CN103878707B - Polishing pad of chemically mechanical polishing and preparation method thereof - Google Patents
Polishing pad of chemically mechanical polishing and preparation method thereof Download PDFInfo
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- CN103878707B CN103878707B CN201410125463.0A CN201410125463A CN103878707B CN 103878707 B CN103878707 B CN 103878707B CN 201410125463 A CN201410125463 A CN 201410125463A CN 103878707 B CN103878707 B CN 103878707B
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Abstract
The invention discloses a kind of polishing pad preparation method of chemically mechanical polishing, solve existing polishing pad technique more complicated, rash delamination, the problem that energy consumption is high, cost is high, the production cycle is long, technical scheme comprises and first manufactures polishing layer, then at polishing layer top casting cushion, obtain polishing pad finally by after slaking, polishing layer and cushion are created by the mode of direct casting, without the need to adhesive, but be connected together by chemical bond-linking.The polishing layer of polishing pad of the present invention and the combination of cushion are very firm, there is not the problem that interlayer adhesive is vulnerable to the chemical erosion of polishing fluid, have that technology difficulty is low, production cost is low, the advantage of long service life.
Description
Technical field
The present invention relates to a kind of polishing pad and preparation method thereof, polishing pad of a kind of chemically mechanical polishing specifically and preparation method thereof.
Background technology
In the manufacture of optical substrate materials, integrated circuit and other electronic device, usually can relate to some chemically mechanical polishings (CMP) technique.In general CMP, polished material to be placed on bracket system and to contact with the polishing layer in polishing pad.Described polishing pad is fixed on platen.Described bracket system is used for providing controlled pressure to polished material, thus is pressed on polishing pad.Under external motivating force, described polishing pad and wafer rotate relative to each other.Meanwhile, polishing fluid (such as comprise the polishing slurries of abrasive material or do not contain the active liquid of abrasive material) is made to flow on polishing pad and in the space of polished material and polishing pad.Thus by chemistry on the surface of polished material of polishing layer and polishing medium and mechanism, the surface of polished material is polished and planarized.
CMP polishing pad comprises at least two-layer usually, such as polishing layer and cushion.They are generally bonding by hot-melt adhesive or contact adhesive and combine.This multilayer polishing mattress is disclosed in such as United States Patent (USP) 5257478.There are some problems in the polishing pad relying on adhesive to be combined by different materials.Such as, these adhesives need solidification 24 hours or longer time, these adhesives are vulnerable to the chemical erosion of polishing fluid, chemical mechanical polishing pads stacked together tends to occur delamination during polishing problem usually, and the technique being connected multilayer material by adhesive is more complicated, energy consumption is high, cost is high, the production cycle is long, and reliability is low.
Summary of the invention
The object of the invention is to solve the problems of the technologies described above, provide a kind of technique simple, without the need to the polishing pad of adhesive, good reliability, adhesive strength is high, difficult drop-off, energy consumption are low, cost is low, efficiency is high, with short production cycle chemically mechanical polishing.
The present invention also provides a kind of polishing pad obtained by above-mentioned process, and polishing layer and cushion combine firmly, have excellent mechanical property and good process industrial art performance.
Polishing pad of the present invention comprises connected polishing layer and cushion, and its preparation method comprises the following steps:
(1) uncured polishing layer preparation: cast on mould after component A and B component being mixed in the ratio of 2:1 to 3:1, gelation 1-15 minute obtains uncured polishing layer at 20-45 DEG C,
Wherein, component A is the isocyanate-terminated performed polymer of the unreacted NCO group containing 5-28 % by weight, and B component comprises multi-functional alefinically unsaturated compounds, high molecular weight polyols (molecular weight is 500-1000), catalyst, polymer microballoon, foam stabilizer and radical initiator;
(2) preparation of cushion: C component and D component are rushed pre-cast liquid in obtaining slow layer after the ratio mixing of 2:3 to 3:1, described cushion pre-cast liquid is cast on the uncured polishing layer described in step (1), then at 60-100 DEG C, gelation 10-60 minute obtains cushion, multi-functional alefinically unsaturated compounds in cushion and carrying out radical polymerization containing multi-functional alefinically unsaturated compounds and form chemical bond and be connected in polishing layer, make cushion be connected with polishing layer; Cast temperature in described step (2) is preferably 60-80 DEG C.
Wherein, C component contains the isocyanate-terminated performed polymer of the unreacted NCO group of 5-28 % by weight; D component comprises multi-functional alefinically unsaturated compounds, high molecular weight polyols, catalyst, polymer microballoon, foam stabilizer and radical initiator.
(3) preparation of polishing pad: obtain polishing pad by after connected polishing layer and cushion slaking.
The Shore D hardness of described polishing layer is 45-70; Density is 0.7-1.1 gram/cc; The Shore D hardness of described cushion is 10-20; Density is 0.2-0.35 gram/cc.
The isocyanate-terminated performed polymer of unreacted NCO group containing 5-28 % by weight in described component A is obtained after the performed polymer polyol reaction of 500-1000 by aromatic polyfunctional's isocyanates and molecular weight, described aromatic polyfunctional's isocyanates is selected from 4,4 '-methyl diphenylene diisocyanate (4,4 '-MDI), 2,4 '-MDI, at least one in liquefied mdi and polymeric MDI.
Described molecular weight is that the performed polymer polyalcohol of 500-1000 is selected from polypropylene ether glycol, polytetramethylene ether diol and composition thereof.Preferred molecular weight is the performed polymer polyalcohol of 500-1000 is polytetramethylene ether diol.
The isocyanate-terminated performed polymer of the unreacted NCO group containing 5-28 % by weight in described C component is obtained after the prepolymer polyol being 1100-2000 by aromatic polyfunctional's isocyanates and molecular weight reacts, described aromatic polyfunctional's isocyanates is selected from 4,4 '-methyl diphenylene diisocyanate (4,4 '-MDI), 2,4 '-MDI, at least one in liquefied mdi and polymeric MDI.
Described molecular weight is the ester group polyol, polytetramethylene ether diol and composition thereof that the performed polymer polyalcohol of 1100-2000 is selected from polypropylene ether glycol, hexanedioic acid second diester or hexanedioic acid fourth diester and so on.Preferred described molecular weight is the performed polymer polyalcohol of 1100-2000 is polypropylene ether glycol.
Multi-functional alefinically unsaturated compounds in described B component and D component is selected from least one in polyhydroxy alefinically unsaturated compounds, polyamino alefinically unsaturated compounds, polyhydroxy polyamino alefinically unsaturated compounds, and containing at least one polymerisable ethylene linkage.
Multi-functional alefinically unsaturated compounds in described B component and D component is selected from least one in following general formula compound.
General formula (A)
General formula (B)
General formula (C)
Wherein, the Y in general formula (A) and (B)
1, Y
2, Y
3, Y
4, Y
5and Y
6independently be selected from hydroxyl, amino, vinyl, acryloxy, hydrogen, C
1-6alkyl and halogen, and have 2 groups selected from hydroxyl or amino at least in a molecule, and have at least 1 group to be selected from vinyl or acryloyl group; Y in general formula (C)
1, Y
2, Y
3and Y
4independently be selected from hydroxyl, amino, vinyl, acryloxy, hydrogen, C
1-6alkyl or halogen, and have 2 groups selected from hydroxyl or amino at least in a molecule, and have at least 1 group to be selected from vinyl or acryloyl group.
Described multi-functional alefinically unsaturated compounds in more preferably described B component and D component is selected from 2,2 '-diaminourea-3,3 '-two chloro-4, the chloro-5-(4-methyl-3 of 4 '-divinyl diphenyl-methane, 2-, 5-divinyl toluene)-1, at least one in 3-diphenylamines, 5-(3,5-diaminourea-4-chlorine Bian Ji)-1,3-phenyl diacrylate.
Described B component adds up to 100%, and the mass percent shared by each composition is respectively: the unsaturated olefinic compounds 19-30% of polyfunctional group, high molecular weight polyols 67-79.6%, catalyst 0.1%, polymer microballoon 0.3-1.0%, foam stabilizer 0.1-0.3%, radical initiator 0.1-0.4%.
Add up to 100% in described D component, the shared mass percent of each composition is respectively: the unsaturated olefinic compounds 15-28.5% of polyfunctional group, high molecular weight polyols 69.1-82%, catalyst 0.1%, polymer microballoon 1.9-3.1%, foam stabilizer 0.1-0.2%, radical initiator 0.1-0.4%.
In polyfunctional group alefinically unsaturated compounds in polyfunctional group alefinically unsaturated compounds in described step (1) and total hydroxy radical content of high molecular weight polyols and described isocyanate-terminated performed polymer in the equivalent proportion (OH/NCO) of unreacted NCO group and described step (2) and total hydroxy radical content of high molecular weight polyols and described isocyanate-terminated performed polymer, equivalent proportion (OH/NCO) scope of unreacted NCO group is all 0.1-0.9.
Equivalent proportion (the NH of unreacted NCO group in the amido of the multi-functional alefinically unsaturated compounds described in described step (1) and described isocyanate-terminated performed polymer
2/ NCO) and the amido of the multi-functional alefinically unsaturated compounds described in described step (2) and described isocyanate-terminated performed polymer in the equivalent proportion (NH of unreacted NCO group
2/ NCO) be all 0.7-0.1.
In described step (3), described curing temperature is 100-160 DEG C, and the curing time is 5-10 hour.
Described in described B component and D component, radical initiator is 2,2 '-azodiisobutyronitrile (AIBN), 2,2 '-azo two (2,4-methyl pentane nitrile), benzoyl peroxide, dicumyl peroxide, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy acetophenones or 1-hydroxy-cyclohexyl phenyl ketone.
Described in described B component and D component, high molecular weight polyols is selected from least one in PPG or PEPA.
The polishing pad of chemically mechanical polishing of the present invention, is obtained by above-mentioned preparation method.
The polishing layer of polishing pad of the present invention and cushion are created by the mode of direct casting, without the need to adhesive, but is connected together by chemical bond-linking, so the combination of the polishing layer of polishing pad of the present invention and cushion very firmly (T
peel offintensity is at least greater than 150 newton under 305mm/min) and there is not the problem that interlayer adhesive is vulnerable to the chemical erosion of polishing fluid.
Preferably, described high molecular weight polyols is selected from polytetramethylene ether diol.
Preferably, described catalyst is selected from least one in organo-bismuth, organic zinc, zinc bismuth composite catalyst.
Preferably, described polymer microballoon is commercial, as the polymer microballoon that A Ke Nobel company (AkzoNobel) produces.
Preferably, described radical initiator is selected from least one in thermal initiator, light trigger.More preferably, described radical initiator is selected from 2,2 '-azodiisobutyronitrile (AIBN), 2,2 '-azo two (2,4-methyl pentane nitrile), benzoyl peroxide, dicumyl peroxide, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy acetophenones or 1-hydroxy-cyclohexyl phenyl ketone.
The present invention is when casting polishing layer, the cross-linked polyurethane materials that chain extension and cross-linking reaction obtain containing thiazolinyl can be there is in the isocyanate-terminated performed polymer in component A and B component and multi-functional alefinically unsaturated compounds (the multi-functional alefinically unsaturated compounds such as containing three hydroxyls and a thiazolinyl) under the effect of catalyst, reaction is carried out 1-15 minute (preferred 1-5 minute) under 20-45 DEG C (preferred 10-30 DEG C), uncured polishing layer can be formed, on this basis, further at the raw material of polishing layer top casting cushion, now have two reactions to occur: one is that same polishing layer is the same, there is the cross-linked polyurethane materials that chain extension and cross-linking reaction obtain containing thiazolinyl in the isocyanate-terminated performed polymer in cushion and multi-functional alefinically unsaturated compounds (the multi-functional alefinically unsaturated compounds such as containing three hydroxyls and a thiazolinyl), two is that the cross-linked polyurethane materials containing thiazolinyl in polishing layer and the cross-linked polyurethane materials containing thiazolinyl in cushion can issue raw radical polymerization in the effect of radical initiator, thus the cross-linked polyurethane materials containing thiazolinyl in polishing layer and the cross-linked polyurethane materials containing thiazolinyl in cushion are connected together by chemical bond-linking.Above-mentioned two chemical reactions can or asynchronously carry out (preferably carrying out) simultaneously simultaneously, and reaction temperature is at 60-100 DEG C (preferred 60-80 DEG C), and the time is 10-60 minute (preferably 30 minutes); It is after the insulating box of 100-160 DEG C (preferably 100 DEG C) carries out slaking 5-10 hour (preferably 6 hours) that above-mentioned connected polishing layer and cushion are put into temperature, can obtain polishing pad polishing layer and cushion connected together by chemical bond, the material of polishing layer and cushion is all cross-linked structure.Because double-layer structure is connected together by chemical bond-linking, therefore more firm than the structure of bonding agent, and owing to being disposable casting, therefore with short production cycle.
Described foam stabilizer is selected from organic silicon surfactant.
Beneficial effect:
1. the present invention adopts the method for direct casting to prepare two-layer polishing pad, makes polishing pad one-shot forming, takes over for traditional physical bonds, process is simple, technology difficulty is low, production cost is low with chemical bond-linking.
2. do not use adhesive completely, between polishing layer and cushion, adopt key to connect, in conjunction with T
peel offintensity is at least greater than 150 newton under 305mm/min, far above using the bonding strength of common adhesive, is not vulnerable to the chemical erosion of polishing fluid, difficult drop-off, extends service life.
3. the material of polishing layer and cushion is all cross-linked structure, and because double-layer structure is connected together by chemical bond-linking, therefore this polishing layer has excellent mechanical property and good process industrial art performance.
4. bonding for a long time without the need to high temperature, without the need to special equipment, equipment investment is low, energy consumption is low, with short production cycle, improve production efficiency.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of technological process.
Detailed description of the invention
Following percentage units is mass percent.
Embodiment 1:
The raw material of polishing layer:
Component A: 4,4 '-methyl diphenylene diisocyanate 50.2%, molecular weight is the polytetramethylene ether diol 49.8% of 800, and 70 DEG C of reactions 2 hours, vacuum (-0.095MPa) deaeration, obtained the performed polymer that isocyano-content is 28.0%.
B component: 2,2 '-diaminourea-3,3 '-two chloro-4,4 '-divinyl diphenyl-methane 20.4%, the polypropylene ether glycol 78.2% of molecular weight 1000, organozinc catalyst 0.1%,
polymer microballoon 1.0%, hard bubble silicone oil 0.1% and 2,2 '-azodiisobutyronitrile 0.2%, obtains finely dispersed mixed liquor after rapid mixing.
According to the quality of 2:1 be mixed for 15 seconds under the condition of 5000rpm than low whipping speed by component A and B component, be cast to early in off-the-shelf mould, at temperature is 20 DEG C, gelation 10 minutes, obtains uncured polishing layer.
The raw material of cushion:
C component: 4,4 '-methyl diphenylene diisocyanate 48.9%, molecular weight is the polypropylene ether glycol 51.1% of 1500, and 70 DEG C of reactions 2 hours, vacuum (-0.095MPa) deaeration, obtained the performed polymer that isocyano-content is 18.2%.
D component: 2,2 '-diaminourea-3,3 '-two chloro-4,4 '-divinyl diphenyl-methane 15%, the polytetramethylene ether diol 82.0% of molecular weight 2500, organozinc catalyst 0.1%,
polymer microballoon 3.1%, soft bubble silicone oil 0.1% and 2,2 '-azodiisobutyronitrile 0.2%, obtains finely dispersed mixed liquor after rapid mixing.
According to the quality of 2:1 be after mixing for 60 seconds under the condition of 5000rpm than low whipping speed by C component and D component, be 4:1 according to the mass ratio of the raw material (component A+B component) of polishing layer and the raw material (C component+D component) of cushion, the raw material of cushion is cast on the uncured polishing layer in above-mentioned mould at temperature is 20 DEG C, then polishing layer and cushion being placed on temperature is gelation after 60 minutes in the insulating box of 60 DEG C, again above-mentioned polishing layer and cushion to be placed in the insulating box of 100 DEG C slaking 6 hours, obtain the two-layer polishing pad with polishing layer and cushion.
Embodiment 2
The raw material of polishing layer:
Component A: liquefaction 4,4 '-methyl diphenylene diisocyanate 40.2%, molecular weight is the polytetramethylene ether diol 59.8% of 800, and 70 DEG C of reactions 2 hours, vacuum (-0.095MPa) deaeration, obtained the performed polymer that isocyano-content is 23.2%.
B component: 2,2 '-diaminourea-3,3 '-two chloro-4,4 '-divinyl diphenyl-methane 19%, the polypropylene ether glycol 79.6% of molecular weight 1000, organozinc catalyst 0.1%,
polymer microballoon 0.8%, hard bubble silicone oil 0.3% and 2,2 '-azodiisobutyronitrile 0.2%, obtains finely dispersed mixed liquor after rapid mixing.
According to the quality of 2:1 be mixed for 25 seconds under the condition of 5000rpm than low whipping speed by component A and B component, be cast to early in off-the-shelf mould, at temperature is 20 DEG C, gelation 15 minutes, obtains uncured polishing layer.
The raw material of cushion:
C component: 4,4 '-methyl diphenylene diisocyanate 40.5%, molecular weight is the polypropylene ether glycol 59.5% of 1500, and 70 DEG C of reactions 2 hours, vacuum (-0.095MPa) deaeration, obtained the performed polymer that isocyano-content is 16.1%.
D component: 2,2 '-diaminourea-3,3 '-two chloro-4,4 '-divinyl diphenyl-methane 19.5%, the polytetramethylene ether diol 77.8% of molecular weight 2500, organozinc catalyst 0.1%,
polymer microballoon 2.3%, soft bubble silicone oil 0.1% and 2,2 '-azodiisobutyronitrile 0.2%, obtains finely dispersed mixed liquor after rapid mixing.
According to the quality of 2:1 be after mixing for 50 seconds under the condition of 5000rpm than low whipping speed by C component and D component, be 4:1 according to the mass ratio of the raw material (component A+B component) of polishing layer and the raw material (C component+D component) of cushion, the raw material of cushion is cast on the uncured polishing layer in above-mentioned mould at temperature is 20 DEG C, then polishing layer and cushion being placed on temperature is gelation after 25 minutes in the insulating box of 65 DEG C, again above-mentioned polishing layer and cushion to be placed in the insulating box of 100 DEG C slaking 6 hours, obtain the two-layer polishing pad with polishing layer and cushion.
Embodiment 3
The raw material of polishing layer:
Component A: 4,4 '-methyl diphenylene diisocyanate 34.9%, molecular weight is the polytetramethylene ether diol 65.1% of 800, and 70 DEG C of reactions 2 hours, vacuum (-0.095MPa) deaeration, obtained the performed polymer that isocyano-content is 20.6%.
B component: 2-chloro-5-(4-methyl-3,5-divinyl toluene)-1,3-diphenylamines 23.1%, the polypropylene ether glycol 75.7% of molecular weight 1000, organic bismuth catalyst 0.1%,
polymer microballoon 0.8%, hard bubble silicone oil 0.1% and benzoyl peroxide 0.2%, obtains finely dispersed mixed liquor after rapid mixing.
According to the quality of 2:1 be mixed for 25 seconds under the condition of 5000rpm than low whipping speed by component A and B component, be cast to early in off-the-shelf mould, at temperature is 25 DEG C, gelation 4 minutes, obtains uncured polishing layer.
The raw material of cushion:
C component: liquefaction 4,4 '-methyl diphenylene diisocyanate 45%, molecular weight is the polypropylene ether glycol 55% of 2000, and 70 DEG C of reactions 2 hours, vacuum (-0.095MPa) deaeration, obtained the performed polymer that isocyano-content is 14.3%.
D component: 2-chloro-5-(4-methyl-3,5-divinyl toluene)-1,3-diphenylamines 26.8%, the polypropylene ether glycol 77.7% of molecular weight 3000, organic bismuth catalyst 0.1%,
polymer microballoon 2.1%, soft bubble silicone oil 0.1% and benzoyl peroxide 0.2%, obtain finely dispersed mixed liquor after rapid mixing.
According to the quality of 2:3 be after mixing for 40 seconds under the condition of 6000rpm than low whipping speed by C component and D component, be 3:1 according to the mass ratio of the raw material (component A+B component) of polishing layer and the raw material (C component+D component) of cushion, the raw material of cushion is cast on the uncured polishing layer in above-mentioned mould at temperature is 25 DEG C, then polishing layer and cushion being placed on temperature is gelation after 10 minutes in the baking oven of 100 DEG C, again above-mentioned polishing layer and cushion to be placed in the insulating box of 100 DEG C slaking 6 hours, obtain the two-layer polishing pad with polishing layer and cushion.
Embodiment 4
The raw material of polishing layer:
Component A: 4,4 '-methyl diphenylene diisocyanate 39.7%, molecular weight is the polytetramethylene ether diol 60.3% of 600, and 70 DEG C of reactions 3 hours, vacuum (-0.095MPa) deaeration, obtained the performed polymer that isocyano-content is 21.3%.
B component: 2-chloro-5-(4-methyl-3,5-divinyl toluene)-1,3-diphenylamines 19.7%, the polypropylene ether glycol 79.1% of molecular weight 2000, organic bismuth catalyst 0.1%,
polymer microballoon 0.8%, hard bubble silicone oil 0.1% and benzoyl peroxide 0.2%, obtains finely dispersed mixed liquor after rapid mixing.
According to the quality of 3:1 be mixed for 25 seconds under the condition of 5000rpm than low whipping speed by component A and B component, be cast to early in off-the-shelf mould, at temperature is 30 DEG C, gelation 4 minutes, obtains uncured polishing layer.
The raw material of cushion:
C component: 4,4 '-methyl diphenylene diisocyanate 21%, liquefaction 4,4 '-methyl diphenylene diisocyanate 20%, molecular weight was the polypropylene ether glycol 59% of 2000,70 DEG C of reactions 2 hours, vacuum (-0.095MPa) deaeration, obtains the performed polymer that isocyano-content is 12.1%.
D component: 2-chloro-5-(4-methyl-3,5-divinyl toluene)-1,3-diphenylamines 28.5%, the polypropylene ether glycol 69.1% of molecular weight 4000, organic bismuth catalyst 0.1%,
polymer microballoon 1.9%, soft bubble silicone oil 0.2% and benzoyl peroxide 0.2%, obtain finely dispersed mixed liquor after rapid mixing.
According to the quality of 3:1 be after mixing for 30 seconds under the condition of 5000rpm than low whipping speed by C component and D component, be 4:1 according to the mass ratio of the raw material (component A+B component) of polishing layer and the raw material (C component+D component) of cushion, the raw material of cushion is cast on the uncured polishing layer in above-mentioned mould at temperature is 20 DEG C, then polishing layer and cushion being placed on temperature is gelation after 15 minutes in the insulating box of 75 DEG C, again above-mentioned polishing layer and cushion to be placed in the insulating box of 120 DEG C slaking 10 hours, obtain the two-layer polishing pad with polishing layer and cushion.
Embodiment 5
The raw material of polishing layer:
Component A: polymerization 4,4 '-methyl diphenylene diisocyanate 31.1%, molecular weight is the polytetramethylene ether diol 68.9% of 500, and 60 DEG C of reactions 3 hours, vacuum (-0.095MPa) deaeration, obtained the performed polymer that isocyano-content is 14.1%.
B component: 2-chloro-5-(4-methyl-3,5-divinyl toluene)-1,3-diphenylamines 30%, the polypropylene ether glycol 68.7% of molecular weight 2000, organic bismuth catalyst 0.1%,
polymer microballoon 0.6%, hard bubble silicone oil 0.2% and 2,2 '-azodiisobutyronitrile 0.4%, obtains finely dispersed mixed liquor after rapid mixing.
According to the quality of 2:1 be mixed for 35 seconds under the condition of 4000rpm than low whipping speed by component A and B component, be cast to early in off-the-shelf mould, at temperature is 25 DEG C, gelation 1 minute, obtains uncured polishing layer.
The raw material of cushion:
C component: 4,4 '-methyl diphenylene diisocyanate 35.1%, molecular weight is the polypropylene ether glycol 64.9% of 1600, and 70 DEG C of reactions 2 hours, vacuum (-0.095MPa) deaeration, obtained the performed polymer that isocyano-content is 13.3%.
D component: 2-chloro-5-(4-methyl-3,5-divinyl toluene)-1,3-diphenylamines 25.7%, the polypropylene ether glycol 31.6% of molecular weight 2500, the polypropylene ether glycol 40% of molecular weight 1000, organic bismuth catalyst 0.1%,
polymer microballoon 2.0%, soft bubble silicone oil 0.2% and benzoyl peroxide 0.4%, obtain finely dispersed mixed liquor after rapid mixing.
According to the quality of 3:1 be after mixing for 30 seconds under the condition of 5000rpm than low whipping speed by C component and D component, be 4:1 according to the mass ratio of the raw material (component A+B component) of polishing layer and the raw material (C component+D component) of cushion, the raw material of cushion is cast on the uncured polishing layer in above-mentioned mould at temperature is 25 DEG C, then be gelation after 25 minutes in the insulating box of 65 DEG C polishing layer and cushion being placed on temperature, again above-mentioned polishing layer and cushion to be placed in the insulating box of 100 DEG C slaking 7 hours, obtain the two-layer polishing pad with polishing layer and cushion.
Embodiment 6
The raw material of polishing layer:
Component A: 4,4 '-methyl diphenylene diisocyanate 25.2%, molecular weight is the polytetramethylene ether diol 74.8% of 1000, and 60 DEG C of reactions 2 hours, vacuum (-0.095MPa) deaeration, obtained the performed polymer that isocyano-content is 5%.
B component: 2-chloro-5-(4-methyl-3,5-divinyl toluene)-1,3-diphenylamines 22.3%, the polypropylene ether glycol 37% of molecular weight 2000, molecular weight is the polytetramethylene ether diol 30% of 1000, zinc bismuth composite catalyst 0.1%,
polymer microballoon 0.3%, hard bubble silicone oil 0.2% and benzoyl peroxide 0.1%, obtains finely dispersed mixed liquor after rapid mixing.
According to the quality of 3:1 be mixed for 25 seconds under the condition of 5000rpm than low whipping speed by component A and B component, be cast to early in off-the-shelf mould, at temperature is 45 DEG C, gelation 2 minutes, obtains uncured polishing layer.
The raw material of cushion:
C component: 4,4 '-methyl diphenylene diisocyanate 33.3%, molecular weight is the polypropylene ether glycol 66.7% of 1800, and 70 DEG C of reactions 2 hours, vacuum (-0.095MPa) deaeration, obtained the performed polymer that isocyano-content is 7.1%.
D component: 5-(3,5-diaminourea-4-chlorine Bian Ji)-1,3-phenyl diacrylate 19.7%, molecular weight is the polytetramethylene ether diol 77.8% of 2500, zinc bismuth composite catalyst 0.1%,
polymer microballoon 2.2%, soft bubble silicone oil 0.1% and benzoyl peroxide 0.1%, obtain finely dispersed mixed liquor after rapid mixing.
According to the quality of 3:1 be after mixing for 30 seconds under the condition of 5000rpm than low whipping speed by C component and D component, be 3:1 according to the mass ratio of the raw material (component A+B component) of polishing layer and the raw material (C component+D component) of cushion, the raw material of cushion is cast on the uncured polishing layer in above-mentioned mould at temperature is 30 DEG C, then polishing layer and cushion being put into temperature is gelation after 25 minutes in the insulating box of 60 DEG C, again above-mentioned polishing layer and cushion to be placed in the insulating box of 160 DEG C slaking 5 hours, obtain the two-layer polishing pad with polishing layer and cushion.
Comparative example 1
In order to compare, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane (MOCA) is used to the chloro-5-(4-methyl-3 of 2-in alternate example 5,5-divinyl toluene)-1,3-diphenylamines, and in other material composition, raw material, the mass fraction of each composition is the same with example 5 with the mode of production of adopted polishing pad.
Comparative example 2
Polishing layer is the same with the raw material of the polishing layer in example 5 and cushion with the raw material of cushion, and polishing layer in polishing pad and cushion are separately fabricated shaping.The raw material of polishing layer cast in a mold after gel 1 minute, then put into the insulating box slaking 7 hours of 100 DEG C, obtain polishing layer.The raw material of cushion is cast in a mold, gelation 25 minutes at 60 DEG C, then puts into the insulating box slaking 7 hours of 100 DEG C, obtains cushion.By compression roller and pressure-sensitive adhesive (be called for short " PSA ", distributors is RohmandHaasElectronicMaterialsCMPTechnologies), polishing layer and cushion are bonded together.
Comparative example 3
Polishing layer is the same with the raw material of the polishing layer in example 5 and cushion with the raw material of cushion, and polishing layer in polishing pad and cushion are separately fabricated shaping.The raw material of polishing layer cast in a mold after gel 1 minute, then put into the insulating box slaking 7 hours of 100 DEG C, obtain polishing layer.The raw material of cushion is cast in a mold, gelation 25 minutes at 60 DEG C, then puts into the insulating box slaking 7 hours of 100 DEG C, obtains cushion.Make hot-melt adhesive that polishing layer and cushion are bonded together (distributors is RohmandHaasElectronicMaterialsCMPTechnologies) by roller coater.
The hardness (with Shore D scale) of polishing layer and cushion is according to ASTMD2240-05, density (g/cm
3) be according to ASTMD1622, elongation at break and hot strength are according to ASTMD412.The T of polishing layer and cushion
peel offintensity is according to ASTMD1876.
The physical property brief summary of the polishing pad of embodiment 1-6 and comparative example 1-3 is in the following table:
The contrast of comparative example 1 and embodiment 5 shows, 2-chloro-5-(4-methyl-3,5-divinyl toluene)-1,3-diphenylamines replaces the T of polishing layer and cushion after MOCA
peel offintensity obviously increases, and 2-chloro-5-(4-methyl-3,5-divinyl toluene is described)-1,3-diphenylamines plays the effect of the unexistent connection polishing layer of general chain extender and cushion.
The contrast of comparative example 2,3 and embodiment 5 shows, the polishing layer in the double-layer chemical mechanical polishing pad that method provided by the invention obtains and the T of cushion
peel offintensity is obviously better than the T of polishing layer and the cushion bondd by pressure-sensitive adhesive or hot melt adhesive
peel offintensity.
Claims (14)
1. a polishing pad preparation method for chemically mechanical polishing, is characterized in that, at least comprise connected polishing layer and cushion, its preparation method comprises the following steps:
(1) uncured polishing layer preparation: cast on mould after component A and B component being mixed in the ratio of 2:1 to 3:1, gelation 1-15 minute obtains uncured polishing layer at 20-45 DEG C,
Wherein, component A is the isocyanate-terminated performed polymer of the unreacted NCO group containing 5-28 % by weight, B component comprises multi-functional alefinically unsaturated compounds, molecular weight is 1000-2000 high molecular weight polyols, catalyst, polymer microballoon, foam stabilizer and radical initiator;
(2) preparation of cushion: C component and D component are rushed pre-cast liquid in obtaining slow layer after the ratio mixing of 2:3 to 3:1, described cushion pre-cast liquid is cast on the uncured polishing layer described in step (1), then at 60-100 DEG C, gelation 10-60 minute obtains cushion, multi-functional alefinically unsaturated compounds in cushion and carrying out radical polymerization containing multi-functional alefinically unsaturated compounds and form chemical bond and be connected in polishing layer, make cushion be connected with polishing layer;
Wherein, C component contains the isocyanate-terminated performed polymer of the unreacted NCO group of 5-28 % by weight; D component comprises multi-functional alefinically unsaturated compounds, molecular weight is 2100-4000 high molecular weight polyols, catalyst, polymer microballoon, foam stabilizer and radical initiator;
(3) preparation of polishing pad: obtain polishing pad by after connected polishing layer and cushion slaking.
2. the polishing pad preparation method of chemically mechanical polishing as claimed in claim 1, it is characterized in that, the Shore D hardness of described polishing layer is 45-70; Density is 0.7-1.1 gram/cc; The Shore D hardness of described cushion is 10-20; Density is 0.2-0.35 gram/cc.
3. the polishing pad preparation method of chemically mechanical polishing as claimed in claim 1, it is characterized in that, the isocyanate-terminated performed polymer of unreacted NCO group containing 5-28 % by weight in described component A is obtained after the performed polymer polyol reaction of 500-1000 by aromatic polyfunctional's isocyanates and molecular weight, described aromatic polyfunctional's isocyanates is selected from 4,4 '-methyl diphenylene diisocyanate (4,4 '-MDI), 2,4 '-MDI, at least one in liquefied mdi and polymeric MDI.
4. the polishing pad preparation method of chemically mechanical polishing as claimed in claim 1, it is characterized in that, the isocyanate-terminated performed polymer of the unreacted NCO group containing 5-28 % by weight in described C component is obtained after the prepolymer polyol being 1100-2000 by aromatic polyfunctional's isocyanates and molecular weight reacts, described aromatic polyfunctional's isocyanates is selected from 4,4 '-methyl diphenylene diisocyanate (4,4 '-MDI), 2,4 '-MDI, at least one in liquefied mdi and polymeric MDI.
5. the polishing pad preparation method of chemically mechanical polishing as claimed in claim 1, it is characterized in that, multi-functional alefinically unsaturated compounds in described component B and D is selected from least one in polyhydroxy alefinically unsaturated compounds, polyamino alefinically unsaturated compounds, polyhydroxy polyamino alefinically unsaturated compounds, and containing at least one polymerisable ethylene linkage.
6. the polishing pad preparation method of the chemically mechanical polishing as described in claim 1 or 5, is characterized in that, the multi-functional alefinically unsaturated compounds in described component B and D is selected from least one in following general formula compound;
Wherein, the Y in general formula (A) and (B)
1, Y
2, Y
3, Y
4, Y
5and Y
6independently be selected from hydroxyl, amino, vinyl, acryloxy, hydrogen, C
1-6alkyl and halogen, and have 2 groups selected from hydroxyl or amino at least in a molecule, and have at least 1 group to be selected from vinyl or acryloyl group; Y in general formula (C)
1, Y
2, Y
3and Y
4independently be selected from hydroxyl, amino, vinyl, acryloxy, hydrogen, C
1-6alkyl or halogen, and have 2 groups selected from hydroxyl or amino at least in a molecule, and have at least 1 group to be selected from vinyl or acryloyl group.
7. the polishing pad preparation method of chemically mechanical polishing as claimed in claim 1, it is characterized in that, described B component adds up to 100%, mass percent shared by each composition is respectively: the unsaturated olefinic compounds 19-23% of polyfunctional group, high molecular weight polyols 67-79.6%, catalyst 0.1%, polymer microballoon 0.3-1.0%, foam stabilizer 0.1-0.3%, radical initiator 0.1-0.4%.
8. the polishing pad preparation method of chemically mechanical polishing as claimed in claim 1, it is characterized in that, 100% is added up in described D component, the shared mass percent of each composition is respectively: the unsaturated olefinic compounds 15-28.5% of polyfunctional group, high molecular weight polyols 69.1-82%, catalyst 0.1%, polymer microballoon 1.9-3.1%, foam stabilizer 0.1-0.2%, radical initiator 0.1-0.4%.
9. the polishing pad preparation method of chemically mechanical polishing as claimed in claim 1, it is characterized in that, in total hydroxy radical content of polyfunctional group alefinically unsaturated compounds and high molecular weight polyols described in described step (1) and step (2) and described isocyanate-terminated performed polymer, equivalent proportion (OH/NCO) scope of unreacted NCO group is 0.1-0.9.
10. the polishing pad preparation method of chemically mechanical polishing as claimed in claim 1, it is characterized in that, the equivalent proportion (NH of unreacted NCO group in the amido of multi-functional alefinically unsaturated compounds described in described step (1) and step (2) and described isocyanate-terminated performed polymer
2/ NCO) be all 0.7-0.1.
The polishing pad preparation method of 11. chemically mechanical polishings as claimed in claim 1, is characterized in that, in described step 3, described curing temperature is 100-160 DEG C, and the curing time is slaking 5-10 hour.
The polishing pad preparation method of 12. chemically mechanical polishings as claimed in claim 1, it is characterized in that, described in described B component and D component, radical initiator is 2,2 '-azodiisobutyronitrile (AIBN), 2,2 '-azo two (2,4-methyl pentane nitrile), benzoyl peroxide, dicumyl peroxide, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy acetophenones or 1-hydroxy-cyclohexyl phenyl ketone.
The polishing pad preparation method of 13. chemically mechanical polishings as claimed in claim 1, is characterized in that, high molecular weight polyols described in described B component and D component is at least one in PPG or PEPA.
The polishing pad of 14. 1 kinds of chemically mechanical polishings, is characterized in that, is obtained by the preparation method described in any one of claim 1-13.
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| US11072050B2 (en) * | 2017-08-04 | 2021-07-27 | Applied Materials, Inc. | Polishing pad with window and manufacturing methods thereof |
| WO2019042428A1 (en) | 2017-08-31 | 2019-03-07 | 湖北鼎汇微电子材料有限公司 | Polyurethane polishing layer, polishing pad containing polishing layer, method for preparing polishing layer and method for planarizing material |
| CN109015342B (en) * | 2018-03-06 | 2020-08-25 | 湖北鼎汇微电子材料有限公司 | Chemical mechanical polishing pad and method for flattening substrate by using same |
| CN110405543B (en) * | 2019-08-05 | 2020-08-04 | 衢州学院 | Ferrite substrate polishing method adopting acidic polishing solution and metal-based polishing disk |
| CN113084695B (en) * | 2021-03-12 | 2022-05-13 | 安徽禾臣新材料有限公司 | Buffering polishing pad for fine polishing of electronic display screen and production method thereof |
| CN115415931B (en) * | 2022-07-26 | 2024-03-15 | 安徽禾臣新材料有限公司 | Chemical mechanical polishing pad for semiconductor processing |
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Address after: 430057 Hubei city of Wuhan Province Economic and Technological Development Zone East Jinghe Road No. 1 Patentee after: Hubei Dinglong Cmi Holdings Ltd Address before: 430057 Hubei city of Wuhan Province Economic and Technological Development Zone East Jinghe Road No. 1 Patentee before: Hubei Dinglong Chemical Co., Ltd. |