CN107922819A - For the CMP slurry constituent of organic film, its preparation method and the method for grinding organic film using it - Google Patents
For the CMP slurry constituent of organic film, its preparation method and the method for grinding organic film using it Download PDFInfo
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- CN107922819A CN107922819A CN201680047980.8A CN201680047980A CN107922819A CN 107922819 A CN107922819 A CN 107922819A CN 201680047980 A CN201680047980 A CN 201680047980A CN 107922819 A CN107922819 A CN 107922819A
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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
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
Abstract
The invention relates to a kind of CMP slurry of organic film, including oxidant and solvent.The CMP slurry of the organic film of the present invention has the Δ θ for being about 5 ° to 90 ° presented by equation (1)w, it changes for water contact angle, and is being coated with organic film and wafer to be ground, is impregnated in measured afterwards when 10 is small in CMP slurry.
Description
Technical field
The invention relates to a kind of for its grinding of the CMP slurry constituent of organic film, its preparation method and use
The method of organic film.More specifically, the invention relates to suitable for grinding the table of target such as semiconductor crystal wafer
CMP slurry constituent, its preparation method and the method using its grinding organic film that the organic film formed on face is ground.
Background technology
It is just increasingly desirable to form finer pattern and multilayer circuit with the high integration of semiconductor device.Therefore, deposit
In a kind of hydrocarbon organic film that uses the inoranic membrane being formed on semiconductor and can exclusively be etched as auxiliary material
Technology.For example, it is proposed that following methods, in the method, inoranic membrane are formed on patterned silicon wafer, with laggard
The processing of row gap filling, is filled in the through hole formed in the inoranic membrane in gap filling processing with organic film material
(via-hole).After the gap filling (gap-fill) processing, planarization process is carried out to pass through CMP (chemical
Mechanical polishing, chemical mechanical grinding) remove excessive organic film.
However, most of CMP slurry are commonly used in grinding copper wire or the inoranic membrane such as silicon oxide film or silicon nitride film, and
It is not suitable for grinding organic film.Organic film is softer than inoranic membrane.Therefore, when using organic to grind for the CMP slurry of inoranic membrane
During film, the mechanism of abrasive grains is disperseed, so as to seriously limit the grinding to organic film.When increase abrasive grains amount or
When size is to improve grinding rate, pit problem, i.e., the phenomenon that wherein inoranic membrane is also ground together with organic film may be present.
In order to overcome those problems, korean patent application case the 2007-0057009th discloses a kind of use on its surface
The upper polymer beads with functional group replace method of the inorganic particle as the abrasive grains of CMP slurry.However, such a method
The problems of be it is such a comprising polymer beads as abrasive grains CMP slurry for grinding there is high film density
Or high rigidity organic film when can not provide abundance grinding rate.
There is different film qualities since organic film is formed according to it, it is therefore necessary to provide and be directed to as grinding target
Organic film and with optimal composition CMP slurry.Different from inoranic membrane, organic film is by the reaction between various compounds
And formed, and it is difficult to the abrasive characteristic that organic film is predicted according to the composition of CMP slurry.Therefore, the CMP for organic film is ground
Slurry is developed in the following manner：The slurry with specific composition is prepared, is needed using the slurry to grind coating
The wafer of organic film is ground, and whether observe film thickness and membrane property appropriate to monitor forming for the slurry.However, such a side
There is the problem of increase production time and production cost and inefficiency in method.
The content of the invention
Technical problem
One embodiment of the present invention is to provide a kind of CMP for organic film with excellent effect when grinding organic film
Slurry constituent.
It is a further object to provide a kind of method for manufacturing the CMP slurry compositions for organic film, its energy
It is enough to provide the abrasive characteristic optimized as organic film to be ground using less time and cost.
It is a further object to provide a kind of CMP slurry composition using for organic film to carry out organic film
The method of grinding, has excellent grinding effect to organic film.
Solution
A mode according to the present invention, there is provided a kind of CMP slurry constituents for organic film, comprising oxidant and molten
Agent.The CMP slurry constituent have by equation (1) calculated for 5 ° to 90 °, specifically 5 ° to 70 °, more
It is 10 ° to 50 ° of water contact angle changes delta θ for bodyw, it is being coated with organic film and wafer to be ground is impregnated in CMP and grinds
Starch measured afterwards when 10 is small in constituent：
Equation (1)：
Water contact angle changes (Δ θw)=| θ1-θ2|,
In equation (1), θ1Represent by being impregnated in the CMP slurry constituents in the wafer for being coated with organic film
In before deionized water (DIWATER) is dropped on the surface of the organic film to the water contact angle of the measured organic film,
And θ2Represent by the wafer is impregnated in the CMP slurry constituent 10 it is small when after by deionized water
(DIWATER) water contact angle of the organic film measured on the surface of the organic film is dropped to.
The oxidant may include to be selected from Fe3+、Ce4+、Ce3+、Cu2+And Ag+At least one of, and optionally can more wrap
Include hydrogen peroxide.Specifically, the oxidant may include Fe3+、Cu2+、Ce3+Or Ce4+, or may include to be selected from Ce4+、Ce3+、
Cu2+And Ag+At least one of metal ion and hydrogen peroxide mixture.
The oxidant can include metal salt and hydrogen peroxide comprising Ce with weight ratio 1: 1.5 to 1: 3.
The oxidant can be present in the CMP slurry constituent with the amount of 0.001 weight % to 5 weight % by weight
In.
The CMP slurry constituent can further include abrasive material, and the abrasive material is included selected from silica, aluminium oxide, cerium oxide, oxygen
Change at least one of titanium and zirconium oxide.Herein, the abrasive material can be present in described with the amount of 0.01 weight % to 5 weight %
In CMP slurry constituents.
The CMP slurry constituent can have by equation (2) calculated for 1 ° to 50 °, specifically 1 ° extremely
20 °, more specifically 1 ° to 10 ° of hexamethylene (cyclohexane) contact angle changes delta θn, being coated with organic film and
Wafer to be ground is impregnated in measured afterwards when 10 is small in CMP slurry constituents：
Equation (2)：Contact angle changes (Δ θn)=| θ3-θ4|,
In equation (2), θ3Represent by being impregnated in the CMP slurry constituents in the wafer for being coated with organic film
In before hexamethylene (cyclohexane) is dropped on the surface of the organic film to the contact angle of the measured organic film,
And θ4Represent by the wafer is impregnated in the CMP slurry constituent 10 it is small when after by hexamethylene (cyclo
Hexane the contact angle of the organic film measured on the surface of the organic film) is dropped to.
The organic film as grinding target can have the carbon content of 50 weight % to 95 weight %.
It is 500 angstrom mins to 10,000 angstrom mins that the CMP slurry constituent, which can have relative to the organic film, tool
It is 1,000 angstrom mins to 8000 angstrom mins for body, more specifically 1,500 angstrom mins grinding to 5,000 angstrom mins
Grind speed.
Another way according to the present invention, there is provided a kind of method for preparing the CMP slurry constituents for organic film, it is described
Method includes：Oxidant is set to be mixed with solvent, wherein carrying out the mixing of the oxidant and the solvent so that the CMP is ground
Slurry constituent have by equation (1) calculated for 5 ° to 90 ° of water contact angle changes delta θwn, it is being coated with organic film
And wafer to be ground be impregnated in slurry constituent 10 it is small when after it is measured.
Another mode according to the present invention, there is provided a kind of method for grinding organic film, the described method includes：Utilize as above institute
That states is ground organic film for the CMP slurry constituent of organic film.
Beneficial effect
The slurry composition for CMP for organic film of the present invention has excellent grinding rate for organic film, and is
Various organic films provide the abrasive characteristic of optimization.
Method of the manufacture for the slurry composition for CMP of organic film according to the present invention, can manufacture for organic film
Slurry composition for CMP, optimizes the polishing characteristic of organic film.
Brief description of the drawings
Fig. 1 is a kind of figure for the method for grinding organic film according to one embodiment of present invention.
Embodiment
Hereinafter, it will be apparent from the embodiment of the present invention.
CMP slurry constituents for organic film
First, the CMP slurry constituents for being used for organic film according to the present invention will be illustrated.
The CMP slurry constituent for organic film includes solvent and oxidant according to the present invention, and has and pass through equation
Formula (1) calculated for 5 ° to 90 ° of water contact angle changes delta θw, it is being coated with organic film and wafer to be ground is impregnated in
It is measured afterwards when 10 is small in CMP slurry constituents.
For example, for organic film CMP slurry constituent can have by equation (1) calculated for 5 °, 6 °,
7°、8°、9°、10°、11°、12°、13°、14°、15°、16°、17°、18°、19°、20°、21°、22°、23°、24°、25°、26°、
27°、28°、29°、30°、31°、32°、33°、34°、35°、36°、37°、38°、39°、40°、41°、42°、43°、44°、45°、
46°、47°、48°、49°、50°、51°、52°、53°、54°、55°、56°、57°、58°、59°、60°、61°、62°、63°、64°、
65°、66°、67°、68°、69°、70°、71°、72°、73°、74°、75°、76°、77°、78°、79°、80°、81°、82°、83°、
84 °, 85 °, 86 °, 87 °, 88 °, 89 ° or 90 ° of water contact angle changes delta θw, it is being coated with organic film and wafer to be ground
It is impregnated in measured afterwards when 10 is small in slurry constituent.It is greater than or equal to one of above numerical value and small in addition, can have
In or equal to one of above numerical value water contact angle changes delta θw.Specifically, can have 5 ° to 70 °, more specifically
For 10 ° to 50 ° of water contact angle changes delta θw：
Equation (1)：
Water contact angle changes (Δ θw)=| θ1-θ2|,
In equation (1), θ1Represent by being impregnated in the CMP slurry constituents in the wafer for being coated with organic film
In before deionized water (DI WATER) is dropped on the surface of the organic film to the water contact angle of the measured organic film,
And θ2Represent by the wafer is impregnated in the CMP slurry constituent 10 it is small when after by deionized water (DI
WATER the water contact angle of the organic film measured on the surface of the organic film) is dropped to.
As noted previously, as organic film has by the chemical reaction between various components the labyrinth that is formed, because
This abrasive characteristic it is difficult to predict organic film.After conducting extensive research, inventor has found the abrasive characteristic of organic film
It is related to water contact angle change, this be by before being impregnated in the wafer for being coated with organic film in CMP slurry constituents and
Measurement afterwards is found as the water contact angle of the organic film of grinding target.
Specifically, when by being ground described in the measurement before and after grinding target is impregnated in CMP slurry constituents
Grind target water contact angle and find water contact angle change between 5 ° to 90 ° of scope when, for example, 5 ° to 70 ° or 10 ° extremely
50 °, excellent grinding efficiency is shown for the organic film as grinding target.If water contact angle change is less than 5 ° or is more than
90 °, then there is rather low grinding rate for organic film.
The wafer for being coated with organic film used when measuring water contact angle can be by being coated on oxidation silicon wafer by organic film
Prepared on circle.
The oxidation Silicon Wafer can be but be not limited to the standard Silicon Wafer wherein in a diameter of 200 millimeters or 300 millimeters
(Silicon) 2,000 angstroms to 12,000 angstroms thick silicon oxide films are formed uniformly on so that the thickness of the silicon oxide film
Wafer of the relative standard deviation within 10%.
The wafer for being coated with organic film can be by being coated on oxidation Silicon Wafer (silicon oxide) by organic film constituent
Above prepare.Herein, the coating of organic film can be carried out by the processing with multiple steps using different revolutions per minute,
But it is not limited only to this.For example, the coating of organic film can pass through three step spin coatings under the following conditions
(spincoating) processing carries out：
Step 1：1000rpm, 2 seconds.
Step 2：1500rpm, 20 seconds.
Step 3：1000rpm, 2 seconds.
The spin-coat process is carried out using the general MS-A200 standard spins bought from three large bamboo hat with a conical crown and broad brim limited companies.
Organic film constituent is coated on wafer, is then toasted (baking) on hot plate (hot plate) with described in curing
Organic film.For example, baking (baking) in 2 minutes is carried out on the hot plate at about 400 DEG C in atmosphere.Toasting
(baking) after, carry out cooling down for 10 minutes at room temperature, thereby form organic film.Handle, can be formed uniformly more than
Organic film with the average thickness for 2,000 angstroms to 3,000 angstroms is so that the relative standard deviation of the thickness of the film is in
Within 5%.
Can be by measuring organic film at 30 points that the diameter along the crystal column surface for being coated with organic film is equally spaced
Thickness and find the relative standard deviation of the average thickness of the organic film and the thickness of the organic film.Herein, such as make
With can be each to measure from the standard spectrum reflectometer (Spectral Reflectometer) that K-MAC limited companies buy
The thickness of organic film at point, and the sweep electron microscope SEM images of the cut surface based on wafer are come to passing through the light
Interference technique and the value that measures are calibrated so that the error between measured value can be within the 5% of measured value.
It can be coated with what is prepared as described above in the whole wafer of organic film or by not causing to damage to organic film
The wafer is cut into 2 centimetres and 2 centimetres of length and width or size more than 2 centimetres and 2 centimetres in the case of evil and is obtained
Water contact angle is measured on the sample obtained.It is to be understood that there is the survey that water contact angle is carried out on the crystal column surface of organic film in coated thereon
Amount.
Oxidant can pass through even flat organic film by the grinding that makes the surface oxidation of organic film to be conducive to organic film
Surface and improve degree of planarization.
The oxidant may include Fe3+、Ce4+、Ce3+、Cu2+And Ag+At least one of.For example, with regard to grinding rate
For, the oxidant may include Fe3+、Cu2+、Ce3+And Ce4+At least one of.Specifically, the oxidant can be containing
There is the metal salt of metal ion as described above, and may include such as ammonium ceric nitrate (ceric ammonium nitrate), sulphur
Sour cerium (ceric sulfate), copper chloride (cupric chloride), copper nitride (cupric nitride), nitrided iron
(ferric nitride), iron chloride (ferric chloride), cerous nitrate (cerous nitrate) and silver nitrate
At least one of (silver nitrate).
In addition to the metal ion, the oxidant can further include hydrogen peroxide.When the oxidant further includes hydrogen peroxide
When, oxidability can be improved, thereby further improves grinding rate.For example, the oxidant may include but be not limited to Ce4 +、Ce3+、Cu2+And Ag+At least one of metal ion and hydrogen peroxide mixture.
The oxidant can be with 0.001 weight %, 0.005 weight %, 0.01 weight %, 0.05 weight %, 0.1 weight
Measure %, 0.5 weight %, 1 weight %, 1.5 weight %, 2 weight %, 2.5 weight %, 3 weight %, 3.5 weight %, 4 weight %,
The amount of 4.5 weight % or 5 weight % are present in the CMP slurry constituent.In addition, it may be present more than or equal to above numerical value
One of and amount less than or equal to one of above numerical value the oxidant.For example, the oxidant can be with
The amount of 0.001 weight % to 5 weight % are present in the CMP slurry constituent, for example, 0.01 weight % to 3 weight % or
0.05 weight % to 3 weight %.Within this range, appropriate etching property can be kept relative to organic film.
Oxidant can include metal salt and hydrogen peroxide comprising Ce with weight ratio 1: 1.5 to 1: 3.
Solvent can be used to reduce friction when with abrasive lapping organic film, and may include such as water, deionized water, organic
Amine, Organic Alcohol, organic alcohol amine, organic ether, organic ketone etc..Solvent can be present in surplus in CMP slurry constituents.
The CMP slurry constituent for organic film can further include abrasive material according to the present invention.Herein, the abrasive material can be gold
Belong to oxide abrasive.The abrasive material can high grinding rate grinding organic film, and may include to be selected from silica, aluminium oxide,
At least one of cerium oxide, titanium oxide and zirconium oxide.Specifically, the abrasive material may include to be capable of providing more preferably stably dispersing
The silica of property and it is capable of providing at least one of cerium oxide of higher grinding rate.
The abrasive material can be spheric granules, and have 10 nanometers to 150 nanometers of average grain diameter, such as 30 nanometers to 70 are received
Rice.Within this range, the abrasive material can provide sufficient grinding rate without producing relative to the organic film as grinding target
It is raw to scrape, and flatness can be improved.
The abrasive material can be with 0.01 weight %, 0.05 weight %, 0.1 weight %, 0.5 weight %, 1 weight %, 1.5 weights
The amount for measuring %, 2 weight %, 2.5 weight %, 3 weight %, 3.5 weight %, 4 weight %, 4.5 weight % or 5 weight % is present in
In the CMP slurry constituent.In addition, CMP slurry constituents may be present more than or equal to one of above numerical value and be less than
Or the abrasive material of the amount equal to one of above numerical value.Specifically, the abrasive material can be with 0.01 weight % to 5 weight %
Amount be present in the CMP slurry constituent, such as 0.01 weight % to 3 weight %.Within this range, the abrasive material can phase
For providing sufficient grinding rate without producing scraping as the organic film of grinding target, and good disperse can be shown
Stability.Specifically, by increasing the average grain diameter of the abrasive material and reducing the abrasive material in the slurry constituent
Amount, can be relative to grinding rate of the organic film with raising and relative to inoranic membrane with low grinding rate.
In CMP slurry constituent according to the present invention, abrasive material can be mixed with 100: 1 to 1: 500 weight ratio with oxidant
Close, specifically 10: 1 to 1: 100.
In certain embodiments, the CMP slurry constituent can be acid.In those embodiments, the CMP slurry
Constituent can increase the amount of grinding of time per unit relative to organic film, improve the flatness on ground surface, and increase to nothing
The grinding selectivity of machine film.Specifically, the CMP slurry constituent can have for 7 or less than 7, be, for example, 6 or less than 6, more
Specifically 1 to 5 pH.For example, by pH adjusting agent, the CMP slurry constituent can be adjusted in as above
PH in the scope.The pH adjusting agent may include but be not limited to：In inorganic acid, such as nitric acid, phosphoric acid, hydrochloric acid and sulfuric acid
At least one；And organic acid, such as with the organic acid for 5 or the pKa less than 5, such as acetic acid and citric acid at least
One.
The CMP slurry constituent can further include additive.The additive is supplementing the CMP slurry constituent
Property can be simultaneously grinding accelerator.When comprising it is described grinding accelerator when, can by relative to inoranic membrane suppress grinding rate come
Improve the grinding selectivity to inoranic membrane.Grinding accelerator may include organic acid, such as malic acid, citric acid, formic acid, penta 2
At least one of acid, oxalic acid, phthalic acid, butanedioic acid, tartaric acid, maleic acid and malonic acid.The grinding accelerator can
It is present in the amount of 0.01 weight % to 1 weight % in the CMP slurry constituent.Within this range, slurry accelerator will not
The surface nature of dispersion stabilization and organic carbon film to grinding rate, slurry has a negative impact.
For organic film CMP slurry constituent can have by equation (2) calculated for 1 °, 2 °, 3 °, 4 °, 5 °,
6°、7°、8°、9°、10°、11°、12°、13°、14°、15°、16°、17°、18°、19°、20°、21°、22°、23°、24°、25°、
26°、27°、28°、29°、30°、31°、32°、33°、34°、35°、36°、37°、38°、39°、40°、41°、42°、43°、44°、
45 °, 46 °, 47 °, 48 °, 49 ° or 50 ° of cyclohexane Contact Angles changes delta θn, it is being coated with organic film and wafer to be ground
It is impregnated in measured afterwards when 10 is small in CMP slurry constituents.In addition, can have be greater than or equal to one of above numerical value and
Less than or equal to the cyclohexane Contact Angles changes delta θ of one of above numerical valuen.For example, can have 1 ° to 50 °, it is specific
For be 1 ° to 20 °, more specifically 1 ° to 10 ° of cyclohexane Contact Angles changes delta θn：
Equation (2)：
Contact angle changes (Δ θn)=| θ3-θ4|,
In equation (2), θ3Represent by being impregnated in the CMP slurry constituents in the wafer for being coated with organic film
In before hexamethylene (cyclohexane) is dropped on the surface of the organic film to the contact angle of the measured organic film,
And θ4Represent by the wafer is impregnated in the CMP slurry constituent 10 it is small when after by hexamethylene
(cyclohexane) contact angle of the organic film measured on the surface of the organic film is dropped to.Herein, measuring
The wafer used during the contact angle is same as the wafer used when measuring water contact angle.
CMP slurry constituent can relative to organic film have for 500 angstrom mins to 10,000 angstrom mins, specifically
1000 angstrom mins to 8000 angstrom mins, more specifically 1500 angstrom mins to 5000 angstrom mins grinding rate, and because
This is with excellent grinding rate.
The method for preparing the CMP slurry constituents for organic film
A kind of method for preparing the CMP slurry constituents for organic film according to the present invention may include to make oxidant with it is molten
Agent mixes, wherein carrying out mixing of the oxidant with the solvent so that the water contact angle calculated by equation (1)
Changes delta θwBetween 5 ° to 90 ° of scope, be coated with organic film and wafer to be ground be impregnated in CMP slurry composition
It is measured afterwards when 10 is small in thing.
Compound abrasive can be further included by oxidant is mixed with solvent.
Additive package can be further included by oxidant is mixed with solvent, such as grind accelerator.
Since the example of oxidant, solvent, abrasive material and additive and the details of amount are same as described above, no longer
It is repeated.
Organic film
Hereinafter, it will be apparent from the organic film as grinding target according to the present invention.
" being substituted " in " be substituted or be unsubstituted " used herein means that at least one hydrogen in functional group is former
Son is through following substitution：Hydroxyl, halogen atom, sulfinyl, mercapto, cyano group, amido, C1 to C30 alkyl, C2 to C30 alkenyls,
C2 is to C30 alkynyls, C3 to C30 cycloalkyl, C3 to C30 cycloalkenyl groups, C6 to C30 aryl, C7 to C30 aralkyl, the miscellaneous alkane of C1 to C20
Base, C2 to C30 Heterocyclylalkyls, C2 to C30 heterocycloalkenyls, C2 to C30 heteroaryls, C2 to C30 heteroarylalkyls, C1 to C20 alkyl
Amido, C1 to C30 alkoxies, C6 to C30 aryloxy group, C1 to C20 aldehyde radicals, C1 to C40 alkylether radicals, C7 to C20 stretch aralkyl
Ether, C1 to C30 haloalkyls, the functional group containing P, contain the functional group of B or its combination.
Herein, " functional group containing P " can be represented by formula A, and " functional group containing B " can be represented by formula B.
<Formula A>
*-(O)n-(CH2)m- P (=O) (Ra)(Rb)
<Formula B>
*-B(Rc)(Rd)
<Formula A>And<Formula B>In, n is 0 or 1；M is 0 to 10 integer；And Ra、Rb、RcAnd RdEach stand alone as hydrogen, hydroxyl,
The C1 for being substituted or being unsubstituted to C20 alkyl, the C2 for being substituted or being unsubstituted to C20 alkenyls, be substituted or be unsubstituted
C3 to C20 cycloalkyl, the C1 for being substituted or being unsubstituted to C20 haloalkyls, the C1 for being substituted or being unsubstituted to C20 alkane
Base sulfonate group, the C1 for being substituted or being unsubstituted to C20 alkyl sulphonyls, the C2 for being substituted or being unsubstituted to C20 alkyl
Amide groups, the C3 for being substituted or being unsubstituted to C20 alkyl ester group, the C2 for being substituted or being unsubstituted to C20 cyanoalkyls, warp
Substitute or the C1 that is unsubstituted to C20 alkoxies, the C6 for being substituted or being unsubstituted to C30 aryl, be substituted or be unsubstituted
C6 to C30 aralkyl or the C6 for being substituted or being unsubstituted to C30 aryloxy group, or RaWith RbOr RcWith RdBe connected to each other with
The C3 that is substituted or is unsubstituted is formed to C20 cycloalkyl or the C3 for being substituted or being unsubstituted to C20 Heterocyclylalkyls.
Specifically, " functional group containing P " is the functional group containing P and O, for example,-O-P (=O) (OH)2,-P (=
O)(OCH2CH3)2And-P (=O) (C2H4C6H5)(OCH2CH3), and " functional group containing B " is the functional group containing B and O, example
Such as ,-B (OH)2、-B(H)(CH3) and-B (CH2CH3)2。
In certain embodiments, organic film can have for 50 weight % to 95 weight %, specifically 65 weight % are extremely
The carbon content of 95 weight % or 70 weight % to 92 weight %.For example, organic film can have for 50 weight %, 51 weights
Measure %, 52 weight %, 53 weight %, 54 weight %, 55 weight %, 56 weight %, 57 weight %, 58 weight %, 59 weight %,
60 weight %, 61 weight %, 62 weight %, 63 weight %, 64 weight %, 65 weight %, 66 weight %, 67 weight %, 68 weights
Measure %, 69 weight %, 70 weight %, 71 weight %, 72 weight %, 73 weight %, 74 weight %, 75 weight %, 76 weight %,
77 weight %, 78 weight %, 79 weight %, 80 weight %, 81 weight %, 82 weight %, 83 weight %, 84 weight %, 85 weights
Measure %, 86 weight %, 87 weight %, 88 weight %, 89 weight %, 90 weight %, 91 weight %, 92 weight %, 93 weight %,
The carbon content of 94 weight % or 95 weight %.Within this range, when being ground with abrasive material, organic film can have high grinding speed
Rate is scraped without being subjected to, and can show high-flatness on ground surface.
In certain embodiments, organic film can have for 0.5 gram/cc to 2.5 grams/cc, specifically
For 1.0 grams/cc to 2.0 grams/cc or 1.2 grams/cc to 1.6 grams/cc of film density.Lift
For example, it is 0.5 gram/cc, 0.6 gram/cc, 0.7 gram/cc, 0.8 gram/cube that organic film, which can have,
Centimetre, 0.9 gram/cc, 1.0 grams/cc, 1.1 grams/cc, 1.2 grams/cc, 1.3 grams/cube li
Rice, 1.4 grams/cc, 1.5 grams/cc, 1.6 grams/cc, 1.7 grams/cc, 1.8 grams/cube li
Rice, 1.9 grams/cc, 2.0 grams/cc, 2.1 grams/cc, 2.2 grams/cc, 2.3 grams/cube li
The film density of rice, 2.4 grams/cc or 2.5 grams/cc.Within this range, it is organic when being ground with abrasive material
Film can have high grinding rate to be scraped without being subjected to, and can show high-flatness on ground surface.
In certain embodiments, organic film can have for 0.4GPa or more than 0.4GPa, specifically 1.0GPa or big
In 1.0GPa or 1.3GPa or hardness more than 1.3GPa.For example, organic film can have for the hard of 1.0GPa to 1.5GPa
Degree, for example, 0.4GPa, 0.5GPa, 0.6GPa, 0.7GPa, 0.8GPa, 0.9GPa, 1.0GPa, 1.1GPa, 1.2GPa, 1.3GPa,
1.4GPa or 1.5GPa.Within this range, when being ground with abrasive material, organic film can have high grinding rate without being subjected to
Scrape, and high-flatness can be shown on ground surface.
In addition, organic film can be with the acid value for being essentially 0mg KOH/g according to the present invention.Herein, term is " real
In matter " mean that the acid value not only includes 0mg KOH/g, but also also include the 0mg KOH/ in acceptable margin for error
g.When it is essentially the acid value of 0mg KOH/g that organic film, which has, the grinding rate of organic film can further improve.
Specifically, organic film according to the present invention can be by including the chemical combination containing the aromatic group for being substituted or being unsubstituted
The organic film constituent of thing is formed.More specifically, organic film according to the present invention can be formed in the following manner：It will contain
The organic film constituent for having the compound for the aromatic group for being substituted or being unsubstituted is coated on inoranic membrane, then at high temperature into
Row baking (baking), such as at a temperature of 200 DEG C to 400 DEG C.
The organic film formed by the organic film constituent comprising the compound containing the aromatic group for being substituted or being unsubstituted
The decomposition of aromatic group is not suffered from after baking, and therefore there is high carbon content.The aromatic group can be with monocyclic knot
Structure or the carbon 6 of two or more rings fusion (fused) polycyclic (polycyclic) structure to 100 aromatic group of carbon, such as carbon 6 to
Carbon 50.For example, the aromatic group can include the compound represented by formula 1-1 to formula 1-26.
<Formula 1-1>
<Formula 1-2>
<Formula 1-3>
<Formula 1-4>
<Formula 1-5>
<Formula 1-6>
<Formula 1-7>
<Formula 1-8>
<Formula 1-9>
<Formula 1-10>
<Formula 1-11>
<Formula 1-12>
<Formula 1-13>
<Formula 1-14>
<Formula 1-15>
<Formula 1-16>
<Formula 1-17>
<Formula 1-18>
<Formula 1-19>
<Formula 1-20>
<Formula 1-21>
<Formula 1-22>
<Formula 1-23>
<Formula 1-24>
<Formula 1-25>
<Formula 1-26>
(formula 1-1 into formula 1-26, Z1To Z18The C1 to C20 for each stand alone as singly-bound, being substituted or being unsubstituted stretches alkane
The C2 to C20 that base, the C2 to C20 for being substituted or being unsubstituted stretch alkenyl, is substituted or is unsubstituted stretches alkynyl, is substituted or not
The C3 to C20 that the C3 being substituted to C20 stretches cycloalkyl, is substituted or is unsubstituted stretches cycloalkenyl group, is substituted or is unsubstituted
The C2 to C20 that C6 to C20 stretches aryl, is substituted or is unsubstituted stretches heteroaryl ,-(C=O)-,-NRe-、-CRfRg-, oxygen (O),
Sulphur (S) or its combination, and Re、RfAnd RgThe C1 for each stand alone as hydrogen, being substituted or being unsubstituted to C10 alkyl, halogen atom,
The C2 to C20 that the C6 for being substituted or being unsubstituted to C20 stretches aryl, is substituted or is unsubstituted stretches heteroaryl or its combination.
Next, the organic film for including the compound containing the aromatic group for being substituted or being unsubstituted will be described in greater detail
The embodiment of constituent.
In the first embodiment, organic film constituent can be used as comprising a kind of material comprising the unit represented by formula 2
Compound containing the aromatic group for being substituted or being unsubstituted.
<Formula 2>
In formula 2, a meets 1≤a ＜ 190；
R1It is hydrogen, hydroxyl, halogen atom, pi-allyl, sulfinyl, mercapto, cyano group, the amine for being substituted or being unsubstituted
Base, the C1 for being substituted or being unsubstituted to C30 alkyl, the C1 for being substituted or being unsubstituted to C30 miscellaneous alkyls, be substituted or without
Substituted C2 is to C30 alkenyls, the C2 for being substituted or being unsubstituted to C30 alkynyls, the C3 for being substituted or being unsubstituted to C30 cycloalkanes
Base, the C2 for being substituted or being unsubstituted to C30 Heterocyclylalkyls, the C3 for being substituted or being unsubstituted to C30 cycloalkenyl groups, be substituted or
The C6 being unsubstituted to C30 aryl, the C7 for being substituted or being unsubstituted to C30 aralkyl, the C2 for being substituted or being unsubstituted extremely
C30 heterocycloalkenyls, the C2 for being substituted or being unsubstituted to C30 heteroaryls, the C2 for being substituted or being unsubstituted to C30 heteroaryl alkane
Base, the C1 for being substituted or being unsubstituted to C20 alkyl amine groups, the C1 for being substituted or being unsubstituted to C30 alkoxies, be substituted or
The miscellaneous alkoxies of the C1 being unsubstituted to C30, the C6 for being substituted or being unsubstituted to C30 aryloxy group, be substituted or be unsubstituted
C1 stretches aralkyl to C20 aldehyde radicals, the C1 for being substituted or being unsubstituted to C40 alkylether radicals, the C7 for being substituted or being unsubstituted to C20
Base ether, the C1 for being substituted or being unsubstituted to C30 haloalkyls, the functional group containing P, contain the functional group of B or its group
Close；
R2Hydrogen, the amido that is substituted or is unsubstituted, the C1 that is substituted or is unsubstituted to C20 alkoxies, be substituted
Or the C6 being unsubstituted is to C20 aryloxy group ,-NRhRi(RhAnd RiThe C1 that is substituted or is unsubstituted each is stood alone as to C10 alkane
Base or the C6 that is substituted or is unsubstituted are to C10 aryl), hydroxyl, halogen atom, pi-allyl, sulfinyl, mercapto, cyanogen
Base, the C1 for being substituted or being unsubstituted to C30 alkyl, the C1 for being substituted or being unsubstituted to C30 miscellaneous alkyls, be substituted or without
Substituted C2 is to C30 alkenyls, the C2 for being substituted or being unsubstituted to C30 alkynyls, the C3 for being substituted or being unsubstituted to C30 cycloalkanes
Base, the C2 for being substituted or being unsubstituted to C30 Heterocyclylalkyls, the C3 for being substituted or being unsubstituted to C30 cycloalkenyl groups, be substituted or
The C6 being unsubstituted to C30 aryl, the C7 for being substituted or being unsubstituted to C30 aralkyl, the C2 for being substituted or being unsubstituted extremely
C30 heterocycloalkenyls, the C2 for being substituted or being unsubstituted to C30 heteroaryls, the C2 for being substituted or being unsubstituted to C30 heteroaryl alkane
Base, the C1 for being substituted or being unsubstituted to C20 alkyl amine groups, the miscellaneous alkoxies of the C1 for being substituted or being unsubstituted to C30, be substituted
Or the C1 being unsubstituted to C20 aldehyde radicals, the C1 for being substituted or being unsubstituted to C40 alkylether radicals, be substituted or be unsubstituted
C7 to C20 stretches aralkyl ether, the C1 for being substituted or being unsubstituted to C30 haloalkyls, the functional group containing P, the official containing B
Can base or its combination；And
R3It is to be selected from by one of material for being substituted or being unsubstituted of following various expression：
-CH2-
For example, R2Can be the C1 that is substituted or is unsubstituted to C10 alkoxies.
After being toasted to organic film constituent, the material comprising the unit represented by formula 2 can increase organic film
Carbon content, film density and hardness.More detailed processing is disclosed in Korean Patent No. 10-0866015.
In addition to the material comprising the unit represented by formula 2, organic film constituent according to first embodiment also can be wrapped more
Containing at least one of linked, acidic catalyst and organic solvent.Specifically, constituent according to first embodiment can wrap
The material comprising the unit represented by formula 2,0.1 weight % containing 1 weight % to 20 weight % to 5 weight % linked,
The acidic catalyst and 75 weight % of 0.001 weight % to 0.05 weight % to 98.8 weight % organic solvent.
The linked may include melmac (for example, N- methoxies-melmac or N- fourth oxygen
Ylmethyl-melmac), methylate or butylation carbamide resin, amine resin, the acetylene carbamide derivatives represented by formula 3, by
At least one of the diepoxides that formula 4 represents and the melamine derivative that is represented by formula 5.
<Formula 3>
<Formula 4>
<Formula 5>
The acidic catalyst may include p-methyl benzenesulfonic acid monohydrate, p-methyl benzenesulfonic acid pyridine ester, 2,4,4,6- tetrabromo rings
Hexadiene ketone, toluenesulfonic acid benzoin ester, toluenesulfonic acid -2- nitrobenzyl esters and organic sulfonic acid Arrcostab at least one
Person.
The organic solvent can fully dissolve the compound containing the aromatic group for being substituted or being unsubstituted to be any
Organic solvent, it is unrestricted to this.For example, the organic solvent may include propylene glycol monomethyl ether acetate, cyclohexanone, breast
Acetoacetic ester etc..
Can by the way that organic film constituent according to first embodiment is applied to 500 angstroms to 4,000 angstroms, specifically 2,
000 angstrom to 3,000 angstroms of thickness, then toasted at a temperature of 200 DEG C to 400 DEG C produced to 10 minutes within 10 seconds it is described organic
Film, but it is not limited only to this.
In a second embodiment, organic film constituent may include to be used as containing being substituted or not by the material that formula 6 represents
The compound for the aromatic group being substituted.
<Formula 6>
<Formula 6>In, R4To R9And X1To X6Each stand alone as hydrogen, hydroxyl, halogen atom, pi-allyl, sulfinyl, mercaptan
Base, cyano group, the amido for being substituted or being unsubstituted, the C1 that is substituted or is unsubstituted to C30 alkyl, be substituted or be unsubstituted
C1 to C30 miscellaneous alkyls, the C2 for being substituted or being unsubstituted to C30 alkenyls, the C2 for being substituted or being unsubstituted to C30 alkynyls,
The C3 for being substituted or being unsubstituted to C30 cycloalkyl, the C2 for being substituted or being unsubstituted to C30 Heterocyclylalkyls, be substituted or not
The C3 being substituted is to C30 cycloalkenyl groups, the C6 for being substituted or being unsubstituted to C30 aryl, the C7 for being substituted or being unsubstituted to C30
Aralkyl, the C2 for being substituted or being unsubstituted to C30 heterocycloalkenyls, the C2 for being substituted or being unsubstituted to C30 heteroaryls, through taking
Generation or the C2 that is unsubstituted to C30 heteroarylalkyls, the C1 for being substituted or being unsubstituted to C20 alkyl amine groups, be substituted or without
Substituted C1 to C30 alkoxies, the miscellaneous alkoxies of the C1 for being substituted or being unsubstituted to C30, the C6 that is substituted or is unsubstituted extremely
C30 aryloxy group, the C1 for being substituted or being unsubstituted to C20 aldehyde radicals, the C1 for being substituted or being unsubstituted to C40 alkylether radicals, warp
Substitute or the C7 to C20 that is unsubstituted stretch aralkyl ether, the C1 for being substituted or being unsubstituted to C30 haloalkyls, containing P's
Functional group, contain the functional group of B or its combination；And n1To n6It is each independent between 0 to 2 scope and to meet 2≤n1+n2
+n3+n4+n5+n6≤6。
For example, R4To R9Can each stand alone as the C1 that is substituted or is unsubstituted to C10 alkyl, be substituted or without
Substituted C6 is to C20 aryl, the C3 for being substituted or being unsubstituted to C20 cycloalkyl, the C3 for being substituted or being unsubstituted to C20 rings
Alkenyl, the functional group containing P or the functional group containing B.
For example, X1To X6Can each stand alone as hydrogen, hydroxyl, the C1 that is substituted or is unsubstituted to C20 alkyl amine groups,
Amido, the functional group containing P or the functional group containing B.
Replaced except organic film constituent according to second embodiment includes the material that is represented by formula 6 comprising being represented by formula 2
Unit material using as beyond the compound containing the aromatic group for being substituted or being unsubstituted, it is according to second embodiment to have
Machine film constituent is essentially the same as organic film constituent according to first embodiment.Therefore, will only elaborate by formula 6 below
The material of expression.
The aromatic compounds represented by formula 6 can have the weight average molecular weight for 500 grams/mol to 4000 grams/mol.
Within this range, organic film constituent can form the excellent film or organic film with appropriate thickness.
The material represented by formula 6 can be prepared by a kind of typical method known in the art.For example, can lead to
Crossing makes chloroacetic chloride, chlorobenzoyl chloride, naphthoyl chlorine or hexamethylene formyl chloride with cool reaction, then carries out also original system to the material of gained
It is standby, but it is not limited only to this.More detailed processing is disclosed in Korean Patent No. 10-1311942.
After being toasted to organic film constituent, it is close that the material that is represented by formula 6 can increase the carbon content of organic film, film
Degree and hardness.Comprising by<Formula 6>The organic film constituent of the material of expression is included in short wavelength (for example, 193 nanometers or 248 receiving
Rice) under show the aromatic ring of strong absorbent, and therefore also occur at high temperature in the case of without using specific catalyst
Crosslinking, thereby prevents from causing pollution because of catalyst.The material represented by formula 6 can be diverse location include substituent two or
The mixture of more compounds.
In the third embodiment, organic film constituent can include containing in following compound (i), (ii) and (iii)
The polymer for having aromatic group is used as the compound containing the aromatic group for being substituted or being unsubstituted.
(i) a kind of compound for including the unit represented by formula 7.
(ii) a kind of compound comprising the unit represented by formula 7 and the compound comprising the unit represented by formula 8 is mixed
Compound.
(iii) a kind of compound for including the unit represented by formula 9.
<Formula 7>
<Formula 8>
<Formula 9>
(for formula 7 into formula 9, b, c, d and e each stand alone as 1 to 750；
2≤c+d ＜ 1500：
R10It is to be selected from by one of material for being substituted or being unsubstituted of following various expression：
(R be the C1 for being substituted or being unsubstituted to C10 alkyl, the C6 for being substituted or being unsubstituted to C20 aryl, through taking
Generation or the C3 that is unsubstituted are to C20 cycloalkyl or the C3 for being substituted or being unsubstituted to C20 cycloalkenyl groups)；
R11Be hydrogen, hydroxyl, halogen atom, sulfinyl, mercapto, cyano group, the amido for being substituted or being unsubstituted, through taking
Generation or the C1 that is unsubstituted to C30 alkyl, the C1 for being substituted or being unsubstituted to C30 miscellaneous alkyls, be substituted or be unsubstituted
C2 to C30 alkenyls, the C2 for being substituted or being unsubstituted to C30 alkynyls, the C3 for being substituted or being unsubstituted to C30 cycloalkyl, warp
Substitute or the C1 that is unsubstituted to C30 Heterocyclylalkyls, the C3 for being substituted or being unsubstituted to C30 cycloalkenyl groups, be substituted or without
Substituted C6 is miscellaneous to C30 aryl, the C7 for being substituted or being unsubstituted to C30 aralkyl, the C2 for being substituted or being unsubstituted to C30
Cycloalkenyl group, the C2 for being substituted or being unsubstituted to C30 heteroaryls, the C2 for being substituted or being unsubstituted to C30 heteroarylalkyls, through taking
Generation or the C1 that is unsubstituted to C20 alkyl amine groups, the C1 for being substituted or being unsubstituted to C30 alkoxies, be substituted or without taking
The C6 in generation is to C30 aryloxy group, the C1 for being substituted or being unsubstituted to C20 aldehyde radicals, the C1 for being substituted or being unsubstituted to C40 alkyl
Ether, the C7 to C20 for being substituted or being unsubstituted stretch aralkyl ether, the C1 for being substituted or being unsubstituted to C30 haloalkyls,
Functional group containing P, contain the functional group of B or its combination；
R12And R14Each stand alone as selected from by one of material for being substituted or being unsubstituted of following various expression：
-H2C-
R13It is to be selected from by one of material for being substituted or being unsubstituted of following various expression：
(R be the C1 for being substituted or being unsubstituted to C10 alkyl, the C6 for being substituted or being unsubstituted to C20 aryl, through taking
Generation or the C3 that is unsubstituted are to C20 cycloalkyl or the C3 for being substituted or being unsubstituted to C20 cycloalkenyl groups)；And
R15It is to be selected from by one of material for being substituted or being unsubstituted of following various expression：
(R be the C1 for being substituted or being unsubstituted to C10 alkyl, the C6 for being substituted or being unsubstituted to C20 aryl, through taking
Generation or the C3 that is unsubstituted are to C20 cycloalkyl or the C3 for being substituted or being unsubstituted to C20 cycloalkenyl groups),
Wherein R10、R13And R15In R each stand alone as hydrogen, hydroxyl, halogen atom, sulfinyl, mercapto, cyano group, warp
Substitute or the amido being unsubstituted, the C1 that is substituted or is unsubstituted are to C30 alkyl, the C1 for being substituted or being unsubstituted to C30
Miscellaneous alkyl, the C2 for being substituted or being unsubstituted to C30 alkenyls, the C2 for being substituted or being unsubstituted to C30 alkynyls, be substituted or
The cycloalkyl of the C3 being unsubstituted to C30, the C3 to C30 for being substituted or being unsubstituted cycloalkenyl group, be substituted or be unsubstituted
C6 to C30 aryl, the C7 for being substituted or being unsubstituted to C30 cyclophanes base, the C2 for being substituted or being unsubstituted to C30 heterocycle alkane
Base, the C2 for being substituted or being unsubstituted to C30 heterocycloalkenyls, the C2 for being substituted or being unsubstituted to C30 heteroaryls, be substituted or
The C2 being unsubstituted to C30 heteroaryl alkyls, the C1 for being substituted or being unsubstituted to C20 alkyl amine groups, be substituted or without taking
The C1 in generation to C30 alkoxies, the C6 for being substituted or being unsubstituted to C30 aryloxy group, be substituted or through unsubstituted C1 to C20 aldehyde
Base, the C1 for being substituted or being unsubstituted to C40 alkylether radicals, the C7 for being substituted or being unsubstituted to C20 stretch aralkyl ether, warp
Substitute or the C1 that is unsubstituted to C30 haloalkyls, the functional group containing P, containing the functional group of B or its combination.
Replaced except organic film constituent according to third embodiment includes the polymer containing aromatic group comprising by 2 table of formula
The material of the unit shown is as beyond the compound containing the aromatic group for being substituted or being unsubstituted, to be essentially the same as basis
The organic film constituent of first embodiment.
After being toasted to organic film constituent, the polymer containing aromatic group can increase organic film carbon content,
Film density and hardness, and can be prepared by any typical method known in the art.More details are in Korean Patent No.
Disclosed in No. 10-0908601.
In the fourth embodiment, organic film constituent can include in following at least both be used as containing being substituted
Or the compound for the aromatic group being unsubstituted：Include the material of the unit represented by formula 2；The material represented by formula 6；And it is selected from
The polymer containing aromatic group of compound (i), (ii) and (iii).Except the organic film constituent according to fourth embodiment includes
Beyond at least two compounds containing the aromatic group for being substituted or being unsubstituted, it is essentially the same as according to first embodiment
Organic film constituent.
The method for grinding organic film
Next, it will illustrate a kind of method for grinding organic film according to the present invention.
A kind of method for grinding organic film according to the present invention includes the use of the CMP slurry constituent for organic film to grind
Organic film, wherein the CMP slurry constituents for organic film may include the according to embodiments of the present invention organic film that is used for
CMP slurry constituents.
(a) of Fig. 1 shows that wherein before being ground to organic film Silicon Wafer, inoranic membrane and organic carbon membrane stack exist
State together.With reference to (a) of Fig. 1, Silicon Wafer (100) is set to be subjected to patterning with intaglio part.On Silicon Wafer (100)
Inoranic membrane (110) is deposited, and organic carbon film (120) is formed on the inoranic membrane, then at a temperature of 200 DEG C to 400 DEG C
Toasted.Dotted line T in (a) of Fig. 1 indicates imaginary grinding stop line.By the CMP slurry constituents for organic film
It is coated on the organic film shown in (a) of Fig. 1, is then mounted thereon grinding pad.Next, by rotating Silicon Wafer
(100) and to organic film it is ground until grinding stop line (T), thereby obtains the Silicon Wafer that wherein organic film is ground, such as
Shown in (b) of Fig. 1.
Embodiment
Next, the present invention will be illustrated in more detail with reference to some examples.It is to be understood that providing those examples is only
In order to illustrate without that the example should be interpreted as the limitation present invention in any way.
For brevity, those who familiarize themselves with the technology obvious details will be repeated no longer.
Example
Preparating example 1- organic film constituents
2000 milliliters of the three-necked flask including thermometer, condenser, mechanical agitator and dropping funel is impregnated in 140
In oil bath at DEG C.Heated and stirred by magnet on hot plate, and the cooling water in condenser is set to 40 DEG C.Will
220 grams, 1.0 moles of 1- methoxyl groups pyrenes and 138 grams, 1.0 moles of Isosorbide-5-Nitraes-bi-methoxy methylbenzene are added in reactor, Ran Hourong
Solution is in 656 grams of propylene glycol monomethyl ether acetates.Then, 4.6 grams, 0.03 mol sulfuric acid diethylester are added in reactor.
The reactor is maintained at 130 DEG C.By during polymerization with Fixed Time Interval measure reaction product molecular weight come
Determine that point is completed in reaction.Herein, by making 1 gram of reaction product be quenched to room temperature and then be diluted using tetrahydrofuran as solvent
0.02 gram of reaction product causes the solids content in solution to be changed into 4 weight % to prepare the sample for measuring molecular weight.For
In identified reaction point place is completed to complete to react, using 4.48 grams 0.03 mole of triethanolamine added in reactor as
Neutralizer, is then stirred the component.Next, reaction product is slowly cooled to room temperature.With 500 grams of propane diols lists
Methyl ether acetate dilutes the reaction product.Next, solvent is added in 2000 milliliters of separatory funnel.Prepare ratio
For 90: 10g/g methanol and 4 kilograms of mixture of ethylene glycol.By the polymer solution through synthesis under fast stirring dropwise
Added in alcohol mixture.The polymer of gained is obtained from the bottom surface of flask, and individually stores supernatant.Removing supernatant
Afterwards, by the way that rotary evaporation 10 minutes from final reacting product removes methanol at a temperature of 60 DEG C under reduced pressure.
The molecular weight of obtained copolymer is measured by gel permeation chromatography GPC using tetrahydrofuran and is disperseed
Degree.The result is that acquisition comprising the unit represented by formula 11 and with the weight average molecular weight for 4000 grams/mol and is 2.3
The polymer of dispersion degree.
<Formula 11>
(wherein a average out to 11, and Me is methyl).
Crosslinking agent (Powderlink 1174, the cyanogen secret service industry that polymer prepared by 0.8 gram, 0.2 gram are represented by formula 4
Company) and 2 milligrams of p-methyl benzenesulfonic acid pyridine esters be dissolved in 9 grams of propylene glycol monomethyl ether acetates, then filter the solution,
Thereby prepare organic film constituent.
Preparating example 2- is coated with the wafer of organic film
, respectively will be in preparating example 1 with following rotating speed and time using the spin coater MS-A200 of three large bamboo hat with a conical crown and broad brim limited companies
The organic film constituent of middle preparation is spun on by forming silicon oxide film on a diameter of 200 millimeters of Silicon Wafer and manufactured oxygen
On the surface of SiClx wafer：2 seconds (steps 1) of the spin coating are carried out, with 1500 revs/min with 1000 revs/min of rotating speed
Rotating speed carries out 20 seconds (steps 2) of the spin coating and carries out 2 seconds (steps 3) of the spin coating with 1000 revs/min of rotating speed.
Then, be used in hot plate at 400 DEG C the organic film constituent is carried out in atmosphere baking in 2 minutes and
Cool down 10 minutes at room temperature.The result is that the organic film that average thickness is 2300 angstroms is formed uniformly on wafer so that thickness
Relative standard deviation is within 5%.Then, wafer is cut into the size of 10 centimetres of 2 centimetre length of width, thereby prepares sample
This.
Prepare the CMP slurry constituent and deionized water for including component listed in table 1.
Detailed description to the component of CMP slurry constituents
(A) oxidant
(a1) ammonium ceric nitrate (three full chemistry limited companies) is used.
(a2) cerous sulfate (An Kelesi organic chemistry company) is used.
(a3) cerous nitrate (Sigma-Aldrich limited company) is used.
(a4) copper nitrate (great Jing Huajin limited companies) is used.
(a5) copper chloride (three full chemistry limited companies) is used.
(a6) ferric nitrate (three full chemistry limited companies) is used.
(a7) hydrogen peroxide (Dong You precision chemicals limited company) is used.
(B) abrasive material：Use colloidal silica cerium (Jie Nusi limited companies).
Property assessment
Distilled water and nonpolar solvent are dropped in preparating example 2 on the surface of the organic film of the sample prepared, to survey
The water contact angle θ of amount before impregnation1And nonpolar solvent contact angle θ3.Then, the sample is impregnated in example and prepared real
Example every CMP slurry constituents in up to 10 it is small when, then the sample is removed and is dried, then measurement dipping after
Water contact angle θ2And nonpolar solvent contact angle θ4.Based on measured value, calculate before impregnation and water contacts after dipping
Angle and the change of nonpolar solvent contact angle.
Herein, contact angle refer at the contact point between solvent droplets and organic film surface by organic film surface and
The angle that tangent line defines.Measurement result is illustrated in [table 1].
In addition, for the abrasive properties of evaluation contents and the CMP slurry constituents of comparative example, it is real using example and comparison
Every CMP slurry constituent of example is ground the wafer for being coated with organic film prepared in preparating example 2.
Grinding pad is used as using Fujiette limited company H0800CMP pads.Use 200 millimeters of MIRRA mills
The lower pressure, the slurry flow rate of 200 ml/mins, 60rpm of (Applied Material Co., Ltd, AMTA) in 1.0psi
Pressing plate (platen) speed and 55rpm head (Head) speed those under the conditions of carry out 30 seconds grind, then utilize
Thickness measurement system measures grinding rate.As a result it is illustrated in table 1.
Table 1
Unit：Thing amount %
It can be seen that from the result shown in [table 1], by measuring before sample wafer is impregnated in CMP slurry and afterwards
The water contact angle of organic film and find, it is 5 ° or the water contact angle more than 5 ° that the CMP slurry constituent of example 1 to example 7, which has,
Change, and therefore there is quite high grinding rate compared to the CMP slurry constituent in comparative example 1 and comparative example 2.
Although elaborate some embodiments herein, it should be appreciated that those embodiments are provided merely to illustrating, and
The embodiment should not be interpreted as the limitation present invention in any way, and can be by those who familiarize themselves with the technology without departing substantially from the present invention
Spirit and scope under conditions of make various retouchings, change, change and equivalent embodiment.
Therefore, the scope of the present invention should be defined by appended claims and its equivalent scope.
Claims (15)
1. a kind of CMP slurry constituent, including oxidant and solvent,
Wherein described CMP slurry constituent have by equation (1) calculated for 5 ° to 90 ° of water contact angle changes delta θw,
Be coated with organic film and wafer to be ground be impregnated in the CMP slurry constituent 10 it is small when after it is measured：
Equation (1)：
Water contact angle changes (Δ θw)=| θ1-θ2|,
In equation (1), θ1Represent by being impregnated in the CMP slurry group in the wafer for being coated with the organic film
The water that deionized water (DIWATER) is dropped to the organic film measured on the surface of the organic film before into thing contacts
Angle, and θ2Represent by the wafer is impregnated in the CMP slurry constituent 10 it is small when after by deionized water
(DIWATER) water contact angle of the organic film measured on the surface of the organic film is dropped to.
2. CMP slurry constituent according to claim 1, wherein the oxidant includes being selected from Fe3+、Ce4+、Ce3+、Cu2+
And Ag+At least one of.
3. CMP slurry constituent according to claim 2, wherein the oxidant further includes hydrogen peroxide.
4. CMP slurry constituent according to claim 1, wherein the oxidant includes Fe3+、Cu2+、Ce3+Or Ce4+。
5. CMP slurry constituent according to claim 1, wherein the oxidant includes being selected from Ce4+、Ce3+、Cu2+And Ag+
At least one of metal ion and hydrogen peroxide mixture.
6. CMP slurry constituent according to claim 1, wherein the oxidant includes bag with weight ratio 1: 1.5 to 1: 3
Metal salt and hydrogen peroxide containing Ce.
7. CMP slurry constituent according to claim 1, wherein the oxidant with 0.001 weight % to 5 weight %'s
Amount is present in the CMP slurry constituent.
8. CMP slurry constituent according to claim 1, wherein the CMP slurry constituent also includes abrasive material.
9. CMP slurry constituent according to claim 8, wherein the abrasive material is included selected from silica, aluminium oxide, oxidation
At least one of cerium, titanium oxide and zirconium oxide.
10. CMP slurry constituent according to claim 8, wherein amount of the abrasive material with 0.01 weight % to 5 weight %
It is present in the CMP slurry constituent.
11. CMP slurry constituent according to claim 1, wherein the CMP slurry constituent, which has, passes through equation
(2) calculated for 1 ° to 50 ° of hexamethylene (cyclo hexane) contact angle changes delta θn, it is being coated with the organic film
And wafer to be ground be impregnated in the CMP slurry constituent 10 it is small when after it is measured：
Equation (2)：
Contact angle changes (Δ θn)=| θ3-θ4|,
In equation (2), θ3Represent by being impregnated in the CMP slurry group in the wafer for being coated with the organic film
Hexamethylene (cyclo hexane) is dropped to connecing for the organic film measured on the surface of the organic film before into thing
Feeler, and θ4Represent by the wafer is impregnated in the CMP slurry constituent 10 it is small when after by hexamethylene
(cyclo hexane) drops to the contact angle of the organic film measured on the surface of the organic film.
12. CMP slurry constituent according to claim 1, wherein the organic film has 50 weight % to 95 weight %
Carbon content.
13. CMP slurry constituent according to claim 12, wherein the CMP slurry constituent has relative to described
Organic film is the grinding rate of 500 angstrom mins to 10000 angstrom mins.
14. a kind of method for preparing the CMP slurry constituents for organic film, including：
Oxidant is set to be mixed with solvent,
The mixing for wherein carrying out the oxidant and the solvent passes through equation so that the CMP slurry constituent has
(1) calculated for 5 ° to 90 ° of water contact angle changes delta θw, it is being coated with organic film and wafer to be ground is impregnated in institute
State measured afterwards when 10 is small in CMP slurry constituents：
Equation (1)：
Water contact angle changes (Δ θw)=| θ1-θ2|,
In equation (1), θ1Represent by being impregnated in it in the CMP slurry constituents in the wafer for being coated with organic film
The preceding water contact angle that deionized water (DIWATER) is dropped to the organic film measured on the surface of the organic film, and θ2
Represent by the wafer is impregnated in the CMP slurry constituent 10 it is small when after deionized water (DIWATER) dripped
The water contact angle of the measured organic film on to the surface of the organic film.
15. a kind of method for grinding organic film, including：
Organic film is ground using CMP slurry constituent according to any one of claim 1 to 13.
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|---|---|---|---|
| KR1020150118245A KR101900540B1 (en) | 2015-08-21 | 2015-08-21 | Cmp slurry composition for organic film, preparing method thereof and polishing method using the same |
| KR10-2015-0118245 | 2015-08-21 | ||
| PCT/KR2016/007937 WO2017034157A1 (en) | 2015-08-21 | 2016-07-21 | Cmp slurry composition for organic film, preparation method therefor, and method for polishing organic film by using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556840A (en) * | 2001-09-24 | 2004-12-22 | Rare earth salt oxidizer based CMP method | |
| WO2014171766A1 (en) * | 2013-04-17 | 2014-10-23 | 제일모직 주식회사 | Organic film cmp slurry composition and polishing method using same |
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| US6830503B1 (en) * | 2002-01-11 | 2004-12-14 | Cabot Microelectronics Corporation | Catalyst/oxidizer-based CMP system for organic polymer films |
| JP2004128211A (en) * | 2002-10-02 | 2004-04-22 | Toshiba Corp | Method for polishing organic film on semiconductor substrate using resin particle and slurry |
| JP4868840B2 (en) * | 2005-11-30 | 2012-02-01 | Ｊｓｒ株式会社 | Manufacturing method of semiconductor device |
| US8920667B2 (en) * | 2013-01-30 | 2014-12-30 | Cabot Microelectronics Corporation | Chemical-mechanical polishing composition containing zirconia and metal oxidizer |
| CN105143390B (en) * | 2013-04-17 | 2019-08-13 | 三星Sdi株式会社 | Organic film chemical and mechanical grinding paste material constituent and the grinding method for using it |
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| CN1556840A (en) * | 2001-09-24 | 2004-12-22 | Rare earth salt oxidizer based CMP method | |
| WO2014171766A1 (en) * | 2013-04-17 | 2014-10-23 | 제일모직 주식회사 | Organic film cmp slurry composition and polishing method using same |
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| CN107922819B (en) | 2020-10-23 |
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| KR101900540B1 (en) | 2018-09-20 |
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