abrasive grains and organic acid and Ca concentration is 100 mass ppt or less.
Description
Technical field
The present invention relates to a kind of lapping liquids and chemical and mechanical grinding method being used in chemical mechanical grinding.
Background technique
In the exploitation of semiconductor equipment, in order to minimize and high speed, require in recent years miniaturization based on wiring and
The densification of stackingization and highly integrated.As the technology for realizing the requirement, chemical mechanical grinding (Chemical is utilized
Mechanical Polishing, hereinafter, being denoted as " CMP ".) etc. various technologies.The CMP is added in progress interlayer dielectric etc.
Required technology in the case where surface planarisation, formation that embolism is formed or metal is sunken cord of work film etc. is being ground the flat of body
The extra barrier layer on extra metallic film or removal insulating film is removed when cunningization, wiring formation.
The usual way of CMP is on grinding pad to be attached to circular abrasive platform (platen), to soak grinding pad surface
Stain presses on the surface for being ground body on pad in lapping liquid, applies the shape of defined pressure (grinding pressure) from its back side
Under state, both make grinding plate and be ground body to be rotated, by generated mechanical friction to the surface for being ground body
It is planarized.
As lapping liquid, such as record that " a kind of chemical mechanical grinding constituent, contains: (a) in patent document 1
Silicon dioxide granule；It (b) is about 5 × 10 selected from including relative to the total weight of grinding composite-3To about 10 mMs/kg's
Calcium, strontium, barium and their mixture group at least one kind of alkaline-earth metal；(c) about 0.1 to about 15wt% oxidant；And
(d) comprising liquid-carrier made of water, and the pH with about 7 to about 13.".If by grinding group documented in patent document 1
It converts at the alkaline-earth metal amount such as calcium in object, is then equivalent to 0.2ppm~400ppm.
Conventional art document
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2011-159998 bulletin
Summary of the invention
The invention technical task to be solved
The present inventor uses grinding composite as recorded in Patent Document 1, implements silicon oxide film or silicon nitride film
The various quilts such as the substrate that equal inorganic insulating membranes, the film for mainly containing polysilicon, Al, Cu, Ti, TiN, W, Ta or TaN etc. are formed a film
The CMP's as a result, knowing being ground and generate more defect on body after grinding of abrasive body.It is carried out in detail for the defect
Research as a result, specifying that its major part is caused by the attachment of residue and scratch (grinding scratch).
Moreover, being attached to the residue being ground on body after grinding, major part contains calcium, on the other hand also specifies,
May be included in the abrasive grains in lapping liquid, for example, used silicon dioxide granule or cerium oxide particles etc. by negatively charged
In the case where the abrasive grains that metal oxide is constituted, more calcium is contained in liquid, is ground to being ground body and implementing chemical machinery
Scratch (grinding scratch) when mill generates more significantly.
Then, the issue of the present invention is to provide one kind is not likely to produce on being ground body in the case where being used in CMP
The lapping liquid of defect.
Also, project of the invention, which also resides in, provides a kind of chemical and mechanical grinding method for having used above-mentioned lapping liquid.
The inventors of the present invention carry out the result of in-depth study to realize the above subject, it was found that specific by having
It forms and reduces the lapping liquid of the concentration of calcium included in liquid and be able to solve the above subject, and complete the present invention.
I.e., it was found that can be realized above-mentioned purpose and with flowering structure.
(1) a kind of lapping liquid is the lapping liquid being used in chemical mechanical grinding,
In the lapping liquid, containing abrasive grains and organic acid, and Ca concentration is 100 mass ppt or less.
(2) lapping liquid according to (1), wherein
In lapping liquid, the content of the metallic found out by SNP-ICP-MS measurement is 100 mass ppt or less.
(3) lapping liquid according to (1) or (2), also contains charge regulating agent,
The content of above-mentioned charge regulating agent relative to the content of above-mentioned organic acid be by quality ratio 0.6 hereinafter,
Above-mentioned Ca concentration is 0.01~100 mass ppt.
(4) lapping liquid according to any one of (1) to (3), wherein
Above-mentioned Ca concentration is 0.01~80 mass ppt.
(5) lapping liquid according to any one of (1) to (4), wherein above-mentioned organic acid contains selected from including the third two
Acid, succinic acid, malic acid and citric acid group in polyacid.
(6) lapping liquid according to any one of (1) to (5), wherein model of the pH 1.5~5.0 or 9.0~12.0
It encloses.
(7) lapping liquid according to any one of (3) to (6), wherein as above-mentioned charge regulating agent, containing being selected from
The ammonium salt of inorganic acid or its ammonium salt or organic acid in group including nitric acid, boric acid and phosphoric acid.
(8) a kind of chemical and mechanical grinding method comprising following process: to the grinding pad for being installed on grinding plate, on one side
The lapping liquid as described in any one of (1) to (7) is supplied, contacts the surface to be polished for being ground body with above-mentioned grinding pad,
Above-mentioned abrasive body and above-mentioned grinding pad is set to relatively move and grind above-mentioned surface to be polished, to obtain ground being ground body.
Invention effect
In accordance with the invention it is possible to provide one kind in the case where being used in CMP, defect is not likely to produce in surface to be polished
Lapping liquid.
Also, in accordance with the present invention it is further possible to provide a kind of chemical and mechanical grinding method for having used above-mentioned lapping liquid.
[embodiment]
Hereinafter, being described in detail to the present invention.
The explanation of documented constitutive requirements is completed sometimes according to representative embodiment of the invention below, but this
Invention is not defined to those embodiments.
In addition, in the present specification, the numberical range indicated with "~", which refers to, makees the numerical value being recorded in front of and after "~"
For lower limit value and upper limit value including range.
In the label of group (atomic group) in the present specification, substitution and unsubstituted label are not recorded, are not damaging this
It also include without substituent group and with the group of substituent group in the range of invention effect.Such as " alkyl " not only includes not having
The alkyl (unsubstituted alkyl) of substituted base, but also including the alkyl (replacing alkyl) with substituent group.This is in each compound
Middle meaning is also identical.
Also, in the present specification, refer to when referred to as " preparing ", except through synthesizing or prepare specific material etc. and
It further include that defined substance is obtained by purchase etc. other than being prepared.
Also, in the present specification, " ppm " refers to " parts per million parts-per-million (10-6) ", and " ppt " is
Refer to " parts per million parts-per-trillion (10-12) ".
Also, in the present invention, 1psi is equivalent to 6894.76Pa.
(lapping liquid)
Lapping liquid of the invention includes abrasive grains and organic acid, and Ca concentration (calcium concentration) is 100 mass ppt or less.
There is lapping liquid of the invention above structure therefore in the case where being used in CMP, to be not easy on being ground body
Generate defect.
Its detailed reason is unclear, but can speculate as follows.
The notable feature of lapping liquid of the invention is to be purified in its preparation process, until by ion exchange and/
Or filtering etc. and Ca concentration become 100 mass ppt or less.
By features described above, calcium is able to suppress as core and forms particle, and be able to suppress calcium and be attached to as residue
It is ground on body.Also, if calcium (in particular, ionic calcium) is largely contained in liquid, because of the silica as abrasive grains
The negative electrical charge of the particle peripheries such as particle is neutralized and zeta current potential reduces, it is believed that is easy to produce the mutual cohesion of particle.However, logical
The cohesion for being set as above structure and being not likely to produce particle is crossed, as a result, can inhibit to grind to being ground body and implement chemical machinery
Scratch (grinding scratch) when mill.
Also, organic acid is complexed to be formed with above-mentioned free calcium ion, reduces the amount of free calcium ion.As a result, energy
Enough further suppress the cohesion of particle.
In addition, the adjustment of the Ca concentration based on ion exchange or filtering etc., can make in the preparation process of lapping liquid
Solvent or material composition are implemented, and can also implement to the lapping liquid after preparation.
It is excellent in lapping liquid according to the viewpoint for being not likely to produce defect on being ground body when lapping liquid is used in CMP
Select Ca concentration be 80 mass ppt hereinafter, more preferable 50 mass ppt hereinafter, further preferred 45 mass ppt hereinafter, particularly preferably
25 mass ppt or less.Also, there is no particular limitation for its lower limit, according to the viewpoint for improving defect performance, preferably 0.01 mass
Ppt or more.
In addition, in the present specification, Ca concentration refer to the ionic calcium being contained in lapping liquid and nonionic calcium (such as
Calcium particle) total concentration in other words refer to the content for the calcium atom being contained in lapping liquid.
Also, " lapping liquid " refers in the present specification, not only includes being used in grinding as long as meeting above-mentioned Ca concentration
When lapping liquid (that is, the lapping liquid being diluted as needed), and the concentrate including lapping liquid.Concentrate is concentrated
Lapping liquid refer to, compared with lapping liquid when being used in grinding, be prepared to the higher lapping liquid of concentration of dissolved matter, be
The lapping liquid for being used in grinding is diluted when being used in grinding by water or aqueous solution etc..Dilution ratio is usually 1~
20 volumes times.In the present specification, " concentration " and " concentrate " and not according to use state but according to expression " sticky " " glue
The usual performance of thick liquid " and use, with from evaporation etc. the meaning of usual term of concentration operation of physics it is different
Usage and use.
Hereinafter, the liquid property and each ingredient to lapping liquid of the invention are described in detail.
< pH >
In general, the pH of above-mentioned lapping liquid is 1.0~14.0, can suitably be set by the material for being ground body.
For example, preferably pH is 9.0~12.0 in the case where grinding object is metal layer as be described hereinafter.Due to pH be 9.0 with
On, therefore surface to be polished is activated, and becomes the state for being easier to be ground, since pH is 12.0 hereinafter, therefore colloidal silica
A possibility that abrasive grains such as silicon are chemically dissolved with the help of a suitable solvent reduction.
Also, such as in the case where grinding object is the inorganic semiconductor layers such as inorganic insulation layer as be described hereinafter or polysilicon,
It is preferred that pH is 1.5~5.0.Since pH is 1.5 or more, the corrosion of various parts relevant to grinding device is prevented, due to
PH is 5.0 hereinafter, therefore surface to be polished is activated, and becomes the state for being easier to be ground.
< abrasive grains >
Above-mentioned lapping liquid contains abrasive grains.
It as above-mentioned abrasive grains, is not particularly limited, and is able to use well known abrasive grains.
As abrasive grains, it can be cited for example that silica, aluminium oxide, zirconium oxide, cerium oxide, titanium dioxide, germanium oxide
And the inorganic matters abrasive grains such as silicon carbide；The organic matters abrasive grains such as polystyrene, polyacrylic acid and polyvinyl chloride.Wherein, according to grinding
The excellent viewpoint of dispersion stabilization and the viewpoint few by the quantity of the CMP scratch generated in grinding fluid, preferably silicon dioxide granule
Or cerium oxide particles are as abrasive grains, more preferable silicon dioxide granule.
It as silicon dioxide granule, is not particularly limited, for example, precipitated silica, fumed silica
And colloidal silicon dioxide etc..Wherein, preferred colloidal silicon dioxide.
The average primary particle diameter of abrasive grains is not particularly limited, but has superior dispersion stabilization according to lapping liquid
Viewpoint, preferably 1~100nm.In addition, above-mentioned average primary particle diameter can be confirmed by the catalogue etc. of manufacturer.
As the commercially available product of above-mentioned abrasive grains, for example, as colloidal silicon dioxide can enumerate PL-1, PL-3, PL-7 and
PL-10H etc. (being product name, FUSO CHEMICAL CO., LTD. manufacture).
Content as abrasive grains is not particularly limited, relative to lapping liquid gross mass, preferably 0.01 mass % or more,
More preferable 0.1 mass % or more, preferably 10 mass % are hereinafter, more preferable 5 mass % or less.If within the above range, inciting somebody to action
In the case that lapping liquid is used in CMP, superior grinding rate can be obtained.
In addition, abrasive grains can be used alone or two or more kinds may be used.In the abrasive grains being used in combination of two or more
In the case of, preferably total content is within the above range.
< organic acid >
Above-mentioned lapping liquid contains organic acid.Organic acid is different from the compound of aftermentioned oxidant, has the oxygen for promoting metal
Change, the pH of lapping liquid adjustment, the absorption (as absorption shape, preferably coordinate bond) of ionic calcium included in liquid and
Effect as buffer.
As organic acid, preferably water-soluble organic acid.
It as organic acid, is not particularly limited, is able to use well known organic acid.
As organic acid, it can be cited for example that formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-Methyl Butyric Acid, n-caproic acid, 3,
3- acid dimethyl, 2 Ethylbutanoic acid, 4- methylvaleric acid, positive enanthic acid, 2 methyl caproic acid, caprylic acid, 2 ethyl hexanoic acid, benzene first
Acid, glycolic, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, adjacent benzene two
Formic acid, malic acid, tartaric acid, citric acid, lactic acid, hydroxyethylamino-diacetic acid, imido oxalic acid and their ammonium salt
And/or the salt such as alkali metal salt.Wherein, the sequestering superior viewpoint of the ionic calcium according to included in liquid is preferably more
First acid or its salt, are more preferably selected from the polyacid of malonic acid, succinic acid, malic acid and citric acid.
As the content of organic acid, be not particularly limited, relative to lapping liquid gross mass, preferably 0.001 mass % with
On, more preferable 0.01 mass % or more, further preferred 0.1 mass % or more, preferably 25 mass % are hereinafter, more preferable 20 matter
% is measured hereinafter, further preferred 10 mass % or less.
If the content of organic acid is 0.001 mass % or more, in the case where lapping liquid is used in CMP, can get
Superior grinding rate, moreover, the generation of defect can be further suppressed.If also, the content of organic acid is 25 mass %
Hereinafter, being less also easy to produce recess in surface to be polished then in the case where lapping liquid is used in CMP.
In addition, organic acid can be used alone or two or more kinds may be used.In the organic acid being used in combination of two or more
In the case of, preferably total content is within the above range.
< charge regulating agent >
Above-mentioned lapping liquid preferably comprises charge regulating agent.Charge regulating agent has such as titanium dioxide of the adjustment as abrasive grains
Silicon particle or the surface charge of cerium oxide particles are to inhibit the function of the mutual cohesion of particle.
As charge regulating agent, there is no particular limitation, according to the viewpoint for being easy to build up on the surface of each particle, preferably selects
From the ammonium salt of inorganic acid or its ammonium salt or organic acid in the group including nitric acid, boric acid and phosphoric acid.
As the inorganic acid or its ammonium salt in the group including nitric acid, boric acid and phosphoric acid, wherein preferred nitric acid or nitric acid
Ammonium.Also, as the ammonium salt of organic acid, the ammonium salt of above-mentioned organic acid can be enumerated, wherein preferred ammonium benzoate.
It in the case where above-mentioned lapping liquid contains charge regulating agent, as its content, is not particularly limited, will grind
When liquid is used in CMP, according to the viewpoint for being less also easy to produce defect on being ground body, relative to lapping liquid gross mass, preferably 3 matter
Measure % hereinafter, more preferable 1 mass % hereinafter, further preferred 0.5 mass % hereinafter, particularly preferred 0.05 mass % or less.And
And there is no particular limitation for lower limit, preferably 0.0001 mass % or more.
Also, when lapping liquid is used in CMP, according to the viewpoint for being less also easy to produce defect on being ground body, charge
The content of regulator relative to organic acid content by quality ratio, preferably 0.6 hereinafter, more preferable 0.3 hereinafter, further preferably
0.1 hereinafter, particularly preferred 0.03 hereinafter, most preferably 0.001 or less.Also, there is no particular limitation for its lower limit, and preferably 0.0001
More than.
In addition, charge regulating agent can be used alone or two or more kinds may be used.In the charge being used in combination of two or more
In the case where regulator, preferably total content is within the above range.
< oxidant >
In the case where the CMP purposes of extra metallic film of the above-mentioned lapping liquid when being used in removal wiring formation etc.,
Preferably comprise oxidant.There is oxidant the metal as grinding object that will be present in the surface to be polished for being ground body to carry out oxygen
The function of change.
It is not particularly limited as oxidant, is able to use well known oxidant.
As oxidant, it can be cited for example that hydrogen peroxide, peroxide, nitric acid, nitrate, iodate, periodates,
Hypochlorite, chlorite, chlorate, perchlorate, persulfate, bichromate, weight manganate, Ozone Water, silver (II) salt
And iron (III) salt etc..Wherein, preferred hydrogen peroxide.
In the case where above-mentioned lapping liquid contains oxidant, it is not particularly limited as its content, relative to lapping liquid
Gross mass, preferably 0.005 mass % or more, more preferable 0.01 mass % or more, preferably 10 mass % are hereinafter, more preferable 5 matter
% is measured hereinafter, further preferred 3 mass % or less.
If the content of oxidant is that 0.005 mass % or more can be obtained in the case where lapping liquid is used in CMP
Obtain superior grinding rate.If oxidant content be 10 mass % hereinafter, if the case where lapping liquid is used in CMP
Under, recess is less also easy to produce in surface to be polished.
In addition, oxidant can be used alone or two or more kinds may be used.In the oxidant being used in combination of two or more
In the case of, preferably total content is within the above range.
< azole compounds >
In the case where the CMP purposes of extra metallic film of the above-mentioned lapping liquid when being used in removal wiring formation etc.,
Preferably comprise azole compounds.Azole compounds are not only improved based on the above-mentioned any ingredient i.e. oxidation of oxidant, but also
It is adsorbed in and is ground body surface face and forms epithelium, and control the corrosion of metal surface, therefore be able to suppress the production of recess or corrosion
It is raw.
In the present specification, azole compounds refer to the compound of the five-ring heterocycles containing the nitrogen-atoms comprising 1 or more,
As nitrogen-atoms numbers, preferably 1~4.Also, azole compounds can also contain the atom other than nitrogen-atoms as miscellaneous original
Son.
Also, said derivative refers to the compound of the substituent group contained with above-mentioned five-ring heterocycles.
As above-mentioned azole compounds, it can be cited for example that having pyrrole skeleton, imidazole skeleton, pyrazol framework, isothiazole
Skeleton, isoxazole skeleton, triazole skeleton, tetrazole skeleton, thiazole skeleton, oxazole skeleton, thiadiazoles skeleton, oxadiazoles skeleton and
The compound etc. of tetrazole skeleton.
As above-mentioned azole compounds, can be includes the also azole of the multiring structure containing condensed ring on above-mentioned skeleton
Compound.As the azole compounds for containing above-mentioned multiring structure, it can be cited for example that having indoles skeleton, purine skeleton, Yin
Azoles skeleton, benzimidazole skeleton, carbazole skelton, benzoxazoles skeleton, benzothiazole skeleton, diazosulfide skeleton and naphtho- miaow
The compound etc. of azoles skeleton.
It as the substituent group that azole compounds contain, is not particularly limited, it can be cited for example that (fluorine is former for halogen atom
Son, chlorine atom, bromine atom or iodine atom), (straight chain, branch or cyclic alkyl can be multi-ring alkyl such as bicyclic alkyl to alkyl
Or may include active methylene), alkenyl, alkynyl, aryl, heterocycle (arbitrary the position of substitution), acyl group, alkoxy carbonyl group, virtue
Oxygen carbonyl, heterocycle oxygen carbonyl, carbamoyl are (as the carbamoyl with substituent group, it can be cited for example that N- hydroxyl ammonia
Base formoxyl, N- acylcarbamoyl base, N- sulfuryl amino formoxyl, N- carbamoylamino formoxyl, sulfo-amino first
Acyl group and N- sulfamoylamino group formoxyl etc..), carbazyl, carboxyl or its salt, oxalyl group, oxamoyl base, cyano, carbon imido grpup,
Formoxyl, hydroxyl, alkoxy (comprising inferior ethoxyl or using inferior ethoxyl as repetitive unit and comprising group), aryloxy group,
It is heterocyclic oxy group, acyloxy, carbonyl oxygroup, carbamoyloxy, sulfonyloxy, amino, acylamino-, sulfoamido, urea groups, thio
Base, N- hydroxyl urea groups, imide, carbonylamino, sulfamoylamino group, amino urea groups, sulfo-amino urea groups, diazanyl, ammonium, grass
Aminoacyl amino, N- (alkyl or aryl) sulfonylurea group, N- acyl group urea groups, N- acyl sulfonamide amino, hydroxyl amino, nitro, packet
Heterocycle (it can be cited for example that pyridyl group, imidazole radicals, quinolyl and isoquinolyl), isocyano group, imido grpup containing quaternary nitrogen atoms,
Sulfydryl, (alkyl, aryl or heterocycle) sulfenyl, (alkyl, aryl or heterocycle) disulfide group, (alkyl, aryl) sulfonyl, (alkane
Base or aryl) sulfinyl, sulfo group or its salt, sulfamoyl is (as the sulfamoyl with substituent group, it can be cited for example that N-
Acylsulfamoyl group and N- sulfonylsulfamoyl) or its salt, phosphino-, phosphinyl, phosphinyl oxygroup, phosphinyl amino and first silicon
Alkyl etc..
Wherein, preferably halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom), alkyl (are straight chain, branch or ring
Shape alkyl also may include active methylene if bicyclic alkyl can be multi-ring alkyl), alkenyl, alkynyl, aryl or heterocycle
(arbitrary the position of substitution).
In addition, here, " active methylene " refers to the methine replaced by 2 electron-withdrawing groups." electron-withdrawing group " refers to example
As acyl group, alkoxy carbonyl group, aryloxy carbonyl, carbamoyl, alkyl sulphonyl, aryl sulfonyl, sulfamoyl, trifluoromethyl,
Cyano, nitro or carbimide base.Also, 2 electron-withdrawing groups can bond together and constitute cyclic structure.Also, " salt " is
Refer to the cations such as alkali metal, alkaline-earth metal and heavy metal；Ammonium ion is Ji the organic cations such as phosphonium ion.
As azole compounds, specifically, 5- methylbenzotrazole, 5- amino benzotriazole, benzo three can be enumerated
Azoles, 5,6- dimethylbiphenyl triazole, 3- amino -1,2,4- triazole, 1,2,4- triazole, 3,5- dimethyl pyrazole, pyrazoles and imidazoles
Deng.
Wherein, it preferably comprises benzotriazole cpd (compound containing BTA skeleton) and is different from benzotriazole
The compound (compound without containing BTA skeleton) of compound.Compound containing BTA skeleton and pass through oxidation
Agent and the copper that is oxidized is easy consumingly to be coordinated.On the other hand, even azole compounds, BTA skeleton is not contained
Compound be easy weaker to be coordinated with the copper that is oxidized.By and with these compounds, grinding rate is further speeded up
While can get inhibit recess effect.
It as the compound for not containing above-mentioned BTA skeleton, is not particularly limited, is ground according to further increasing
The viewpoint of speed, preferably 3- amino-1,2,4-triazole, 1,2,4- triazoles or imidazoles.
As the content of above-mentioned azole compounds, it is not particularly limited, according to the viewpoint for further increasing grinding rate,
Relative to lapping liquid gross mass, preferably 0.001~2 mass %, more preferable 0.001~1 mass %, further preferred 0.001~
0.1 mass %.
Using azole compounds of more than two kinds, preferably its total amount includes within the above range.
< grinds promotor >
Above-mentioned lapping liquid can contain grinding promotor.Body is ground by being easier to improve containing grinding promotor
The inner evenness (flatness) of process face (for example, inorganic insulation layer) after grinding.
As grinding promotor, sulfoacid compound, phosphinic acid compounds can be enumerated, preferably there is sulfonic group (- SO3H) and
Amino (- NH2,-NHR or-NRR ') compound.In addition, above-mentioned R and R ' independently indicate alkyl, replace alkyl or aryl.
As the compound with sulfonic group and amino, it can be cited for example that 3- phenalgin sulfonic acid, 4- phenalgin sulfonic acid, NSC 209983,1-
The sulfamic acids classes, amido sulfuric acid (amine such as tarine, 2- amino -1- ethanesulfonic acid (taurine), 1- aminopropane -2- sulfonic acid
Sulfonic acid) and N- methanesulfonic acid.Wherein, more preferable 4- phenalgin sulfonic acid or amido sulfuric acid.
In the case where above-mentioned lapping liquid contains grinding promotor, it is not particularly limited as its content, according to by face
Interior uniformity and grinding rate are set as more good viewpoint, relative to lapping liquid gross mass, preferably 0.001~10.0 mass %,
More preferable 0.01~5.0 mass %.
In addition, grinding promotor can be used alone or two or more kinds may be used.In the grinding being used in combination of two or more
In the case where promotor, preferably total content is within the above range.
< water >
Above-mentioned lapping liquid preferably comprises water.As the water that above-mentioned lapping liquid contains, be not particularly limited, be able to use from
Sub- exchanged water or pure water etc..
It as the content of water, is not particularly limited, in lapping liquid gross mass, generally, it is preferred to 50~99 mass %.
< surfactant and/or hydrophilic polymer >
Above-mentioned lapping liquid can contain surfactant and/or hydrophilic polymer.Surfactant and hydrophilic polymer
Object has the function of that the contact angle of reduction lapping liquid and surface to be polished, lapping liquid are easily wetted extension in surface to be polished.
It as surfactant, is not particularly limited, is able to use selected from including anionic surfactant, cation
Well known surfactant in the group of surfactant, amphoteric surfactant and nonionic surfactant etc..As yin
Ionic surface active agent, it can be cited for example that the sulfonate such as carboxylate, alkyl benzene sulphonate, sulfuric acid and phosphate ester salt etc..
As cationic surfactant, it can be cited for example that aliphatic amine salt, aliphatic quaternary ammonium salt, benzalkonium chloride salt,
Benzethonium chloride, pyridiniujm and imidazoline salt etc..
As amphoteric surfactant, it can be cited for example that carboxybetaine class, aminocarboxylate, imidazolinium betaine,
Lecithin and alkyl amine oxide etc..
As nonionic surfactant, it can be cited for example that ether type, Etheric ester type, ester type, nitrogenous type, diol type and fluorine system
Surfactant etc..
It in the case where above-mentioned lapping liquid contains surfactant, is not particularly limited as its content, according in general
When lapping liquid is used in CMP, the viewpoint of defect is less also easy to produce on being ground body, relative to lapping liquid gross mass, preferably
0.00001~1.0 mass %, more preferable 0.0001~0.2 mass %, further preferred 0.0001~0.05 mass %.
In addition, surfactant can be used alone or two or more kinds may be used.On the surface being used in combination of two or more
In the case where activating agent, preferably total content is within the above range.
As hydrophilic polymer, it can be cited for example that the alkyl ether of the polyethanol such as polyethylene glycol class, polyethanol class, poly- second
The polymer carboxylic-containing acid such as the polysaccharides such as enol, polyvinylpyrrolidone, alginic acid, polymethylacrylic acid and polyacrylic acid,
Polyacrylamide, polymethacrylamide and poly- ethyleneimine etc..As the concrete example of those hydrophilic polymers, can enumerate
In 0042~0044 paragraph of Japanese Unexamined Patent Publication 2009-088243 bulletin, 0026 paragraph of Japanese Unexamined Patent Publication 2007-194261 bulletin
Documented water soluble polymer.
Hydrophilic polymer is preferably selected from including polyacrylamide, polymethacrylamide, poly- ethyleneimine and polyethylene
Water soluble polymer in the group of base pyrrolidones.As polyacrylamide and polymethacrylamide more preferably on nitrogen-atoms
With hydroxy alkyl (such as N- (2- hydroxyethyl) acrylamide polymer etc.) or with the substituent group comprising polyalkylene oxide chain,
Further preferred weight average molecular weight is 2000~50000.There is polyalkylene oxide chain preferably on nitrogen-atoms as poly- ethyleneimine, more
It is preferred that having the repetitive unit indicated by the following general formula (A), wherein further preferred weight average molecular weight is 2000~50000.Separately
Outside, in the present specification, weight average molecular weight is indicated as the polystyrene scaled value based on GPC (gel permeation chromatography) method and table
The value shown.
General formula (A)
[chemical formula 1]
In general formula (A), EO indicates that oxyethylene group, PO indicate oxypropylene group.
M, n indicates 0~200 number (being its average in the case where mixture), and m+n is 2~200.
Oxyethylene group and oxypropylene group, which are formed by alkylene oxide chain, can be random chain, be also possible to block chain.
It also, is 16 it is preferable to use HLB (hydrophilic-lipophilic equilibrium Hydrophile-Lipophile Balance) value
~19 poly- ethyleneimine.
It in the case that above-mentioned lapping liquid contains hydrophilic polymer, is not particularly limited, will grind as its content
When liquid is used in CMP, according to the viewpoint for being less also easy to produce defect on being ground body, relative to lapping liquid gross mass, preferably
0.0001~2.0 mass %, more preferable 0.01~1.0 mass %, further preferred 0.03~0.4 mass %.
In addition, hydrophilic polymer can be used alone or two or more kinds may be used.In the parent being used in combination of two or more
In the case where waterborne polymeric, preferably total content is within the above range.
And it is possible to and with surfactant and hydrophilic polymer.
< organic solvent >
Above-mentioned lapping liquid can contain organic solvent.It as organic solvent, is not particularly limited, is able to use well known
Organic solvent.Wherein, preferably water-soluble organic solvent.
As organic solvent, it can be cited for example that ketone series solvent, ether series solvent, alcohol series solvent, two alcohol series solvents, glycol ethers
Series solvent and acid amides series solvent etc..
More specifically, it can be cited for example that acetone, methyl ethyl ketone, tetrahydrofuran, dioxanes, dimethyl acetamide, N- first
Base pyrrolidones, dimethyl sulfoxide, acetonitrile, methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, ethylene glycol, propylene glycol and ethoxy
Base ethyl alcohol etc..
Wherein, preferably methyl ethyl ketone, tetrahydrofuran, dioxanes, N-Methyl pyrrolidone, methanol, ethyl alcohol or ethylene glycol etc..
In the case where containing organic solvent, it is not particularly limited as its content, relative to the gross mass of lapping liquid,
It is preferred that 0.001~5.0 mass %, more preferable 0.01~2.0 mass %.
If the content of organic solvent, in the range of 0.01~2.0 mass %, available defect performance further obtains
To improved lapping liquid.
In addition, organic solvent can be used alone or two or more kinds may be used.It is organic molten what is be used in combination of two or more
In the case where agent, preferably total content is within the above range.
< pH regulator and/or pH buffer >
Above-mentioned lapping liquid can also contain pH regulator and/or pH buffer to be set as defined pH.As pH tune
Whole dose and/or pH buffer, can enumerate sour agent and/or alkaline agent.In addition, pH regulator and pH buffer are that have different from above-mentioned
The compound of machine acid or charge regulating agent.
It as sour agent, is not particularly limited, it can be cited for example that sulfuric acid.
It as alkaline agent, is not particularly limited, ammonia can be enumerated；Ammonium hydroxide and organic hydroxide ammonium (such as the tetrabutyl
Ammonium hydroxide)；The ethyl alcohol amines such as diethanol amine, triethanolamine and triisopropanolamine；Sodium hydroxide, potassium hydroxide and lithium hydroxide
Equal alkali metal hydroxides；The carbonate such as sodium carbonate；The phosphate such as tertiary sodium phosphate；Borate and tetraborate；Hydroxybenzoic acid
Salt etc..
In addition, organic hydroxide ammonium (such as tetrabutylammonium hydroxide) is used as above-mentioned pH regulator and/or pH in addition to having
Other than the function of buffer, also there is the function of the stabilizer as abrasive grains.
As pH regulator and/or the content of pH buffer, as long as required amount when range desired by pH maintenance,
It is then without particular limitation, in general, in the gross mass of lapping liquid, preferably 0.001~0.1 mass %.
(manufacturing method of lapping liquid)
Above-mentioned lapping liquid can be manufactured by well known method.
Hereinafter, being described in detail to the manufacturing method of above-mentioned lapping liquid.
< feed purification process >
In the manufacture of above-mentioned lapping liquid, in order to reduce the Ca concentration in liquid, it is desirable to pass through distillation, ion exchange in advance
Or filtering etc. and purify be used to prepare in the raw material of lapping liquid wantonly a kind or more.It is purified to as the degree of purifying, such as preferably
99% or more material purity is more preferably purified to as 99.9% or more purity.In order to obtain based on significant effect of the invention
Fruit is important using the raw material of these high-purities.
As purification process, there is no particular limitation, can enumerate in ion exchange resin or RO film (reverse osmosis membrane
Reverse Osmosis Membrane) etc. in pass through method, distillation or it is aftermentioned filtering the methods of.Specifically, for example making
For liquid by carrying out 1 time after purifying in reverse osmosis membrane etc., making liquid is including cation exchange resin, anion exchange
By implementing the method etc. that 2 times purify in the purification devices of resin or mixed bed formula ion exchange resin.
In addition, purification process can also combine a variety of above-mentioned well known purification process and implement.
Also, purification process also can be implemented repeatedly.
(filtering)
As filter, as long as can be then not particularly limited from the filter for being used in filtration applications etc. in the past
And it uses.It can be cited for example that being based on polytetrafluoroethylene (PTFE) (PTFE) and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA)
The polyolefin resins such as polyamide resins and polyethylene and polypropylene (PP) such as equal fluororesin, nylon (including high density, superelevation
Molecular weight) etc. filter.In these materials, it is preferably selected from including polyethylene, polypropylene (including high density poly propylene), PTFE
And the material in the group of the polyamide resins such as the fluororesin such as PTA and nylon, wherein the fluororesin such as more preferable PTFE and PTA
Filter.By using the filter formed by these materials, the polarity for being easy to constitute defect cause can be effectively removed
High foreign matter, but also Ca concentration can be effectively reduced.
As the critical surface tension of filter, preferably 70mN/m or more, more preferable 95mN/m is hereinafter, further preferably
75mN/m or more and 85mN/m or less.In addition, the value of critical surface tension is the nominal value of manufacturer.By using critical surfaces
Tension is the filter of above range, can be effectively removed the high foreign matter of the polarity for being easy to constitute defect cause, and can also
Enough it is effectively reduced Ca concentration.
The aperture of filter preferably 2~20nm degree, more preferable 2~15nm.By being set as these ranges, can inhibit
Filter blocking, and the fine foreign matter such as the impurity being contained in raw material or condensation product can be reliably removed, and can be effectively
Reduce Ca concentration.
When using filter, different filters can also be combined.At this point, the filtering using the 1st filter can be only
It is 1 time, can also carries out 2 times or more.In the case where combining different filter progress 2 times or more filterings, filtered with the 1st time
Aperture compare, preferably the 2nd later aperture is same or less.Also, different pore size within the above range can also be combined
The 1st filter.Here, aperture can be referring to the nominal value of filter manufacturer's.It, can be from for example as commercially available filter
NIHON PALL LTD., A dvantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (former Nippon
Squirrel co., Ltd.) or the various filters of offers such as KITZ MICROFILTER CORPORATION. in selected
It selects.Also, also it is able to use polyamide system " P- nylon filter (0.02 μm of aperture, critical surface tension 77mN/m) "；
(NIHON PALL LTD. manufacture), high density polyethylene (HDPE) system " PE cleans filter (0.02 μm of aperture) "；(NIHON PALL
LTD. manufacture) and high density polyethylene (HDPE) system " PE cleans filter (0.01 μm of aperture) "；(NIHON PALL LTD. manufacture).
2nd filter is able to use by the filter of the formation such as material identical with above-mentioned 1st filter.2nd filter
Aperture be preferably 1~10nm degree.
Also, in the present invention, filter progress is preferably carried out in room temperature (25 DEG C) below.More preferably 23 DEG C hereinafter, into
One step is preferably 20 DEG C or less.Also, preferably 0 DEG C or more, more preferably 5 DEG C or more, further preferably 10 DEG C or more.
In filter progress, corpuscular property foreign matter or impurity can be removed, but if above-mentioned temperature, is then dissolved in the feed
The quantitative change of above-mentioned corpuscular property foreign matter and/or impurity is few, therefore can be more effectively removed by filtering.
Also, used filter is preferably handled before filter stock.Liquid used in the processing is simultaneously
It is limited without special, preferably metal containing ratio can be enumerated less than 0.001 mass ppt, such as other than above-mentioned water by other
Organic solvent is purified so that tenor to be set as to the liquid of above range.By being reduced with metal containing ratio as described above
Liquid can be effectively reduced Ca concentration to be pre-processed to filter.
< quantitative approach >
Ca concentration included in raw material or lapping liquid etc. can pass through ICP-MS method (inductivity coupled plasma mass spectrometry
Method is able to use such as Yokogawa Analytical Systems, Inc. manufacture, Agilent as measurement device
7500cs type.) etc. analyzed.
The Ca concentration measured by ICP-MS method is the total concentration of ionic calcium and nonionic calcium (such as calcium particle), is changed
Yan Zhi is equivalent to the content of calcium atom included in lapping liquid.
Also, according to SNP-ICP-MS (the single nanoparticle inductively coupled plasma mass spectrum Single being developed recently
Nano Particle-Inductively Coupled Plasma-Mass Spectrometry) measurement, ion can be divided into
Property metal and nonionic metal (metallic) measure the amount of the metallic atom to exist in solution.Here, nonionic
Metal (metallic) is not dissolved in liquid and as ingredient existing for solid.
In lapping liquid of the invention, nonionic metal (metallic) when being measured by SNP-ICP-MS method contains
Amount, according to the viewpoint for improving defect performance, relative to lapping liquid gross mass, preferably 100 mass ppt are hereinafter, more preferably 50
Quality ppt or less.Lower limit is not particularly limited, and is in most cases 0.1 mass ppt or more.
In addition, in the present specification, as nonionic metal (metallic), in the case where unlimited metallic element
Refer to all metallic elements included in liquid.
Also, in the case where measuring the amount of nonionic metal (metallic) included in lapping liquid, as long as grinding
Ultra-high purity hydrofluoric acid is added in grinding fluid, after the solid components such as abrasive grains included in lapping liquid are dissolved, is carried out
Measurement based on SNP-ICP-MS method.
Preparation, processing analysis and the measurement of lapping liquid of the invention all carry out preferably in dust free room.Dust free room is preferred
Meet 14644-1 dust free room benchmark.Preferably satisfy ISO (the International Organization for Stand) grade 1, ISO grade 2, ISO grade 3 or ISO
Any grade in class 4 more preferably meets ISO grade 1 or ISO grade 2, further preferably meets ISO grade 1.
< tune liquid process >
There is no particular limitation for the tune liquid of lapping liquid of the invention, for example, can be manufactured by mixing above-mentioned each ingredient.
The sequence and/or opportunity for mixing above-mentioned each ingredient are not particularly limited, for example, can enumerate is scattered in abrasive grains in advance
In the water for adjusting pH, the method for defined ingredient is successively mixed.
In addition, as needed, the purification process such as filtering as described above can be carried out to by the lapping liquid of tune liquid, with adjustment
Ca concentration.
< grinding device >
It is not particularly limited as grinding device, being able to use can be using the side CMP involved in above embodiment
The well known chemical mechanical polishing device of method (hereinafter, also referred to as " CMP device ").
As CMP device, it is able to use for example common CMP device, which, which has, keeps having surface to be polished
The bracket for being ground body (for example, semiconductor substrate etc.) and (motor etc. for being equipped with variable speed) for attaching grinding pad grind flat
Platform.As commercially available product, it is able to use such as Reflexion (Applied Materials, Inc. manufacture).
(chemical and mechanical grinding method)
The chemical and mechanical grinding method of lapping liquid of the invention is used, there is no particular limitation, can be using well known
Chemical and mechanical grinding method.
As chemical and mechanical grinding method involved in an embodiment of lapping liquid of the invention, Ke Yiju can be used
The chemical and mechanical grinding method comprised the following steps out is (hereinafter, also referred to as " CMP method ".): it is ground to grinding plate is installed on
Mill pad, supplies above-mentioned lapping liquid on one side, contacts the surface to be polished for being ground body with grinding pad, make abrasive body and grinding pad
It relatively moves and grinds surface to be polished, so that has been ground is ground body.
< is ground body >
It is ground body as can apply CMP method involved in above embodiment, is not particularly limited.As
It is ground an example of body, can enumerate has on surface selected from the group including metal layer, inorganic insulation layer and inorganic semiconductor layer
In at least one kind of substrate.That is, grinding above-mentioned metal layer, inorganic insulation by CMP method involved in above embodiment
Layer or inorganic semiconductor layer.In addition, these layers can also be stacked.
There is no particular limitation for substrate, for example including the semiconductor substrate being made of single layer and the semiconductor being made up of multiple layers
Substrate.
Constitute the material of semiconductor substrate being made of single layer, there is no particular limitation, generally, it is preferred to by such as silicon, SiGe,
The group iii-v compound of the class of GaAs or their any combination are constituted.
In the case where the semiconductor substrate being made up of multiple layers, there is no particular limitation for structure, such as also can have
Expose interconnection architecture (the in terconnect of the class such as metal wire and dielectric material on the semiconductor substrates such as above-mentioned silicon
) etc. features integrated circuit structure.
There is no particular limitation for metal layer, can enumerate the wiring layer that can form wiring and barrier metal layer etc..It can be formed
Metal component included in the wiring layer of wiring, it can be cited for example that copper system metal (copper or copper alloy etc.).Also, as structure
It at the metal material of barrier metal layer, is not particularly limited, is able to use well known low-resistance metal material.As low resistance
Metal material, such as preferred TiN, TiW, Ta, TaN, W or WN, wherein more preferable Ta or TaN.
As the material for constituting inorganic insulation layer, there is no particular limitation, it can be cited for example that silica, silicon nitride, carbon
SiClx, carbonitride of silicium, silicon oxide carbide and silicon oxynitride etc..Wherein, preferred silicon oxide or silicon nitride.
Also, as the material for constituting inorganic semiconductor layer, there is no particular limitation, it can be cited for example that polysilicon, more
The modified silicon of the impurity elements such as B or P is adulterated in crystal silicon.
< grinding pressure >
It is preferably in surface to be polished and grinding pad with grinding pressure in the CMP method involved in above embodiment
3000~25000Pa of pressure that contact surface generates is ground, and is more preferably ground with 6500~14000Pa.
The revolving speed > of < grinding plate
In the CMP method involved in above embodiment, preferably ground with 50~200rpm of revolving speed of grinding plate
Mill, is more preferably ground with 60~150rpm.
In addition, in order to relatively move abrasive body and grinding pad, and bracket can be made to rotate and/or swing, it can also be with
So that grinding plate is carried out planetary rotation, can also make band-like grinding pad along a direction of long dimension direction linearly to move.Separately
Outside, bracket can be the free position in fixed, rotation or swing.As long as these grinding method keep abrasive body and grinding pad opposite
It is mobile, then it can be properly selected by surface to be polished and/or grinding device.
The supply method > of < lapping liquid
It is with pump etc. that lapping liquid is continuous during grinding surface to be polished in the CMP method involved in above embodiment
The grinding pad being supplied on grinding plate.To the supply amount, there is no limit, but the surface of preferably grinding pad is ground liquid packet always
It covers.In addition, the form about lapping liquid, as described above.
Embodiment
Hereinafter, being illustrated in more details according to embodiment to the present invention.Material, usage amount shown in following embodiment,
Ratio, process content or processing step etc. just can be changed suitably without departing from purport of the invention.To of the invention
Range is not explained by embodiment described below with limiting.In addition, as long as " % " refers to " matter without special explanation
Measure % ".
(purifying of raw material etc.)
Each raw material used in each embodiment as shown below and each catalyst, using purity be 99% or more it is high-purity
Grade is spent, and is purified in advance by distillation, ion exchange or filtering etc..In particular, before adding polishing particles
Under solution state, by carrying out the available high-precision medical fluid such as ion exchange or filtering.
In addition, in the present embodiment, implementing above-mentioned filtering by following methods.Specifically, as filter,
First stage uses Entegris, the 15nm IEX PTFE of Inc. manufacture, uses Entegris, Inc. manufacture in second stage
12nm ALL PTFE, and be carried out continuously filtering (cycle-index be 10 times).In addition, each filter impregnates before the use
It carries out using after hydrophilicity-imparting treatment in IPA (isopropanol).
The ultrapure water used in embodiment, by documented method in Japanese Unexamined Patent Publication 2007-254168 bulletin into
Row purifying, and by the measurement based on aftermentioned common ICP-MS method, the containing ratio of Ca atom is set as less than 10 mass
ppt。
1. the preparation and its evaluation of the lapping liquid of Examples 1 to 4, comparative example 1
(embodiment 1)
Each ingredient shown in will be following mixes, and prepares lapping liquid.In addition, suitably adding dilute sulfuric acid or hydroxide
Sodium, so that the pH of lapping liquid becomes documented value in table 1.
[various measurements and evaluation]
Following evaluations have been carried out to the lapping liquid of obtained embodiment 1.
< Ca concentration mensuration >
In ICP-MS analysis (be not aftermentioned SNP-ICP-MS analysis and refer to common ICP-MS analysis), it will analyze soft
Part replaces with the analysis software (Syngistix for ICP-MS software) as aftermentioned ICP-MS analytical equipment, in addition to this,
Ca concentration is determined to analyze identical method with aftermentioned SNP-ICP-MS.Here, " the Ca concentration " that is measured is ionic
The total concentration of calcium and nonionic calcium (such as calcium particle) is in other words equivalent to the content of calcium atom included in lapping liquid.
< SNP-ICP-MS (Single Nano Particle-Inductively Coupled Plasma-Ma ss
Spectrometry >) is measured
About the containing ratio of metallic, carried out using " Nexion350S " that Perkinelmer Co., Ltd. manufactures
Measurement.Here, metallic is non-cationic metal, it is to be not dissolved in liquid and as ingredient existing for solid.
1) preparation of standard substance
About standard substance, ultrapure water metering is devoted in clean glass container, by the measurement of median particle diameter 50nm
After object metallic is added in a manner of as the concentration of 10000/ml, it will be carried out using supersonic wave cleaning machine
The dispersion liquid of processing in 30 minutes is used as transfer efficiency measurement and uses standard substance.
2) determination condition
Using PFA coaxial type sprayer (in addition, " PFA " is the copolymerization of tetrafluoroethylene-perfluoroalkyl vinyl ether
Object.), quartz Cyclonic spray chamber processed, quartz internal diameter processed be 1mm torch pipe (Torch Inje ctor), with about 0.2mL/min
Measure object liquid is aspirated.It is cleaned based on oxygen additive amount 0.1L/min, plasma output 1600W, ammonia.When
Between analyzed under analysis degree 50us.
3) containing ratio of metallic is measured using the attached following analysis software of manufacturer.
The containing ratio of metallic: nanoparticle analyzes " SNP-ICP-MS " dedicated Syngistix nano application mould group
The evaluation > of < grinding rate
Under the following conditions, lapping liquid is supplied to grinding pad on one side, is ground on one side, carry out commenting for grinding rate
Valence.
Grinding device: Reflexion (Applied Materials, Inc. manufacture)
It is ground body (wafer):
Grinding rate, which calculates, to be used；
The diameter for forming the Cu film with a thickness of 0.5 μm on a silicon substrate is the blank wafer of 300mm
The diameter for forming the Ta film with a thickness of 0.15 μm on a silicon substrate is the blank wafer of 300mm
The SiO with a thickness of 1.0 μm is formed on a silicon substrate2The diameter of film is the blank wafer of 300mm
Grinding pad: IC1010 (Rodel Inc. manufacture)
Grinding condition:
Grinding pressure (contact pressure of surface to be polished and grinding pad): 1.5psi
Lapping liquid feed speed: 200ml/min
Grinding plate revolving speed: 110rpm
Grinding head revolving speed: 100rpm
The calculating of grinding rate:
Grinding rate calculating blank wafer is ground 60 seconds, to equally spaced 49 position on wafer face, by
Resistance value is converted and is found out the metal film thickness of grinding front and back, by (film thickness after film thickness-grinding before grinding) divided by grinding
Time and the average value of value found out is set as grinding rate (unit: nm/min).
It shows the result in table 1.
< defect performance >
To the wafer for having evaluated grinding rate, the device " SP-1 " manufactured using KLA-Tencor Japan Ltd., measurement
As caused by entire 0.30 μm of wafer or more of residue and scratch defect.
Implement the classification of defect to obtained evaluation result, residue number and scratch number are carried out according to following benchmark respectively
Evaluation.
(residue quantitative assessment)
" A ": residue quantity is 10 or less
" B ": residue quantity is more than 10 and 50 or less
" C ": residue quantity is more than 50 and 100 or less
" D ": residue quantity is more than 100
(scratch quantitative assessment)
" A ": scratch quantity is 10 or less
" B ": scratch quantity is more than 10 and 50 or less
" C ": scratch quantity is more than 50 and 100 or less
" D ": scratch quantity is more than 100
(embodiment 2~4, comparative example 1)
Other than the use level or Ca concentration that change each ingredient, prepared in method identical with above-described embodiment 1 real
The lapping liquid of example 2~4, comparative example 1 is applied, and has carried out identical evaluation.It shows the result in table 1.In addition, Ca concentration is by changing
Become feed purification when condition and adjust.
The generation for inhibiting defect using lapping liquid of the invention is specified by the result of table 1.Especially confirm
To charge regulating agent in a liquid content relative to the content of organic acid be by quality ratio 0.3 or less (preferably 0.03 with
Under) in the case where, the generation (comparison of Examples 1 to 3) of defect can be further suppressed.Also, it confirms by by liquid
In Ca concentration be set as 80 mass ppt or less and the generation (comparison of embodiment 1,4) of defect can be further suppressed.
2. the preparation and its evaluation of the lapping liquid of embodiment 5~9, comparative example 2
(embodiment 5)
Each ingredient shown in will be following mixes, and prepares lapping liquid.In addition, suitably adding dilute sulfuric acid or hydroxide
Calcium, so that the pH of lapping liquid becomes value documented by table 2.
[various measurements and evaluation]
To the lapping liquid of obtained embodiment 5, implementing Ca concentration mensuration in the same manner as in Example 1, (Ca is former
Son amount measurement), SNP-ICP-MS measurement (measurement of amount of metal particles), grinding rate evaluation and defect performance evaluation.In addition,
About grinding rate evaluate, will be ground body be set as following shown in grinding rate calculating blank wafer.
(being ground body)
Grinding rate, which calculates, to be used；
The blank wafer for being 300mm with a thickness of the diameter of 1.0 μm of SiN film is formed on a silicon substrate
The SiO with a thickness of 1.0 μm is formed on a silicon substrate2The diameter of film is the blank wafer of 300mm
The diameter for forming 1.0 μm of thickness of poly-Si film on a silicon substrate is the blank wafer of 300mm
It shows the result in table 2.
(embodiment 6~9, comparative example 2)
Other than the use level or Ca concentration that change each ingredient, prepared in method identical with above-described embodiment 5 real
The lapping liquid of example 6~9, comparative example 2 is applied, and has carried out identical evaluation.It shows the result in table 2.In addition, Ca concentration is by changing
Become feed purification when condition and adjust.
The generation for inhibiting defect in the case where having used lapping liquid of the invention is specified by the result of table 2.In particular, really
Recognize the content of charge regulating agent in a liquid relative to the content of organic acid be by quality ratio 0.6 or less (preferably 0.3 with
Under) in the case where can further suppress the generation (comparison of embodiment 5~8) of defect.Also, it confirms by will be in liquid
Ca concentration be set as 45 mass ppt or less and the generation (comparison of embodiment 5,8,9) of defect can be further suppressed.
3. the preparation and its evaluation of the lapping liquid of embodiment 10~14, comparative example 3
(embodiment 10)
Each ingredient shown in will be following mixes, and prepares lapping liquid.In addition, suitably adding dilute sulfuric acid or hydroxide
Calcium, so that the pH of lapping liquid becomes documented value in table 3.
[various measurements and evaluation]
To the lapping liquid of obtained embodiment 10, implementing Ca concentration mensuration in method same as Example 5, (Ca is former
Son amount measurement), SNP-ICP-MS measurement (measurement of amount of metal particles), grinding rate evaluation and defect performance evaluation.It will knot
Fruit is shown in Table 3.
(embodiment 11~14, comparative example 3)
Other than the use level or Ca concentration that change each ingredient, prepared in method identical with above-described embodiment 10 real
The lapping liquid of example 11~14, comparative example 3 is applied, and has carried out identical evaluation.It shows the result in table 3.In addition, Ca concentration passes through
Feed change purify when condition and adjust.
The generation for inhibiting defect in the case where having used lapping liquid of the invention is specified by the result of table 3.Especially really
Recognize the content of charge regulating agent in a liquid relative to the content of organic acid is energy in 0.01 situation below by quality ratio
Enough further suppress the generation (comparison of embodiment 10~12) of defect.Also, it confirms by setting the Ca concentration in liquid
It can be further suppressed scarce for 80 mass ppt or less (preferably 45 mass ppt are hereinafter, more preferably 25 mass ppt or less)
Sunken generation (comparison of embodiment 10,13,14).
4. the preparation and its evaluation of the lapping liquid of embodiment 15~22, comparative example 4
(embodiment 15)
Each ingredient shown in will be following mixes, and prepares lapping liquid.In addition, suitably adding dilute sulfuric acid or hydroxide
Calcium, so that the pH of lapping liquid becomes documented value in table 4.
[various measurements and evaluation]
To the lapping liquid of obtained embodiment 15, implementing Ca concentration mensuration in the same manner as in Example 1, (Ca is former
Son amount measurement), SNP-ICP-MS measurement (measurement of amount of metal particles), grinding rate evaluation and defect performance evaluation.In addition,
About grinding rate evaluate, will be ground body (wafer) be set as following shown in grinding rate calculating blank wafer.
Grinding rate, which calculates, to be used；
The SiO with a thickness of 1.0 μm is formed on a silicon substrate2The diameter of film is the blank wafer of 300mm
The blank wafer for being 300mm with a thickness of the diameter of 1.0 μm of SiN film is formed on a silicon substrate
It shows the result in table 4.
(embodiment 16~22, comparative example 4)
Other than the use level or Ca concentration that change each ingredient, prepared in method identical with above-described embodiment 15 real
The lapping liquid of example 16~22, comparative example 4 is applied, and has carried out identical evaluation.It shows the result in table 4.In addition, Ca concentration passes through
Feed change purify when condition and adjust.
Hereinafter, being illustrated about the ingredient for being used as other additives in table 4.
(weight average molecular weight (Mw) 46000, EO:PO=8: 1, is equivalent to hydrophilic polymer to alkylidene polyethylene polyamines.)
(weight average molecular weight (Mw) 1500, is equivalent to hydrophilic polymer to polyglycereol.)
(weight average molecular weight (Mw) 5000, is equivalent to hydrophilic polymer to polyallylamine.)
(weight average molecular weight (Mw) 4000, is equivalent to hydrophilic polymer to polyethylene glycol.)
(it is poly- to be equivalent to hydrophily to diallyl dimethyl ammonium-acrylamide copolymer for weight average molecular weight (Mw) 20000
Close object.)
The generation for inhibiting defect in the case where having used lapping liquid of the invention is specified by the result of table 4.In particular, really
Recognize charge regulating agent in a liquid content be by quality ratio relative to the content of organic acid can in 0.1 situation below
Further suppress the generation (comparison of embodiment 15~17) of defect.Also, it confirms by the way that the Ca concentration in liquid to be set as
80 mass ppt or less (preferably 25 mass ppt or less) and can further suppress defect generation (embodiment 15,18,19
Comparison).
Claims (8)
1. a kind of lapping liquid is the lapping liquid for being used in chemical mechanical grinding,
In the lapping liquid, containing abrasive grains and organic acid, and Ca concentration is 100 mass ppt or less.
2. lapping liquid according to claim 1, wherein
In lapping liquid, the content of the metallic found out by SNP-ICP-MS measurement is 100 mass ppt or less.
3. lapping liquid according to claim 1 or 2, also contains charge regulating agent,
The content of the charge regulating agent relative to the content of the organic acid be by quality ratio 0.6 hereinafter,
The Ca concentration is 0.01~100 mass ppt.
4. lapping liquid according to any one of claim 1 to 3, wherein
The Ca concentration is 0.01~80 mass ppt.
5. lapping liquid according to any one of claim 1 to 4, wherein
The organic acid contains the polyacid in the group including malonic acid, succinic acid, malic acid and citric acid.
6. lapping liquid according to any one of claim 1 to 5, wherein
Range of the pH 1.5~5.0 or 9.0~12.0.
7. lapping liquid according to any one of claim 3 to 6, wherein
As the charge regulating agent, containing the inorganic acid or its ammonium salt in the group including nitric acid, boric acid and phosphoric acid or have
The ammonium salt of machine acid.
8. a kind of chemical and mechanical grinding method comprising following process:
To the grinding pad for being installed on grinding plate, lapping liquid described in any one of claims 1 to 7 is supplied on one side, is made on one side
The surface to be polished for being ground body is contacted with the grinding pad, relatively move the abrasive body and the grinding pad and described in grinding
Surface to be polished, to obtain ground being ground body.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2016112944 | 2016-06-06 | ||
| JP2016-112944 | 2016-06-06 | ||
| PCT/JP2017/018151 WO2017212874A1 (en) | 2016-06-06 | 2017-05-15 | Polishing liquid, chemical mechanical polishing method |
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| CN109312213A true CN109312213A (en) | 2019-02-05 |
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| JP (1) | JP6808731B2 (en) |
| KR (2) | KR102340528B1 (en) |
| CN (1) | CN109312213B (en) |
| TW (1) | TWI727052B (en) |
| WO (1) | WO2017212874A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109746771A (en) * | 2019-02-14 | 2019-05-14 | 南京航空航天大学 | A kind of CsPbX3The polishing method of inorganic perovskite crystalline material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7002354B2 (en) * | 2018-01-29 | 2022-02-04 | ニッタ・デュポン株式会社 | Polishing composition |
| KR102261822B1 (en) * | 2019-05-23 | 2021-06-08 | 에스케이씨솔믹스 주식회사 | Cmp slurry composition with reduced defect occurrence and preparation method thereof |
| CN114507478B (en) * | 2022-02-24 | 2023-05-09 | 北京通美晶体技术股份有限公司 | Polishing solution for gallium arsenide wafer processing and preparation method thereof |
| CN115044299B (en) * | 2022-07-04 | 2023-11-17 | 浙江奥首材料科技有限公司 | Water-soluble high-specific-gravity large-size abrasive suspension auxiliary agent, preparation method and application thereof, and grinding fluid containing water-soluble high-specific-gravity large-size abrasive suspension auxiliary agent |
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| TW274625B (en) * | 1994-09-30 | 1996-04-21 | Hitachi Seisakusyo Kk | |
| CN1849378A (en) * | 2003-09-11 | 2006-10-18 | 卡博特微电子公司 | Chemical-mechanical polishing composition and method for using the same |
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| KR100982870B1 (en) * | 2008-08-22 | 2010-09-16 | 주식회사 케이티 | Method of Prototyping Mobile User Interface and Mobile User Interface Prototyping Tool and Record Media Recorded Program for Realizing the Method of Prototyping Mobile User Interface |
| JP6038640B2 (en) * | 2012-12-17 | 2016-12-07 | 株式会社フジミインコーポレーテッド | Substrate wettability promoting composition, polishing composition containing the same, and method for producing a substrate using the same |
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- 2017-05-15 JP JP2018522390A patent/JP6808731B2/en active Active
- 2017-05-15 KR KR1020217025420A patent/KR102340528B1/en active IP Right Grant
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- 2017-05-15 WO PCT/JP2017/018151 patent/WO2017212874A1/en active Application Filing
- 2017-05-15 CN CN201780034712.7A patent/CN109312213B/en active Active
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Patent Citations (4)
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| TW274625B (en) * | 1994-09-30 | 1996-04-21 | Hitachi Seisakusyo Kk | |
| CN1849378A (en) * | 2003-09-11 | 2006-10-18 | 卡博特微电子公司 | Chemical-mechanical polishing composition and method for using the same |
| TW200944582A (en) * | 2008-02-18 | 2009-11-01 | Jsr Corp | Aqueous dispersion for chemical mechanical polishing and chemical mechanical polishing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109746771A (en) * | 2019-02-14 | 2019-05-14 | 南京航空航天大学 | A kind of CsPbX3The polishing method of inorganic perovskite crystalline material |
| CN109746771B (en) * | 2019-02-14 | 2020-11-20 | 南京航空航天大学 | CsPbX3Polishing method of inorganic perovskite crystal material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2017212874A1 (en) | 2019-05-16 |
| CN109312213B (en) | 2021-11-30 |
| KR20190005918A (en) | 2019-01-16 |
| KR20210104161A (en) | 2021-08-24 |
| TW201742899A (en) | 2017-12-16 |
| TWI727052B (en) | 2021-05-11 |
| KR102340528B1 (en) | 2021-12-20 |
| WO2017212874A1 (en) | 2017-12-14 |
| JP6808731B2 (en) | 2021-01-06 |
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