CN103866326A - Chemo-mechanical polishing slurry for metal, and its application - Google Patents
Chemo-mechanical polishing slurry for metal, and its application Download PDFInfo
- Publication number
- CN103866326A CN103866326A CN201210528946.6A CN201210528946A CN103866326A CN 103866326 A CN103866326 A CN 103866326A CN 201210528946 A CN201210528946 A CN 201210528946A CN 103866326 A CN103866326 A CN 103866326A
- Authority
- CN
- China
- Prior art keywords
- acid
- mechanical polishing
- chemical mechanical
- polishing
- metals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
The invention provides a chemo-mechanical polishing slurry for copper, and its application. The slurry comprises abrasive particles, a complexing agent, an oxidant, a corrosion inhibitor, and at least one organic phosphate surfactant. The slurry has the advantages of maintenance of a high copper removal rate, improvement of the saucerization and the over polishing window of polished core wires, few pollutants the surface of polished copper, and no corrosion.
Description
Technical field
The present invention relates to a kind of chemical mechanical polishing slurry and application thereof, relate in particular to a kind of chemical mechanical polishing slurry for copper and application thereof.
Background technology
Along with the development of semiconductor technology, the microminiaturization of electronic unit, has comprised millions of transistors in a unicircuit.In operational process, integrating the transistor of the rapid switch of energy of huge quantity like this, traditional aluminium or aluminium alloy interconnection line, signal transmission speed is reduced, and in current delivery process, need to consume mass energy, in a sense, also hinder the development of semiconductor technology.In order to further develop, people start to find the use that adopts the material replacement aluminium that has higher electrical properties.As everyone knows, the resistance of copper is little, has good electroconductibility, and this has accelerated in circuit the transmission speed of signal between transistor, and less stray capacitance ability also can be provided, and small electric road is for electromigratory susceptibility.These electrical advantages all make copper in semiconductor technology evolves, have good development prospect.
But we find in the ic manufacturing process of copper, copper can move or diffusion way enters into the transistor area of unicircuit, thereby have a negative impact for semi-conductive transistorized performance, thereby the interconnection line of copper can only be with inlay manufacture, that is: in the first layer, form groove, in groove, fill copper barrier layer and copper, form plain conductor and cover on dielectric layer.Then by chemically machinery polished, copper/copper barrier layer unnecessary on dielectric layer is removed, in groove, left single interconnection line.The CMP (Chemical Mechanical Polishing) process of copper is generally divided into 3 steps, the 1st step is first to use higher overdraft, remove copper a large amount of on substrate surface to remove soon and efficiently speed, the 2nd step is in the time soon approaching blocking layer, to reduce overdraft, reduce and remove the remaining metallic copper of speed polishing and be parked in blocking layer, the 3rd step is removed blocking layer and part dielectric layer and metallic copper with barrier polishing solution again, realizes planarization.
Copper polishing on the one hand will be removed copper unnecessary on blocking layer as early as possible, will reduce on the other hand the butterfly depression of copper cash after polishing as far as possible.Before copper polishing, metal level has part depression above copper cash.When polishing, the copper on dielectric material (higher) under main body pressure is easy to be removed, and the suffered polish pressure of the copper of recess is lower than main body pressure, and it is little that copper is removed speed.Along with the carrying out of polishing, the difference of altitude of copper can reduce gradually, reaches planarization.But in polishing process, if the chemical action of copper polishing fluid is too strong, static etch rate is too high, even if the passive film of copper is under lower pressure, (as copper cash recess) is also easy to be removed, cause planarization efficiency to reduce, the butterfly depression after polishing increases.
Along with the development of unicircuit, on the one hand, in traditional IC industry, in order to improve integrated level, reduce energy consumption, shorten time of lag, live width is more and more narrow, the number of plies of wiring is also more and more, in order to guarantee performance and the stability of unicircuit, also more and more higher to the requirement of copper CMP.Require to reduce polish pressure the removal speed in the case of guaranteeing copper, improve the planarization of copper line surface, control surface defect.On the other hand, due to physical limitation, live width can not infinitely be dwindled, and semicon industry no longer merely relies on integrated more device on one chip and improves performance, and turns on multi-chip package.Silicon through hole (TSV) technology, realizes the state-of-the-art technology interconnecting between chip and obtains the extensive approval of industry member by between chip and chip, make vertical conducting between wafer and wafer as one.TSV can make chip in the stacking density maximum of three-dimensional, and physical dimension minimum is improved the performance of chip speed and reduce power consumption greatly.Current TSV technique is the copper perforation that forms through-silicon substrate in conjunction with traditional IC technique, in TSV opening, fills copper and realizes conducting, and after filling, unnecessary copper also needs to utilize chemically machinery polished removal to reach planarization.Different from traditional IC industry, because silicon through hole is very dark, filling the unnecessary copper in rear surface has a few to tens of micron thickness conventionally.In order to remove fast these unnecessary copper.Conventionally need to have very high copper and remove speed, the surface finish after polishing is simultaneously good.In order to make copper better application in semiconductor technology, people constantly attempt the improvement of new polishing fluid.
Chinese patent CN1256765C provides a kind of polishing fluid of the chelating organic acid buffer system that contains citric acid, Tripotassium Citrate composition.CN1195896C adopts and contains oxygenant, carboxylate salt as the polishing fluid of ammonium citrate, abrasive water, a kind of optional triazole or triazole derivative.CN1459480A provides a kind of chemical mechanical polishing liquid of copper, and it has comprised membrane-forming agent and film coalescence aid: membrane-forming agent mixes by highly basic and acetic acid the buffered soln forming and forms, and film coalescence aid is saltpetre (sodium) salt.U.S. Pat 552742 provides a kind of chemical mechanical polishing of metals slurry, comprises a kind of tensio-active agent that contains aramid fiber silica, alkane polysiloxane, polyoxyalkylene ether and multipolymer thereof.US6821897B2 provides the copper chemical mechanical polishing method of the rumbling compound that a kind of employing contains polymeric complexing agents, and it adopts the polymkeric substance containing negative charge, comprising thiosulfonic acid and salt thereof, vitriol, phosphoric acid, phosphoric acid salt, phosphoric acid ester etc.And US5527423 chemical mechanical polishing of metals slurry comprises a kind of tensio-active agent: aramid fiber siloxanes, polysiloxane, polyoxyalkylene ether and multipolymer thereof.
Technology in above-mentioned patent, all makes every effort in the polishing process of copper, reduces spot corrosion and the burn into control static etch rate of copper layer part, thereby can remove better copper layer, improves the polishing speed of copper and obtains good copper-connection planarity.Above-mentioned patent has overcome the problem that above-mentioned copper runs in polishing process to a certain extent, but effect not obvious has defect on copper surface after use, and planeness is low, and copper cash occurs that saucerization is large and crosses throwing window narrows after polishing; Or polishing speed is not high enough, can not be applied to removing the higher technique of rate requirement.
Summary of the invention
The invention provides a kind of chemical mechanical polishing of metals slurry, in described polishing slurries, add the tensio-active agent take phosphoric acid ester as main component, thereby lowered the corrosion of copper, in the polishing speed of the higher copper of maintenance, improve the planarization of the glazed surface of copper, strengthen polishing effect.
Chemical mechanical polishing of metals slurry of the present invention is achieved through the following technical solutions its object:
A kind of chemical mechanical polishing of metals slurry, comprises abrasive grains, complexing agent, corrosion inhibitor, oxygenant, wherein, also at least contains a kind of phosphoric acid ester tensio-active agent; Described phosphoric acid ester tensio-active agent contains one or both of following structural formula:
Wherein X=RO, RO-(CH
2cH
2o)
n, RCOO-(CH
2cH
2o)
n; R is the alkyl of C8 ~ C22 or alkylbenzene, glyceryl (C
3h
5o
3-) etc.; N=2 ~ 30, M=H, K, NH
4, (CH
2cH
2o)
1 ~ 3nH
3 ~ 1and/or Na.
Wherein, preferably comprise the compound of said structure (1) and these two kinds of structures of structure (2) simultaneously.Preferably, tensio-active agent is for to be selected from a compound of structure (1) and to be selected from the combination of a compound of structure (2).
Wherein when R is C
8～C
22alkyl time, tensio-active agent is polyoxyethylene ether phosphate or its salt, as alkylpolyoxyethylene phosphoric acid ester, alkylpolyoxyethylene phosphate kalium salt, octadecyl polyoxyethylene ether phosphate, octadecyl polyoxyethylene ether phosphate sylvite etc.In the time that R is alkylbenzene, tensio-active agent is alkylphenol polyoxyethylene phosphoric acid ester or its salt, comprises polyoxyethylene octylphenol ether phosphoric acid ester, polyoxyethylene nonylphenol ether phosphoric acid ester, octadecyl phenol polyethenoxy ether phosphoric acid ester sodium etc.Experimental results show that, in the static etch rate that can effectively be controlled copper by the chemical rightenning slurry of the compositions such as above-mentioned tensio-active agent and abrasive grains, complexing agent, oxygenant, alleviate the local corrosion of copper, in the removal speed of the higher copper of maintenance, improve the butterfly depression of copper cash after polishing and cross throwing window, obtaining the glazed surface of more smooth copper.
Above-mentioned chemical mechanical polishing of metals slurry, wherein, the content of described phosphoric acid ester tensio-active agent is weight percentage 0.0005 ~ 1%, is preferably weight percent 0.001 ~ 0.5%.
Above-mentioned chemical mechanical polishing of metals slurry, wherein, described abrasive grains is one or more mixing in silicon-dioxide, cerium dioxide, titanium dioxide and/or the polymer abrasive grains of silicon-dioxide, aluminum oxide, adulterated al or aluminium coating.
Above-mentioned chemical mechanical polishing of metals slurry, wherein, the particle diameter of described abrasive grains is 20 ~ 200nm.
Above-mentioned chemical mechanical polishing of metals slurry, wherein, the reference area of described abrasive grains is 5～1000m
2/ g.
Above-mentioned chemical mechanical polishing of metals slurry, wherein, the content of described abrasive grains is weight percentage 0.1～20%.
Above-mentioned chemical mechanical polishing of metals slurry, wherein, described complexing agent is one or more in ammonia carboxylation compound and salt, organic carboxyl acid and salt thereof, organic phospho acid and salt thereof and/or organic amine.
Above-mentioned chemical mechanical polishing of metals slurry, wherein, described ammonia carboxylation compound is selected from one or more in glycine, L-Ala, α-amino-isovaleric acid, leucine, proline(Pro), phenylalanine, tyrosine, tryptophane, Methionin, arginine, Histidine, Serine, aspartic acid, Threonine, L-glutamic acid, l-asparagine, glutamine, nitrilotriacetic acid(NTA), ethylenediamine tetraacetic acid (EDTA), hexanaphthene tetraacethyl, ethylenediamine disuccinic acid, diethylene triamine pentacetic acid (DTPA) and triethylenetetramine hexaacetic acid; Described organic carboxyl acid is one or more in acetic acid, oxalic acid, citric acid, tartrate, propanedioic acid, succinic acid, oxysuccinic acid, lactic acid, gallic acid and sulphosalicylic acid; Described organic phospho acid is 2-phosphonic acids butane-1, one or more in 2,4-tricarboxylic acid, Amino Trimethylene Phosphonic Acid, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid, ethylene diamine tetra methylene phosphonic acid and polyamino polyether base methylenephosphonic acid; Described organic amine is quadrol, diethylenetriamine, pentamethyl-diethylenetriamine, polyethylene polyamine, triethylene tetramine, tetraethylene pentamine; Described salt is sylvite, sodium salt and/or ammonium salt.
Above-mentioned chemical mechanical polishing of metals slurry, wherein, the content of described complexing agent is weight percentage 0.05～10%.Be preferably weight percent 0.1 ~ 5%
Above-mentioned chemical mechanical polishing of metals slurry, wherein, described oxygenant is one or more in hydrogen peroxide, urea peroxide, peroxyformic acid, Peracetic Acid, persulphate, percarbonate, Periodic acid, perchloric acid, high boric acid, potassium permanganate and iron nitrate.
Above-mentioned chemical mechanical polishing of metals slurry, wherein, the content of described oxygenant is weight percentage 0.05 ~ 10%.
Above-mentioned chemical mechanical polishing of metals slurry, wherein, described corrosion inhibitor is one or more in nitrogen azoles, imidazoles, thiazole, pyridine and pyrimidines.
Above-mentioned chemical mechanical polishing of metals slurry, wherein, nitrogen azole compounds comprises: benzotriazole, 5-methyl benzotriazazole, 5-carboxy benzotriazole, 1-hydroxyl-benzotriazole, 1, 2, 4-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 3, 5-diaminostilbene, 2, 4-triazole, 5-carboxyl-3-amino-1, 2, 4-triazole, 3-amino-5-sulfydryl-1, 2, 4-triazole, 5-acetic acid-1H-tetrazole, 5-methyl tetrazole, 5-phenyl tetrazole, 5-amino-1H-tetrazole and 1-phenyl-5-sulfydryl-tetrazole.Described glyoxaline compound comprises benzoglyoxaline and 2-mercaptobenzimidazole.Described thiazole compound comprises 2-sulfydryl-benzothiazole, 2-dimercaptothiodiazole and 5-amino-2-mercapto phenyl formic-1,3,4-thiadiazoles; Described pyridine comprises 2,3 diamino pyridine, PA and 2-pyridine carboxylic acid.Described pyrimidine is 2-aminopyrimidine.
Above-mentioned chemical mechanical polishing of metals slurry, wherein, the content of described corrosion inhibitor is weight percentage 0.001 ~ 2%, is preferably weight percent 0.005 ~ 1%.
Above-mentioned chemical mechanical polishing of metals slurry, wherein, pH is 3 ~ 11, is preferably 3 ~ 9.
Above-mentioned chemical mechanical polishing of metals slurry, wherein, also comprises pH adjusting agent, viscosity modifier, defoamer, the additive of this area routines such as sterilant.
Above-mentioned chemical mechanical polishing of metals slurry can be prepared into concentrating sample by other components except oxygenant, before using, is diluted to concentration range of the present invention and adds oxygenant with deionized water.
The application of polishing slurries of the present invention in the chemically machinery polished of the base material that contains copper.Adopt its advantage of chemical mechanical polishing of metals slurry of the present invention to be:
1. chemical mechanical polishing of metals slurry of the present invention has higher copper removal speed, can effectively control the corrosion of copper simultaneously, and the copper surface after polishing is corrosion-free.
2. chemical mechanical polishing of metals slurry of the present invention has strengthened the polishing effect of copper, improves the butterfly depression of copper cash after polishing and crosses throwing window.
Accompanying drawing explanation
Figure 1A and 1B are the copper wafer surface electron scanning micrograph adopting after polishing slurries polishing of the present invention;
Fig. 2 A and 2B are the copper wafer surface electron scanning micrograph adopting after polishing slurries polishing of the present invention immersion.
Embodiment
Further set forth the present invention below by embodiment.
embodiment 1 ~ 49
Table 1 has provided the embodiment 1 ~ 49 of chemical mechanical polishing liquid of the present invention, by the formula of giving in table, other components except oxygenant is mixed, and water is supplied mass percent to 100%.With KOH or HNO
3be adjusted to needed pH value.Oxidizer before using, mixes.
Table 1 embodiment 1 ~ 49
effect embodiment
Table 2 has provided embodiment 50 ~ 71 and the comparative example 1 ~ 6 of chemical mechanical polishing liquid of the present invention, by the formula of giving in table, other components except oxygenant is mixed, and water is supplied mass percent to 100%.With KOH or HNO
3be adjusted to needed pH value.Oxidizer before using, mixes.
Table 2, comparative example 1 ~ 6 and embodiment 50 ~ 71
Adopt contrast polishing fluid 1 ~ 3 and polishing fluid of the present invention 50 ~ 65, to empty sheet copper (Cu) wafer with there is the copper wafer of figure to carry out polishing.The polishing speed of the copper of gained is in table 3, and the dish-like depression value of the polishing condition of graphical wafer and copper billet is in table 4.
Empty sheet copper wafer polishing condition: overdraft 1 ~ 3psi; Polishing disk and rubbing head rotating speed 93/87rpm, polishing pad IC1010, polishing fluid flow velocity 150ml/min, polishing machine platform is 8 " Mirra.
Figuratum copper wafer polishing processing condition: polishing disk and rubbing head rotating speed 93/87rpm, polishing pad IC1010, polishing fluid flow velocity 150ml/min, polishing machine platform is 8 " Mirra.On polishing disk 1 with the figuratum copper wafer of corresponding overdraft polishing to the about 3000A of remaining copper, and then on polishing disk 2, by corresponding overdraft, residual copper is removed and is crossed and throw 20 seconds.Measure the dish-like depression value of the copper billet of 80um*80um on figuratum copper wafer by XE-300P atomic force microscope.
Graphical wafer after polishing is soaked 30 minutes in polishing fluid, and copper line surface situation before and after soaking with sem observation, is shown in attached Fig. 1 and 2.
Copper under the different polish pressures of table 3, polishing fluid is removed speed
The saucerization value at 80um*80um copper billet place after the polishing condition of the figuratum copper wafer of table 4 and polishing
Can learn from form 3: compared with contrast polishing fluid, chemical mechanical polishing of metals slurry of the present invention can effectively reduce the removal speed of copper under low overdraft, and little on the removal speed impact under higher overdraft.This specific character can make polishing fluid still can obtain more smooth glazed surface under the higher removal speed of maintenance, has greatly improved production efficiency, has reduced again the saucerization value of the copper billet after polishing.With the approaching condition of removal speed of contrast polishing fluid 2 under, also can obtain lower saucerization value.(in table 4)
See accompanying drawing 1 ~ 2 with the SEM figure of the graphical wafer after embodiment 57 polishings and after polishing and immersion, as seen from the figure, corrosion-free by the wafer surface after this polishing fluid polishing, zero defect.In polishing fluid, soak 30 minutes, copper cash still, without obviously corroding and defect, illustrates that polishing fluid of the present invention has the ability of very strong inhibition metallic corrosion.
Adopt contrast polishing fluid 5 and polishing fluid of the present invention 66 ~ 71, to empty sheet copper (Cu) wafer, empty sheet silica wafers, empty sheet tantalum wafer and have the copper wafer of figure to carry out polishing.The dish-like depression value of the polishing speed of gained and copper billet is in table 5.
Empty sheet polishing condition: overdraft 1 ~ 3psi; Polishing disk and rubbing head rotating speed 93/87rpm, polishing pad IC1010, polishing fluid flow velocity 150ml/min, polishing machine platform is 8 " Mirra.
Figuratum copper wafer polishing processing condition: polishing disk and rubbing head rotating speed 93/87rpm, polishing pad IC1010, polishing fluid flow velocity 150ml/min, polishing machine platform is 8 " Mirra.On polishing disk 1, use the figuratum copper wafer of overdraft polishing of 3psi to the about 5000A of remaining copper, and then the overdraft with 2psi is removed residual copper on polishing disk 2.Measure the dish-like depression value at the copper cash place of 10um/10um (copper cash/silicon-dioxide) on figuratum copper wafer by XE-300P atomic force microscope.
Saucerization value after the empty sheet removal speed of table 5, polishing fluid and polishing condition and the polishing of figuratum copper wafer
Can learn from form 5: compared with contrast polishing fluid 5, chemical mechanical polishing of metals slurry 66～68 of the present invention can still can obtain more smooth glazed surface under the higher removal speed of maintenance, from embodiment 69～71, this polishing fluid copper remove speed adjustable in, the removal speed of higher silicon-dioxide and tantalum also can be provided.This polishing fluid can meet different application demands.
Adopt contrast polishing fluid 5,6 and polishing fluid of the present invention 66～68, figuratum copper wafer is carried out to polishing.Polishing technological conditions: polishing disk and rubbing head rotating speed 93/87rpm, polishing pad IC1010, polishing fluid flow velocity 150ml/min, polishing machine platform is 8 " Mirra.On polishing disk 1, use the figuratum copper wafer of overdraft polishing of 3psi to residual copper approximately 5000 dusts, and then the overdraft with 2psi is removed remaining copper on polishing disk 2.Observe after polishing on figuratum copper wafer the residual condition of copper in table 6
Copper residual condition on table 6, chip surface after polishing
| Embodiment | Copper is residual |
| Contrast 5 | Nothing |
| Contrast 6 | Have |
| 66 | Nothing |
| 67 | Nothing |
| 68 | Nothing |
From table 6, in the polishing fluid of contrast 6, use separately phosphate ester surfactants, chip surface after polishing has copper residual, uses separately azole corrosion inhibitor in the polishing fluid of contrast 5, although surface of polished is residual without copper, dish-like depression is larger.And in embodiment 66～68, used the combination of azole corrosion inhibitor and phosphate ester surfactants, and can reduce dish-like depression, residual without copper again after polishing.
Should be understood that, wt% of the present invention all refers to quality percentage composition.
Above specific embodiments of the invention be have been described in detail, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and alternative also all among category of the present invention.Therefore, equalization conversion and the modification done without departing from the spirit and scope of the invention, all should contain within the scope of the invention.
Claims (20)
1. a chemical mechanical polishing of metals slurry, comprises abrasive grains, complexing agent, corrosion inhibitor, oxygenant, it is characterized in that, also at least contains a kind of phosphoric acid ester tensio-active agent.
2. chemical mechanical polishing of metals slurry as claimed in claim 1, is characterized in that, described phosphoric acid ester tensio-active agent at least contains one or more of following structural formula:
3. chemical mechanical polishing of metals slurry as claimed in claim 1, is characterized in that, described phosphoric acid ester tensio-active agent at least contains two or more of following structural formula:
4. chemical mechanical polishing of metals slurry as claimed in claim 1, is characterized in that, the content of described phosphoric acid ester tensio-active agent is weight percentage 0.0005 ~ 1%.
5. chemical mechanical polishing of metals slurry as claimed in claim 4, is characterized in that, the content of described phosphoric acid ester tensio-active agent is weight percentage 0.001 ~ 0.5%.
6. chemical mechanical polishing of metals slurry as claimed in claim 1, it is characterized in that, described abrasive grains is one or more in the silicon-dioxide, cerium dioxide, titanium dioxide, polymer abrasive grains of silicon-dioxide, aluminum oxide, adulterated al or aluminium coating.
7. chemical mechanical polishing of metals slurry as claimed in claim 1, is characterized in that, the particle diameter of described abrasive grains is 20～200nm.
8. chemical mechanical polishing of metals slurry as claimed in claim 1, is characterized in that, the weight percent concentration of described abrasive grains is 0.1～20%.
9. chemical mechanical polishing of metals slurry as claimed in claim 1, is characterized in that, described complexing agent is one or more in ammonia carboxylation compound and salt, organic carboxyl acid and salt thereof, organic phospho acid and salt thereof and organic amine.
10. metallochemistry polishing slurries as claimed in claim 9, it is characterized in that, described ammonia carboxylation compound is selected from one or more in glycine, L-Ala, α-amino-isovaleric acid, leucine, proline(Pro), phenylalanine, tyrosine, tryptophane, Methionin, arginine, Histidine, Serine, aspartic acid, Threonine, L-glutamic acid, l-asparagine, glutamine, nitrilotriacetic acid(NTA), ethylenediamine tetraacetic acid (EDTA), hexanaphthene tetraacethyl, ethylenediamine disuccinic acid, diethylene triamine pentacetic acid (DTPA) and triethylenetetramine hexaacetic acid; Described organic carboxyl acid is one or more in acetic acid, oxalic acid, citric acid, tartrate, propanedioic acid, succinic acid, oxysuccinic acid, lactic acid, gallic acid and sulphosalicylic acid; Described organic phospho acid is 2-phosphonic acids butane-1, one or more in 2,4-tricarboxylic acid, Amino Trimethylene Phosphonic Acid, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid, ethylene diamine tetra methylene phosphonic acid and polyamino polyether base methylenephosphonic acid; Described organic amine is quadrol, diethylenetriamine, pentamethyl-diethylenetriamine, polyethylene polyamine, triethylene tetramine, tetraethylene pentamine; Described salt is sylvite, sodium salt and/or ammonium salt.
11. chemical mechanical polishing of metals slurries as claimed in claim 1, is characterized in that, the content of described complexing agent is weight percentage 0.05～10%.
12. chemical mechanical polishing of metals slurries as claimed in claim 11, is characterized in that, the content of described complexing agent is preferably weight percent 0.1～5%.
13. chemical mechanical polishing of metals slurries as claimed in claim 1, it is characterized in that, described oxygenant is one or more in hydrogen peroxide, urea peroxide, peroxyformic acid, Peracetic Acid, persulphate, percarbonate, Periodic acid, perchloric acid, high boric acid, potassium permanganate and iron nitrate.
14. chemical mechanical polishing of metals slurries as claimed in claim 1, is characterized in that, the content of described oxygenant is weight percentage 0.05～10%.
15. chemical mechanical polishing of metals slurries as claimed in claim 1, is characterized in that, described corrosion inhibitor is one or more in nitrogen azoles, imidazoles, thiazole, pyridine and pyrimidines.
16. chemical mechanical polishing of metals slurries as claimed in claim 15, it is characterized in that, described nitrogen azole compounds is selected from benzotriazole, 5-methyl benzotriazazole, 5-carboxy benzotriazole, 1-hydroxyl-benzotriazole, 1, 2, 4-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 3, 5-diaminostilbene, 2, 4-triazole, 5-carboxyl-3-amino-1, 2, 4-triazole, 3-amino-5-sulfydryl-1, 2, 4-triazole, 5-acetic acid-1H-tetrazole, 5-methyl tetrazole, 5-phenyl tetrazole, 5-amino-1H-tetrazole and 1-phenyl-5-sulfydryl-tetrazole.Described glyoxaline compound comprises benzoglyoxaline and 2-mercaptobenzimidazole.Described thiazole compound comprises 2-sulfydryl-benzothiazole, 2-dimercaptothiodiazole and 5-amino-2-mercapto phenyl formic-1,3,4-thiadiazoles; Described pyridine is selected from one or more in following: 2,3 diamino pyridine, PA and 2-pyridine carboxylic acid.Described pyrimidine is 2-aminopyrimidine.
17. chemical mechanical polishing of metals slurries as claimed in claim 1, is characterized in that, the content of described corrosion inhibitor is weight percentage 0.001～2%.
18. chemical mechanical polishing of metals slurries as claimed in claim 17, is characterized in that, the content of described corrosion inhibitor is weight percentage 0.005～1%.
19. chemical mechanical polishing of metals slurries as claimed in claim 1, is characterized in that, described abrasive grains specific surface area is 5～1000m
2/ g
The application in the chemically machinery polished of the base material that contains copper of 20. 1 kinds of polishing slurries as described in any one in claim 1～19.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210528946.6A CN103866326A (en) | 2012-12-10 | 2012-12-10 | Chemo-mechanical polishing slurry for metal, and its application |
| PCT/CN2013/001493 WO2014089905A1 (en) | 2012-12-10 | 2013-12-03 | Metal chemical mechanical polishing slurry and application thereof |
| TW102145087A TW201422741A (en) | 2012-12-10 | 2013-12-09 | Chemical mechanical polishing slurry and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210528946.6A CN103866326A (en) | 2012-12-10 | 2012-12-10 | Chemo-mechanical polishing slurry for metal, and its application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103866326A true CN103866326A (en) | 2014-06-18 |
Family
ID=50905321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210528946.6A Pending CN103866326A (en) | 2012-12-10 | 2012-12-10 | Chemo-mechanical polishing slurry for metal, and its application |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN103866326A (en) |
| TW (1) | TW201422741A (en) |
| WO (1) | WO2014089905A1 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104745094A (en) * | 2013-12-26 | 2015-07-01 | 安集微电子（上海）有限公司 | Chemically mechanical polishing liquid |
| CN105350000A (en) * | 2015-12-02 | 2016-02-24 | 苏州捷德瑞精密机械有限公司 | Environment-friendly type aluminum alloy material polishing solution and preparation method thereof |
| WO2017114301A1 (en) * | 2015-12-31 | 2017-07-06 | 安集微电子科技(上海)有限公司 | Chemical and mechanical polishing slurry for metal |
| WO2017169743A1 (en) * | 2016-03-28 | 2017-10-05 | 株式会社フジミインコーポレーテッド | Polishing composition used for polishing of polishing object having layer that contains metal |
| JP2017179333A (en) * | 2016-03-28 | 2017-10-05 | 株式会社フジミインコーポレーテッド | Composition for polishing used for polishing of polishing object having metal-containing layer |
| WO2018030006A1 (en) * | 2016-08-09 | 2018-02-15 | 株式会社フジミインコーポレーテッド | Surface treatment composition and surface treatment method in which same is used |
| CN108250234A (en) * | 2016-12-28 | 2018-07-06 | 安集微电子（上海）有限公司 | A kind of synthesis technology of phosphate ester surfactants and its application |
| CN111378376A (en) * | 2018-12-29 | 2020-07-07 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution and application thereof |
| CN113122142A (en) * | 2019-12-31 | 2021-07-16 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing solution |
| CN113748179A (en) * | 2020-03-31 | 2021-12-03 | 富士胶片电子材料美国有限公司 | Polishing composition and method of use thereof |
| WO2022143719A1 (en) * | 2020-12-30 | 2022-07-07 | 安集微电子科技（上海）股份有限公司 | Chemical-mechanical polishing solution and use method therefor |
| CN115928073A (en) * | 2022-11-28 | 2023-04-07 | 广东红日星实业有限公司 | A kind of abrasive liquid and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463225A (en) * | 2007-12-21 | 2009-06-24 | 安集微电子（上海）有限公司 | Chemico-mechanical polishing solution for barrier layer |
| CN102533118A (en) * | 2010-12-10 | 2012-07-04 | 安集微电子（上海）有限公司 | Chemical mechanical polishing size |
| CN103160207A (en) * | 2011-12-16 | 2013-06-19 | 安集微电子（上海）有限公司 | Metal chemico-mechanical polishing sizing agent and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101266539B1 (en) * | 2008-12-29 | 2013-05-23 | 제일모직주식회사 | CMP slurry composition for polishing copper wiring and polishing method using the same |
| CN102453440A (en) * | 2010-10-22 | 2012-05-16 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
-
2012
- 2012-12-10 CN CN201210528946.6A patent/CN103866326A/en active Pending
-
2013
- 2013-12-03 WO PCT/CN2013/001493 patent/WO2014089905A1/en active Application Filing
- 2013-12-09 TW TW102145087A patent/TW201422741A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463225A (en) * | 2007-12-21 | 2009-06-24 | 安集微电子（上海）有限公司 | Chemico-mechanical polishing solution for barrier layer |
| CN102533118A (en) * | 2010-12-10 | 2012-07-04 | 安集微电子（上海）有限公司 | Chemical mechanical polishing size |
| CN103160207A (en) * | 2011-12-16 | 2013-06-19 | 安集微电子（上海）有限公司 | Metal chemico-mechanical polishing sizing agent and application thereof |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104745094A (en) * | 2013-12-26 | 2015-07-01 | 安集微电子（上海）有限公司 | Chemically mechanical polishing liquid |
| CN104745094B (en) * | 2013-12-26 | 2018-09-14 | 安集微电子（上海）有限公司 | A kind of chemical mechanical polishing liquid |
| CN105350000A (en) * | 2015-12-02 | 2016-02-24 | 苏州捷德瑞精密机械有限公司 | Environment-friendly type aluminum alloy material polishing solution and preparation method thereof |
| WO2017114301A1 (en) * | 2015-12-31 | 2017-07-06 | 安集微电子科技(上海)有限公司 | Chemical and mechanical polishing slurry for metal |
| CN106929858A (en) * | 2015-12-31 | 2017-07-07 | 安集微电子科技(上海)有限公司 | Chemical mechanical polishing of metals slurry |
| WO2017169743A1 (en) * | 2016-03-28 | 2017-10-05 | 株式会社フジミインコーポレーテッド | Polishing composition used for polishing of polishing object having layer that contains metal |
| JP2017179333A (en) * | 2016-03-28 | 2017-10-05 | 株式会社フジミインコーポレーテッド | Composition for polishing used for polishing of polishing object having metal-containing layer |
| US10876073B2 (en) | 2016-08-09 | 2020-12-29 | Fujimi Incorporated | Composition for surface treatment, and method for surface treatment using the same |
| WO2018030006A1 (en) * | 2016-08-09 | 2018-02-15 | 株式会社フジミインコーポレーテッド | Surface treatment composition and surface treatment method in which same is used |
| JP2018024745A (en) * | 2016-08-09 | 2018-02-15 | 株式会社フジミインコーポレーテッド | Surface-treatment composition and cleaning method using the same |
| CN108250234A (en) * | 2016-12-28 | 2018-07-06 | 安集微电子（上海）有限公司 | A kind of synthesis technology of phosphate ester surfactants and its application |
| CN111378376A (en) * | 2018-12-29 | 2020-07-07 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution and application thereof |
| CN113122142A (en) * | 2019-12-31 | 2021-07-16 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing solution |
| CN113122142B (en) * | 2019-12-31 | 2024-04-12 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing solution |
| CN113748179A (en) * | 2020-03-31 | 2021-12-03 | 富士胶片电子材料美国有限公司 | Polishing composition and method of use thereof |
| WO2022143719A1 (en) * | 2020-12-30 | 2022-07-07 | 安集微电子科技（上海）股份有限公司 | Chemical-mechanical polishing solution and use method therefor |
| CN115928073A (en) * | 2022-11-28 | 2023-04-07 | 广东红日星实业有限公司 | A kind of abrasive liquid and its preparation method and application |
| CN115928073B (en) * | 2022-11-28 | 2025-01-07 | 广东红日星实业有限公司 | A grinding liquid and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014089905A1 (en) | 2014-06-19 |
| TW201422741A (en) | 2014-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103160207A (en) | Metal chemico-mechanical polishing sizing agent and application thereof | |
| CN103866326A (en) | Chemo-mechanical polishing slurry for metal, and its application | |
| CN106929858A (en) | Chemical mechanical polishing of metals slurry | |
| CN101747843A (en) | Chemical-mechanical polishing solution | |
| CN101747844B (en) | Chemically mechanical polishing solution and application thereof | |
| CN102101982A (en) | Chemical mechanical polishing solution | |
| CN102533118B (en) | Chemical mechanical polishing size | |
| CN102477262B (en) | Chemically mechanical polishing slurry | |
| CN103865400A (en) | Application of organic phosphate surfactant in self-stopping polishing | |
| CN105637986B (en) | The manufacturing method of polishing composition and printed wiring board | |
| CN102093818A (en) | Chemical mechanical polishing slurry and application thereof | |
| CN108250977A (en) | A kind of chemical mechanical polishing liquid for barrier layer planarization | |
| CN103898510A (en) | Chemico-mechanical polishing solution and technique for copper interconnection | |
| CN101665664B (en) | Quaternary ammonium salt cationic surfactant and application of chemical mechanical polishing solution | |
| CN103897602B (en) | A kind of chemical mechanical polishing liquid and polishing method | |
| CN104745086A (en) | Chemical mechanical polishing solution for barrier layer planarization, and use method thereof | |
| CN108251845A (en) | A kind of chemical mechanical polishing liquid and its application | |
| CN103898512B (en) | A kind of chemical mechanical polishing liquid and technique for copper-connection | |
| CN103897600A (en) | Chemical mechanical polishing liquid and application thereof | |
| CN104745088B (en) | A kind of chemical mechanical polishing liquid and its application method for barrier layer planarization | |
| CN108250973A (en) | A kind of chemical mechanical polishing liquid for barrier layer planarization | |
| CN102477259B (en) | Chemically mechanical polishing slurry | |
| CN105273636A (en) | Chemical mechanical polishing liquid | |
| CN103898511A (en) | Technology for copper interconnection polishing | |
| CN109971357A (en) | A kind of chemical mechanical polishing liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140618 |