CN106891246B - It is a kind of for semiconductor, the chemical mechanical polishing pads of optical material and magnetic material surface planarisation - Google Patents
It is a kind of for semiconductor, the chemical mechanical polishing pads of optical material and magnetic material surface planarisation Download PDFInfo
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- CN106891246B CN106891246B CN201710202788.8A CN201710202788A CN106891246B CN 106891246 B CN106891246 B CN 106891246B CN 201710202788 A CN201710202788 A CN 201710202788A CN 106891246 B CN106891246 B CN 106891246B
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- polyalcohol
- polishing
- microballoon
- chemical mechanical
- mechanical polishing
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/24—Lapping pads for working plane surfaces characterised by the composition or properties of the pad materials
-
- 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
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/26—Lapping pads for working plane surfaces characterised by the shape of the lapping pad surface, e.g. grooved
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D18/00—Manufacture of grinding tools or other grinding devices, e.g. wheels, not otherwise provided for
- B24D18/009—Tools not otherwise provided for
Abstract
The present invention relates to one kind to be used for semiconductor, the chemical mechanical polishing pads of optical material and magnetic material surface planarisation, it prepares by the following method: being copolymerized two or more epoxyalkane to obtain polyalcohol, gained polyalcohol and multicomponent isocyanate react to form performed polymer, the hollow microsphere that end group is reacted with base material is added into the performed polymer, after mixing, chain extender is added to be uniformly mixed, it injects in mold, carry out polymerization reaction, the polishing layer of microballoon and base material by chemical bonds is obtained after demoulding, and process groove structure, upper buffer layer is pasted using adhesive at the polishing layer back side again, obtain polishing pad.When this chemical mechanical polishing pads is used for semiconductor device fabrication, removal efficiency and polishing defect performance can be balanced well, and can still keep good and stable polishing effect after prolonged use.
Description
Technical field
The present invention relates to a kind of chemically mechanical polishings for semiconductor, optical material and magnetic material surface planarisation
Pad, belongs to chemical material field.
Background technique
Chemically mechanical polishing (Chemical Mechanical Polishing, abbreviation CMP) is to utilize chemical action simultaneously
The technology for carrying out planarization process to body surface with mechanism is particularly suitable for since it has global planarizartion feature
Surface planarisation processing in semiconductor integrated circuit process.CMP technique is applied to semiconductor devices by IBM Corporation earliest
Manufacture, polishing pad and polishing fluid are two crucial consumptive materials used in the process.
In ic manufacturing process, uneven surface a part is deposited from silica or silicon nitride film
In preparatory patterned silicon wafer surface.In the multilayered structure of silicon wafer, dielectric film depositions are used to be isolated on each layer
Metal wire, dielectric material is kept and the consistent layout structure of metal wire, so as to cause the unevennessization on surface.CMP makes crystalline substance
Piece surface becomes to planarize, to ensure that device has suitable function.In advanced process, interlayer interconnection is more and more,
Uneven surface is significantly increased, and the requirement to planarization also can be higher.It is even more important in addition, CMP seems in copper wiring technique,
Copper is difficult simply to be corroded, and the thin copper film of mainstream takes Damascus technics at present, and copper deposition is corroded in blank oxide layer
At groove out, then polishing removes extra copper.CMP can apply to various types of structure, including naked silicon wafer, shallow ridges
Recess isolating structure, polysilicon capacitance structure, metal wire, interlayer dielectric layer (ILD) etc..CMP technique, which greatly improved, advanced partly leads
The product qualification rate of body device such as memory, microprocessor and specific integrated circuit etc., is currently advanced semiconductor fabrication
In indispensable key technology.
Polyurethane is considered as the optimal material of currently manufactured polishing layer, has substantially adjustable hardness and modulus model
Enclose, the planarization process of each key link suitable for semiconductors manufacture, can by isocyanates, polyalcohol, chain extender,
The selection of the type of pore former, the adjustment of ratio obtain target capabilities, can be applied to 14nm advanced process semiconductor device
The manufacture of part.Its detailed description manufactured may refer to for example, US patent 8557005,9481070, US application publication
14/017998,14/761297 and No. 14/365023, CN patent 2014100259571, CN application publication
201010199875 and No. 2016103919661.
The key problem for needing to solve during the polishing process first is that polishing removal efficiency and wafer defect between find
One balance, i.e., reduce physical friction to the greatest extent while improving removal efficiency as far as possible to improve processing efficiency and chemical attack cause
Semiconductor devices damage and defect, another critical issue is the stability of polishing performance, although repairing during the polishing process
Whole disk is persistently modifying polishing layer surface, however still suffer from after prolonged use abrasion because of surface or hardness,
The fluctuation of modulus and caused by polishing effect unstability.
Summary of the invention
In order to solve the above-mentioned technical problem the present invention, provides a kind of for semiconductor, optical material and magnetic material surface
The chemical mechanical polishing pads of planarization can balance well when this chemical mechanical polishing pads is used for semiconductor device fabrication
Except efficiency and polishing defect performance, and good and stable polishing effect can be still kept after prolonged use.
Polishing layer prepared by the present invention is with the polymerization of the reactables base material such as multicomponent isocyanate, polyalcohol and chain extender
The polyurethane material of formation has microcellular structure in the polishing layer, and the microcellular structure with end group with base material by that can react
The microballoon of group formed, this microballoon is by the group and base material with chemical bonds.
The technical scheme to solve the above technical problems is that a kind of for semiconductor, optical material and magnetic material
The chemical mechanical polishing pads for expecting surface planarisation, prepare by the following method:
Two or more epoxyalkane is copolymerized to obtain polyalcohol, gained polyalcohol and multicomponent isocyanate react to be formed it is pre-
The hollow microsphere that end group is reacted with base material is added into the performed polymer for aggressiveness, after mixing, adds chain extender mixing
Uniformly, it injects in mold, carries out polymerization reaction, the polishing layer of microballoon and base material by chemical bonds is obtained after demoulding,
And groove structure is processed, then paste upper buffer layer using adhesive at the polishing layer back side, polishing pad is obtained,
Wherein, polyalcohol, multicomponent isocyanate and the chain extender that the epoxyalkane is copolymerized are base material, described
Microballoon is the hollow microsphere that shell is made of resin material, and the end group of the resin component contains the base reacted with base material
Group.
Based on the above technical solution, the present invention can also be improved as follows.
Further, the microballoon resin end moieties are at least one of hydroxyl, sulfydryl, amino, and microballoon can be selected from
Matsumoto Yushi-Seiyaku Co., Ltd.'s production and commercial goods, model FA-30DE, FT-30DE, FH-30DE.
Further, the dosage of the microballoon accounts for the 0.1wt%-5wt% of base material weight, the number average bead diameter of the microballoon
It is 10-80 μm.
Further, the polyalcohol is the copolymerization product of two kinds of epoxyalkane, wherein any epoxyalkane accounts for two kinds of rings
The 10%-90% of oxygen alkane total weight.Preferably, the polyalcohol is the copolymerization product of tetrahydrofuran and propylene oxide, wherein
The tetrahydrofuran accounts for the 10%-90% of tetrahydrofuran and propylene oxide total weight.
Further, the multicomponent isocyanate be in aromatic dicarboxylic isocyanates and binary aliphatic isocyanates extremely
Few one kind.
Further, the chain extender is polyamines, the mixture of polyamines, polyalcohol, the mixture of polyalcohol, polyamines and polynary
At least one of mixture of alcohol.
Further, the Shore hardness of the polishing pad is 40-70D, preferably 50-65D.
Further, the density of the polishing pad is 0.5-1.2g/cm3, preferably 0.7-1.1g/cm3。
The beneficial effects of the present invention are:
1, the present invention is formed using multicomponent isocyanate and by the polyalcohol that two or more epoxyalkane are copolymerized pre-
Aggressiveness, adds microballoon and chain extender is polymerize, and obtains polishing layer, which has the group reacted with base material, from
And form the polishing layer of microballoon and base material by chemical bonds.
2, the hollow microsphere that the present invention uses and polishing layer substrate is acted on by chemical bonding, can solve in production process
Ordinary resin microballoon disperse in base material uneven, microballoon fall off from polishing layer surface, microballoon in solidification because by thermal conductivity
The problems such as causing the further expansion of microballoon and causing " explosion " of microballoon, to solve polishing pad Local Mechanical Property not
, it is formed simultaneously more firm porous structure, in use since the polishing pad has structure more evenly, polishing effect is more
For stabilization, i.e. the reproducibility of polishing removal efficiency and ratio of defects is all greatly improved.
3, the Shore D hardness of chemical mechanical polishing pads prepared by the present invention is 40-70D, density 0.5-1.2g/cm3。
Specific embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
The current mainstream of material of chemical mechanical polishing pads suitable for semiconductor device surface planarization is elastic polyurethane
Body material, since such material can adjust its physical property in very large range, such as hardness, density, tensile strength, modulus
Deng, and adjusting in larger scope can be carried out by introducing micropore, therefore, such material has obtained extensively in polishing pad field
General research and application.
The manufacturing method of polyurethane elastomer can be divided into one-step method and prepolymer method.One-step method is i.e. by isocyanates, polynary
The pure and mild direct mixed injection mold of chain extender, solidifies at a certain temperature.The method advantage is easy to operate, high production efficiency,
Production cost is low, but is difficult to control due to reacting, and products molecule structural arrangement is irregular, causes mechanical property bad, so system
Standby elastomer is less to use one-step method.And performed polymer rule is to form isocyanate group first with isocyanates and polyol reaction
The performed polymer of group's sealing end, then polymerize to form polyurethane elastomer with chain extender, the method heat release when with chain extender reaction is controllable,
Products molecule compound with regular structure, mechanical property is good, has been widely used in the manufacture of elastomer at present.
Isocyanates for manufacturing polyurethane elastomer is commonly mainly diisocyanate, such as toluene di-isocyanate(TDI)
(TDI), '-diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), dimethylenebenzene diisocyanate
(XDI), naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), dicyclohexyl methyl hydride diisocyanate
(H12MDI) etc., it can be used alone, wherein several be used cooperatively also may be selected.
Polyalcohol for manufacturing polishing pad is generally oligomer polyol, is commonly the pure and mild polyester polyols of polyether polyols
Alcohol.Since the polishing pad of polyether polyol preparation has preferable hydrolytic stability, low-temperature flexibility, weatherability and higher strong
Degree has suitable operable time producing its upper performed polymer, and polyether polyol is widely used in the manufacture of polishing pad.Though
The polyurethane elastomer of right polyester polyol preparation is due to that can form stronger intramolecular hydrogen bond, so that product has preferably by force
The mechanical properties such as degree, wearability, but the disadvantage is that cause hydrolytic resistance poor since there are ester groups for intramolecular, and polishing pad needs to grow
Time works (and polishing fluid cooperation) under the aqueous environments of various different pH value, causes polyester polyol is less to be used to manufacture
Polishing pad.
There is rigidity in polyurethane elastomer and flexible chain is disconnected, and form block structure each other, in addition to isocyanates and more
First alcohol influences properties of product, and the type selection of chain extender and dosage also have a huge impact the performance of elastomer.It is common to expand
Chain agent type is polyalcohol and polyamines class, and the chain extender of appropriate functionality is selected according to crosslinking degree, in polishing pad the most often
For dihydric alcohol or Diamines chain extender.The kind of di-alcohols chain extender is more, mainly have 1,4-butanediol, ethylene glycol,
Propylene glycol, diglycol, neopentyl glycol etc..Trihydric alcohols have glycerine, trimethylolpropane (TMP) etc..Diamines
Although class compound and isocyanates reaction speed are fast, it is more difficult to control, since there are cohesive energy height in the product structure of formation
Urea groups so that elastomer has good mechanical property, wherein the most widely used is 3,3 '-two chloro- 4,4 '-diamino
Diphenyl methane (MOCA).
In order to preferably balance removal efficiency and wafer defect during the polishing process, generally also need to introduce in polishing pad
Microcellular structure does not influence tensile strength significantly while reducing polishing pad hardness, but modulus, tearing strength, resistance to
Warm nature but can further get a promotion, and can suitably reduce cost.The most commonly used mode is that the various expansion hollows of addition are micro-
Ball, since it is with lesser density, the additive amount of very little can obtain good effect.The particle size range of microballoon is preferably
10-80 μm, further preferably 10-50 μm, the polishing pad for adding microballoon in this particle size range will obtain optimum performance.
Porous structure is formed after base material solidification, since microballoon is hollow structure, the shell of microballoon is flexible
The compatibility of the polyurethane compositions of resin component, microballoon resin and polishing layer base material be not it is especially good, in production process
The middle possible microballoon that occurs disperses unevenly to lead to the non-uniform problem of pad performance in base material, or in use process
Situations such as middle generation microballoon resin falls off from polishing layer surface, and lead to that polishing wafer surface is caused to damage, in addition such as
Between fruit microballoon and base material be simple physical mixed, be likely to occur while solidify because be heated cause microballoon into
One step expansion tendency, and " explosion " of microballoon is caused, so as to cause the fragment for occurring microballoon shell resin at hole, when serious
It can lead to the collapsing of hole, so as to cause the inhomogeneities of polishing pad Local Mechanical Property.
The inventors discovered that using the microballoon acted on polishing layer substrate by chemical bonding, it is more firm by being formed
Porous structure will not generate adverse effect above-mentioned.And find that there is knot more evenly due to the polishing pad in actual use
Structure, polishing effect is more stable, i.e. the reproducibility of polishing removal efficiency and ratio of defects is all greatly improved.
Reactable group is mainly isocyanate group, hydroxyl, sulfydryl and amino etc. in polishing pad base material, is preferably existed
Hydroxyl, sulfydryl or amino are introduced on microballoon end group, in the isocyanate group and microballoon in cured base material in the process
Hydroxyl or amino form polyurethane or polyureaurethane structure, and the stability for considerably increasing microcellular structure and microballoon are in base material
The uniformity of middle dispersion and binding force with base material.
Having suitable removal efficiency and ratio of defects when in order to ensure that obtained polishing layer is polished, it is necessary to have suitable
Hardness and density, if hardness is too high, although removal efficiency can be relatively high, also result in simultaneously it is more serious polishing lack
It falls into, and if hardness is too low, although ratio of defects is low, also it is difficult to ensure suitable polishing removal efficiency simultaneously.Polishing pad hardness
OK range be 40-70D, preferably 50-65D.Density mainly determines by the partial size of microballoon, density and additive amount, inhomogeneity
The microballoon of type and different adding proportions will cause different degrees of porosity, these holes have multiple effect, on the one hand polish
When layer is pressurized, the impact that slight deformation can occur for hole to absorb rubbing head to polishing layer, the presence meeting of another aspect hole
The contact area of polishing layer and grinding wafers is influenced, and different degrees of contact area can also cause larger shadow to polishing effect
It rings.The suitable density range of polishing pad is 0.5-1.2g/cm3, preferably 0.7-1.1g/cm3, due to not adding the solid of microballoon
Less, the polishing layer density after adding microballoon is mainly determined by porosity the fluctuation of polishing layer density of material, and porosity is then by micro-
The density and additive amount of ball determine that porosity is too big, and density is too small to be easy to cause polishing pad extrusion in use,
And porosity is too small, density, which then will lead to greatly very much polishing pad, leads to wafer defect due to lacking cushion space when being hit.
Embodiment 1
The preparation of THF-PO copolymer polyalcohol I
By the tetrahydrofuran of 500g, 32g initiator 1,2-PD, 15g catalyst boron trifluoride ether is sequentially added
In polymeric kettle, starting stirring is cooled to -5 DEG C, 500g propylene oxide is slowly added dropwise, and maintain temperature in -5-5 DEG C, is added dropwise
Continue 4-5 hours, after being added dropwise, to keep material reaction abundant, be further continued for 0-5 DEG C insulation reaction 3 hours, reaction terminates,
2L washing is added, stirs 20min, after washing, catalyst reacts generation acid with water, is neutralized to pH=8-9 with ammonium hydroxide, continues to stir
20min, until pH stable is until pH=7-8, stopping stirring, stratification 3h, upper layer is thick polyethers, and lower layer is washing
Water, the air-distillation after filtering of thick polyethers remove the propylene oxide, tetrahydrofuran and most of water that unreacted is complete in thick ether, when
Water yield reaches 90% or more theoretical weight, stops distillation, is cooled to 60 DEG C of dischargings, then be evaporated under reduced pressure 2h, water content is down to
For 0.5wt% hereinafter, being detected by exclusion chromatography, the THF-PO copolymer for obtaining number-average molecular weight 993 is polynary
Alcohol.
The preparation of performed polymer A
696g THF-PO copolymer polyalcohol obtained above is added in reaction flask, leads to nitrogen, under stirring
50 DEG C are warming up to, 250g TDI is slowly added dropwise to, half an hour is added dropwise, and then heats to 80 DEG C, and the reaction was continued 4 hours, this
Constantly monitoring NCO% value (weight percent, similarly hereinafter) variation in the process, the variation of NCO% value is judged as less than 0.1% in half an hour
Reaction end.The NCO% value that performed polymer A is measured after cooling is 8.53%.
The preparation of polishing layer
The performed polymer A of the above-mentioned preparation of 850g is added in the A batch can of test-type casting machine, and is heated to 60 DEG C, adds
0.86g volume average particle size d50 is 20nm, density 0.07g/cm3Polymer microballoon (loose this grease pharmacy containing terminal hydroxy group
Co., Ltd.'s production and commercial goods, model FH-30DE), it is sufficiently mixed so that microballoon is evenly dispersed into performed polymer, then
220g MOCA is added in B batch can, is heated to 120 DEG C of fusings, the two is injected in mold after mixed at high speed at casting head,
It is down to room temperature after solidifying 15 hours at 100 DEG C and demoulds and obtains polishing layer.
The preparation of polishing pad
By polishing layer using after groove machining groove structure, it is uniformly coated with adhesive at the polishing layer back side, will be buffered
Layer sticks in the polishing layer back side, obtains polishing pad finished product.
Embodiment 2
The preparation of THF-PO copolymer polyalcohol II
By the tetrahydrofuran of 700g, 1,2 propylene glycol of 37g initiator, catalyst boron trifluoride ether sequentially adds polymeric kettle
In, starting stirring is cooled to -5 DEG C, 300g propylene oxide is slowly added dropwise, and maintain temperature in -5-5 DEG C, is added dropwise 5 hours,
After being added dropwise, to keep material reaction abundant, it is further continued for insulation reaction 3 hours, reaction terminates, and 2L washing, stirring is added
20min, after washing, catalyst reacts generation acid with water, is neutralized to pH=8-9 with ammonium hydroxide, continues to stir 20min, until pH value
Stablize until pH=7-8, stop stirring, stratification 3h, upper layer is thick polyethers, and lower layer is washing water, and thick polyethers is through filtering
Air-distillation afterwards, propylene oxide, tetrahydrofuran and the most of water removed in thick ether stop distillation, drop when water yield very little
Temperature discharges to 60 DEG C, then is evaporated under reduced pressure 2h, water content is down to 0.5% hereinafter, by exclusion chromatography detection, obtains molecular weight
976 THF-PO copolymer polyalcohol.
Subsequent preparation step and inventory with embodiment 1, obtained in the nco value of performed polymer A be 8.41%.
Embodiment 3
The preparation of THF-PO copolymer polyalcohol III
By the tetrahydrofuran of 900g, 1,2 propylene glycol of 43g initiator, catalyst boron trifluoride ether sequentially adds polymeric kettle
In, starting stirring is cooled to -5 DEG C, 100g propylene oxide is slowly added dropwise, and maintain temperature in -5-5 DEG C, is added dropwise 5 hours,
After being added dropwise, to keep material reaction abundant, it is further continued for heat preservation 3 hours, reaction terminates, and 2L washing is added, stirs 20min, water
After washing, catalyst reacts generation acid with water, is neutralized to pH=8-9 with ammonium hydroxide, continues to stir 20min, until pH stable is in pH
Until=7-8, stop stirring, stratification 3h, upper layer is thick polyethers, and lower layer is washing water, and normal pressure steams thick polyethers after filtering
It evaporates, removes the propylene oxide in thick ether, tetrahydrofuran and most of water and stop distillation when water yield very little, be cooled to 60 DEG C
Discharging, then it is evaporated under reduced pressure 2h, water content is down to 0.5% hereinafter, by exclusion chromatography detection, obtains the four of molecular weight 1037
Hydrogen furans-propylene oxide copolyethers polyalcohol.
Subsequent preparation step and inventory with embodiment 1, obtained in the nco value of performed polymer A be 8.58%.
Embodiment 4
The preparation of THF-PO copolymer polyalcohol IV
By the tetrahydrofuran of 300g, 1,2 propylene glycol of 27g initiator, catalyst boron trifluoride ether sequentially adds polymeric kettle
In, starting stirring is cooled to -5 DEG C, 700g propylene oxide is slowly added dropwise, and maintain temperature in -5-5 DEG C, is added dropwise 5 hours,
After being added dropwise, to keep material reaction abundant, it is further continued for heat preservation 3 hours, reaction terminates, and 2L washing is added, stirs 20min, water
After washing, catalyst reacts generation acid with water, is neutralized to pH=8-9 with ammonium hydroxide, continues to stir 20min, until pH stable is in pH
Until=7-8, stop stirring, stratification 3h, upper layer is thick polyethers, and lower layer is washing water, and normal pressure steams thick polyethers after filtering
It evaporates, removes the propylene oxide in thick ether, tetrahydrofuran and most of water and stop distillation when water yield very little, be cooled to 60 DEG C
Discharging, then it is evaporated under reduced pressure 2h, water content is down to 0.5% hereinafter, by exclusion chromatography detection, obtains the four of molecular weight 1016
Hydrogen furans-propylene oxide copolyethers polyalcohol.
Subsequent preparation step and inventory with embodiment 1, obtained in the nco value of performed polymer A be 8.63%.
Embodiment 5
The preparation of THF-PO copolymer polyalcohol V
By the tetrahydrofuran of 100g, 1,2 propylene glycol of 23g initiator, catalyst boron trifluoride ether sequentially adds polymeric kettle
In, starting stirring is cooled to -5 DEG C, 900g propylene oxide is slowly added dropwise, and maintain temperature in -5-5 DEG C, is added dropwise 5 hours,
After being added dropwise, to keep material reaction abundant, it is further continued for heat preservation 3 hours, reaction terminates, and 2L washing is added, stirs 20min, water
After washing, catalyst reacts generation acid with water, is neutralized to pH=8-9 with ammonium hydroxide, continues to stir 20min, until pH stable is in pH
Until=7-8, stop stirring, stratification about 3h, upper layer is thick polyethers, and lower layer is washing water, thick polyethers normal pressure after filtering
Distillation removes the propylene oxide in thick ether, tetrahydrofuran and most of water and stops distillation when water yield very little, be cooled to 60
DEG C discharging, then is evaporated under reduced pressure 2h, water content is down to 0.5% hereinafter, by exclusion chromatography detection, obtains molecular weight 973
THF-PO copolymer polyalcohol.
Subsequent preparation step and inventory with embodiment 1, obtained in the nco value of performed polymer A be 8.43%.
Embodiment 6
In addition to the polymer microballoon in embodiment 1 containing terminal hydroxy group to be changed to polymer microballoon (this loose grease containing Amino End Group
Pharmaceutical Co., Ltd's production and commercially available commodity, model FA-30DE), other conditions are constant.
Embodiment 7
Polymer microballoon (this loose grease in addition to the polymer microballoon in embodiment 1 containing terminal hydroxy group to be changed to the sulfydryl containing end
Pharmaceutical Co., Ltd's production and commercially available commodity, model FT-30DE), other conditions are constant.
Comparative example 1
In addition to microballoon is changed to the microballoon not reacted with polishing pad base material, (Matsumoto Yushi-Seiyaku Co., Ltd. is produced simultaneously
Commercially available commodity, model FN-80SDE), other conditions are the same as embodiment 1.
Comparative example 2
The preparation of performed polymer A
The polytetrahydrofuran (PTMEG) of 500g molecular weight 650 and the polycyclic oxygen of 500g molecular weight 1000 are added in there-necked flask
Propane (PPG) leads to nitrogen, 50 DEG C is warming up under stirring, is slowly added dropwise to 490gTDI, half an hour is added dropwise, and then heats to
80 DEG C, the reaction was continued 4 hours, and constantly monitoring NCO% value variation during this, the variation of NCO% value is sentenced less than 0.1% in half an hour
Break as reaction end.The NCO% value that performed polymer is measured after cooling is 8.61%.
Subsequent operation and inventory are the same as comparative example 1.
Comparative example 3
Performed polymer A is changed to the TDI-PTMEG system that 440g NCO% is 8.57% (wherein PTMEG molecular weight is 650)
The performed polymer of the TDI-PTMEG system for being 8.9% with 410g NCO% (wherein PPG molecular weight is 1000) physical mixed, it is subsequent
Operation and inventory are the same as comparative example 1.
Test experiments
1, Determination of Hardness
Hardness is measured referring to Unite States Standard ASTM D2240,5 days in the environment of sample is placed in 23 ± 2 DEG C, is made
It is measured with ASKERD type hardness tester meter, selects on sample 5 to be measured apart from the point on 12 millimeters of each side or more, seek average
Value measures the superposition of three pieces sample since thickness of sample is 2 millimeters.
2, density measure
Density is measured referring to Chinese Industrial Standards (CIS) GBT 6343-2009.
3, polishing performance is tested
Using the Mirra polishing machine of Applied Materials (Applied Materials.Inc.) to embodiment and comparative example
Polishing performance tested, using platen revolving speed 93rpm, chip support head revolving speed is 87rpm, pressure 5psi, to chip
TEOS/SiN processing procedure is polished, and carries out 80 hours marathon tests, is to sentence with the time that average removal rate drops to 20%
The foundation of disconnected polishing pad stability.Removal efficiency is judged using Opti-Probe2600 topographic data, uses SEMVision
The Compass300 of G2 detects polishing defect, using CeIexis CX2000 polishing fluid, uses Diagrid AD3BG-
150855 correction-plates carry out repairing in situ to pad interface.
The physical data and polishing performance of mainstream polishing pad IC 1000 by embodiment and comparative example and on the market compares
Compared with relevant test data is shown in Table 1:
1 test result data of table
As it can be seen from table 1 using the embodiment 1 of the polymer microballoon containing terminal hydroxy group, using the polymer containing Amino End Group
The embodiment 6 of microballoon is compared with using 7 three of embodiment of polymer microballoon of the sulfydryl containing end, hardness and stablizes polishing time phase
When polishing pad prepared by embodiment 1 is far longer than embodiment 6 and is implemented in density, TOES removal rate and SiN removal rate
Example 7 is examined although polishing pad overall defect prepared by embodiment 1 is slightly larger than embodiment 6 and embodiment 7 from polishing pad overall performance
Consider, polishing pad prepared by embodiment 1 is better than both other.I.e. under the same reaction conditions, micro- using the polymer containing terminal hydroxy group
The pad performance of ball preparation is better than using the polymer microballoon containing Amino End Group or is prepared using the polymer microballoon of the sulfydryl containing end
Polishing pad.
Polishing pad prepared by embodiment 1- embodiment 5 is compared, and five embodiments prepare THF-PO copolymer
The technique of polyalcohol is slightly different, and polishing pad prepared by embodiment 1 is first-class in density, TOES removal rate and SiN removal rate
In other four groups, although polishing pad hardness values highest prepared by embodiment 5, overall defect is far longer than other four groups, from throwing
The overall performance of light pad considers that polishing pad prepared by embodiment 1 more meets market and the demand of client.
Polishing pad prepared by embodiment 1 is compared with polishing pad prepared by comparative example 1-3, the polishing pad of comparative example 1-3 preparation
It is far smaller than embodiment 1 in TOES removal rate and SiN removal rate, and overall defect is larger, stable polishing time is very short, throws
Light pad performance is compared far from the polishing pad prepared with embodiment 1, is not able to satisfy market and the demand of client.Due to comparative example 1
It is only that do not have to be added the microballoon reacted with polishing pad base material when preparing polishing pad with the difference of embodiment 1, and comparative example 2
The composition for not also being added and changing performed polymer A with 3, therefore, we can be concluded that is be added in embodiment 1 contains terminal hydroxy group
Polymer microballoon have improvement effect to the performance of polishing pad.
The polishing pad of preparation of the embodiment of the present invention can reach the speed of the removal greater than IC1000 on TEOS and SiN chip
Rate, and overall defect significantly reduces, and shows that polishing pad prepared by the present invention can obtain more preferably comprehensive performance.
From the point of view of stablizing polishing time, pad performance prepared by the present invention is also slightly above IC1000, from the knot of comparative example
From the point of view of fruit, it can also obviously embody the polishing pad for taking invention to implement and have excellent stability.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of for semiconductor, the chemical mechanical polishing pads of optical material and magnetic material surface planarisation, which is characterized in that
It prepares by the following method:
Two or more epoxyalkane is copolymerized to obtain polyalcohol, gained polyalcohol and multicomponent isocyanate react to form pre-polymerization
The hollow microsphere that end group is reacted with base material is added into the performed polymer for body, after mixing, it is equal to add chain extender mixing
It is even, it injects in mold, carries out polymerization reaction, the polishing layer of microballoon and base material by chemical bonds is obtained after demoulding, and
Groove structure is processed, then pastes upper buffer layer using adhesive at the polishing layer back side, obtains polishing pad,
Wherein, polyalcohol, multicomponent isocyanate and the chain extender that the epoxyalkane is copolymerized are base material, the microballoon
For the hollow microsphere that shell is made of resin material, the end group of the resin material contains the group reacted with base material, institute
Stating microballoon resin end moieties is at least one of hydroxyl, sulfydryl, amino.
2. chemical mechanical polishing pads according to claim 1, which is characterized in that the dosage of the microballoon accounts for base material weight
The 0.1wt%-5wt% of amount, the number average bead diameter of the microballoon are 10-80 μm.
3. chemical mechanical polishing pads according to claim 1, which is characterized in that the polyalcohol is two kinds of epoxyalkane
Copolymerization product, wherein any epoxyalkane accounts for the 10%-90% of two kinds of epoxyalkane total weights.
4. chemical mechanical polishing pads according to claim 3, which is characterized in that the polyalcohol is tetrahydrofuran and epoxy
The copolymerization product of propane, wherein the tetrahydrofuran accounts for the 10%-90% of tetrahydrofuran and propylene oxide total weight.
5. chemical mechanical polishing pads according to claim 1, which is characterized in that the multicomponent isocyanate is aromatic series two
At least one of first isocyanates and binary aliphatic isocyanates.
6. chemical mechanical polishing pads according to claim 1, which is characterized in that the chain extender be polyamines, polyamines it is mixed
Close at least one of object, polyalcohol, the mixture of polyalcohol, polyamines and mixture of polyalcohol.
7. chemical mechanical polishing pads according to claim 1, which is characterized in that the Shore hardness of the polishing pad is 40-
70D。
8. chemical mechanical polishing pads according to claim 1, which is characterized in that the density of the polishing pad is 0.5-
1.2g/cm3。
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| CN107553313B (en) * | 2017-08-31 | 2019-12-31 | 湖北鼎龙控股股份有限公司 | Polishing pad, polyurethane polishing layer and preparation method thereof |
| US11179822B2 (en) | 2017-08-31 | 2021-11-23 | Hubei Dinghui Microelectronics Materials Co., Ltd | Polyurethane polishing layer, polishing pad comprising polishing layer, method for preparing polishing layer and method for planarizing material |
| CN108047420B (en) * | 2017-11-28 | 2021-01-12 | 湖北鼎龙控股股份有限公司 | Polyurethane polishing layer and preparation method thereof |
| CN108789135B (en) * | 2018-05-25 | 2019-11-22 | 湖北鼎龙控股股份有限公司 | Chemical mechanical polishing pads |
| JPWO2021201088A1 (en) * | 2020-03-31 | 2021-10-07 | ||
| CN111793186A (en) * | 2020-06-30 | 2020-10-20 | 山东一诺威聚氨酯股份有限公司 | Preparation method of polyurethane polishing pad layer |
| CN113231968B (en) * | 2021-05-28 | 2022-08-09 | 广东伟艺抛磨材料有限公司 | Solvent-free non-woven fabric polishing wheel and manufacturing 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 |
| CN115284166B (en) * | 2022-08-16 | 2024-02-23 | 湖北鼎汇微电子材料有限公司 | Polishing pad |
| CN116833900B (en) * | 2023-07-31 | 2024-01-26 | 广东工业大学 | Magnetorheological elastic polishing pad for semiconductor wafer chemical mechanical polishing, preparation method and application thereof |
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