CN104416454A - Polyurethane polishing pad - Google Patents
Polyurethane polishing pad Download PDFInfo
- Publication number
- CN104416454A CN104416454A CN201410448504.XA CN201410448504A CN104416454A CN 104416454 A CN104416454 A CN 104416454A CN 201410448504 A CN201410448504 A CN 201410448504A CN 104416454 A CN104416454 A CN 104416454A
- Authority
- CN
- China
- Prior art keywords
- polishing pad
- isocyanate
- astm
- base material
- terminated product
- 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.)
- Granted
Links
Classifications
-
- 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
- B24B37/245—Pads with fixed abrasives
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a polishing pad suitable for planarizing semiconductor, optical and magnetic substrates. The polishing pad includes a cast polyurethane polymeric material formed from a prepolymer reaction of a polypropylene glycol and a toluene diisocyanate to form an isocyanate-terminated reaction product. The toluene diisocyanate has less than 5 weight percent aliphatic isocyanate; and the isocyanate-terminated reaction product having 5.55 to 5.85 weight percent unreacted NCO. The isocyanate-terminated reaction product being cured with a 4,4'-methylene-bis(3-chloro-2,6-diethylaniline) curative agent. The non-porous cured product having a tan delta of 0.04 to 0.10, a Young's modulus of 140 to 240 MPa and a Shore D hardness of 44 to 56.
Description
Background
The present invention relates to the polishing pad for polishing and complanation base material, particularly produce the complanation polishing pad of Low Defectivity.
Polyurethane polishing pad is the main polishing pad type applied for the polishing of various exact requirements.These polyurethane polishing pads can be effectively used to polished silicon wafer, the wafer of patterning, flat-panel monitor and magnetic disc store.Particularly, polyurethane polishing pad is provide mechanical integrity and chemical resistance for the manufacture of most of polishing operations of integrated circuit.Such as, polyurethane polishing pad has in order to resist the high strength of tearing; Avoid the wearability that wear problem occurs in polishing process; The stability that tolerance strong acid and strong causticity polishing fluid corrode.
Semiconductor production is usually directed to some chemical-mechanical planarizations (CMP) technique.In each CMP, by polishing pad and polishing fluid (such as comprise abrasive material polishing slurries or not containing the active liquid of abrasive material) combination, with complanation or keep flatness, to receive the mode of lower one deck to remove unnecessary material.These layers are combined into stacking in the mode forming integrated circuit.Because people need the device with the higher speed of service, lower leakage current and reduction power consumption, become increasingly complex so the manufacture of these semiconductor devices is becoming always.For the structure of device, this means to require meticulousr feature geometries structure, and higher metallization level.These more and more stricter device layout require to impel people to adopt the copper metallization technology with the new dielectric material coupling with lower dielectric constant.The physical property reduced, makes the demand of people to CMP running stores (such as polishing pad and polishing fluid) larger continually with the complexity that low k and ultralow-k material film are combined and device increases.
Particularly, compared with conventional dielectric materials, low k and ultra low k dielectric materials often have lower mechanical strength and poor cohesive, show more difficult complanation.In addition, along with the reduction of integrated circuit feature size, the defect produced by CMP, such as cut, become larger problem.In addition, the film thickness that integrated circuit reduces requires while improvement degree of imperfection as wafer substrate provides acceptable pattern; The requirement of these pattern aspects needs base material to have stricter flatness, depression and corrosion specification.
Having confirmed polyurethane to be cast into pan and this pan having been cut into several pieces of thin polishing pads is effective ways preparation to the polishing pad of consistent reproducible polishing character.M.J.Kulp at United States Patent (USP) the 7th, disclose in 414, No. 080 with based on low-without toluene di-isocyanate(TDI) polishing pad to improve the uniformity of product.Unfortunately, necessary complanation and copper depression character are applied in the low defect polishing that the polyurethane polishing pad prepared by these formulas lacks peak demand.
Summary of the invention
An aspect of of the present present invention provides one to be applicable to planarized semiconductor base material, the polishing pad of at least one base material in optical element and magnetic base material, described polishing pad contains the polyether polyols with reduced unsaturation material of casting, described polyether polyols with reduced unsaturation material is prepared by the prepolymer reaction of polypropylene glycol with the toluene di-isocyanate(TDI) forming isocyanate-terminated product, described toluene di-isocyanate(TDI) has and is less than 5 % by weight aliphatic isocyanates and described isocyanate-terminated product has the unreacted NCO of 5.55-5.85 % by weight, described isocyanate-terminated product is by 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline) curing agent solidification, the polymer of this solidification obtains with atresia state measurement: be 0.04-0.10 (ASTM 5279) with the tangent Δ that torsion fixture (torsion fixture) records from 20 DEG C to 100 DEG C, Young's modulus under room temperature is 140-240MPa (ASTM-D412), Shore D hardness under room temperature is 44-56 (ASTM-D2240).
Another aspect of the present invention provides one to be applicable to planarized semiconductor base material, the polishing pad of at least one base material in optical element and magnetic base material, described polishing pad contains the polyether polyols with reduced unsaturation material of casting, described polyether polyols with reduced unsaturation material is prepared by the prepolymer reaction of polypropylene glycol with the toluene di-isocyanate(TDI) forming isocyanate-terminated product, described toluene di-isocyanate(TDI) has and is less than 5 % by weight aliphatic isocyanates and described isocyanate-terminated product has the unreacted NCO of 5.55-5.85 % by weight, described isocyanate-terminated product is by 4, 4'-methylene-bis-(3-chloro-2, 6-diethylaniline) curing agent solidification, the polymer of this solidification obtains with atresia state measurement: be 0.04-0.10 (ASTM 5279) with the tangent Δ that torsion fixture records from 20 DEG C to 100 DEG C, Young's modulus under room temperature is 180-240MPa (ASTM-D412), Shore D hardness under room temperature is 46-54 (ASTM-D2240).
Accompanying drawing explanation
Fig. 1 represents the curve map of Young's modulus and the pad material hardness of being solidified by different curing agent.
Fig. 2 is the comparison of the tangent Δ of polishing pad polymer at 0-100 DEG C prepared by different curing agent.
Detailed Description Of The Invention
Described polishing pad is applicable to carry out polishing at least one in semiconductor substrate, optical element and magnetic base material.Most preferably, this polishing pad is used for polishing semiconductor base material.Described polishing pad comprises the polyether polyols with reduced unsaturation material of casting, and described polyether polyols with reduced unsaturation material is prepared by the prepolymer reaction of polypropylene glycol with the toluene di-isocyanate(TDI) forming isocyanate-terminated product.Described toluene di-isocyanate(TDI) is solidified by 4,4'-methylene-bis-(3-chloro-2,6-diethyl aniline) curing agent.For consistent polishing behavior until high temperature time, the tangent Δ that the product of described non porous solidified is measured between 20-100 DEG C is 0.04-0.10.In addition, the Young's modulus of the product of this non porous solidified is 140-240MPa.This modulus provides the complanation of excellence, TEOS corrodes and the combination of copper depression performance.Preferably, the Young's modulus of the product of this non porous solidified is 180-240MPa.For low defective, the Shore D hardness of the product of this non porous solidified is 44-56.Most preferably, the Shore D hardness of the product of this non porous solidified is 46-54.
This polymer can be effectively used to the polishing pad forming atresia polishing pad and porose polishing pad or filling.In this manual, particle or the spheroid of solid particle and the liquid underfill evicted from or dissolve is included in polishing process for the filler of polishing pad.In this manual, the hole that porosity comprises the particle of gas filling, the spheroid of gas filling and formed by other method, gas mechanical foaming is such as entered sticky system, gas injection is entered melt polyurethane body, introduces gas by the chemical reaction original position with gaseous products or reduces pressure and forms bubble to cause dissolved gases by described method.The porosity of described porose polishing pad or packing density are at least 0.1 volume %.This porosity or filler are that polishing pad provides the ability shifting polishing fluids in polishing process.Preferably, the porosity of this polishing pad or packing density are 0.2-70 volume %.Most preferably, the porosity of this polishing pad or packing density are 0.25-60 volume %.Optionally, the average diameter in described hole is less than 200 microns.Preferably, the weight-average diameter of described hole or filler particles is 10-100 micron.Most preferably, the weight-average diameter of described hole or filler particles is 15-90 micron.The nominal range of the weight-average diameter of the hollow polymer microsphere expanded is 15-50 micron.
Optionally, described polishing pad is atresia.Atresia polishing pad is specially adapted to the application needing excellent polishing pad life-span and complanation.Particularly, the atresia polishing pad of the rough surface having big groove and formed by diamond corrector can be effectively used to the application of copper and tungsten.Usually, the increase of macrostructure or microtexture adds the removal speed of atresia polishing pad.
The concentration controlling unreacted NCO is effective especially for the hole uniformity controlling the hole directly or indirectly formed by filler gas.This is because gas often carries out thermal expansion and larger than the degrees of expansion of solid and liquid under much bigger speed.Such as, the method is effective especially for the porosity formed by the following method, and described method is: the tiny balloon of casting original position preexpanding or expansion; Adopt CBA; Mechanical bubble in gas; Use dissolved gases, as argon gas, carbon dioxide, helium, nitrogen and air, or use supercritical liq as supercritical carbon dioxide, or the gas being used as the original position of product to be formed.
Described polymeric material is the polyurethane formed by polytrimethylene ether glycol [PPG] and 4,4'-methylene-bis--(3-chloro-2,6-diethyl aniline) [MCDEA].In this manual, " polyurethane " is the product derived from two senses or polyfunctional isocyanate, such as polyethers urea, polyester-urea, poly-isocyanurate, polyurethane, polyureas, polyurethane-urea, their copolymer and their mixture.The method controlling the polishing character of polishing pad changes its chemical composition.In addition, the selection impact of raw material and manufacture method is for the manufacture of the polymer morphology of the material of polishing pad and final character.
Preferably, the production of carbamate relates to and prepares isocyanate-terminated carbamate prepolymer by multifunctional aromatic isocyanate and prepolymer polyol.Concerning this description, term prepolymer polyol is polytrimethylene ether glycol [PPG], their copolymer and their mixture.It is preferred that described multifunctional aromatic isocyanate (as toluene di-isocyanate(TDI)) comprises the aliphatic isocyanate being less than 5 % by weight, more preferably comprise the aliphatic isocyanate being less than 1 % by weight.
Especially, described prepolymer reaction product be with 4,4'-methylene-bis--(3-chloro-2,6-diethyl aniline) or its mixture (as with other polyamines) react or solidify.In this manual, polyamines comprises diamines and other polyfunctional amine.Other exemplary solidification polyamines comprises aromatic diamine or polyamines, such as 4,4 '-methylene-two o-chloraniline [MOCA]; Dimethythiotoluene diamine; Two p-aminobenzoic acid-1,3-propylene diesters; PolyTHF two P aminobenzoates; PolyTHF list P aminobenzoates; PPOX two P aminobenzoates; PPOX list P aminobenzoates; 1,2-bis-(2-aminobenzene-thio) ethane; 4,4 '-methylene-diphenylamines; Diethyl toluene diamine; The 5-tert-butyl group-2,4-and the 3-tert-butyl group-2,6-toluenediamine; 5-tertiary pentyl-2,4-and 3-tertiary pentyl-2,6-toluenediamine and chlorotoluene diamines.Preferably, described prepolymer reaction product is reacted separately with 4,4'-methylene-bis-(3-chloro-2,6-diethyl aniline) curing agent or solidify.Optionally can be used for the urethane polymer of polishing pad with independent blend step manufacture, avoid using prepolymer.
Described polyether polyols with reduced unsaturation material is preferably formed by the prepolymer reaction product of toluene di-isocyanate(TDI) and polytrimethylene ether glycol and 4,4'-methylene-bis-(3-chloro-2,6-diethyl aniline).Preferably, the unreacted NCO of 5.55-5.85 % by weight is contained in described prepolymer reaction product.Preferably, this prepolymer has and is less than 0.1 % by weight free TDI monomer, and has the prepolymer molecular weight distribution more consistent than conventional prepolymer, thus promotes to form the polishing pad with excellent polishing characteristic.The prepolymer molecular weight uniformity improved and low free isocyanate monomer make the initial viscosity of prepolymer lower thus trend towards gel more quickly, are beneficial to and control viscosity to improve the uniformity of porosity distribution and polishing pad further.In addition, the low molecular weight polyols additive of such as diethylene glycol (DEG), butanediol and tripropylene glycol and so on is conducive to the percentage by weight of the unreacted NCO controlling prepolymer reaction product.
Except controlling the percetage by weight of unreacted NCO, OH or NH in described curing agent and prepolymer reaction product
280-120% is preferably with the stoichiometric proportion of unreacted NCO; It is still further preferred that, wherein OH or NH
2be 100-112% with the stoichiometric proportion of unreacted NCO.
If polishing pad is polyurethane material, so the density of this polishing pad is preferably 0.5-1.25 gram per centimeter
3.The density of this polyurethane polishing pad most preferably is 0.6-1.15 gram per centimeter
3.
For atresia polishing pad, it is effective that typical circle or circle add radial groove pattern.Preferred groove pattern is the overlap of two groove patterns, and first larger pattern is for removing fragment, and second less passage is for increasing removal speed.Such as, the degree of depth is 30 mils (0.760mm), width is 20 mils (0.508mm), spacing is that the circular groove of 120 mils (3.05mm) represents first comparatively major path, the degree of depth is 15 mils (0.381mm), width is 10 mils (0.254mm), and spacing is that second group of three circular groove of 30 mils (0.760mm) provide less passage.The efficient combination that the combination of sized passageways can be Low Defectivity, processing stability and two-forty is made contributions.
Embodiment
Prepare cast polyurethane cake by (a), (b) and (c) controlled mixing of following composition: (a) 51 DEG C (or according to various formula needs temperature) under, by polyfunctional isocyanate's (i.e. toluene di-isocyanate(TDI)) and based on polyethers polyalcohol (such as
lF750D and other list in product in the commercially available prod list of Chi Mute company (Chemtura Corporation)) the isocyanate-terminated prepolymer be obtained by reacting; (b) curing agent at 116 DEG C, and optional (c) cavity filling (namely purchased from Akzo Nobel N.V. (Akzo Nobel)
551DE40d42,551DE20d60,461DE20d70 or 920DE80d30).Set the ratio of isocyanate-terminated prepolymer and curing agent, thus stoichiometric proportion is set according to often kind of formula listed in form, described stoichiometric proportion is by (that is ,-OH group and the-NH of active hydrogen group in curing agent
2the summation of group) determine with the ratio of unreacted isocyanates (NCO) group in isocyanate-terminated prepolymer.Before interpolation curing agent, described cavity filling is mixed with described isocyanate-terminated prepolymer.High shear mixing head is used to be mixed by the isocyanate-terminated prepolymer including the cavity filling included in subsequently.After leaving mixing head, in 5 minutes, said mixture is assigned in the circular die of diameter 86.4 centimetres (34 inches), obtains the total cast thickness being approximately 8 centimetres (3 inches).Before mould is inserted curing oven, make the mixture gelling 15 minutes of distribution.Then use following circulation that mould is solidified in curing oven: in 30 minutes by the design temperature of curing oven from room temperature to 104 DEG C; Then the design temperature of curing oven is remained on lower 15.5 hours of the design temperature of 104 DEG C; In 2 hours, the design temperature of curing oven is cooled to 21 DEG C from 104 DEG C again.
Then, from mould, shift out the polyurethane cake of solidification, at the temperature of 30-80 DEG C, be cut into (using moving blade cutting) average thickness is multiple polishing layers that 2.0 millimeters (80 mil) is thick.Cut from the top of each cake.
embodiment 1
Table 1 comprises the formula of a series of polishing pads for the preparation of said method with various prepolymer, amount of isocyanate and curing agent.
table 1
with
the carbamate prepolymer product of Shi Chimute company, all nco values represent nominal amount.
LFG963A is TDI-PPG prepolymer, and its unreacted NCO nominal content is 5.75 % by weight, and content range is 5.55-5.85 % by weight.
The physical property of the several samples in the table 1 prepared by said method with initial filler test.The specimen geometry of the method for testing (ASTM-D412) of Young's modulus is as follows: overall length is 4.5 inches (11.4cm), beam overall is 0.75 inch (0.19cm), neck length is 1.5 inches (3.8cm), and neck width is the dumbbell shape of 0.25 inch (0.6cm).The speed that clamping is separated is 20 inch per minute clocks (50.8 cm per minute).Measure hardness according to ASTM-D2240, with the Shore S1 with D tip, Shore D hardness measured by 902 type survey tools.Following table 2 compares based on the change with NCO and curing agent of the hardness of prepolymer and modulus.
table 2
As shown in Figure 1, the sample 1 containing 5.75 % by weight (5.55-5.85 % by weight) NCO and sample 2 provide the combination of beyond thought Shore D hardness and Young's modulus.
The DMA of sample 1 and I-2 formula compares and carries out according to ASTM 5279, employing sample size is the atresia sample of 40mm x 6.5mm x 1.27mm, speed is 10 radian per seconds, the rate of heat addition be 3 DEG C per minute, nurse one's health after 5 days in 50% humidity chamber at ambient temperature, carry out on Rheometric Scientific RDA3 DMA instrument by torsion rectangle fixture (TorsionRectangular fixture).As shown in Figure 2, beyond thought smooth tangent Δ is provided compared with the formula that the formula that the MCDEA with 5.75 % by weight (5.55-5.85 % by weight) NCO solidifies and MOCA solidify.Concrete, this combination provides the tangent Δ of the 0.04-0.10 recorded between 20-100 DEG C.Be less than 5.55 % by weight with NCO content and lacked with the polishing pad polishing that the MOCA that NCO content is greater than 5.85 % by weight solidifies the complanation of improvement and the combinatorial property of low depression that are obtained by the formula of similar MCDEA solidification.
embodiment 2
As shown in table 3, modification is carried out to the porous formula of the polishing pad sample tested for bulk copper polishing.
table 3
Polishing defect contrast is completed between formula 1A and comparative example formula E-4.The polishing condition of this polishing pad is, the degree of depth on material reflects LK (the Applied Materials Reflection LK) instrument of application is 30 mils (0.760mm), width is 18 mils (0.457mm), spacing is the groove of 70 mils (1.778mm), wafer rotation is 87rpm, platform rotating speed is 93rpm, adopt in-situ condition, use KinikAD3BG-15085 diamond truer and use Planar Solution CSL9044C slurries.Check the wafer of copper protection with the KLA-Tencor Surfscan SP1TBI that threshold values is 0.07 micron, defect map is exported by KLARF v1.2 to check defect system with KLA-Tencor eDR5210 Review SEM further.
Defect Comparison between table 4E-4 and 1-A of Fig. 3
Although these data display modulus is similar, formula 1-A provides low ratio of defects.Particularly, compared with the Comparative Example E-4 containing MOCA, formula 1-A provides significantly reduced micro-scuffing.
embodiment 3
The depression of the polishing pad of test chart 3 on the material reflects LK instrument of application subsequently.Following table 5 and table 6 provide the depression under various density after polishing in 60 seconds.
Table 5
Table 6
Table 5 and table 6 show MCDEA polishing pad of the present invention under test density, have best depression performance.Because the polishing pad with low defect has higher depression usually, this represent beyond thought feature of the present invention.Other tests display, and stoichiometric proportion is that 100-112% provides best depression performance and has best pattern performance.
embodiment 4
In addition, anapsid formula is attractive especially for tungsten polishing.Polishing condition is, the degree of depth on the material reflects instrument of application is 30 mils (0.760mm), width is 20 mils (0.508mm), spacing is the groove of 120 mils (3.05mm), wafer rotation is 111rpm, platform rotating speed is 113rpm, adopts ex situ condition, uses Saesol AM02BSL8031C1-PM diamond truer and uses CabotSS2000 tungsten slurries.Particularly, it exceedes industrial standard IC1010, to be head to head compared as follows:
Table 7
Table 7 shows MCDEA of the present invention formula tool in tungsten removal speed and is significantly improved.In addition, the combination that the low TEOS ratio of defects of table 4 and the tungsten of raising remove speed provides the polishing composite behaviour of the not obtainable excellence of conventional polishing pad.
On the whole, the NCO polypropylene glycol of 5.55-5.85 % by weight and the particular combination of the MCDEA curing agent combinatorial property of low copper depression that provides excellent complanation, Low Defectivity and copper polishing is applied.In addition, for the homogeneous polishing of very little variations in temperature, this formula has tangent Δ stable between 20-100 DEG C.Finally, this formula provides and has excellent tungsten removal speed and the atresia polishing pad of low TEOS ratio of defects.
Claims (10)
1. one kind is applicable to planarized semiconductor base material, the polishing pad of at least one base material in optical element and magnetic base material, described polishing pad contains the polyether polyols with reduced unsaturation material of casting, described polyether polyols with reduced unsaturation material is prepared by the prepolymer reaction of polypropylene glycol with the toluene di-isocyanate(TDI) forming isocyanate-terminated product, described toluene di-isocyanate(TDI) has and is less than 5 % by weight aliphatic isocyanates and described isocyanate-terminated product has the unreacted NCO of 5.55-5.85 % by weight, described isocyanate-terminated product is by 4, 4'-methylene-bis-(3-chloro-2, 6-diethylaniline) curing agent solidification, the polymer of this solidification obtains with atresia state measurement: be 0.04-0.10 (ASTM 5279) with the tangent Δ that torsion fixture records from 20 DEG C to 100 DEG C, Young's modulus under room temperature is 140-240MPa (ASTM-D412), Shore D hardness under room temperature is 44-56 (ASTM-D2240).
2. polishing pad as claimed in claim 1, it is characterized in that, described polishing pad is atresia.
3. polishing pad as claimed in claim 1, is characterized in that, the NH that described isocyanate-terminated product and 4,4'-methylene-bis-(3-chloro-2,6-diethyl aniline) have
2be 80-120% with NCO stoichiometric proportion.
4. polishing pad as claimed in claim 1, it is characterized in that, described polishing pad comprises the hole that average diameter is less than 200 microns.
5. polishing pad as claimed in claim 4, it is characterized in that, described polishing pad comprises polymer microballoon to form hole.
6. one kind is applicable to planarized semiconductor base material, the polishing pad of at least one base material in optical element and magnetic base material, described polishing pad contains the polyether polyols with reduced unsaturation material of casting, described polyether polyols with reduced unsaturation material is prepared by the prepolymer reaction of polypropylene glycol with the toluene di-isocyanate(TDI) forming isocyanate-terminated product, described toluene di-isocyanate(TDI) has and is less than 5 % by weight aliphatic isocyanates and described isocyanate-terminated product has the unreacted NCO of 5.55-5.85 % by weight, described isocyanate-terminated product is by 4, 4'-methylene-bis-(3-chloro-2, 6-diethylaniline) curing agent solidification, the polymer of this solidification obtains with atresia state measurement: be 0.04-0.10 (ASTM 5279) with the tangent Δ that torsion fixture records from 20 DEG C to 100 DEG C, Young's modulus under room temperature is 180-240MPa (ASTM-D412), Shore D hardness under room temperature is 46-54 (ASTM-D2240).
7. polishing pad as claimed in claim 6, it is characterized in that, described polishing pad is atresia.
8. polishing pad as claimed in claim 6, is characterized in that, the NH that described isocyanate-terminated product and 4,4'-methylene-bis-(3-chloro-2,6-diethyl aniline) have
2be 100-112% with NCO stoichiometric proportion.
9. polishing pad as claimed in claim 6, it is characterized in that, described polishing pad comprises the hole that average diameter is 5-100 micron.
10. polishing pad as claimed in claim 9, it is characterized in that, described polishing pad comprises polymer microballoon to form hole.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/017,998 US20150059254A1 (en) | 2013-09-04 | 2013-09-04 | Polyurethane polishing pad |
| US14/017,998 | 2013-09-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104416454A true CN104416454A (en) | 2015-03-18 |
| CN104416454B CN104416454B (en) | 2017-03-08 |
Family
ID=52470551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410448504.XA Active CN104416454B (en) | 2013-09-04 | 2014-09-04 | Polyurethane polishing pad |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20150059254A1 (en) |
| JP (1) | JP6423205B2 (en) |
| KR (1) | KR102160987B1 (en) |
| CN (1) | CN104416454B (en) |
| DE (1) | DE102014013023A1 (en) |
| FR (1) | FR3009990A1 (en) |
| TW (1) | TW201522404A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10086494B2 (en) * | 2016-09-13 | 2018-10-02 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | High planarization efficiency chemical mechanical polishing pads and methods of making |
| US20180345449A1 (en) | 2017-06-06 | 2018-12-06 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing pads for improved removal rate and planarization |
| US10391606B2 (en) | 2017-06-06 | 2019-08-27 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing pads for improved removal rate and planarization |
| US10464187B2 (en) * | 2017-12-01 | 2019-11-05 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | High removal rate chemical mechanical polishing pads from amine initiated polyol containing curatives |
| JP7072429B2 (en) * | 2018-03-30 | 2022-05-20 | 富士紡ホールディングス株式会社 | Polishing pads, methods of manufacturing polishing pads, and methods of polishing the surface of optical or semiconductor materials. |
| KR102058877B1 (en) * | 2018-04-20 | 2019-12-24 | 에스케이씨 주식회사 | POROUS POLYURETHANE POLISHING PAD and PREPARATION METHOD THEREOF |
| WO2023104041A1 (en) * | 2021-12-06 | 2023-06-15 | 华为技术有限公司 | Material and preparation method therefor, application of material, and abrasive material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09117855A (en) * | 1995-10-25 | 1997-05-06 | Nec Corp | Polishing pad |
| CN1914241A (en) * | 2004-02-03 | 2007-02-14 | 罗门哈斯电子材料Cmp控股股份有限公司 | Polyurethane polishing pad |
| CN101077569A (en) * | 2006-05-25 | 2007-11-28 | 罗门哈斯电子材料Cmp控股股份有限公司 | Chemical mechanical polishing pad |
| JP2009090397A (en) * | 2007-10-05 | 2009-04-30 | Nitta Haas Inc | Polishing pad |
| WO2010038724A1 (en) * | 2008-09-30 | 2010-04-08 | Dic株式会社 | Two liquid-type urethane resin composition for polishing pad, polyurethane polishing pad obtained using the same, and method for producing polyurethane polishing pad |
| CN101961854A (en) * | 2009-07-24 | 2011-02-02 | 罗门哈斯电子材料Cmp控股股份有限公司 | Multi-functional polishing pad |
| CN102015812A (en) * | 2008-04-25 | 2011-04-13 | 东洋高分子股份有限公司 | Polyurethane foam and polishing pad |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG111222A1 (en) * | 2003-10-09 | 2005-05-30 | Rohm & Haas Elect Mat | Polishing pad |
| US20060089093A1 (en) * | 2004-10-27 | 2006-04-27 | Swisher Robert G | Polyurethane urea polishing pad |
| US7371160B1 (en) * | 2006-12-21 | 2008-05-13 | Rohm And Haas Electronic Materials Cmp Holdings Inc. | Elastomer-modified chemical mechanical polishing pad |
| JP2012521478A (en) * | 2009-03-24 | 2012-09-13 | ピーピージー インダストリーズ オハイオ，インコーポレイテッド | Polyurethane, articles and coatings prepared from polyurethane, and methods for their production |
| US8512427B2 (en) * | 2011-09-29 | 2013-08-20 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Acrylate polyurethane chemical mechanical polishing layer |
-
2013
- 2013-09-04 US US14/017,998 patent/US20150059254A1/en not_active Abandoned
-
2014
- 2014-09-01 TW TW103130077A patent/TW201522404A/en unknown
- 2014-09-02 DE DE201410013023 patent/DE102014013023A1/en not_active Withdrawn
- 2014-09-03 JP JP2014178703A patent/JP6423205B2/en active Active
- 2014-09-04 CN CN201410448504.XA patent/CN104416454B/en active Active
- 2014-09-04 KR KR1020140117547A patent/KR102160987B1/en active IP Right Grant
- 2014-09-04 FR FR1458272A patent/FR3009990A1/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09117855A (en) * | 1995-10-25 | 1997-05-06 | Nec Corp | Polishing pad |
| CN1914241A (en) * | 2004-02-03 | 2007-02-14 | 罗门哈斯电子材料Cmp控股股份有限公司 | Polyurethane polishing pad |
| CN101077569A (en) * | 2006-05-25 | 2007-11-28 | 罗门哈斯电子材料Cmp控股股份有限公司 | Chemical mechanical polishing pad |
| JP2009090397A (en) * | 2007-10-05 | 2009-04-30 | Nitta Haas Inc | Polishing pad |
| CN102015812A (en) * | 2008-04-25 | 2011-04-13 | 东洋高分子股份有限公司 | Polyurethane foam and polishing pad |
| WO2010038724A1 (en) * | 2008-09-30 | 2010-04-08 | Dic株式会社 | Two liquid-type urethane resin composition for polishing pad, polyurethane polishing pad obtained using the same, and method for producing polyurethane polishing pad |
| CN101961854A (en) * | 2009-07-24 | 2011-02-02 | 罗门哈斯电子材料Cmp控股股份有限公司 | Multi-functional polishing pad |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20150027722A (en) | 2015-03-12 |
| US20150059254A1 (en) | 2015-03-05 |
| DE102014013023A1 (en) | 2015-03-05 |
| JP6423205B2 (en) | 2018-11-14 |
| KR102160987B1 (en) | 2020-09-29 |
| CN104416454B (en) | 2017-03-08 |
| TW201522404A (en) | 2015-06-16 |
| JP2015051498A (en) | 2015-03-19 |
| FR3009990A1 (en) | 2015-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104416454A (en) | Polyurethane polishing pad | |
| CN1914241B (en) | Polyurethane polishing pad | |
| CN107813219B (en) | High planarization efficiency chemical mechanical polishing pad and method of making | |
| KR102456044B1 (en) | Polyurethane polishing pad | |
| EP2151299B1 (en) | Chemical mechanical polishing pad | |
| CN105710794B (en) | Controlled expansion CMP pad pouring procedure | |
| CN105711015B (en) | The CMP pouring procedures of controlled viscosity | |
| KR20160000856A (en) | Chemical mechanical polishing layer formulation with conditioning tolerance | |
| JP6113331B2 (en) | Polishing pad and manufacturing method thereof | |
| CN103802018A (en) | Soft and conditionable chemical mechanical polishing pad | |
| WO2006123559A1 (en) | Polishing pad | |
| TW200528233A (en) | Polishing pad | |
| TW201903047A (en) | Removal rate and flattening improved chemical mechanical polishing pad | |
| JP2015047691A (en) | Chemical mechanical polishing pad | |
| JP4722446B2 (en) | Polishing pad | |
| CN105710762B (en) | High stability polyurethane polishing pad | |
| JP2014233833A (en) | Chemical mechanical polishing pad stack which is soft and capable of being conditioned | |
| KR101952361B1 (en) | Polyurethane composition and multilayer polishing pad having high acid resistance obtained therefrom | |
| TWI833924B (en) | Polishing pads, methods for polishing the surface of optical materials or semiconductor materials, and methods for reducing scratches when polishing the surface of optical materials or semiconductor materials | |
| TW202237683A (en) | Polishing pad, method for producing polishing pad, and method for polishing surface of optical material or semiconductor material | |
| KR101769328B1 (en) | Preparing method of polishing pad | |
| JP2023049625A (en) | Polishing pad, method for manufacturing polishing pad, and method for polishing surface of optical material or semiconductor material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |