CN1295758C - CMP sizing material, polishing method and method for manufacturing semiconductor device - Google Patents
CMP sizing material, polishing method and method for manufacturing semiconductor device Download PDFInfo
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- CN1295758C CN1295758C CNB2004100383151A CN200410038315A CN1295758C CN 1295758 C CN1295758 C CN 1295758C CN B2004100383151 A CNB2004100383151 A CN B2004100383151A CN 200410038315 A CN200410038315 A CN 200410038315A CN 1295758 C CN1295758 C CN 1295758C
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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
- C09K3/1409—Abrasive particles per se
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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
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
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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
There is disclosed a CMP slurry comprising composite type particles composed of a resin component and an inorganic component, which are complexed with each other, and resin particles, the CMP slurry having a viscosity of less than 10 mPas.
Description
The cross reference of related application
The application based on and require Japan's patent application formerly of submitting on May 4th, 2003, application number is the priority of 2003-136014, and the full content of introducing this application is as a reference.
Technical field
The present invention relates to be used for CMP (chemico-mechanical polishing Chemical Mechanical Polishing) slurry, use the manufacture method of its finishing method and semiconductor device.
Background technology
High-performance LSI of future generation, element must be highly integrated, and the present strictness of design standard of connecting up by the damascene of CMP formation is designed to wiring width between 0.07-30 μ m, and thickness is 100nm.
Forming under the situation of damascene wiring that thickness is 100nm, in existing C MP method, form free particles from the polishing cloth polishing particles that dissociates during polishing, and be pressed into polished surface, produce the pit of about 80nm.In this case, the wiring material (Cu, Al, W etc.) that should be embedded in the groove nearly all is removed.If produce too much pit, then the cloth line resistance uprises, and the performance of semiconductor device reduces.In addition, owing to may break in operation, aspect reliability, also have problems.Therefore, require that pit is controlled at 20nm or below it.
In the past, studied by in polishing process, reducing free particles, and considered method corresponding to this bonded-abrasive type CMP liner that requires to use free particles few (for example the bonded-abrasive type liner of 3M company etc.).By adopting this liner, pit can be controlled at 20nm or below it, but working (machining) efficiency, price, machined surface grade, stable aspect existing problems.
In addition, interactional method between so-called raising polishing particles and the polishing underlay has also been proposed.For example, though adopted slurry as the organic compound of the composite particle of polishing particles and surfactant or organic acid etc., because it is polishing strength is little, therefore impracticable.
Summary of the invention
One aspect of the present invention is a kind of CMP slurry, and it comprises composite particle and resin particle, and wherein composite particle contains the resinous principle and the inorganic constituents of compoundization, and described CMP slurry has the viscosity less than 10mPas.
Another aspect of the present invention is a kind of finishing method, and it comprises, touches with the polishing cloth that has been attached on the rotating platform when making the semiconductor substrate rotation with polished surface; And on above-mentioned polishing cloth, drip the CMP slurry, above-mentioned polished surface is polished; Described CMP slurry has the viscosity less than 10mPas, and comprises composite particle and resin particle, and wherein composite particle contains the resinous principle and the inorganic constituents of compoundization.
Another aspect of the present invention is a kind of preparation method of semiconductor device, and it is included in and forms dielectric film on the semiconductor substrate; On above-mentioned dielectric film, form recess; On the inside of above-mentioned recess and above-mentioned dielectric film, pile up conductive material, form layer with conductivity; Remove the above-mentioned conductive material of piling up on the above-mentioned dielectric film by the CMP that adopts the CMP slurry, the surface of exposing above-mentioned dielectric film, make above-mentioned conductive material remain in the inside of above-mentioned recess thus, wherein said CMP slurry has the viscosity less than 10mPas, and comprise composite particle and resin particle, wherein composite particle contains the resinous principle and the inorganic constituents of compoundization.
Description of drawings
Fig. 1 is the give instructions in reply sketch of mould assembly particle and resin particle profile status of the pattern face of land.
Fig. 2 A and 2B are the profile of top ring.
Fig. 3 A and 3B are the process profiles of manufacture method of the semiconductor device of expression an embodiment of the invention.
Fig. 4 is the sketch of the state of expression CMP.
Fig. 5 is the figure of the relation between the content of resin particle in the polishing velocity of expression W film and the slurry.
Fig. 6 A is the process profile of manufacture method of the semiconductor device of expression another embodiment of the present invention to 6C.
Fig. 7 A and 7B are the process profiles of manufacture method of the semiconductor device of expression another embodiment of the present invention.
Embodiment
Below embodiments of the present invention are described.
Present inventors find; for the slurry that will be fed on the polishing cloth is used for polished surface effectively; when when reducing pit and abrasion, polishing; the granulate mixture that adopts composite particle and resin particle is as polishing particles, and viscosity to be limited under the situation of not enough 10mPas be effective.
Fig. 1 is the ideograph of composite particle and resin particle.Composite particle 10 is by constituting as the polymer beads of resinous principle 11 with the inorganic constituents 12 of this compoundization of polymer beads.Compoundization is meant chemistry or combination non-chemically.Inorganic constituents 12 for example, can be used as silicon compound portion or metallic compound portion and forms.Inorganic constituents 12 not only can be combined in the surface of resinous principle 11 as shown in the figure like that, also can be covered by inside.On the other hand, the preferred functional group that has COOH etc. on the surface of resin particle 13.
As composite particle 10, can adopt the particle of putting down in writing in No. 6454819 communiques of U.S. Pat for example, generally can adopt following method to synthesize.At first on the divinyl benzene polymers particle that constitutes resinous principle 11 etc. in conjunction with silane coupling agent etc., itself and specific silanol compound, silica colloidal are reacted.Thus, at polymer beads on the inner and surface formation as the silicon compound portion that constitutes by polysiloxane structure etc. of inorganic constituents 12 etc.Silicon compound portion etc. also can be without formation such as silane coupling agents.Inorganic constituents is preferably by silane coupling agent etc. or directly be combined on the polymer beads.In addition, the compound with aluminium, titanium or zirconium etc. uses the composite particle 10 that can obtain having same formation as inorganic constituents 12.
Below the polymer beads as resinous principle 11 in the composite particle 10 is elaborated.
Polymer beads is the particle that is formed by the polymer that makes various monomer polymerization gained.As monomer, can use the beta-unsaturated esters class of the unsaturated aromatic compound class, vinylacetate, propionate etc. of styrene, AMS, halogenated styrenes and divinylbenzene etc., and the nitrile of acrylonitrile etc. etc.In addition, can also use the esters of acrylic acid and the methyl acrylic ester of methyl acrylate, methyl methacrylate, ethyl acrylate, EMA, 2-EHA, methacrylic acid 2-Octyl Nitrite, lauryl acrylate, lauryl methacrylate, ethylene glycol diacrylate, Ethylene glycol dimethacrylate, glycidyl acrylate, glycidyl methacrylate, acrylic acid 2-hydroxyl ethyl ester, allyl acrylate and allyl methacrylate etc.
In addition, can also use butadiene, isoprene, acrylic acid, methacrylic acid, acrylamide, Methacrylamide, N hydroxymethyl acrylamide and N-methylol methacrylamide etc.These monomers can use separately, also can or also use more than it two kinds.
Polymer beads can make as mentioned above by the whole bag of tricks such as emulsion polymerization, suspension polymerisation and dispersin polymerizations, and monomer polymerization obtains.Can adjust the particle diameter of polymer beads arbitrarily by the control polymerizing condition.In addition, also can form the polymer beads of desired particle diameter by the mode that the polymer of bulk etc. is pulverized.Seek out particularly that intensity etc. is big, during the polymer beads of excellent heat resistance, also can and use multi-functional monomer when making polymer beads, in molecule, import cross-linked structure.Cross-linked structure also can be in making the process of polymer beads or after making polymer beads, adopts crosslinked etc. the method for chemical crosslinking, electronics line to implement to import.
The shape of polymer beads is not particularly limited, but more preferably is similar to sphere.Its average grain diameter is preferably 0.03-100 μ m as the diameter suitable with ball, and more preferably 0.05-20 μ m most preferably is 0.05-1.0 μ m.During average grain diameter less than 0.03 μ m, particle diameter is too small, is difficult to obtain enough polishing performances.On the other hand, when average grain diameter surpassed 100 μ m, the dispersed variation of composite particle may make storage stability significantly descend.
Preferably in the polymer beads of gained, import the functional group of hydroxyl, epoxy radicals, carboxyl etc.In this case, can inorganic constituents be combined on the polymer beads by the connection compound of silane coupling agent etc.And with have can with the situation of the silane coupling agent of the functional group that imports to the functional group reaction on the polymer beads etc. under, can further promote inorganic constituents to combine with polymer beads, obtained performance is the composite particle of excellence more.
As polymer beads, can also use the particle of the various polymer formation of polyamide, polyester, Merlon and polyolefin etc.In these polymer beads, also can with the above-mentioned base of import feature similarly, and then, can import cross-linked structure to granule interior.
Though can use aforesaid various polymer, from industrial viewpoint of buying easily, preferred especially polymethyl methacrylate (PMMA) and polystyrene (PST).
Below silicon compound portion and metallic compound portion as inorganic constituents 12 are elaborated.At least a portion is combined on the polymer beads directly or indirectly in the inorganic constituents, preferred chemical bonding.Thus, can not produce so-called when polishing inorganic constituents remain in problem on the polished surface easily from the polymer particles abscission.As chemical bond, can enumerate ionic bond and coordinate bond etc., because that covalent bonds gets is firmer, therefore more preferably.Inorganic constituents 12 also can be closed non-bonding modes such as effect by hydrogen bond, surface charge key, complex bonds, anchor and is combined on the polymer beads.
As shown in Figure 1, on the surface that is combined in resinous principle 11, inorganic constituents must liken to into the polymer beads of resinous principle littler.By calculating as can be known, if the longest diameter of inorganic constituents the polymer beads particle diameter 1/4 or below it, then combination equably.But in order to ensure polishing force, the longest diameter of preferred inorganic constituents is at 10nm or more than it.
As the silicon compound portion of inorganic constituents, can constitute by the part that contains siloxane bond and at least a of silica dioxide granule portion.In addition, at least a kind of formation selecting the group that metallic compound portion can be made up of portion, alumina particle portion, titanium dioxide granule portion and the zirconium dioxide particle portion from containing metal oxygen alkane (メ ロ キ サ Application) key.
This inorganic constituents can and form on its whole surface in polymer beads inside, also can form on its part.Containing the portion of siloxane bond and the portion of containing metal oxygen alkane (メ ロ キ サ Application) key can be made of unimolecule, but is preferably 2 molecules or its above chain structure.Under the situation that is chain structure, can be wire, but three-dimensional structure more preferably.
Inorganic constituents can be directly or the connection by silane coupling agent etc. be combined on the polymer beads with compound.Use compound as connecting, for example can list, silane coupling agent, the agent of aluminium class even summation, the even summation agent of titanium class and zirconium class coupling agent etc., but special preferred silane coupling agent.As silane coupling agent, can enumerate following (a) and (b) and (c).
(a) vinyl three chloro silane, ethene three ('beta '-methoxy ethyoxyl) silane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-Qiu Jibingjisanjiayangjiguiwan and γ-Lv Daibingjisanjiayangjiguiwan etc.
(b) γ-glycidoxypropyltrimewasxysilane and γ-glycidoxypropyl methyldiethoxysilane etc.
(c) N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N-β (amino-ethyl) gamma-amino propyl group methyl dimethoxysilane and γ-An Jibingjisanyiyangjiguiwan etc.
As silane coupling agent, preferably its have can be easily and the functional group who imports to the functional group's reaction in the polymer beads.For example, imported from the teeth outwards under the situation of polymer beads of carboxyl, preferably had epoxy radicals, amino (b) and silane coupling agent (c).In these coupling agents, preferred especially γ-glycidoxypropyltrimewasxysilane and N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane.
As aluminium class coupling agent, can enumerate acetyl aluminum alkoxide diisopropyl hydrochlorate etc.As titanium class coupling agent, can enumerate isopropyl three isostearoyl base titanate esters, isopropyl tridecyl benzenesulfonyl titanate esters etc.These various types of coupling agents can use separately, also can or also use more than it 2 kinds.In addition, different types of coupling agent also can and be used.
The use amount of coupling agent for 1 mole of functional group who imports on the polymer beads, is preferably the 0.1-50 mole.Its use amount is the 0.5-30 mole more preferably, most preferably is the 1.0-20 mole.During 0.1 mole of the use amount deficiency of coupling agent, inorganic constituents can not combine fully securely with polymer beads, in polishing process easily from the polymer particles abscission.On the other hand, when use amount surpassed 50 moles, coupling agent molecule generation condensation reaction may generate undesired polymer.In this case, hinder combining of inorganic constituents and polymer beads sometimes.
When making coupling agent and polymer beads generation chemical bonding, can promote the carrying out that reacts by the catalyst that uses bronsted lowry acids and bases bronsted lowry etc.For promoting reaction, also can improve the temperature of reaction system.
In addition, the compound that also following general formula (1) can be represented uses as the raw material of inorganic constituents.
RnM(OR’)z-n (1)
Wherein, R is that carbon number is any monovalent organic radical group of 1-8, specifically can enumerate alkyl, phenyl, vinyl and the glycidol propyl group etc. of methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group and n-pentyl etc.R ' is that carbon number is that the alkyl of 1-5, acyl group or the carbon number that carbon number is 2-6 are the aryl of 6-9, is specially methyl, ethyl, n-pro-pyl and isopropyl, acetyl group, propiono, bytyry, valeryl and caproyl, phenyl and tolyl etc.R and R ' are with 2 or more than it and when depositing, it can be identical, also can be different.
M is Al, Si, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ge, Zr, Nb, Mo, Sn, Sb, Ta, W, Pb or Ce.Preferred especially Al, Si, Ti and Zr.
In addition, z is the valence of M, and n represents 0～(z-1) integer.
At this, describe as the compound of M containing Al, Si, Ti or Zr.As M is the compound of Si, can list tetramethoxy-silicane, tetraethoxysilane (TEOS), tetraisopropoxysilan, four tert-butoxy silane, methyltrimethoxy silane and methyl triethoxysilane etc.Form silicon compound portion by these compounds as inorganic constituents.In addition, can enumerate M is that Al aluminium ethylate etc., M are that the titanium ethanolate (IV) of Ti etc. and M are zirconium tert-butoxide of Zr etc.Form portion, alumina particle portion, titanium dioxide granule portion or zirconium dioxide particle portion by these compounds as the containing metal oxygen alkane key of inorganic constituents.
Aforesaid compound can use separately, also can or also use more than it 2 kinds.In addition, also can be compound and the usefulness of Si, Al, Ti or Zr with M.In above-mentioned general formula (1), (z-n) be 2 or situation more than it under owing to form finer and close the siloxane bond portion that contains or containing metal oxygen alkane key portion, therefore preferred.
Not only can use the compound of above-mentioned general formula (1) expression, and can use at least a in its hydrolysate and the partial condensate.Just can hydrolysis or part condensation although the compound of general formula (1) expression need not special operation, can make required ratio hydrolysis or part condensation as required in advance.
The use amount of these compounds is with respect to polymer beads, with SiO
2, Al
2O
3, TiO
2Or ZrO
2The weight ratio meter that converts is preferably 0.001-100.This weight ratio is 0.005-50 more preferably, most preferably is 0.01-10.This weight ratio is under the situation of less than 0.001, and inorganic constituents can not fully form on the inside of polymer beads and surface, and polishing performance may reduce.On the other hand, when surpassing 100,, can not expect significantly improving of polishing performance even strengthen weight ratio.
In addition, also can adopt at least a kind of raw material from the group that colloidal silicon dioxide, colloidal aluminium oxide, colloidal titanium dioxide and colloidal zirconium dioxide are formed, selecting as inorganic constituents.This colloidal composition can be that microparticulate silica, aluminium oxide, titanium dioxide or the zirconium dioxide etc. of 5-500nm are dispersed in the decentralized medium of water etc. and prepare by making average grain diameter.Particulate can be by the method that makes grain growth in aqueous alkali or by acquisitions such as vapor phase methods.
These particulates can be combined on the polymer beads by the aforesaid portion of siloxane bond or the portion of containing metal oxygen alkane key etc. of containing.Perhaps, be combined in polymer beads, contain in the portion of siloxane bond or the portion of containing metal oxygen alkane key etc., can constitute each particulate portion by importing to hydroxyl on the particulate etc.The use amount of colloid is with respect to polymer beads, with SiO
2, Al
2O
3, TiO
2Or ZrO
2The weight ratio meter that converts is preferably 0.001-100.This weight ratio is 0.01-50 more preferably, most preferably is 0.1-10.This weight ratio is difficult to fully form inorganic constituents under the situation of less than 0.001.On the other hand, when surpassing 100, also can't see the further raising of polishing performance.
Make mentioned component and polymer beads when reaction, can carry out in as the dispersion of decentralized medium with the various organic solvents of water or alcohol etc.Decentralized medium can adopt independent solvent, also can be the mixture of 2 kinds or its above solvent.Under the situation that is moisture decentralized medium, stable and disperse equably for making polymer beads, preferably in polymer beads, import the hydrophily functional group of hydroxyl, epoxy radicals and carboxyl etc. in advance.By importing these functional groups, can will be combined on the polymer beads more easily as above-mentioned inorganic constituents.
As can be used as the alcohol that decentralized medium uses, can list the rudimentary representative examples of saturated aliphatic alcohol of methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, the tert-butyl alcohol etc.Alcohol can use separately, also can or also use more than it 2 kinds.As the organic solvent beyond the alcohol, for example can enumerate methylethylketone and dimethyl formamide etc.These organic solvents, water and alcohol can predetermined ratio mix use.
In the reaction at this moment, the content of polymer beads is preferably 0.001-70 weight % in the decentralized medium, and more preferably 0.01-50 weight % most preferably is 0.1-25 weight %.When less than 0.001 weight %, be difficult to obtain composite particle with enough output.On the other hand, when surpassing 70 weight %, the dispersion stabilization that so-called polymer beads can take place descends, and the defective of gel took place easily in the compound stage.
In the reaction that makes the inorganic constituents combination, can or add catalyst by heating and promote this reaction.Under the situation of heating, the temperature of reaction system is preferably 40-100 ℃.As catalyst, can use for example acid, alkali, aluminium compound and tin compound etc.Particularly acid catalyst and Al catalysts are bigger to the facilitation effect of reaction, and be therefore preferred.
In addition, also can use by mechanical thermokarst phenomenon by the composite particle of heat bonding (for example with reference to United States Patent (USP): the US6576554 communique).
Can use aforesaid various composite particle.
On the other hand, as resin particle 13, can use for example special resin particle of putting down in writing in the 2000-204275 communique of opening.Particularly, resin particle 13 can be made of the material the same with resinous principle in the above composite particle, and its shape is preferably spherical.What is called is spherical to be meant the shape that is roughly ball with acute angle portion, and need not to really spherical.
Resin particle preferably has cross-linked structure, for example can obtain by cross-linkable monomer and other monomer copolymerizations are synthesized.When making its combined polymerization, the ratio of cross-linkable monomer is preferably 5-80 weight %, and more preferably 5-60 weight % most preferably is 7-60 weight %.When cross-linkable monomer less than 5 weight %, the resin particle that is difficult to obtain to have enough hardness.On the other hand, when surpassing 80 weight %, though hardness uprises, resin particle may become fragile.By making it have cross-linked structure, can improve the hardness and the intensity of resin particle.
Preferably on the surface of resin particle, has hydrophilic group as the functional group.The polarity of the zeta potential by hydrophilic group may command resin particle surface.In addition, except hardness, intensity, also make characteristics such as preventing charging property, thermal endurance and discoloration-resistant improve.And, have the resin particle of hydrophilic group on the surface and the intermiscibility that has between the compound of polar group also excellent.
Have hydrophilic group resin particle can by import 0.1 mM to every 100g resin particle or more than it, the hydrophily base that is preferably hydroxyl, carboxyl and salt thereof, anhydride group, sulfonic group and salt thereof, phosphate and salt thereof, amino and the salt thereof etc. of 1-100 mM forms.
In slurry, be combined on the surface of resin particle for making the hydrophily base, also can cooperate surfactant in addition with predetermined hydrophily base.As surfactant, can use in cationic surface active agent, anionic surfactant and the nonionic surface active agent etc. any one.As cationic surface active agent, for example can enumerate aliphat amine salt and aliphat ammonium salt etc.As anionic surfactant, can enumerate phosphate ester salt of the sulfuric acid of sulfonate, higher alcohol sulfate salt, alkyl ether sulfate, polyoxyethylene alkyl phenyl ether etc. of the carbonate, alkylbenzenesulfonate, alkylnaphthalene sulfonate, alpha-alkene sulfonate etc. of for example fatty acid soaps, alkyl ether carbonate etc. and alkyl phosphate etc. etc.As nonionic surface active agent, can list the ester type etc. of Etheric ester type, cithrol, glyceride and the sorbitan ester etc. of the ether type of polyoxyethylene alkyl ether etc., APEO of glyceride etc.
Slurry in the invention process form can be by making polarity become predetermined relationship the combination of aforesaid composite particle and resin particle, and it is dispersed in the water prepares.Particularly, can with composite particle and resin particle makes up so that the surface becomes identical polar.
Zeta potential can be measured by for example laser dopper flowmeter method ゼ- potential measurement device (manufacturing of BROOKHAVENINSTRUMENTS society, trade name " ゼ- プ ラ ス ").Carrying out zeta potential when measuring, inorganic constituents is being dispersed in the water etc., to be mixed with the dispersion with predetermined pH.Adopt above-mentioned ゼ- potential measurement device that dispersion is measured, can obtain the zeta potential of the inorganic constituents of any pH value.When the zeta potential of measurement function base, also can make solution by making the purpose functional group be combined on the surface of resin particle and being dispersed in water etc. with predetermined pH, similarly measure.
The polarity of composite particle depends on inorganic constituents, for example the zeta potential of silicon dioxide pH be 1.4 o'clock be 0 (isopotential point), surpassing at 1.4 o'clock at pH is negative value.The zeta potential of aluminium oxide pH be 7 o'clock be 0, when pH less than 7 be on the occasion of.On the other hand, resin particle is determined its zeta potential by the functional group that exists on the surface.For example being under the situation of carboxyl (COOH), not have isopotential point, is negative value at whole pH scope (0.5-14) zeta potentials.Amino (NH
2) zeta potential whole pH scopes be on the occasion of.
Perhaps, either party the be in isopotential point in composite particle and the resin particle.So-called isopotential point refers to zeta potential that above-mentioned ゼ- potential measurement device determines in the scope of 0 ± 5mV.With zeta potential be 0 o'clock pH value as benchmark, in the scope of this pH value ± 1, the current potential of particle surface is unsettled.Therefore, such scope can be regarded isopotential point as too.For example, has sulfonic group (SO as functional group
3The zeta potential of granules of polystyrene H) is that 2 vicinity are almost 0 at pH.That is, composite particle and resin particle can not be that the mode of opposite polarity is used in combination with the surface.
In the slurry of granulate mixture as polishing particles of composite particle that contains opposite polarity each other and resin particle and since particle by strong electric attraction in conjunction with and agglomerated together, so the viscosity of slurry significantly improves, and reaches 10mPaS or more than it.Have full-bodied like this slurry when dripping on polishing cloth, can not implement CMP polished surface.Present employed slurry delivery system is a pump formula liquid circulation type, and when using full-bodied slurry, slurry will produce obstruction.In addition, because the storage stability of highly viscous slurry is also poor, therefore sedimentation easily is difficult to disperse again.
For slurry viscosity being controlled at not enough 10mPaS, use composite particle and resin particle with identical polar.When a side of composite particle and resin particle is in isopotential point, the viscosity of slurry also will be controlled in not enough 10mPaS.
Under the situation that is any combination, the particle diameter of the resin particle preferably maximum particle diameter than inorganic constituents in the composite particle is bigger.Specifically, the particle diameter of resin particle is preferably 2 times of the inorganic constituents maximum particle diameter or more than it.As mentioned above, in composite particle, inorganic constituents be preferably resinous principle 1/4 or its following about.In addition, the particle diameter of preferred composite particle is 2 times of the resin particle particle diameter or more than it.In addition, under the stress of CMP, when the composite particle distortion is also destroyed, become the particle that replaces the composite particle resinous principle for making resin particle, preferably it is bigger than inorganic constituents at least.If consider these factors, the particle diameter of resin particle is preferably 2 times of inorganic constituents in the composite particle or more than it.But for guaranteeing polishing force, the longest diameter of inorganic constituents is preferably at 10nm or more than it, if the interaction between consideration and the polishing underlay, special preferred resin particle grain size is about 300nm or below it.
For guaranteeing higher polishing velocity, the average grain diameter d of preferred composite particle
1Average grain diameter d with resin particle
2Size ratio (d
1/ d
2) 2 or more than it.By the control size ratio, can obtain desired polishing velocity.But, for guaranteeing the effect of abundant hybrid particles, the upper limit of size ratio is limited to about 10.When resin particle is too small with respect to composite particle, may be that the state that has approached to add the little surfactant of volume causes.
The average grain diameter of resin particle is preferably 0.05-1 μ m.During less than 0.05 μ m, be difficult to obtain spheroid.On the other hand, when surpassing 1 μ m, aforesaid size ratio (d
1/ d
2) 2 or its when above, the average grain diameter of composite particle surpasses 2 μ m.At this moment, because the surface area of particle is little, may make the polishing force deficiency.In addition, the average grain diameter of resin particle is 0.1-0.5 μ m more preferably, most preferably is 0.1-0.3 μ m.The average grain diameter of composite particle, resin particle can be obtained by TEM observation.
In addition, in the granulate mixture of composite particle and resin particle, the ratio of resin particle is preferably in the scope of 10 weight %～90 weight %.When use comprises the granulate mixture of resin particle with this ratio, can obtain extra high polishing velocity.If for example be the W film, can guarantee 100nm/ minute or the high polishing velocity more than it.
Total particle concentration of the granulate mixture of composite particle and resin particle is preferably 0.1 weight %～40 weight % in slurry.When less than 0.1 weight %, be difficult to obtain enough polishing effects.On the other hand, when surpassing 40 weight %, particle may condense.More preferably total particle concentration is 0.5 weight %～30 weight % in slurry.
As required, add the various additives of oxidant, pH conditioning agent etc., can make the slurry of the invention process form.
In the slurry of the invention process form, because the granulate mixture that contains composite particle and resin particle is as polishing particles, so these particles form the most intensive interstitital texture on polishing cloth in polishing process.Thus, can produce suitable eyelet and block, particle is fixed on the polishing cloth surface, reduce free particles.As a result, when can suppress to produce pit, polish with sufficiently high polishing velocity.And because the surface of composite particle and resin particle is an identical polar, perhaps wherein a side is an isopotential point, therefore slurry viscosity is fully descended.
Even the inorganic constituents in the composite particle is when being subjected to polishing stress, can be from as the polymer particles abscission of resinous principle and firmly combination yet, and resinous principle may be out of shape or destroy when being subjected to polishing stress.Therefore, in polishing process, in the surface of ruined resinous principle, the inorganic constituents with polishing force is combined, forms the composite particle of small particle diameter.The composite particle of this small particle diameter mixes equably with resin particle.
In addition, resin particle is hydrophobic, and the polishing cloth surface also is hydrophobic.Therefore, resin particle is attracted on the polishing cloth surface when rolling the composite particle of small particle diameter.The result can reduce free particles and implement polishing.
In the time will using with resin particle, can not obtain aforesaid effect as the resinous principle in the composite particle of the invention process form and inorganic constituents as other composition.At this moment, particle is fixed to resin particle and inorganic constituents is embedded in the gap of resinous principle.There is deficiency from the teeth outwards owing to have the inorganic constituents of polishing force, can not polishes.
In addition, when composite particle was replaced into the inorganic particle with equal particle diameter, the particle diameter of inorganic particle with polishing force was excessive with respect to resin particle.For implementing the texture fine grinding, the particle diameter that requires inorganic constituents is at 100nm or below it, and in order fully to suppress pit, preferably it is at 50nm or below it.When containing with the equal inorganic particle of composite particle, be difficult to suppress the generation of pit, can not achieve the goal.
By adopting the slurry of the invention process form, can solve the whole issue of the existing working (machining) efficiency of bonded-abrasive type liner, price, machined surface grade and stable aspect in the prior art.
In addition, the apical ring by suitable selection keeps semiconductor substrate to use can more effectively be fixed on polishing particles on the polishing cloth, can further improve the effect of the slurry of the invention process form.
Fig. 2 A and 2B are the profiles of the brief configuration of the spendable apical ring example of expression.
Apical ring 67 shown in Fig. 2 A is made of the basket 63 that is provided with air supply pipe 64, guard ring 61, clamping plate 65 and air bag 66.Remain on the polished surface of the semiconductor substrate 60 on the apical ring 67 of this structure and the end face of guard ring 61 and form same plane in fact.Also can keep semiconductor substrate 60 that polished surface is positioned at than the end face of guard ring 61 top about 0.2mm more upwards.
Therefore, guard ring 61 is pressed on the polishing cloth 62 by the pressure with semiconductor substrate 60 equal extent.According to concrete situation, guard ring 61 also can be exceeded the pressure of semiconductor substrate more than 60 and be pressed on the polishing cloth 62.Be provided to the slurry (not shown) on the polishing cloth 62, at first be pressed on the polishing cloth 62, make polishing particles be fixed by guard ring 61.Then, because slurry is provided for the polished surface of semiconductor substrate 60, so under the state that has reduced free particles, implement polishing.
In contrast, when the apical ring 68 that adopts shown in Fig. 2 B, polished surface is earlier polished, and polishing particles can not be fixed on the polishing cloth 62.That is,, therefore be provided to the polished surface that slurry (not shown) on the polishing cloth 62 is provided directly to semiconductor substrate 60 because the polished surface that remains on the semiconductor substrate 60 on the apical ring 68 by substrate film 69 is more outstanding than the end face of guard ring 61.Therefore, polishing particles is fixed on the polishing cloth 62 by semiconductor substrate 60, and the fixing and polishing of polishing particles is implemented simultaneously.
The slurry of the invention process form owing to contain composite particle and resin particle, even therefore under the fixing of particle and situation that polishing is carried out simultaneously, also can reduce free particles.But in order further to improve the fixed effect of particle, the apical ring 67 of structure is used in combination shown in preferred especially and Fig. 2 A.
(form of implementation 1)
At first, in capacity is 2 liters flask, pack into 94 parts of methyl methacrylates (following " part " expression " weight portion "), 1 part of methacrylic acid, 5 parts of hydroxy methyl methacrylate, 0.03 part of Texapon Special, 0.6 part of ammonium persulfate and 400 parts of ion exchange waters.Under nitrogen atmosphere, be warming up to 70 ℃ while stir this mixture, make its polymerization 6 hours.Thus, obtain containing the resin particle stoste of 20 weight % concentration PMMA particles, this PMMA particle surface has carboxyl, average grain diameter is 200nm.
On the other hand, by on as the PMMA particle of resinous principle, making composite particle in conjunction with silica dioxide granule as inorganic constituents.Can use the particle that synthesizes by aforesaid way as the PMMA particle.The particle diameter of silica dioxide granule is 15nm, by changing the average grain diameter of PMMA particle, the overall average grain diameter of composite particle (d1) is changed.Particularly, preparing average grain diameter is 5 kinds of composite particles of 100nm, 200nm, 300nm, 400nm and 1000nm.
Carrying out compound tense, the capacity of at first 100 parts of aqueous dispersions that comprise 10 weight %PMMA particles being packed into is in 2 liters the flask, to wherein adding 1 part of methyltrimethoxy silane.Under 40 ℃, this mixture was stirred 2 hours.After this, add nitric acid the pH value is adjusted to 2, obtain the aqueous dispersion of resinous principle.In addition, with the concentration of 10 weight % cataloid (Misao Kusano makes, trade name " ス ノ-テ ッ Network ス 0 ") is dispersed in the water, and the pH value is adjusted to 8, obtain the aqueous dispersion of inorganic constituents with potassium hydroxide.After this, in the aqueous dispersion of 100 parts of resinous principles, add the aqueous dispersion of 50 parts of inorganic constituentss at leisure with 2 hours, and mix.Further stirred 2 hours, obtain containing the aqueous dispersion for preparing particle, this preparation particle is the particle that is attached with silica dioxide granule on the PMMA particle as resinous principle.Then, in this aqueous dispersion, add 2 parts of vinyltriethoxysilane, stir after 1 hour, add 1 part of TEOS, be warming up to 60 ℃.After this, continue to stir 3 hours,, obtain the stoste of composite particle, wherein contain the composite particle of 10 weight % by cooling.
Stoste combination by the composite particle stoste that will so obtain and above-mentioned resin particle obtains having 5 kinds of (0.5,1,1.5,2 and 5) size ratio (composite particle d
1/ resin particle d
2) granulate mixture.
By with the granulate mixture of composite particle and resin particle as polishing particles, can go out the slurry of this form of implementation according to following formulated.
At first, mix the stoste of above-mentioned resin particle and the stoste of composite particle, dilute with water.Further mix 5 weight % as the ferrous nitrate of oxidant, 90 weight % pure water, the mode that its concentration with 5 weight % contains polishing particles is prepared as solvent.Owing to contain ferrous nitrate, the gained pH value of slurry is about 2.5 acidic region.Further by changing the cooperation ratio of 2 kinds of stostes, make the ratio of composite particle of resin particle change, make multiple slurry.
Adopt the various slurries of so preparing out, implement W-CMP in such a way, research W polishing velocity.
Fig. 3 A and 3B are the engineering profile of expression W-CMP.
At first, as shown in Figure 3A, the thickness with 300nm on semiconductor substrate 20 is piled up dielectric film 21, forms hole 22 (0.1 μ m φ).The W film 24 of 200nm is piled up on TiN film 23 ground that further exist 10nm on its whole surface in the centre.
Remove TiN film 23 and W film 24 unwanted parts, the surface of shown in Fig. 3 B, exposing dielectric film 21 by CMP.
During polishing W film 24, adopt IC1000 (ロ デ-Le ニ ッ society makes), and implement in such a way by above-mentioned slurry as polishing cloth.In other words, as shown in Figure 4, when the speed with 100rpm makes panoramic table 30 rotations that are pasted with polishing cloth 31, with 300gf/cm
2The polishing loading itself and the apical ring 33 that maintains semiconductor substrate 32 are touched.The rotation number of apical ring 33 is 102rpm, provides slurry 37 with 200cc/ minute flow to polishing cloth 31 from slurry supply nozzle 35.In addition, in Fig. 4, show water supply nozzle 34 and trimmer 36 in the lump.
Relation in the polishing velocity of W film 24 and the slurry between the resin particle ratio of granulate mixture is shown in the curve chart of Fig. 5.In the curve chart of Fig. 5, curve a, b, c, d and e represent size ratio (d in the granulate mixture respectively
1/ d
2) be the result of 0.5,1,1.5,2 and 5 slurry.
Shown in the curve of Fig. 5, when using composite particle or resin particle separately respectively, the W polishing velocity is at 10nm/ minute or below it.In contrast, when using the slurry that mixes composite particle and resin particle formation, any size ratio all demonstrates the tendency that the W polishing velocity improves.Its reason can think that composite particle and resin particle form the most intensive interstitital texture on polishing cloth, produces suitable eyelet thus and blocks, and makes particle be fixed.
Particularly as curve d, shown in the e, when size ratio 2 or more than it, and the ratio of resin particle is in the scope of 10-90 weight % the time, can 100nm/ minute or its above high polishing velocity polishing W film.
Then, size ratio is 2 except making, the fixed ratio of resin particle is 10 weight %, the material of change composite particle and resin particle, adopt the formulated various slurries the same with the above.Adopt the slurry of gained under the condition the same, to polish the W film, the polishing velocity of research W film with the above.Its result is documented in the following table 1 with the polarity of the zeta potential of the composition of the viscosity of each slurry, granulate mixture and each particle.Because pH value of slurry is 2.5, so the polarity of the zeta potential of each particle is to be measurement result under 2.5 the environment at pH.
Table 1
| Composite particle | Resin particle | W polishing velocity (nm/min) | Viscosity (mPaS) | |||||
| Inorganic constituents | Zeta potential | Resinous principle | Resin material | Functional group | Zeta potential | |||
| 1 | Silicon dioxide | - | PST | PMMA | COOH | - | 150 | 1 |
| 2 | Silicon dioxide | - | PST | PST | COOH | - | 180 | 1 |
| 3 | Silicon dioxide | - | PST (crosslinked) | PST | COOH | - | 175 | 1 |
| 4 | Silicon dioxide | - | PST | PST | COOH | - | 170 | 1 |
| 5 | Silicon dioxide | - | PST (crosslinked) | PST | COOH | - | 155 | 1 |
| 6 | Aluminium oxide | + | PST | PST | COOH | - | Can not implement CMP | 12 |
| 7 | Aluminium oxide | + | PST | PST | NH 2 | + | 120 | 1 |
| 8 | Silicon dioxide | - | PST | PST | SO 3H | Zero | 140 | 1 |
| 9 | Silicon dioxide | - | PMMA | PMMA | * | Zero | 110 | 1 |
| 1 0 | Silicon dioxide | - | PMMA | PMMA | COOH | - | 170 | 1 |
*: the proportioning of Potassium dodecylbenzenesulfonate: 0.05 weight %
As shown in table 1, the zeta potential of composite particle and resin particle any for negative situation under (No.1-5,10) and any be that the viscosity of slurry is 1mPaS under the positive situation (No.7).Similarly, at the zeta potential of resin particle (No.8,9) under zero the situation, slurry has the low viscosity of 1mPaS.Adopting under the situation of these slurries, can 110nm/ minute or its above high polishing velocity the W film is polished.In either case, the pit of surface of polished can be suppressed in 10nm or below it.
Under the situation that changes resin particle surface functional group kind, and then when having added surfactant, also can obtain high polishing velocity equally.It is the same with the material of resin particle that resinous principle in the composite particle need not, even also can obtain same effect under the situation of different materials.In addition, composite particle and resin particle with 2 kinds or when being used in combination more than it, also can obtain high polishing velocity respectively.
The pH of the slurry of No.1-10 is about 2.5, even under the situation of low like this pH value, the slurry of the invention process form also can be guaranteed sufficiently high polishing velocity.On the contrary, be 10 or high pH value situation more than it under, the slurry of the invention process form also can have been given play to same effect.
In containing resin particle or composite particle slurry separately, use in only can be about the 3-7 narrower pH scope as the prior art of polishing particles.This is owing to surfactant has been added in interaction between polishing particles and the polishing underlay and organic compound causes in order to improve.In strong acid and highly basic zone, because these additive inactivations, so can not obtain effect.
In form of implementation of the present invention, owing to mix composite particle and resin particle uses as polishing particles, so can make the enough interactions of acquisition between polishing particles and the polishing underlay.Therefore, also can use in the impracticable in the prior art wide pH scope.
As shown in table 1, when to comprise zeta potential be positive composite particle and zeta potential for the granulate mixture of negative resin particle (No.6), the viscosity of slurry is 12mPaS, and is very high.Have full-bodied like this slurry and be difficult to be added drop-wise on the polishing cloth 31, can not implement CMP from slurry supply nozzle 37.
(form of implementation 2)
In Cu damascene Wiring technique, when Cu being carried out the 2nd polishing, except the Cu film being carried out the planarization polishing, also to for example TaN film and SiO
2The such kinds of materials of film is carried out the planarization polishing.In the prior art, under these circumstances, make the polishing velocity ratio be about 1, carry out nonselective polishing.But, under the situation that is organic insulating film,, when polishing under these conditions, produce bigger abrasion owing to be subjected to the influence of physical properties such as hardness or surface hydrophobic.
By adopting the slurry of the invention process form,, also can hang down wearing and tearing ground and form Cu damascene wiring even be 1 or more than it, when carrying out the selectivity polishing in polishing velocity.And the surface of organic insulating film after polishing and Cu film also produces scratch hardly.
Fig. 6 A is to the engineering profile of 6C for expression Cu-CMP.
At first, as shown in Figure 6A, on the semiconductor substrate 40 that is formed with the element (not shown), pile up dielectric film 41, form joint 42.On dielectric film 41, pile up the LKD5109 (JSR manufacturing) of 200nm as film having low dielectric constant 43, further pile up the carbonado (AMAT make, below be called BD) of 100nm as cover film 44 with the CVD method.After forming groove 45 on film having low dielectric constant 43 and the cover film 44, pile up TaN film 46 (20nm) and Cu film 47 (500nm) by RIE by sputtering method and galvanoplastic comprehensively.
Then, remove the unwanted part of Cu film 47 under the following conditions by CMP, TaN film 46 is exposed.
Slurry: CMS7303/7304 (JSR society)
Flow: 250cc/ minute
Polishing cloth: IC1000 (ロ デ-Le ニ ッ society makes)
Loading: 300gf/cm
2
Make the revolution of carrier and platform be 100rpm, carry out 1 minute polishing.In this operation, owing to stop polishing at TaN film 46 places, so hydrophobic cover film 44 does not expose.Therefore, can adopt commercially available slurry to implement polishing.
After this, shown in Fig. 6 C, by rebuilding the unwanted part that operation is removed TaN film 46.The CMP of this moment adopts the slurry of the invention process form.
When the preparation slurry, prepare average grain diameter (d
1) be composite particle and the average grain diameter (d of 200nm
2) be that the granulate mixture of resin particle of 100nm is as polishing particles.Size ratio (the d of composite particle and resin particle
1/ d
2) be 2.Composite particle comprises PMMA particle that average grain diameter as resinous principle is 150nm and is the silica dioxide granule of 25nm as the average grain diameter of inorganic constituents.Resin particle is formed by PMMA, and its surface has the COOH base as functional group.By the method the same, composite particle and resin particle are prepared the stoste of same concentration with the above.
The stoste of above-mentioned composite particle and the stoste of resin particle are mixed, with the pure water dilution, make that the concentration of composite particle is 2.7 weight %, the concentration of resin particle is 0.3 weight %.Further add 0.1 weight % as the hydrogen peroxide of oxidant, 0.8 weight % as the quinolinic acid of oxidation retarder and additive etc., the KOH that is used as the pH conditioning agent is adjusted to 10 with pH.
In addition, except polishing particles being changed to 2 kinds of different cataloids of average grain diameter, by the slurry of above-mentioned formulated comparative example equally.Adopting 0.6 weight % average grain diameter particularly is that the mixture of the cataloid of 40nm and the cataloid that 2.4 weight %, average grain diameter are 20nm is as polishing particles.
Adopt each slurry, with above-mentioned the same condition under polishing 2 minutes, the polishing velocity of research Cu film 47, TaN film 46 and cover film 44.Adjust polishing time, make to be polished to 50nm as the BD that covers film 44.As a result, when using the slurry of the invention process form, the polishing velocity of Cu film, TaN film and cover film is respectively 100nm/ minute, 45nm/ minute and 20nm/ minute.And in contrast, when adopting the slurry of comparative example, the polishing velocity of the polishing velocity 70nm/ of Cu film minute, TaN film and cover film is 60nm/ minute.
Like this, when adopting the slurry of comparative example, the polishing velocity of cover film 44 is bigger, is 60nm/ minute, therefore produces abrasion, and its part comes off.And the section official post between the film 44 of Cu film and cover gets Cu film side and is the shape that flies out, and denudes to be 120nm.Because cover film 44 must protect dielectric film 43 to avoid the damage that subsequent processing produces, therefore must do one's utmost to avoid its breakage.In contrast, when adopting the slurry of the invention process form, denude and be 20nm, demonstrate lower value, and breakage does not take place cover film 44.Owing to contain the resin particle that forms by organic material, thus the slurry of the invention process form can and organic membrane between the suitable interaction of generation.
In addition, on Cu film 47 surfaces after the polishing, pit is suppressed in 20nm or below it.And 1cm on polishing back Cu film 47 and the cover film 44
2The scratch at size place is about 10000 when using the comparative example slurry, in contrast, when using the slurry of the invention process form, scratch is reduced to 100 or below it.By with the adding ingredient optimization, can further reduce scratch.
(form of implementation 3)
As the slurry of the invention process form also applicable to the formation of STI (shallow ridges separation).Fig. 7 A and 7B form the engineering profile of technology for showing STI.
At first, shown in Fig. 7 A, on the semiconductor substrate 50 that is provided with CMP barrier film 51, form groove, pile up dielectric film 52 thereon.Herein, can use SiN as CMP barrier film 51, the application type dielectric film that uses organic SOG for example etc. is as dielectric film 52.
Then, the part that do not need of dielectric film 52 is removed, shown in Fig. 7 B, expose the surface of CMP barrier film 51 by the CMP that adopts the invention process form slurry.Slurry is with average grain diameter (d
1) be composite particle and the average grain diameter (d of 200nm
2) prepare as polishing particles for the granulate mixture of the resin particle of 100nm.Size ratio (the d of composite particle and resin particle
1/ d
2) be 2.Composite particle contain as resinous principle, average grain diameter be 200nm the PST particle and as inorganic constituents, average grain diameter is the silica dioxide granule of 40nm.When synthetic this composite particle, the capacity of at first 92 parts of styrene, 4 parts of methacrylic acids, 4 parts of hydroxy-ethyl acrylates, 0.1 part of Texapon Special, 0.5 part of ammonium persulfate and 400 parts of ion exchange waters being packed into is in 2 liters the flask.Under nitrogen atmosphere, be warming up to 70 ℃ while stir this mixture, make its polymerization 6 hours.Thus, obtain containing the resin particle stoste of PST particle with carboxyl with the concentration of 20 weight %.In addition, when synthetic PST particle, add 1 part of divinylbenzene (purity 55%), as crosslinking agent.During functional group beyond forming COOH, can use pyridine ring compound (amino), sulfonate (sulfonyl) etc.
Implementing compound tense, the capacity of at first 100 parts of aqueous dispersions that comprise 10 weight %PST particles being packed into is in 2 liters the flask, and adds 1 part of methyltrimethoxy silane.Under 40 ℃, this mixture was stirred 2 hours.After this, add nitric acid, the pH value is adjusted into 2, obtain the aqueous dispersion of resinous principle.In addition, with the concentration of 10 weight % cataloid (Misao Kusano makes, trade name " ス ノ-テ ッ Network ス 0 ") is dispersed in the water, and the pH value is adjusted to 8, obtain the aqueous dispersion of inorganic constituents with potassium hydroxide.After this, in the aqueous dispersion of 100 parts of resinous principles, add the aqueous dispersion of 50 parts of inorganic constituentss at leisure with 2 hours, and mix.Further stirred 2 hours, obtain containing the aqueous dispersion for preparing particle, this preparation particle is attached with silica dioxide granule on polymer beads.Then, in this aqueous dispersion, add 2 parts of vinyltriethoxysilane, stir after 1 hour, add 1 part of TEOS, be warming up to 60 ℃.After this, continue to stir 3 hours,, obtain the stoste of composite particle, wherein contain the composite particle of 10 weight % concentration by cooling.
Mix the concentrate of stoste of above-mentioned composite particle and the stoste of resin particle, and make that with the pure water dilution concentration of composite particle is that the concentration of 18 weight %, resin particle is 2 weight %.In addition, at this, remove the top clarified solution of composite particle stoste by using the particles settling method, using the concentration of composite particle is concentrate and the above-mentioned resin particle stoste that contains crosslinked PST particle with 20 weight % concentration of 20 weight %.And use KOH that pH is adjusted to 11 as the pH conditioning agent.
Adopt the slurries of gained, polish dielectric film 52 under the following conditions.
Slurry flow: 300cc/ minute
Polishing cloth: IC1000 (ロ デ-Le ニ ッ society makes)
Polishing loading: 300gf/cm
2
Make the revolution of apical ring and platform be 100rpm, carry out 3 minutes polishing.
C or SiN as the material of CMP barrier film 51 is used have hydrophobicity as a rule, and its zeta potential is an isopotential point.Therefore, be in the environment that is easy to generate scratch.
By adopting the slurry of the invention process form, no more than 2 of the scratch on the wafer surface after the polishing, and abrasion is suppressed at 30nm or below it.Like this, can determine when the dielectric film on the CMP barrier film that is easy to generate scratch is implemented CMP, also to have preferable effect.
As mentioned above, according to form of implementation of the present invention, can provide when reducing pit and abrasion, polishing velocity that can be practical is implemented the slurry of polishing to polished surface.According to other form of the present invention, can provide when reducing pit and abrasion, polished surface is implemented the method for polishing with the polishing velocity of practicality.According to other form of the present invention, provide the manufacture method of semiconductor device with high reliability.
According to the present invention, can produce high-performance, semiconductor device at a high speed, it has desired design standard for example of future generation is 0.1 μ m or its following wiring, its industrial value is very big.
Other advantage of the present invention and improvement are apparent to those skilled in the art.Therefore, the invention is not restricted to this paper is shown and describe detail and representative embodiment, have wideer scope.Therefore, do not depart from claims and etc. under the situation of the spirit and scope of total inventive concept that thing limited, can make various distortion.
Claims (18)
1. CMP slurry, it comprises composite particle and resin particle, wherein composite particle contains the resinous principle and the inorganic constituents of compoundization, the zeta potential of described composite particle and described resin particle is negative or just is, or at least one side in described composite particle and the described resin particle is in isopotential point, and described CMP slurry has the viscosity less than 10mPaS.
2. CMP slurry as claimed in claim 1, the average grain diameter d of wherein said composite particle
1Average grain diameter d with described resin particle
2Size ratio d
1/ d
2Be 2 or more than it.
3. CMP slurry as claimed in claim 1, the content of wherein said resin particle are the 10 weight %～90 weight % of described composite particle and described resin particle total amount.
4. CMP slurry as claimed in claim 1, wherein said resinous principle is selected from polymethyl methacrylate and polystyrene.
5. CMP slurry as claimed in claim 1, wherein said resin particle is at its surperficial possess hydrophilic property base.
6. finishing method, it comprises touches semiconductor substrate with polished surface and the polishing cloth that is attached on the panoramic table; And on above-mentioned polishing cloth, drip the CMP slurry, above-mentioned polished surface is polished; Described CMP slurry has the viscosity less than 10mPaS, and comprises composite particle and resin particle, and wherein composite particle contains the resinous principle and the inorganic constituents of compoundization.
7. finishing method as claimed in claim 6, the zeta potential of composite particle and described resin particle described in the wherein said CMP slurry are negative or just are.
8. finishing method as claimed in claim 6, at least one side described in the wherein said CMP slurry in composite particle and the described resin particle is in isopotential point.
9. finishing method as claimed in claim 6, the average grain diameter d of composite particle described in the wherein said CMP slurry
1Average grain diameter d with described resin particle
2Size ratio d
1/ d
2Be 2 or more than it.
10. finishing method as claimed in claim 6, the content of resin particle described in the wherein said CMP slurry are the 10 weight %～90 weight % of described composite particle and described resin particle total amount.
11. finishing method as claimed in claim 6, wherein said semiconductor substrate remains in the guard ring, described polished surface be positioned at than described guard ring end face more the top 0～0.2mm the position.
12. finishing method as claimed in claim 6, wherein said composite particle and described resin particle were fixed on the described polishing cloth before the described polished surface of polishing.
13. the manufacture method of a semiconductor device, it comprises,
On semiconductor substrate, form dielectric film;
On above-mentioned dielectric film, form recess;
On the inside of above-mentioned recess and above-mentioned dielectric film, pile up conductive material, form layer with conductivity;
Remove the above-mentioned conductive material of piling up on the above-mentioned dielectric film by the CMP that adopts the CMP slurry, described dielectric film surface is exposed, make above-mentioned conductive material remain in the inside of above-mentioned recess thus, wherein said CMP slurry has the viscosity less than 10mPas, and comprise composite particle and resin particle, wherein composite particle contains the resinous principle and the inorganic constituents of compoundization.
14. method as claimed in claim 13, the zeta potential of composite particle and described resin particle described in the wherein said CMP slurry are negative or just are.
15. method as claimed in claim 13, at least one side described in the wherein said CMP slurry in composite particle and the described resin particle is in isopotential point.
16. method as claimed in claim 13, the average grain diameter d of composite particle described in the wherein said CMP slurry
1Average grain diameter d with described resin particle
2Size ratio d
1/ d
2Be 2 or more than it.
17. method as claimed in claim 13, the content of resin particle described in the wherein said CMP slurry are the 10 weight %～90 weight % of described composite particle and described resin particle total amount.
18. having, method as claimed in claim 13, wherein said conductive material on the TaN film, pile up the structure that the Cu film is arranged.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP136014/2003 | 2003-05-14 | ||
| JP2003136014A JP2004342751A (en) | 2003-05-14 | 2003-05-14 | Cmp slurry, polishing method, and method of manufacturing semiconductor device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1551304A CN1551304A (en) | 2004-12-01 |
| CN1295758C true CN1295758C (en) | 2007-01-17 |
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|---|---|
| US (1) | US20050003743A1 (en) |
| JP (1) | JP2004342751A (en) |
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| TW (1) | TWI252506B (en) |
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| GB0513910D0 (en) * | 2005-07-07 | 2005-08-10 | Univ Newcastle | Immobilisation of biological molecules |
| KR101067095B1 (en) * | 2006-03-20 | 2011-09-22 | 미쓰이 가가쿠 가부시키가이샤 | Polishing composition |
| US20070264829A1 (en) * | 2006-05-12 | 2007-11-15 | Hynix Semiconductor Inc. | Slurry and method for chemical mechanical polishing |
| US8010094B2 (en) * | 2006-06-06 | 2011-08-30 | Turner Broadcasting System, Inc. | Mobile device with themed multimedia effects |
| JP2009267367A (en) * | 2008-03-31 | 2009-11-12 | Toshiba Corp | Semiconductor device manufacturing method |
| BRPI0911453A2 (en) * | 2008-04-18 | 2018-03-20 | Saint Gobain Abrasifs Sa | surface modification of hydrophilic and hydrophobic silanes of abrasive organs |
| US20110126890A1 (en) * | 2009-11-30 | 2011-06-02 | Nicholas Francis Borrelli | Textured superstrates for photovoltaics |
| CN102101976A (en) * | 2009-12-18 | 2011-06-22 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
| US20110177623A1 (en) * | 2010-01-15 | 2011-07-21 | Confluense Llc | Active Tribology Management of CMP Polishing Material |
| US8568610B2 (en) * | 2010-09-20 | 2013-10-29 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Stabilized, concentratable chemical mechanical polishing composition and method of polishing a substrate |
| JP2017037918A (en) * | 2015-08-07 | 2017-02-16 | エスアイアイ・セミコンダクタ株式会社 | Polishing head, cmp polishing device having the same, and method of manufacturing semiconductor integrated circuit using the device |
| JP6788988B2 (en) * | 2016-03-31 | 2020-11-25 | 株式会社フジミインコーポレーテッド | Polishing composition |
| CN112872916B (en) * | 2020-12-28 | 2023-03-10 | 富联裕展科技(深圳)有限公司 | Polishing system and polishing method |
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| EP1020488A2 (en) * | 1999-01-18 | 2000-07-19 | Kabushiki Kaisha Toshiba | Composite particles and production process thereof, aqueous dispersion composition for chemical polishing, and process for manufacture of semiconductor device |
| EP1138733A2 (en) * | 2000-03-27 | 2001-10-04 | JSR Corporation | Aqueous dispersion for chemical mechanical polishing of insulating films |
| CN1333319A (en) * | 2000-07-14 | 2002-01-30 | 株式会社东芝 | Slurry for chemical-mechanical polishing and forming method, semiconductor device making method |
| US6530968B2 (en) * | 2000-11-24 | 2003-03-11 | Nec Electronics Corporation | Chemical mechanical polishing slurry |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004342751A (en) | 2004-12-02 |
| TW200509184A (en) | 2005-03-01 |
| CN1551304A (en) | 2004-12-01 |
| TWI252506B (en) | 2006-04-01 |
| US20050003743A1 (en) | 2005-01-06 |
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