CN108202436A - For manufacturing the chemical-mechanical planarization with overall window（CMP）The method of polishing pad - Google Patents
For manufacturing the chemical-mechanical planarization with overall window（CMP）The method of polishing pad Download PDFInfo
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- CN108202436A CN108202436A CN201711179988.2A CN201711179988A CN108202436A CN 108202436 A CN108202436 A CN 108202436A CN 201711179988 A CN201711179988 A CN 201711179988A CN 108202436 A CN108202436 A CN 108202436A
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- CN
- China
- Prior art keywords
- reaction mixture
- chunk
- diaphragms
- cmp
- window
- Prior art date
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Classifications
-
- 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
- B24D18/0009—Manufacture of grinding tools or other grinding devices, e.g. wheels, not otherwise provided for using moulds or presses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C39/10—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. casting around inserts or for coating articles
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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
- B24B37/205—Lapping pads for working plane surfaces provided with a window for inspecting the surface of the work being lapped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C39/12—Making multilayered or multicoloured articles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
Abstract
The present invention provides manufacture chemical-mechanical planarization (CMP) polishing layer or polishing pad method, it includes：Chunk is provided, with the surface with the spill looks that can generate flat or forming CMP planarization layer surface and with one or more the end point detection windows pieces for keeping appropriate location on it；Liquid isocyanate component with liquid polyhydric alkoxide component is mixed, forms solvent-free reaction mixture；The reaction mixture is ejected on the chunk, while one or more described diaphragms are held in place, each diaphragm is located at predetermined position, then cures the reaction mixture.
Description
Technical field
The present invention relates to for generating the side of porous polyurethanes (PU) chemical-mechanical planarization (CMP) polishing pad
Method, it includes will not reveal and in use will not protrusion or warpage end point detection windows.
Background technology
Chemical-mechanical planarization (CMP) polishing pad includes one or more windows, so that user can be from starting knot
Beam detects the state of polishing operation.With overall window (be defined as will pad or its shaping surface before be merged into or be attached to
Window in polishing pad) CMP pad can be formed by known method.It is moulding in Technology for Scraping, the method includes
One window raw material is embedded into the polyurethanes cake of molding so that when after solidification from the cake scraping or cutting
During individual CMP pad, window is cut together with pad.In curing process, the meeting of window material block and cushion material
With reference to being fixed in position.In such technique, the window is precisely the thickness padded, and in grooving step
Groove exclusionary zone is must be introduced into, to prevent damage window surface.In this way, pad is cut or grinds, to include, there are one or more
The groove of window.This needs the wherein protected laborious method of window.But the mechanical force and heat generated by scraping can be right always
Window surface damages and leads to window contraction and/or collapse (deformation is herein recess) or excessively swell (to deform at this
In be protrusion).Window can also be damaged by the power for cutting or grinding generation and cause to collapse.Manufacture is used for the window of CMP pad
Another known method be to fill in (plug in place, PIP) method in place, wherein, CMP pad is being made and is slotting
Afterwards, one piece of region is cut from CMP pad, accommodates the diaphragm for having been cut into specific thicknesses and external dimensions.Window is to CMP
The adherency of polishing pad is depended on as synthetic rubber, acrylic compounds hot melt, polyvinyl acetate or cyanoacrylate plastics are molten
Window is fixed to appropriate position by contact adhesive as glue (PSA).The method can when using CMP pad
Lead to CMP slurry leakage across window.
The U.S. Patent No. 8,609,001B2 of Pai etc. is disclosed for manufacturing the CMP pad with detection window
Method, the method be included in do not cut pad in the case of formed with detection window space polishing layer.Polishing layer can divide
From virtual detection window or enclosed mold mold protrusion point in the presence of formed.After polishing layer is moulded, removal is empty
Intend detection window or mold protrusion gets the polishing layer with detection window space；Window precursor is filled into detection window
In space and cure.Separate curing window precursor is needed after removal virtual window or protrusion.The technique of Pai etc. can be by
The influence of injection molding shortcoming, the shortcoming can lead to homogeneity question and demoulding difficulty in single molding；In addition, only close limit
Material can be injection moulded, this is because they allow for flowing through entire mold before curing, and then foot in a mold
Enough cure well to allow to be demoulded.
The present inventor try hard to solve provide be used for manufacture the chemical mechanical polishing pads with improved uniformity application or
The problem of injection method.
Invention content
1. according to the present invention, the method for manufacturing chemical-mechanical planarization (CMP) polishing pad or polishing layer includes：It provides open
Mold has with the spill looks (femaletopography) that can generate flat or forming CMP planarization layer surface
Surface, and with one or more diaphragms for keeping appropriate location on it；By liquid isocyanate component and liquid polyhydric
Alkoxide component mixes to form reaction mixture, the reaction mixture preferably without solvent and substantially free of water；Reaction is mixed
Object is sprayed onto on chunk, while one or more diaphragms are held in place, and each diaphragm is respectively positioned on predetermined
Position；Then by reaction mixture cured, to form Gelatin finish layer by reaction mixture, demoulding, and by Gelatin finish
Layer curing, so as to form polyurethanes reaction product as CMP planarization layer.
2. according to the method for the present invention described in above 1st, wherein one or more diaphragms are far from chunk surface
Back side on it is shielded or blocking, so as to prevent reaction mixture diaphragm masking side or stop side on accumulation, side by side
Except to smoothing out back side with the needs on the surface of one or more exposed diaphragms.
3. according to the method for the present invention described in any one of above 1st or the 2nd, wherein reaction mixture is at 80 DEG C
With 2 seconds to 600 seconds or preferably 5 to 300 seconds or the preferably gelling time of 5 to 120 seconds.
4. according to the method for the present invention described in any one of above 1st, the 2nd or the 3rd, wherein the curing packet
Containing from environment temperature to 130 DEG C of initial solidifications period of 30 seconds to 30 minutes or preferably 30 seconds to 5 minutes with formed gel throwing
Photosphere demoulds Gelatin finish layer, and then finally cure 1 minute to 16 at a temperature of 60 to 130 DEG C from chunk
Hour or period of preferably 5 minutes to 15 minutes, to form porous polyurethanes reaction product, as with one or
Multiple end point detection windows and the CMP with density for 0.5gm/cc to 1gm/cc or preferred 0.75gm/cc to 0.95gm/cc
Polishing layer.
5. according to the method for the present invention described in any one of above 1st, the 2nd, the 3rd or the 4th, wherein described
One or more diaphragms include polyurethanes, the polyurethanes be selected from by polyalcohol and aromatic series, aliphatic or
Polyurethanes that the reaction of cycloaliphatic diisocyanates or polyisocyanates is formed or by isocyanate-terminated amino first
The polyurethanes or the two-part reaction mixture shape by isocyanate component and polyol component that acid esters prepolymer is formed
Into polyurethanes.
6. according to the method for the present invention described in any one of above 1st, the 2nd, the 3rd, the 4th or the 5th,
Described in one or more diaphragms include polyurethanes, the polyurethanes be selected from (i) polyol component and isocyanide
The product of acid esters component contains total restatement with the isocyanates in the polyalcohol and isocyanate component in polyol component
2wt.% or less aromatic isocyanate group and (ii) polyol component and isocyanate-terminated carbamate
The polyurethanes of prepolymer, the prepolymer is with 5.5 to 9.5wt% unreacted NCO group and is following anti-
Answer product：(a) aromatic series polyfunctional isocyanate, (b) prepolymer polyol and (c) curing agent, the curing agent include 0
The polyol curatives caused to the two function curing agent of 90wt% and 10 to 100wt% amine, the polyalcohol that the amine causes
There is curing agent per molecule at least one nitrogen-atoms and per molecule to be averaged at least three hydroxyl；And wherein described diaphragm can be shown
>1g/cm3Density, the porosity less than 0.1vol%, 35 to 65 Shore D hardness (Shore D hardness) and<
300% elongation at break.
7. according to the method for the present invention described in above 6th, wherein being used to form the liquid isocyanide of one or more diaphragms
Acid esters component is included as ethylidene diisocyanate, 2,2,4- trimethyl hexamethylene diisocyanates and 1,6- hexa-methylenes two
Aliphatic diisocyanate as isocyanates, as l, 4- cyclohexane diisocyanates, two isocyanide of 4,4'- dicyclohexyl methyl hydrides
Acid esters, isophorone diisocyanate, alicyclic diisocyanate and its mixture as norbornene alkyl diisocyanate.
8. according to the sheet described in any one of above 1st, the 2nd, the 3rd, the 4th, the 5th, the 6th or the 7th
Inventive method, wherein one or more described diaphragms, which have, uses D type Rex hardometers (Rex Type D gauge) (its feature
Be 35 ° of indentors of acute taper head) Shore D hardness be 15 to 90 hardness.
9. according to any one of above 1st, the 2nd, the 3rd, the 4th, the 5th, the 6th, the 7th or the 8th institute
The method of the present invention stated, wherein the CMP planarization layer has using D type Rex hardometers (it is characterized in that 35 ° of acute taper head
Indentor) 15 to 90 or preferably 20 to 70 Shore D hardness.
11. according to above 1st, the 2nd, the 3rd, the 4th, the 5th, the 6th, the 7th, the 8th, the 9th or
The method of the present invention described in any one of 10, wherein one or more described diaphragms are respectively round, rectangular or rectangle or more
Side shape, and the chunk has flat site or groove, be suitable for accommodating one or more diaphragms each simultaneously
With each identical shape and external dimensions with one or more diaphragms, for example, the diameter identical with circular window piece or
Person and length and width rectangular or that rectangular window piece is identical.
12. according to above 1st, the 2nd, the 3rd, the 4th, the 5th, the 6th, the 7th, the 8th, the 9th, the 10th
Or any one of the 11st described in the method for the present invention, wherein one or more described diaphragms are protected by any in the following manner
Hold the appropriate location on chunk surface：To one or more windows during spraying and being cured to form Gelatin finish layer
The downside applying vacuum of mouth piece；By adhesive or double faced adhesive tape be applied to one or more diaphragms described in chunk be placed in it is spacious
Position on mouth mold tool；And providing flat site or bag body to chunk, the bag body is from the circumferential surface of chunk
Slight depression and cause its size one or more diaphragms is allowed to closely adhere to the appropriate location in chunk.
13. according to above 1st, the 2nd, the 3rd, the 4th, the 5th, the 6th, the 7th, the 8th, the 9th, the 10th
, the method for the present invention described in any one of the 11st or the 12nd, can be thrown wherein the chunk has in gained gel
Groove is generated in photosphere and its pattern will not generate the spill looks of any exclusionary zone around one or more diaphragms.
14. according to above 1st, the 2nd, the 3rd, the 4th, the 5th, the 6th, the 7th, the 8th, the 9th, the 10th
, the 11st, the method for the present invention described in any one of the 12nd or the 13rd, wherein one or more diaphragms in molding and
On the window pads for being placed in solidification process with the external dimensions identical with diaphragm and being flushed with diaphragm downside, preferably
Dismountable window pads, such as the window pads made of polytetrafluoroethylene (PTFE).
15. according to the method for the present invention described in any one of above 1st to the 14th, the method, which further includes, smears
CMP planarization layer on flat or cutting window back side, with the surface of exposure one or more diaphragms.
16. in another aspect of this invention, a kind of use passes through according to any one of above 8th to the 15th
The method of CMP planarization layer includes made from method：Chemical mechanical polishing apparatus with platen, light source and light-sensitive device is provided；
At least one substrate is provided；Chemical machinery (CMP) polishing layer is provided；CMP planarization layer is installed on platen, CMP planarization layer table
Face is exposed to substrate；Polishing medium, such as metal oxidation are provided on the interface optionally between CMP planarization layer surface and substrate
Object or half-metal oxide it is water-soluble serous；Dynamic Contact is formed between CMP planarization layer surface and substrate, wherein at least some
Material is removed from substrate；And by by end point detection windows and analyzing the optical transport from light source from substrate surface
Reflection passes back through end point detection windows and is incident on the light on light-sensitive device to determine polishing end point.
For the purpose of this specification, formulation is expressed with wt.%, unless otherwise specifically indicated.
Unless otherwise noted, temperature and pressure condition is environment temperature and normal pressure.All ranges mentioned all are packets
It is containing both ends and can combining.
Unless otherwise noted, any term containing bracket selectively refers to the entire term as bracket is not present and does not have
There are their term and each alternative combination.Therefore, term " (more) isocyanates " refers to isocyanates, polyisocyanic acid
Ester or its mixture.
All ranges are all comprising both ends and can combine.For example, " 50 arrive 3000cPs or 100 or more cPs to term
Range " will be including 50 to 100cPs, 50 to 3000cPs and 100 to each in 3000cPs.
Unless otherwise noted, as used herein, the term " average molecular weight " of polymer refers to through gel infiltration color
Spectrometry is surveyed for proper standard object (such as poly(ethylene glycol) for polyalcohol) known to indicating or (if not indicating)
Fixed result.
As used herein, the term " exclusionary zone " in the top side of CMP planarization layer or polished side refers to surround terminal inspection
Survey the flat site of window.
As used herein, unless otherwise noted, for the gelling time longer than 30 seconds, term " gelling time " meaning
It is the result obtained by following operation：By given reaction mixture in the VM-2500 laboratories for being set as 1000rpm at 80 DEG C
Mixing 30s in turbine mixer (Statemix Ltd., Winnipeg, Canada), while timer is set as zero and opens timing
Device causes it to start timing at the end of mixing, reaction mixture is poured into aluminium cup immediately and is placed in cup is set as 65 DEG C of glue
(Gardco Hot Pot in the hot tank of solidifying timerTMBe gelled timer, Paul N.Gardner Company, Inc., Pang Panuo
Than strange, Florida State), mixture is stirred to react under 20RPM with wire stirrer, when wire stirrer stops in the sample
Gelling time is recorded when mobile.For the gelling time more shorter than 30 seconds, laboratory turbine mixer be set as 80 DEG C and
1000rpm, and reaction mixture is mixed 2 seconds；Timer is set as starting timing at the end of mixing at 2 seconds, then that reaction is mixed
It closes object to be poured into aluminium cup, cup is placed in the hot tank of gelling timer being set as above and records gelling time.It is if given anti-
It answers mixture that cannot be dumped after mixing 2 seconds, that is, assigns its gelling time of 2 seconds.
As used herein, term " ASTM " refers to the ASTM international organizations (ASTM of Pennsylvania Xikang She Huoken
International publication).
As used herein, term " polygon " refers to tool there are three (such as triangle) or more side, preferably 3 to 12
The two-dimentional boundary on a side or shape.
As used herein, term " polyisocyanates " means any containing containing two or more isocyanate groups
Molecule isocyanate groups, and including diisocyanate.
As used herein, term " polyurethanes " refers to two functions or the polymerisation production of polyfunctional isocyanate
Object, such as polyethers urea, poly-isocyanurate, polyurethanes, polyureas, polyurethanes urea, its copolymer and its mixing
Object.
As used herein, term " reaction mixture " includes non-reaction as any image surface activating agent and additive
Property additive, to reduce the hardness of the polyurethanes reaction product in CMP pad, the hardness is according to ASTM
D2240-15 is measured for (2015).
As used herein, term " Shore D hardness " refers to define such as ASTM D2240 (2015) permanent
The resistance of impression.It is measured within (2015) according to ASTM D2240 for the data of end point detection windows record.D type Rex hardometers
Use 35 ° of indentors of acute taper head (rex measuring instrument company (Rex Gauge Company), Buffalo Ge Luofu, Erie
Nooy state).
As used herein, the reaction mixture of term " stoichiometry " refers in reaction mixture that (free OH+ dissociates
NH2Group) with dissociateive NCO group molar equivalent ratio.
As used herein, term " SG " or " proportion " refer to the square cut from polishing pad according to the present invention or polishing layer
The weight/volume of shape.
As used herein, term " solid " refers to be maintained at any in the polyurethanes reaction product of the present invention
Material；Therefore, solid includes the reactivity and non-reacted additive that will not be volatilized during curing.Solid does not include water and volatility
Solvent.
As used herein, unless otherwise noted, term means that given combination object does not have " substantially free of water " and adds
The water added, and the material for entering composition does not have the water of addition.The reaction mixture of " substantially free of water " may include original
To the water in the range of 2000ppm or preferably 50 to 1000ppm or it may include that condensation reaction is formed 50 present in material
Reaction water or carry out the steam of the ambient moisture that reaction mixture uses wherein.
As used herein, unless otherwise noted, term " viscosity " refer to the given material of pure form (100%) to
Determine to be set as the 50mm that the rheometer of 0.1-100rad/sec is 100 μm in gap using oscillation swing shearing speed range at temperature
Parallel-plate geometry in the viscosity that measures.
As used herein, unless otherwise noted, term " wt.%NCO " refers to given isocyanates or isocyanates
The amount of unreacted or free isocyanate groups in the carbamate prepolymer composition of end seal.
As used herein, term " wt.% " represents weight %.
Description of the drawings
Fig. 1 shows the perspective view of CMP pad obtained according to the method for the present invention.
Specific embodiment
The invention enables contain porous polyurethanes CMP planarization layer or polishing pad by the manufacture of two-part reaction mixture
The simple injection applying methods of end point detection windows be possibly realized.The injection for manufacturing CMP planarization layer on chunk is applied
Adding method opens the preparation of the composition (such as those with short gelling time) of a wide formation polyurethanes
Object window.Short gelling time means that curing is less and cures the chance smaller of damage window or pad.And the method makes
Obtaining end point detection windows can be embedded in when it is cast in pad, form the strong combination with polishing layer material.In addition, curing
Polishing layer material rather than diaphragm finally allow just preferably to combine when cured rings of material is around diaphragm.In short, this hair
Bright method allows manufacture without leakage end point detection windows and prevents window from collapsing, swelling from CMP pad or protrude.
The method of the present invention makes it possible to be formed the CMP planarization layer or polishing pad of the end point detection windows with any configuration.
The present invention provides for example for manufacturing the straightforward procedure of CMP planarization layer, the CMP planarization layer is in upward prolonging to window edge
In the polished surface stretched there is groove, that is, do not have window exclusionary zone.In addition, the method for the present invention causes CMP planarization layer any
In pad there are many windows of customization configuration and variable configuration, including different shape, size, thickness, window material and exist
Or lack exclusionary zone.
In order to manufacture CMP pad and so that formed in the methods of the invention overall window can allow polishing pad with it is more
CMP planarization system compatible with end point determination.The method of the present invention be can adjust to change window surface and CMP pad polished surface
Relationship.In addition, the exclusionary zone of thereabout can be changed by changing for generating the mold of window.When generating polishing pad
Masking or blocking can be used on window back side.For top pad or heelpiece, this can prevent cushion material from depositing on window back side, from
Carry out window of exposure without smoothing out back side.
The method of the present invention makes it possible to provide the CMP planarization layer with one or more end point detection windows, the terminal inspection
It surveys window and contains eddy current sensor, such as Real Time Profile ControlTMSensor (Applied Materials
(Applied Materials), Santa Clara, California).
Preferably, one or more end point detection windows pieces are arranged on the flat or sunk part of chunk, described recessed
Concave portion point is from neighbouring die surface slight depression, so that gained end point detection windows slightly protrude above CMP planarization layer or polishing pad.
Such slight convex be it is desired, so as to end point detection windows be flattened when in use and will not be in use window
Upper formation slurries bag body.
Preferably, the method for the present invention, which includes, provides the open-top mold with the pattern that can generate one or more end point detection windows
Tool, the end point detection windows have recess exclusionary zone (such as around window in polishing process guide slurry stream move
Groove), and with the window for the sunk area or engaging zones of CMP planarization layer surface being in coplanar relationship.
Preferably, it is remained unchanged in the dressing process of pad or until polishing for end point detection windows, this
Inventive method, which includes, provides the open-top mold with the pattern that can generate one or more end point detection windows without exclusionary zone
Tool, the engaging zones of the window from CMP planarization layer surface are slightly concave.
As shown in Figure 1, the method for the present invention makes it possible to provide CMP pad (4), there is groove in its surface
(1) and with exclusionary zone (2) end point detection windows (3).
The CMP pad of the present invention is formed by spraying applying method, and the injection applying method makes higher productivity
Lower cost is possibly realized.Porosity is introduced by spraying reaction mixture in pad.
The mixing for forming the reaction mixture of the present invention can be by carrying out impacting with high pressure mixing or quiet in internal chamber
Low pressure static mixing is carried out in state mixer to carry out.
In the methods of the invention, injection is comprising from internal chamber (such as the airless spray gun or equipped with tool under pressure
There are the device of the nozzle of desired mouth size or the static mixer equipped with nozzle and gas blast cap or with useful
In bi-component entrance and with downstream nozzle or opening and pass through slot or nozzle (preferably a diameter of 0.5 arrive the circle of 2.0mm
Mouthful) impingement mix device) openend discharge reaction mixture stream.In no gas or blasting jet, not into reaction mixture
Air or gas and foaming agent are added, including chemically or mechanically foaming agent.
In blasting jet, suitable static mixer includes the gas on the nozzle of the downstream of static mixer
Blast cap.Suitable nozzle is equipped with atomizing air inlets or the gas blast cap on the outside of nozzle, so that air stream flows through spray
Sharp-tongued head and the axial of reaction mixture stream then along discharge flows.Reaction mixture (appointing so under high pressure) is sprayed to generate
Atomization generates hole across slot from surrounding air, and drop is moved to substrate across surrounding air from the injection tip of device
Injection method may include spraying air pressure from mixing chamber (such as impingement mix device) of the end with nozzle downstream
Reaction mixture.The air pressure mixture includes air or gas, more to be introduced in Gelatin finish layer and gained CMP planarization layer
Permeability.In such method, the gas pressure in air pressure reaction mixture is far above environmental pressure, such as 7000 to 28,
000kPa。
In the injection of gas blast cap, reaction mixture sprays under ambient pressure or under slightly higher than environmental pressure
It penetrates.Therefore, in such method, reaction mixture can further include the miniature element as hollow polymeric microballoon with to
Porosity is introduced in CMP planarization layer.Suitable injection apparatus is Nordson 160AA series disposable static mixers, is matched
There are the Nordson Air Cap of the Nuo Xin EFD companies (Nordson EFD) of Rhode Island ProvidenceTMBlower chamber.
In the internal chamber of airless spray gun, for such as 7500 to 18,000kPa, (1100 arrive the pressure of each component injection
2600psi), the pressure is sufficiently high to ensure uniformly to mix.Upper pressure limit is determined by the limit of equipment；But pressure is preferred
Low-level is maintained at, so that the density of gained CMP pad is maintained at more than acceptable lower limit.The example of suitable equipment is
The Graco Probler conveyed by high-pressure metering pumpTMP2 two-component spray guns (Graco company (Graco), Ming Nia Pohles
This, the Minnesota State) or equipped with the nozzle with desired diameter and with pump or other Graco for connecting of metering device
Airless spray gun, the pump or metering device can be for manufacturing bi-component under the desired pressure of the CMP pad of the present invention
Reaction mixture is transported to spray gun.
Into two kinds of elder generations of air pressure injection apparatus, air-blast nozzle static mixer device or airless spray gun according to the present invention
Leading object (lead) (liquid polyhydric alkoxide component and each one kind of liquid isocyanate component) may include metering system or transport system, example
Such as a pair of of gas-powered positive displacement piston pump.The example of the equipment is commercially available PosiratioTMMini PRM are measured
Device (fluid Heat ＆ Control Pty Ltd. (Liquid Control Corp), Lake Bu Lafu, Illinois).
According to the method for the present invention, the injection that reaction mixture is flowed on chunk may include：Jet mould tool is crossed, then just
Beginning curing reaction mixture removes Gelatin finish layer to form Gelatin finish layer, from mold, and curing gel polishing layer is to form CMP
Then the periphery of CMP pad is punched or cut out desired diameter by polishing layer or polishing pad.
Injection can be automatically brought into operation by airless spray gun or other injection apparatus, and the airless spray gun or other injection apparatus lead to
The mechanical actuator for making it possible to move in the plane parallel with chunk surface is crossed to be held in place, such as with
The program-controlled electronic actuator of the mechanical connection of program-controlled movement is allowed for, preferably can carry out XY axial movements with 4
Armshaft or 6 can carry out XYZ axial movement and moving in rotation armshaft robot.
The chunk of the present invention is as the non-adhesive material as polytetrafluoroethylene (PTFE) or polyurethanes release surface system
Into or fitted lining described in non-adhesive material or polyurethanes release surface.Preferably, mold is processed to form spill looks, is made
Obtaining gained molding polyurethanes reaction product has desired flute configuration.
According to the method for the present invention, liquid polyhydric alkoxide component and liquid isocyanate component can be mixed to form reaction mixing at it
30 to 100 DEG C of temperature T1 and T2 are respectively individually preheating to before object.
According to the method for the present invention, in liquid polyhydric alkoxide component of the mixing in temperature T1 and the liquid isocyanide in temperature T2
During acid esters component, respectively there is 1 to 1000cPs or preferably 100 viscosity for arriving 500cPs.
Gained CMP pad has 10 to 80 μm or preferably 10 to 40 μm of average pore size.
The method of the present invention makes it possible to manufacture and is suitable at least one of planarized semiconductor, optics and magnetic substrates
CMP pad.
The method of the present invention also allows for forming stacking CMP pad, and wherein reaction mixture is discharged to established
On chemical mechanical polishing layer substrate surface, the chemical mechanical polishing layer has one or more diaphragms being arranged therein, and
Homologation reaction mixture solidifies to form heelpiece on the substrate surface of chemical mechanical polishing layer；Wherein heelpiece is thrown with chemical machinery
Photosphere combines, and heelpiece has the heelpiece porosity different from chemical mechanical polishing layer；And wherein chemical machinery
Polishing layer has >=porosity of 10vol.% and the polished surface suitable for polishing substrate.Diaphragm will be than substrate surface more
Thickness, to adapt to the CMP planarization layer at top.Diaphragm is held in place when with forming polishing layer it is identical in a manner of
Appropriate location is held it in when forming substrate surface.
In the method according to the present invention for stacking pad is manufactured, the substrate surface of CMP planarization layer can pass through following operation shape
Into：Mixing liquid polyol component and liquid isocyanate component bi-component form primary reactant mixture, then will be described anti-
Mixture is answered to be discharged on chunk surface and is cured to form substrate surface or base in a mold, then by the present invention's
Reaction mixture is discharged on substrate surface and is cured as described in above 1st and the 4th.It is all it is such discharge with with
Upper 1st to the 15th identical mode carries out, in addition to the layer that reaction mixture is different and they are formed is separation.
The reaction mixture of the present invention is without solvent and without the water added in, in addition to can be added in liquid polyhydric alkoxide component
The at most water of 2000ppm to form hole to help.
The reaction mixture of the present invention may include very fast cured composition, wherein isocyanate component and polyalcohol
Component can be gelled in most short 2 seconds or longest 600 seconds or the preferably gelling time of 10 to 300 seconds.Form polyurethanes
Reaction must be slow enough, so that reaction mixture can mix in static or impingement mix device after two kinds of components merge.Glue
The sole limitation of solidifying time is that the reaction of reaction mixture must be slow enough, so as not to can block its mix wherein it is mixed
Syncephalon, and mold is sufficient filling with when applying it to die surface.
The liquid isocyanate component of the present invention may include diisocyanate, triisocyanate, isocyanuric acid ester isocyanic acid
Any one of carbamate prepolymer or its mixture of ester end seal.Preferably, liquid isocyanate component includes：Virtue
Fragrant race's polyisocyanates, for example, it is different selected from methylenediphenyl diisocyanates (MDI), toluene di-isocyanate(TDI) (TDI), naphthalene two
Cyanate (NDI), two isocyanide of aromatic series to phenylene vulcabond (PPDI), o- toluidine diisocyanate (TODI)
Acid esters；Modified methyl diphenylene diisocyanate, such as the methyl diphenylene diisocyanate of carbodiimide modified, urea groups first
Methyl diphenylene diisocyanate, the biuret modified methyl diphenylene diisocyanate of acid esters modification；Aromatic series isocyanide urea
Acid esters, such as MDI isocyanuric acid esters；The carbamate prepolymer of linear isocyanates end seal, such as linear isocyanates end
The MDI carbamate prepolymers or MDI of envelope and the dimer of one or more polyisocyanate chain extending agents.
Suitable aromatic polyisocyanate may be selected from the group being made up of：2,4 toluene diisocyanate, 2,6- first
It is phenylene diisocyanate, 4,4'- methyl diphenylene diisocyanates, naphthalene -1,5- diisocyanate, toluidine diisocyanate, right
Phenylene vulcabond, xylylene diisocyanate and its mixture
Suitable polyisocyanate chain extending agent is ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,2- butanediols, 1,3- fourths
Glycol, 2- methyl-1,3-propanediols, 1,4- butanediols, neopentyl glycol, 1,5- pentanediols, 3- methyl-1s, 5- pentanediols, 1,6-
Hexylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol and its mixture.
The liquid isocyanate component of the present invention can have very high unreacting isocyanate (NCO) concentration, with aromatic series
Total restatement of isocyanate component can be 10 to 40wt.% or preferably 15 to 35wt.%.
The carbamate prepolymer of suitable isocyanates end seal is the carbamate of low free isocyanate sealing end
Ester prepolymer has free toluene diisocyanate (TDI) content of monomer less than 0.1wt%.
The liquid polyhydric alkoxide component of the present invention can appoint one or more glycol or polyether polyol with terminal hydroxyl,
Such as glycol, polyalcohol, polyalcohol glycol, its copolymer and its mixture.Preferably, it is more to be selected from polyethers for one or more polyalcohols
First alcohol (such as poly- (oxygen tetramethylene) glycol, poly- (oxygen propylidene) glycol and its mixture)；Polycarbonate polyol；Polyester is more
First alcohol；Polycaprolactone polyol；Its mixture；And it is more with one or more low molecular weights selected from the group being made up of
The mixture of first alcohol：Ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,2- butanediols, 1,3 butylene glycol, 2- methyl-1s, 3- third
Glycol, 1,4- butanediols, neopentyl glycol, 1,5- pentanediols, 3- methyl-1s, 5- pentanediols, 1,6-HD, diethylene glycol, two
Propylene glycol and tripropylene glycol.
It is highly preferred that one or more polyalcohols of the liquid polyhydric alkoxide component of the present invention are selected from polytetramethylene ether diol
(PTMEG), containing in ester polyol (such as hexanedioic acid vinyl ester, adipic acid butene esters), polypropylene ether glycol (PPG), poly- caproic acid
Ester polyol, its copolymer and its mixture.
Suitable polyalcohol may include number-average molecular weight MNFor 2,500 to 100,000 high molecular weight polyols.It is preferred that
Ground, high molecular weight polyols used have 5,000 to 50,000 or more preferable 7,500 to 25,000, most preferably 10, and 000 arrives
12,000) number-average molecular weight MN.Such high molecular weight polyols preferably have 3 to 10 hydroxyls of average per molecule.
The curing agent of the present invention is polyamine or the aromatic polyamine preferably as aromatic diamine and aromatic polyamine.
Curing agent must be slow enough, two-part reaction mixture to be allowed to mix.When with aromatic isocyanate component and polyalcohol group
Division and when, curing agent must cause at least 2 seconds or preferably at least 3-5 second gelling (thus reaction mixture combination no longer
Flowing).Therefore, curing agent of the invention does not include the N as solid more than 10wt.%, N- primary alkyl aryl diamines, but can
Comprising N, N- secondary alkyls or tertiary alkyl diamines.
It is highly preferred that the curing agent of the present invention is included selected from one or more aromatic polyamines of group being made up of：Two
Methylsulfany toluenediamine；Two-p- Aminobenzoates of trimethylene；Two-p- Aminobenzoates of PolyTHF；It is poly-
Tetrahydrofuran list-p- Aminobenzoates；Two-p- Aminobenzoates of polypropylene oxide；Polypropylene oxide list-p- aminobenzoics
Acid esters；Bis- (the 2- aminophenyls sulfenyl) ethane of 1,2-；Toluenediamine, such as diethyl toluene diamine, 5- tertiary butyl -2,4- toluene
Diamines, 3- tertiary butyl -2,6- toluenediamines, 5- tertiary pentyl -2,4- toluenediamines, 3- tertiary pentyl -2,6- toluenediamines, uncle 5- penta
Base -2,4- chlorotoluenes diamines and 3- tertiary pentyl -2,6- chlorotoluene diamines；Methylene dianiline (MDA), such as 4,4'- methylene-
Dianil；Isophorone diamine；1,2- diaminocyclohexanes；Bis- (4- aminocyclohexyls) methane, 4,4'- diamino-diphenyls
Sulfone；M- phenylenediamines；Dimethylphenylene diamine；1,3- bis- (aminomethyl cyclohexanes)；And its mixture, preferred dimethyl sulfenyl first
Phenylenediamine (DMTDA).
The curing agent of the present invention may include that in terms of the total solids of reaction mixture 5 to 20wt.% or preferably 10 arrive
20wt.% or more preferable 13-17wt.%.
In order to increase the reactivity of polyol component and diisocyanate or polyisocyanates, catalyst can be used.But
Reaction mixture according to the present invention can not include the catalyst of any addition.Suitable catalyst includes any art technology
Catalyst known to personnel, such as oleic acid, azelaic acid, dibutyl tin laurate, tin octoate, Bismuth Octoate, 1,8- diazas two
11 carbon -7- alkene (DBU) of ring [5.4.0], as DabcoTMTertiary amine catalyst as TMR catalyst, as DABCOTM33LV is in this way
Triethylenediamine and above mixture.
In general, ammonia (NH in reaction mixture2) group total mole number and hydroxyl (OH) group total mole number and with reacting
The stoichiometric ratio of the total mole number of unreacted isocyanates (NCO) group is 0.8 in mixture:1.0 to 1.1:1.0
Or preferably 0.90:1 to 1.05:1.0.
Preferably, liquid polyhydric alkoxide component contains in terms of the total solid weight by reaction mixture of sufficient amount 0.1 and arrives
1.0wt.% or preferably 0.2 arrives the nonionic surfactant of 0.8wt.%, preferably organopolysiloxane copolymerization ether surface active
Agent, to help the growth of reaction mixture inner pore.
The proportion of gained CMP pad is from 1.17 down to 0.5, preferably 0.7 to 1.0.With the increase of porosity,
The bulk property of CMP pad weakens, and removal rate (RR) rises, but planarization efficiency (PE) declines.
Polyurethanes reaction product polishing layer can be only included by chemical mechanical polishing pads made from the method for the present invention
Or it is stacked on the polishing layer on heelpiece or bottom.In porous configuration and non-porous configuration or it is not filled by both configurations can be used
The polishing layer of polishing pad of the present invention or the polishing pad in the case where stacking pad.
Preferably, for the present invention chemical mechanical polishing pads polishing layer have 500 to 3750 microns (20 to 150 is close
Ear) or 750 to 3150 microns more preferable (30 to 125 mil) or even more preferably 1000 to 3000 microns (40 to 120 is close
Ear) or most preferably 1250 to 2500 microns (50 to 100 mil) average thickness.
The chemical mechanical polishing pads of the present invention optionally further include at least one extra play being connect with polishing layer.It is excellent
Selection of land, chemical mechanical polishing pads optionally further include the compressible heelpiece for adhering to polishing layer or base.Compressible base
Preferably improve polishing layer and the consistency on the surface of substrate polished.
The polishing layer of the chemical mechanical polishing pads of the present invention has the polished surface for being suitable for polishing substrate.Preferably, it throws
Optical surface has the macro-texture selected from perforation at least one of groove.Perforation can be extended partially or entirely from polished surface
Across polishing layer thickness.
Preferably, groove be arranged so as on a polished surface, so as in polishing process rotate chemical mechanical polishing pads when,
The surface for the substrate that at least one groove is inswept to be polished.
Preferably, the polishing layer of chemical mechanical polishing pads of the invention has the polished surface for being suitable for polishing substrate,
Middle polished surface have a kind of macro-texture, it includes the groove mode wherein formed and selected from crooked groove, linear grooves, wear
Hole and combinations thereof.Preferably, groove mode includes multiple grooves.It is highly preferred that groove mode is designed selected from a kind of groove, such as
Groove design selected from the group being made up of：Concentric grooves (it can be annular or spiral shape), intersect line groove at crooked groove
It is (such as being arranged as the X-Y grids on pad surface), other conventional designs (such as hexagon, triangle), tire tread type-scheme, non-
Conventional design (such as fractal pattern), and combinations thereof.It is highly preferred that groove design is selected from the group being made up of：It is random recessed
Slot, spiral groove, intersects line groove, X-Y grid grooves, hex-shaped recess, triangular groove, fractal groove at concentric grooves
And combinations thereof.Most preferably, polished surface has the spiral groove pattern wherein formed.Groove profile is preferably selected from front
The rectangle or groove cross section of wall can be " V " shape, " u "-shaped, zigzag, and combinations thereof.
According to the method for manufacturing polishing pad according to the present invention, may be molded has macro-texture or recessed in its polished surface
The chemical mechanical polishing pads of trough pattern, slurries to be promoted to flow and remove polishing fragment from pad-wafer interface.It can be by die surface
The shape in (i.e. the place of spill looks form of the chunk with macro-texture) forms such in the polished surface of polishing pad
Groove.
The chemical mechanical polishing pads of the present invention can be used for polishing in magnetic substrates, optical substrate and Semiconductor substrate
At least one substrate.For example, the CMP pad of the present invention is effective for layer insulation (ILD) and inorganic oxide polishing
's.In order to illustrate the purpose of book, removal rate refer toThe removal rate of expression.
Preferably, the method for polishing substrate of the present invention includes：It provides selected from magnetic substrates, optical substrate and Semiconductor substrate
The substrate of at least one of (preferred semiconductor substrate, such as semiconductor wafer)；Chemical machinery according to the present invention is provided to throw
Light pad；Dynamic Contact is formed between the polished surface and substrate of polishing layer, to polish substrate surface；And it is repaiied with cutting down device
Whole polished surface.
Finishing polishing pad includes (" dystopy during the interval break time polished in a cmp process when being suspended
(exsitu) ") or when CMP process is carrying out (" (in situ) in situ ") contacts conditioner discs with polished surface.Finishing
Disk has coarse finishing surface, is usually made of embedded diamond particles point, diamond particles point can be cut in surface is padded
Miniature raceway groove is cut out, cushion material is ground and plane is scraped, and restores to polish texture.Usual conditioner discs are relative to polishing
The fixed position rotation of rotary shaft is padded, an annular dressing area is scanned out with the rotation of polishing pad.
Example：It now will the present invention will be described in detail in following non-limiting examples：
In the following example, unless otherwise noted, all pressure units be normal pressure (about 101kPa), all temperature lists
Position is room temperature (21-23 DEG C).
Although other raw materials of following discloses, following raw material has been used in example：
EthacureTM300 curing agent：Dimethyl sulfenyl toluenediamine (DMTDA), aromatic diamine (Ya Bao companies
(Albemarle), Xia Luote, the North Carolina state).
VoranolTMV5055HH polyalcohols：Multifunctional polyether polyol (OH equivalent weights 2000), number-average molecular weight MNFor
High molecular weight epoxy ethane (Dow Chemical (the Dow that the propylene oxide polyol that 12,000 degree of functionality is 6 blocks
Chemical Company), Midland, the state of Michigan (Dow)).
MDI prepolymers：The carbamate MDI prepolymers and small molecule dipropylene glycol of linear isocyanates end seal
(DPG) and tripropylene glycol (TPG), there is the NCO content and 182 equivalent weight of about 23wt.%.The MDI of 100wt.%
Prepolymer is taken as hard segment.
NiaxTML5345 surfactants：Nonionic organosilicon surfactant (Mai Tu company (Momentive), brother's human relations
Cloth, Ohio).
DABCO 33LV amine catalysts (Air Products Company (AirProducts), Ai Lundun, Pennsylvania), by
Diazabicyclononane (triethylenediamine) is made, and DABCO 33LV are the triethylenediamines and 67wt.% of 33wt.%
The blend of dipropylene glycol.
UnilinkTM4200 curing agent：N, N'- dialkyl amido-diphenyl methane (doffer Kate company
(DorfKetal), Stafford, Texas)
PTMEG####：Poly- (THF) or polytetramethylene glycol, pass through the ring-opening polymerization system of tetrahydrofuran (THF)
, and sell and make PolyTHFTMPolyalcohol (BASF, Leverkusen, Germany).Number (####) after PTMEG is manufacturer's report
Average molecular weight.
Occurs following abbreviation in example：
PO：Propylene oxide/propylene glycol；EO：Ethylene oxide/ethylene glycol；MDI：Methylenediphenyl diisocyanates TDI：
Toluene di-isocyanate(TDI) (the 2 of about 80%, 4 isomers, the 2 of about 20%, 6 isomers)；DEG：Diethylene glycol；DPG：Dipropyl two
Alcohol；pbw：Parts by weight.
2- component air-injection systems：With (P) side liquid inlet opening, (I) side liquid inlet opening and 4 tangential compressed gas
Axial backmixing device (MicroLine 45CSM, Heng Neiji Co., Ltds (Hennecke GmbH), the Sheng Aogu of body feed inlet
This, Germany).More (poly) sides (P) liquid component and iso sides (I) liquid component are added using (P) side of 16,500-18,500kPa
Plus-pressure, 15,500-17,500kPa (I) side addition pressure pass through their corresponding throat-feds to axial backmixing device.
(I)/(P) flow-rate ratio is bound in each example.Compressed gas passes through tangential compressed gas with the supply pressure of 830kPa
Feed inlet, it is 3.7 to obtain across the liquid component of the merging of axial backmixing device and the velocity ratio of gaseous mass:1, and form conjunction
And body.The merging body is discharged to mold from axial backmixing device, and a cake is formed in mold base.
In following operational instances, overall window CMP pad uses the wind equipped with impingement mix device to send injection apparatus
It generates, the impingement mix device is used for receiving two kinds of components of the reaction mixture for forming polyurethanes, each group respectively
Divide from the tank equipped with pipeline He the pump for guiding impingement mix device into.Injection is arranged on paragraphs below and is described in detail.Reaction
Mixture is fanned using the spray of 80mm wide to be sprayed with X-Y patterns.Total injecting time of jet polishing pad is 135 seconds.
The impingement mix device for being used to form reaction mixture is mixed from 2 tanks.First tank (tank 1) is containing at 48.9 DEG C
The liquid polyhydric alkoxide component pumped under (120 °F) with the flow velocity of 15.14L/s (4g/s).Tank 1 contains：EthacureTM300 curings
Agent (18.816pbw), PTMEG 650 (49.434pbw), NiaxTML5345 (1.295pbw) surfactants and DABCO 33LV
(0.455pbw) catalyst.Tank 2 contains the liquid pumped under 48.9 DEG C (120 °F) with the flow velocity of 13.25L/s (3.5g/s)
MDI pre-polymer components.
Die surface is polytetrafluoroethylene (PTFE) (PTFE) piece of 6.35mm (0.25 ") thickness；Chunk, which has, to be suitable for generating
The female surface of polishing pad, annular concentric groove and 32 of the polishing pad with 0.51mm wide × 0.76mm depth × 1.78mm spacing
The K7+R32 groove modes of fluting radius deep 0.76mm wide × 0.76mm, the mold have 19.1mm × 57.2mm ×
The polytetrafluoroethylene (PTFE) window pads of 4.6mm (0.75 " × 2.25 " × 0.18 ").Unless otherwise noted, gained window has and throwing
The identical thickness of light pad.
Window material used is as shown in following table A-1.In the following example, diaphragm formulation as shown in following table A-1
It prepares, then by the way that deaerated under vacuum of the formulation at 1016 millibars is cast as given shape and size, and 50 in 5 minutes
Cure at DEG C 5 hours, then cure 19 hours at 110 DEG C, they are then cut into desired thickness.Diaphragm is located at
At 190.5mm (from mold center 7.5 "), and it is present in window pocket body.When injection forms the bi-component material of polyurethanes
During material, window is combined with the matrix padded and is held in place in the curing process.Then, round lathe is used on lathe
Cutting tool smoothes out pad, with the back surface of window of exposure.
Table A -1：Window formulation
Example 1：(a kind of hard formulation and one kind are soft as 2 kinds of circular window materials shown in more than Table A -1 for CMP pad
Formulation) it is made, the thickness of radius and 2mm (0.08 ") of each window with 6mm (0.24 ").Hard window and soft window are respectively
Teflon-coating substrate mold is adhered to, and the porous polyurethanes that Shore D hardness is 39, proportion is 0.67
The height equal with thickness window is cast as by two-part reaction mixture.
In example 1-1, hard window insert and be cast into 2mm with spray technology that CMP pad includes formulation 3
The porous polyurethane pad of (0.08 ") thickness.In example 1-2, CMP pad includes the poly- ammonia identical with example 1-1
Carbamate formulation and thickness but the soft window insert with formulation 1.
Comparative example in example 1-B has used the commercially available Shore D made of porous polyurethanes formulation hard
Spend the K2010H for being 0.8 for 15, proportionTMThe window of pad and formulation 1；But polyurethanes is poured into 914.4mm
In the mold of (36 "), until the thickness of about 101.6mm (4 "), then it is cured to the period of 960 minutes at 180 DEG C,
And scraping is about 2mm (0.08 " thick pad).Gained pads unslotted.
Window curvature：It is measured using 3 measuring systems, the measuring system utilizes MitutoyoTM542-222 linear thicknesses
Count (rex measuring instrument company, Buffalo Ge Luofu, Illinois) digital thickness meter and MitutoyoTM542-075A numbers
It shows (Rex Gauge).Polishing pad sample with overall window is placed on planar table.Each window measures at top,
In 3 position polished surfaces：The central point and window edge of window and the crosspoint of diameter.Curvature calculates in the following manner：
It averages to external marginal point, it is subtracted from central point, with the general curvature of measure window.Positive value represents protrusion or protrusion
Window shape, and negative value then represents recess or concave shape.As a result in table 1 listed below.
Table 1：Window curvature
| Example 1-B* | Example 1-1 | Example 1-2 | Example 1-3 | |
| Formulation | 1 | 3 | 1 | 2 |
| Window # | 6 | 2 | 2 | 2 |
| Curvature (μm) | 153.2 | 11.4 | 19.1 | 7.6 |
*-expression comparative example.
Example 2：Each experiment is carried out in a manner of identical with above example 1, in addition to porous polyurethane pad material quilt
It is changed to the harder pad formulation that Shore D hardness is 57, proportion is 0.8.Window curvature measurement can be found in table 2 below.
Comparative example in example 2-A has used the IK4250HTM that commercially available Shore D hardness is 60, proportion is 0.8 porous
The window of polyurethanes formulation and formulation 3, but polyurethanes is poured into 914.4mm (36 ") mold directly
To the thickness of about 101.6mm (4 "), then it is cured to the period of 960 minutes at 180 DEG C, and scraping is about 2mm
(0.08 " thick pad).Gained pads unslotted.
Table 2：Window curvature
| Example 2-A* | Example 2-1 | Example 2-2 | |
| Formulation | 3 | 3 | 1 |
| Window # | 9 | 2 | 2 |
| Curvature (μm) | -20.9 | 19.0 | 11.43 |
*-expression comparison example.
As shown in more than Tables 1 and 2, the basis material hardness of pipe pad is not how, and the method for the present invention makes it possible to manufacture tool
There is the CMP pad of significantly more flat or more horizontal diaphragm.In addition, in the methods of the invention, hard packing and cushion material are equal
Hard window and soft window are suitable for without collapsing or swelling.
Claims (11)
1. a kind of method for manufacturing chemical-mechanical planarization (CMP) polishing layer or polishing pad, comprising：
Chunk is provided, there is the surface with the spill looks that can generate flat or forming CMP planarization layer surface, and
And with one or more diaphragms for keeping appropriate location on it；
Liquid isocyanate component with liquid polyhydric alkoxide component is mixed, forms solvent-free reaction mixture；
The reaction mixture is ejected on the chunk, while one or more described diaphragms are maintained at appropriate position
It puts, each diaphragm is located at predetermined position, then；
By the reaction mixture cured, to form Gelatin finish layer by the reaction mixture, demoulding, and by the gel
Polishing layer cures, so as to form polyurethanes reaction product as CMP planarization layer.
2. according to the method described in claim 1, one or more wherein described diaphragms are on the separate chunk surface
Shielded or blocking on back side, so as to prevent accumulation of the reaction mixture on the masking side of the diaphragm or blocking side
And it excludes to smoothing out back side with the needs on the surface of the exposure diaphragm.
3. according to the method described in claim 1, wherein described reaction mixture has the gelling of 2 seconds to 600 seconds at 80 DEG C
Time.
4. according to the method described in claim 1, wherein described curing includes：
From environment temperature to 130 DEG C of initial solidifications period of 30 seconds to 30 minutes, the Gelatin finish layer is formed；
Then the Gelatin finish layer is demoulded, and from the chunk surface；
Finally cure the period of 1 minute to 16 hours at a temperature of 60 to 130 DEG C, form porous polyurethanes reaction
Product, as with the CMP planarization layer of one or more end point detection windows and density for 0.5gm/cc to 1gm/cc ranges.
5. according to the method described in claim 1, one or more wherein described diaphragms include polyurethanes, the poly- ammonia
Carbamate is selected from reacts what is formed by polyalcohol and aromatic series, aliphatic or cycloaliphatic diisocyanates or polyisocyanates
Polyurethanes or the polyurethanes formed by isocyanate-terminated carbamate prepolymer or by isocyanic acid
The polyurethanes that the two-part reaction mixture of ester component and polyol component is formed.
6. according to the method described in claim 5, one or more wherein described diaphragms include polyurethanes, the poly- ammonia
Carbamate is selected from the product of (i) polyol component and isocyanate component, contains with described in the polyol component
The total restatement 2wt.% or less aromatic isocyanate of the isocyanates in polyalcohol and the isocyanate component
Group.
7. according to the method described in claim 1, wherein described diaphragm has using the scleroscopic Shore D hardness of D types Rex is
15 to 90 hardness.
8. according to the method described in claim 1, wherein described CMP planarization layer has 15 to the 90 scleroscopic Shores of D types Rex
D hardness.
9. according to the method described in claim 1, one or more wherein described diaphragms are respectively round, rectangular, rectangle or more
Side shape, and the chunk has flat site or groove, is suitable for accommodating each of one or more diaphragms
It is a and with each identical external dimensions with one or more diaphragms.
10. according to the method described in claim 1, one or more wherein described diaphragms are maintained at institute by any in the following manner
State the appropriate location on the surface of chunk：To described one or more during spraying and being cured to form Gelatin finish layer
Adhesive or double faced adhesive tape are applied to one or more windows described in the chunk by the downside applying vacuum of a diaphragm
Piece is placed in the position on the chunk and provides flat site or bag body to the chunk, and the bag body is from institute
It states the circumferential surface slight depression of chunk and so that its size allows one or more described diaphragms to closely adhere to institute
State the appropriate location in chunk.
11. according to the method described in claim 1, wherein described reaction mixture is substantially free of water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15/382342 | 2016-12-16 | ||
| US15/382,342 US20180169827A1 (en) | 2016-12-16 | 2016-12-16 | Methods for making chemical mechanical planarization (cmp) polishing pads having integral windows |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108202436A true CN108202436A (en) | 2018-06-26 |
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|---|---|---|---|
| CN201711179988.2A Withdrawn CN108202436A (en) | 2016-12-16 | 2017-11-23 | For manufacturing the chemical-mechanical planarization with overall window（CMP）The method of polishing pad |
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| Country | Link |
|---|---|
| US (1) | US20180169827A1 (en) |
| JP (1) | JP2018108636A (en) |
| KR (1) | KR20180070466A (en) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021135849A1 (en) * | 2019-12-31 | 2021-07-08 | 深圳市中光工业技术研究院 | Wafer polishing device |
| CN114683166A (en) * | 2020-12-29 | 2022-07-01 | 罗门哈斯电子材料Cmp控股股份有限公司 | Chemical mechanical polishing pad having window with transparency at low wavelength and material for such window |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7395853B2 (en) * | 2019-06-12 | 2023-12-12 | Dic株式会社 | Polishing pad and resin composition for polishing pad |
| US20220226958A1 (en) * | 2021-01-21 | 2022-07-21 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Formulations for chemical mechanical polishing pads with high planarization efficiency and cmp pads made therewith |
| US20220226961A1 (en) * | 2021-01-21 | 2022-07-21 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Formulations for high porosity chemical mechanical polishing pads with high hardness and cmp pads made therewith |
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| CN1569398A (en) * | 2003-04-22 | 2005-01-26 | Jsr株式会社 | Polishing pad and method of polishing a semiconductor wafer |
| CN101106905A (en) * | 2004-04-05 | 2008-01-16 | 瑞派技术有限公司 | Polishing pad and method of making same |
| CN101448607A (en) * | 2006-05-17 | 2009-06-03 | 东洋橡胶工业株式会社 | Polishing pad |
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| TWI410314B (en) * | 2005-04-06 | 2013-10-01 | 羅門哈斯電子材料Ｃｍｐ控股公司 | Apparatus for forming a porous reaction injection molded chemical mechanical polishing pad |
| US9484212B1 (en) * | 2015-10-30 | 2016-11-01 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing method |
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2016
- 2016-12-16 US US15/382,342 patent/US20180169827A1/en not_active Abandoned
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- 2017-11-17 TW TW106139854A patent/TW201822982A/en unknown
- 2017-11-23 CN CN201711179988.2A patent/CN108202436A/en not_active Withdrawn
- 2017-11-30 KR KR1020170162743A patent/KR20180070466A/en unknown
- 2017-12-13 JP JP2017238425A patent/JP2018108636A/en active Pending
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| CN1569398A (en) * | 2003-04-22 | 2005-01-26 | Jsr株式会社 | Polishing pad and method of polishing a semiconductor wafer |
| CN101106905A (en) * | 2004-04-05 | 2008-01-16 | 瑞派技术有限公司 | Polishing pad and method of making same |
| TWI410314B (en) * | 2005-04-06 | 2013-10-01 | 羅門哈斯電子材料Ｃｍｐ控股公司 | Apparatus for forming a porous reaction injection molded chemical mechanical polishing pad |
| CN101448607A (en) * | 2006-05-17 | 2009-06-03 | 东洋橡胶工业株式会社 | Polishing pad |
| TW201121710A (en) * | 2009-12-31 | 2011-07-01 | Iv Technologies Co Ltd | Method of manufacturing polishing pad having detection window and polishing pad having detection window |
| US9484212B1 (en) * | 2015-10-30 | 2016-11-01 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021135849A1 (en) * | 2019-12-31 | 2021-07-08 | 深圳市中光工业技术研究院 | Wafer polishing device |
| CN114683166A (en) * | 2020-12-29 | 2022-07-01 | 罗门哈斯电子材料Cmp控股股份有限公司 | Chemical mechanical polishing pad having window with transparency at low wavelength and material for such window |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018108636A (en) | 2018-07-12 |
| TW201822982A (en) | 2018-07-01 |
| US20180169827A1 (en) | 2018-06-21 |
| KR20180070466A (en) | 2018-06-26 |
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Application publication date: 20180626 |