WO2017057936A1 - Organic film cmp slurry composition and polishing method using same - Google Patents
Organic film cmp slurry composition and polishing method using same Download PDFInfo
- Publication number
- WO2017057936A1 WO2017057936A1 PCT/KR2016/010940 KR2016010940W WO2017057936A1 WO 2017057936 A1 WO2017057936 A1 WO 2017057936A1 KR 2016010940 W KR2016010940 W KR 2016010940W WO 2017057936 A1 WO2017057936 A1 WO 2017057936A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- substituted
- unsubstituted
- organic film
- polishing
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 106
- 239000000203 mixture Substances 0.000 title claims abstract description 83
- 239000002002 slurry Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 25
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 25
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 19
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- 230000000694 effects Effects 0.000 description 2
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- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical class OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical class NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Images
Classifications
-
- 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
Definitions
- the present invention relates to an organic film CMP slurry composition and a polishing method using the same.
- the CMP process is an oxide CMP process, a metal CMP process, a poly-Si CMP process, and an organic film CMP process depending on the material to be polished. It may be classified as such.
- a semiconductor process to which the CMP process of polishing an organic film (C-SOH) is applied is typically an ILD (Inter Layer Dielectric) process.
- the ILD process is a process for removing an organic layer (C-SOH) formed in excess as a process for forming a fine pattern.
- An object of the present invention is to provide an organic film CMP slurry composition having excellent selectivity to the organic film compared to the inorganic film.
- Another object of the present invention is to provide an organic film CMP slurry composition having excellent selectivity and polishing amount for an organic film having a higher carbon content than an inorganic film.
- Still another object of the present invention is to provide a polishing method using the organic film CMP slurry composition.
- the organic membrane CMP slurry composition of the present invention comprises ceria and cerium nitrate, and has a selectivity ratio of about 100 or more according to the following Equation 1:
- ⁇ is the polishing amount ( ⁇ / min) for the organic film, and ⁇ is the polishing amount ( ⁇ / min) for the inorganic film).
- the organic layer may have a carbon content of about 90 atom% or more.
- the ceria may have an average particle diameter of about 10 to about 150 nm.
- the ceria may be included in about 0.01 to about 10.0% by weight of the composition.
- the cerium nitrate may be included in about 0.01 to about 5.0% by weight of the composition.
- the CMP slurry composition may have a pH of about 3 to about 5.
- the organic layer may have a film density of about 0.5 to about 2.5 g / cm 3 and a hardness of about 0.4 GPa or more.
- the organic film polishing method of the present invention may include polishing the organic film using the organic film CMP slurry composition.
- the present invention provides a CMP slurry composition excellent in selectivity and polishing amount with respect to an organic film having an excellent organic matter compared to an inorganic film and having a high carbon content and a polishing method using the same.
- 1 is a schematic diagram of an organic film polishing method of an embodiment of the present invention.
- the organic film CMP slurry composition of one embodiment of the present invention may include ceria and cerium nitrate.
- the organic layer may include a C-SOH (spin on hardmask) film, an amorphous carbon layer (ACL), or an NCP film as a carbon-based film containing a carbon-hydrogen bond, and the C-SOH film has a selective polishing effect on the organic film. It is more preferable as the grinding
- the inorganic film may be a film formed of at least one of silicon oxide and silicon nitride, but is not limited thereto.
- Ceria (CeO 2 ) is a metal oxide abrasive and can polish an organic film having a high carbon content with a high polishing amount.
- the polishing surface flatness could be increased by preventing scratches and the like from occurring during polishing of the organic film, which is the polishing target of the present invention.
- Ceria may be free of oxidants or at least increase the amount of polishing.
- Ceria is a spherical particle having an average particle diameter of about 10 to about 150 nm, for example, about 30 to about 70 nm, in the above range can obtain a sufficient polishing amount for the organic film to be polished of the present invention, It can be prevented from occurring and the flatness can be increased.
- Ceria may be included in about 0.01 to about 10.0% by weight, for example about 0.05 to about 5.0% by weight in the CMP slurry composition, in the above range can be obtained a sufficient polishing amount for the organic film to be polished, the scratch Can be prevented from occurring and dispersion stability can be good.
- the average particle diameter of ceria is increased but the amount of slurry in the slurry composition may be lowered to achieve improved polishing amount for the organic film and lower polishing amount for the inorganic film.
- cerium (III) Nitrate a salt in the form of a hydrate having a chemical formula of Ce (NO 3 ) 3 can be used, for example.
- the cerium nitrate may increase the polishing amount of the organic film and reduce the polishing amount of the inorganic film, compared to conventional reducing agents, for example, titanium trichloride, to secure an excellent selection ratio for the organic film.
- the cerium nitrate may be present in the slurry composition in the form of an ionic compound or a chelate compound, and when used in this form, may provide an excellent polishing amount for the organic film, and reduce the polishing amount of the inorganic film, thereby making an excellent choice for the organic film. Rain can be secured.
- the cerium nitrate may be included in about 0.01 to about 5.0% by weight, preferably about 0.01 to about 2.0% by weight, more preferably about 0.04 to about 0.4% by weight of the total CMP slurry composition, in the range of It is possible to provide an excellent polishing amount for the organic film with respect to the organic film, and to reduce the polishing amount of the inorganic film to ensure an excellent selectivity to the organic film compared to the inorganic film.
- the CMP slurry composition according to one embodiment of the present invention may have a selectivity calculated by Equation 1 below about 100, specifically about 300 to about 500.
- Equation 1 ⁇ is the polishing amount ( ⁇ / min) for the organic film, and ⁇ is the polishing amount ( ⁇ / min) for the inorganic film.
- CMP slurry compositions may be acidic.
- the CMP slurry composition may have a pH of about 3 to about 5.
- the CMP slurry composition of one embodiment of the present invention can be adjusted to the pH in the above-described range.
- the pH adjusting agent may comprise one or more of inorganic acids such as nitric acid and sulfuric acid, and may include but are not limited to organic acids such as organic acids such as pKa 5 or less, specifically one or more of acetic acid and citric acid.
- the pH adjusting agent may be included in about 0.01 to about 5.0% by weight, preferably about 0.01 to about 2.0% by weight, more preferably about 0.04 to about 0.4% by weight of the total CMP slurry composition, in the above range It is possible to provide an excellent polishing amount for the organic film with respect to the organic film, and to reduce the polishing amount of the inorganic film to ensure an excellent selectivity to the organic film compared to the inorganic film.
- the CMP slurry composition may further comprise an oxidizing agent.
- the oxidizing agent oxidizes the surface layer of the organic film to facilitate the polishing of the organic carbon film having a high carbon content to facilitate polishing of the organic film, and evens the surface of the organic film even when the inorganic film is exposed by polishing, thereby providing surface roughness even after polishing. You can make it good.
- the residue of the organic film present in the inorganic film can be easily removed to allow a more uniform polishing.
- the oxidizing agent may include at least one of a metal salt having a multivalent oxidation state and a chelate compound of a transition metal.
- Multivalent means divalent or more, for example trivalent or more, for example tetravalent or more.
- Metal salts having a polyvalent oxidation state can increase the polishing rate for the organic film and lower the polishing rate for the inorganic film.
- the metal salt may include a metal such as a transition metal, a lanthanide element, and may further include halogen, ammonium, nitrate, or the like.
- the metal salt may include ceric ammonium salt, ferric halogen salt, ferric nitrate salt, and the like, and may include, for example, ceric ammonium nitrate, ferric nitrate, ferric chloride, and the like.
- the chelating compound of the transition metal can increase the polishing rate for the organic film and lower the polishing rate for the inorganic film.
- the transition metals include conventionally known transition metals of groups 3 to 12 of the periodic table, which may be iron, copper, manganese or chromium, for example.
- Chelates are oxalic acid, amino-substituted carboxylic acids (e.g., iminodiacetic acid, ethylenediaminedisuccinic acid, iminodisuccinic acid, aminopolycarboxylates such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, alpha-amino acids such as glycine, beta- Amino acids), hydroxyl-substituted carboxylic acids (eg, polycarboxylic acids including recipients such as glycolic acid, lactic acid, malic acid, citric acid, tartaric acid), phosphonocarboxylic acids, aminophosphonic acids; Combinations thereof.
- amino-substituted carboxylic acids e.g., iminodiacetic acid, ethylenediaminedisuccin
- the chelating compound of the transition metal may include, but is not limited to, one or more of Fe-containing compounds including propylenediaminetetraacetic acid-Fe and the like, Mn-containing compounds including propylenediaminetetraacetic acid-Mn and the like.
- the oxidant may comprise from about 0.001% to about 15% by weight, such as from about 0.01% to about 5% by weight, such as from about 0.05% to about 3% by weight, in the CMP slurry composition, with suitable etching properties for the organic film in this range. Can be maintained. As the CMP slurry composition becomes acidic, the stability of the oxidant may be increased to increase the polishing amount per unit time for the organic film, to improve the flatness of the polishing surface, and to increase the polishing selectivity for the inorganic film.
- the CMP slurry composition may further comprise an additive.
- the CMP slurry composition may further include a polishing accelerator as an additive.
- the polishing rate for the inorganic film can be suppressed to increase the polishing selectivity for the inorganic film.
- the polishing promoter may include one or more of an organic acid such as malic acid, formic acid, glutaric acid, oxalic acid, phthalic acid, succinic acid, tartaric acid, maleic acid, malonic acid.
- the polishing accelerator may be included in an amount of about 0.02 to about 0.5% by weight in the CMP slurry composition, and may have no adverse effect on the amount of polishing, dispersion stability of the slurry, and surface characteristics of the organic film in the above range.
- substituted means that at least one hydrogen atom of the functional group is a hydroxy group, a halogen atom, a thionyl group, a thiol group, a cyano group, an amino group, a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, C3 to C30 cycloalkyl group, C3 to C30 cycloalkenyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C20 heteroalkyl group, C2 to C30 heterocycloalkyl group, C2 to C30 heterocycloalkenyl group, C2 to C30 heteroaryl group , C2 to C30 heteroarylalkyl group, C1 to C20 alkylamine group, C1 to C30 alkoxy group, C6 to C30 aryloxy group, C1 to C20 al
- the "functional group including P” may be represented by the following Chemical Formula 1
- the “functional group including B” may be represented by the following Chemical Formula 2:
- n is 0 or 1
- m is an integer of 0 to 10
- R a , R b , R c and R d are each independently hydrogen, a hydroxyl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C1 to C20 haloalkyl group, substituted or unsubstituted C1 to C20 alkylsulfonate group, substituted or unsubstituted C1 to C20 alkylsulfonyl group, substituted or unsubstituted C2 To C20 alkylamide group, substituted or unsubstituted C3 to C20 alkyl ester group, substituted or unsubstituted C2 to C20 cyanoalkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsub
- R a and R b or R c and R d are connected to each other to form a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C3 to C20 heterocycloalkyl group.
- the functional group may include -B (OH) 2 , -B (H) (CH 3 ), -B (CH 2 CH 3 ) 2, or the like.
- the organic film fills the resulting via-holes.
- the CMP slurry composition should be able to polish the organic film to a sufficient polishing rate and increase the flatness of the polished surface, so that the residues remaining in the inorganic film after polishing should be easily removed.
- the inorganic film may be a film formed of at least one of silicon oxide and silicon nitride, but is not limited thereto.
- the inorganic membrane may have a carbon content of less than about 1 atom%, for example 0 to about 1 atom% or for example 0 atom%.
- the organic film may have a large difference in polishing amount per unit time and flatness after polishing depending on the material of the organic film.
- the organic film CMP slurry composition of the present invention is a composition for polishing an organic film having a high carbon content, and may increase the polishing amount per unit time of the organic film during the polishing of the organic film and have a high selectivity to the inorganic film.
- the organic film may have a carbon content of about 90 atom% or more, such as about 90 to about 99 atom% or about 95 to about 99 atom%, and in the above range, the amount of polishing and the degree of scratching when polishing with ceria are high. It does not occur, and the flatness of the polishing surface may be high.
- the organic film has a film density of about 0.5 to about 2.5 g / cm 3 , For example, it may be about 1.0 to about 2.0g / cm 3 , for example about 1.2 to about 1.6g / cm 3 , in the above range when polishing with ceria has a high amount of polishing, no scratches and flatness of the polishing surface Can also be high.
- the organic film may have a hardness of about 0.4 GPa or more, for example about 1.0 GPa or more, for example about 1.3 GPa or more, for example about 1.3 to about 1.5 GPa, and in the above-mentioned range, polishing when polishing with ceria The amount is high, there is no scratch, and the flatness of the polished surface may be high.
- the organic film to be polished of the present invention may have an acid value of substantially 0 mgKOH / g.
- an organic film CMP slurry composition including a conventional polymer abrasive there is a problem that the polishing rate is lowered.
- the CMP slurry composition of the present invention can secure the amount of polishing per unit time of the organic film applicable to the CMP process.
- substantially includes not only the case where the acid value is 0 mgKOH / g but also a slight error at 0 mgKOH / g.
- the organic film to be polished of the present invention may be prepared by applying a composition for forming an organic film on an inorganic film and then thermosetting (baking) at a high temperature, for example, 200 to 400 ° C.
- the organic film forming composition may include a compound having a substituted or unsubstituted aromatic group.
- the "compound having a substituted or unsubstituted aromatic group” refers to a compound that does not decompose even after thermal curing so that the organic film formed of the composition can exhibit a high carbon content.
- the unsubstituted aromatic group refers to a single or fused polycyclic aromatic group having about 6 to about 100 carbon atoms, for example, about 6 to about 50 carbon atoms, specifically, the following Chemical Formulas 3-1 to 3- Can contain 26 units:
- composition for organic film formation containing the compound which has a substituted or unsubstituted aromatic group is demonstrated in detail.
- the composition for forming an organic film may be a compound having a substituted or unsubstituted aromatic group may include a material including the following formula (4):
- a is 1 ⁇ a ⁇ 190
- R 1 is hydrogen, a hydroxy group, a halogen atom, an allyl group, thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group , Substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalky
- R 2 is hydrogen, an amino group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C20 aryloxy group, a dialkylamino group (-NRR ', where R and R' are independently substituted with each other) Or unsubstituted C1 to C10 alkyl group or substituted or unsubstituted C6 to C10 aryl group), hydroxy group, halogen atom, allyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted or Unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C
- R 2 may be a substituted or unsubstituted C 1 to C 10 alkoxy group.
- composition for forming an organic film including Chemical Formula 4 may increase carbon content, film density, and hardness after thermosetting, and refer to Korean Patent No. 10-0866015 for a more detailed manufacturing method thereof.
- the composition for forming an organic film according to the first embodiment may further include at least one of a crosslinking component, an acid catalyst, and an organic solvent, in addition to the material containing Formula 4 above. Specifically, it may include 1 to 20% by weight of the material represented by Formula 4, 0.1 to 5% by weight of the crosslinking component, 0.001 to 0.05% by weight of the acid catalyst, and 75 to 98.8% by weight of the organic solvent.
- the crosslinking component may be a melamine resin (eg, N-methoxymethyl-melamine resin, N-butoxymethylmelamine resin), methylated or butylated urea resin, amino resin, glycoluril derivative of Formula 5, A bisepoxy compound, one or more of the melamine derivatives of Formula 7:
- a melamine resin eg, N-methoxymethyl-melamine resin, N-butoxymethylmelamine resin
- methylated or butylated urea resin amino resin
- glycoluril derivative of Formula 5 A bisepoxy compound, one or more of the melamine derivatives of Formula 7:
- Acid catalysts include p-toluenesulfonic acid monohydrate, pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, alkyl of euphonic acid It may include one or more of the esters.
- the organic solvent is not particularly limited as long as it is an organic solvent having sufficient solubility in a compound having a substituted or unsubstituted aromatic group, and examples thereof include propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate and the like.
- the organic film-forming composition of the first embodiment may be coated with a thickness of about 500 to about 4000 kPa, and thermally cured at about 200 to about 400 ° C. for about 10 seconds to about 10 minutes to form an organic film, but is not limited thereto. .
- the composition for forming an organic film may be a compound having a substituted or unsubstituted aromatic group and may include a material represented by Formula 8 below:
- R 4 to R 9 , X 1 to X 6 are each independently hydrogen, hydroxy group, halogen atom, allyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted or Unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycle Alkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted
- n 1 to n 6 are each independently in a range of 0 to 2, and 2 ⁇ n 1 + n 2 + n 3 + n 4 + n 5 + n 6 ⁇ 6 ).
- R 4 to R 9 are each independently a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or It may be an unsubstituted C3 to C20 cycloalkenyl group, a functional group including P, or a functional group including B.
- X 1 to X 6 may be each independently hydrogen, a hydroxy group, a substituted or unsubstituted C 1 to C 20 alkylamine group, an amino group, a functional group including P, a functional group including B.
- the compound having a substituted or unsubstituted aromatic group is substantially the same as the organic film composition of the first embodiment except for including the material represented by the formula (8) instead of the material represented by the formula (4). Therefore, hereinafter, only the substance represented by Chemical Formula 8 will be described.
- the material represented by Chemical Formula 8 may be a mixture of two or more compounds having different positions of substituents, and may include an aromatic ring having strong absorption in a short wavelength region (eg, 193 nm and 248 nm), even if no special catalyst is used. Since the cross-linking reaction proceeds at a high temperature, it is possible to prevent contamination by a catalyst, especially an acid, and the aromatic group compound of Formula 8 may have an average molecular weight of about 500 to about 4000. Can be formed.
- the material represented by Chemical Formula 8 may increase carbon content, film density, and hardness after thermal curing of the organic film composition.
- the material represented by Chemical Formula 8 may be prepared by a conventional method, for example, it may be prepared by reacting and reducing acetyl chloride, benzoyl chloride, naphthoyl chloride, cyclohexanecarbonyl chloride to coronene, but It is not limited.
- acetyl chloride benzoyl chloride, naphthoyl chloride, cyclohexanecarbonyl chloride to coronene, but It is not limited.
- Korea Patent Registration No. 10-1311942 For more detailed manufacturing method refer to Korea Patent Registration No. 10-1311942.
- the organic film composition may include an aromatic group-containing polymer selected from (i), (ii) and (iii) as a compound having a substituted or unsubstituted aromatic group:
- R 11 is hydrogen, a hydroxy group, a halogen atom, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or Unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or
- R 12 is
- R 13 is
- each R is independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, substituted Or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkenyl group
- the compound having a substituted or unsubstituted aromatic group is substantially the same as the organic film composition of the first embodiment except that the aromatic group-containing polymer is included instead of the material represented by the formula (4). Therefore, hereinafter, only the aromatic group-containing polymer will be described.
- the aromatic group-containing polymer may increase carbon content, film density and hardness after thermal curing of the organic film composition, and may be prepared by a conventional method, and refer to Korean Patent No. 10-0908601 for more details.
- the organic film composition is a compound having a substituted or unsubstituted aromatic group material comprising the formula (4); A substance represented by Formula 8; It may contain two or more of the aromatic group-containing polymers selected from the above (i), (ii) and (iii). It is substantially the same as the composition of the first embodiment except that it contains two or more kinds.
- the organic film polishing method of the present invention may include polishing an organic film having a high carbon content using the organic film CMP slurry composition, and the organic film CMP slurry composition may include the organic film CMP slurry composition of the embodiment of the present invention.
- FIG. 1A illustrates a lamination state of a silicon wafer, an inorganic film, and an organic film before polishing an organic film, and the silicon wafer 100 is intaglio patterned locally.
- a recess is formed, and an inorganic film 110 is deposited on the silicon wafer 100, an organic film 120 is coated on the inorganic film, and manufactured by thermal curing at 200 ° C. to 400 ° C.
- FIG. 1A represents an imaginary polishing stop line. After coating the organic film CMP slurry composition on the organic film of FIG. 1A and installing the polishing pad, the silicon wafer 100 is rotated and polished, and polished until the polishing stop line T is reached. Polish to the polishing stop line T of (b).
- a 2000 ml three-necked flask equipped with a thermometer, a condenser, a mechanical stirrer, and a dropping funnel was prepared and soaked in a 140 oil bath. Heating and stirring with magnets were performed on a hotplate and the cooling water temperature of the condenser was fixed at 40. 220 g of 1 mol of 1-methoxypyrene was added to the reactor, and 138 g of 1.0 mol of 1,4-bismethoxymethylbenzene was added and then dissolved in 656 g of propylene glycol monomethyl ether acetate. Then 4.6 g of 0.03 mol of diethylsulfate were added. The temperature of the reactor was maintained at 130.
- the molecular weight was measured at regular time intervals to determine the completion time of the reaction.
- the sample for measuring the molecular weight was prepared by diluting 1 g of the reactant, quenching to room temperature, 0.02 g of the sample was diluted to 4% by weight using tetrahydrofuran as a solvent.
- 0.03 mol of triethanolamine 4.48 g was added to the reactor as a neutralizing agent and terminated. The reaction was then slowly cooled to room temperature.
- the reaction was diluted with 500 g of propylene glycol monomethyl ether acetate. The solvent was then added to a 2000 ml separatory funnel.
- the molecular weight and dispersion degree of the obtained copolymer were measured by GPC under tetrahydrofuran, and the polymer containing the unit of the following formula (12) of the weight average molecular weight 4000 and dispersion degree 2.3 was obtained.
- a 5000 mm thick silica film was deposited on the pattern wafer having the negative pattern formed on the surface thereof, and an organic film of 2650 mm thick was formed to fill the negative pattern formed on the surface of the silica film.
- the organic film was prepared by applying the composition for forming an organic film on a silica film and thermosetting at 400 ° C.
- the hardness was measured using a Nanoindentor (Hysitron TI750 Ubi) for the specimen of the thickness of 4700 ⁇ 4800 ⁇ prepared by applying the organic film-forming composition and thermal curing at 400 °C for 120 seconds.
- the tip of the nanoindentor was measured by loading the specimen for 5 seconds, holding for 2 seconds and then unloading for 5 seconds, and the hardness was 0.9 GPa.
- the carbon content was measured using an elemental analyzer (EA1112, Thermo) on the same specimen. Specifically, the exact amount of the sample was burned under O 2 coexistence to measure the carbon content, the carbon content was 72 atom%.
- Membrane density was measured on the same specimen using an X-RAY REFLECTIVITY (XRR) instrument (X'Pert PRO, PANalytical). Specifically, the diffraction pattern irradiated with X-rays was measured by comparing with a known diffraction pattern, and the film density was 1.4 g / cm 3 . The acid value was measured for the same specimen, and the acid value was 0 mg KOH / g.
- XRR X-RAY REFLECTIVITY
- (C) pH adjuster Nitric acid of Samjeon Pure Pharmaceutical Co., Ltd. was used.
- FUJIBO's H0800 CMP pad was used as the polishing pad.
- AMAT Applied Materials
- 200mm MIRRA equipment with a down pressure of 0.8psi, slurry flow rate of 200mL / min, platen speed of 60rpm and head speed of 55rpm
- the amount of polishing was measured and shown in Table 1 below.
- the thickness (unit: mm) of the polishing film was measured on the polished surface using a thin film thickness meter (ST4000, K-MAC), and the amount of polishing (unit: mm / min) was measured from the measured thickness. Calculate The selectivity was calculated by the following formula 1 on the basis of the measured polishing amount.
- Equation 1 ⁇ is the polishing amount ( ⁇ / min) for the organic film, and ⁇ is the polishing amount ( ⁇ / min) for the inorganic film.
- Comparative Examples 1 to 4 which do not include the ceria or cerium nitrate of the present invention, it can be confirmed that the polishing amount for the organic film is low, and the selectivity for the organic film is low compared to the inorganic film.
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Abstract
The present invention relates to an organic film CMP slurry composition and a polishing method using same. The organic CMP slurry composition comprises ceria and cerium nitrate, wherein the selectivity in accordance with following formula (1) is approximately 100 or higher: [Formula (1)] Selectivity = α/β (wherein α is a polishing amount (Å/min) of an organic film and β is a polishing amount (Å/min) of an inorganic film).
Description
본 발명은 유기막 ＣＭＰ 슬러리 조성물 및 이를 이용한 연마방법에 관한 것이다.The present invention relates to an organic film CMP slurry composition and a polishing method using the same.
최근 반도체 소자의 고집적화 및 고성능화에 따라 배선 패턴의 선 폭은 더욱 미세해지고 구조는 점점 다층화되는 추세이다. 포토리소그래피(photolithography)의 정밀도 향상을 위해서 각 공정에서의 층간 평탄도가 매우 중요한 요소로 작용하고 있다. 이러한 평탄화 기술로서 현재 가장 각광받고 있는 것이 CMP 공정이며, CMP 공정은 연마 대상 물질에 따라 산화막(oxide) CMP 공정, 금속(metal) CMP 공정, 폴리실리콘(poly-Si) CMP공정, 유기막 CMP 공정 등으로 분류되기도 한다. In recent years, as the integration and performance of semiconductor devices become higher, the line widths of wiring patterns become finer and structures become increasingly multilayered. In order to improve the precision of photolithography, the interlayer flatness in each process is a very important factor. The most popular spotlighting technology is the CMP process, and the CMP process is an oxide CMP process, a metal CMP process, a poly-Si CMP process, and an organic film CMP process depending on the material to be polished. It may be classified as such.
유기막(C-SOH)을 연마하는 CMP 공정이 적용되는 반도체 공정으로는 대표적으로 ILD(Inter Layer Dielectric) 공정을 들 수 있다. ILD 공정은 미세 패턴을 형성하기 위한 공정으로 과량으로 형성된 유기막(C-SOH)을 제거하기 위한 공정이다.A semiconductor process to which the CMP process of polishing an organic film (C-SOH) is applied is typically an ILD (Inter Layer Dielectric) process. The ILD process is a process for removing an organic layer (C-SOH) formed in excess as a process for forming a fine pattern.
종래에는 유기막용 CMP 슬러리 조성물에 Titanium trichloride 등 의 환원제를 첨가하여 사용하였으나, 이러한 종래의 유기막용 CMP 슬러리 조성물을 사용할 경우, ILD 공정에 필요한 무기막 대비 유기막에 대한 선택적 연마비를 얻을 수 없었다. 본 발명의 배경기술은 한국공개특허 제2014-00125316호에 개시되어 있다.Conventionally, a reducing agent such as titanium trichloride was added to the CMP slurry composition for organic membranes. However, when such a conventional CMP slurry composition for organic membranes was used, a selective polishing ratio for the organic membrane compared to the inorganic membrane required for the ILD process could not be obtained. Background art of the present invention is disclosed in Korea Patent Publication No. 2014-00125316.
본 발명의 목적은 무기막 대비 유기막에 대한 선택비가 우수한 유기막 CMP 슬러리 조성물을 제공하는 것이다.An object of the present invention is to provide an organic film CMP slurry composition having excellent selectivity to the organic film compared to the inorganic film.
본 발명의 다른 목적은 무기막 대비 탄소 함량이 높은 유기막에 대한 선택비 및 연마량이 우수한 유기막 CMP 슬러리 조성물을 제공하는 것이다. Another object of the present invention is to provide an organic film CMP slurry composition having excellent selectivity and polishing amount for an organic film having a higher carbon content than an inorganic film.
본 발명의 또 다른 목적은 상기 유기막 CMP 슬러리 조성물을 이용한 연마방법을 제공하는 것이다.Still another object of the present invention is to provide a polishing method using the organic film CMP slurry composition.
본 발명의 유기막 CMP 슬러리 조성물은 세리아 및 세륨질산염을 포함하고, 하기 식 1에 의한 선택비가 약 100 이상이다:The organic membrane CMP slurry composition of the present invention comprises ceria and cerium nitrate, and has a selectivity ratio of about 100 or more according to the following Equation 1:
[식 1][Equation 1]
선택비 = α/βSelectivity = α / β
(상기 식 1에서, α는 유기막에 대한 연마량(Å/min)이며, β는 무기막에 대한 연마량(Å/min)이다).(In Formula 1, α is the polishing amount (Å / min) for the organic film, and β is the polishing amount (Å / min) for the inorganic film).
상기 유기막은 탄소 함량이 약 90 atom% 이상일 수 있다.The organic layer may have a carbon content of about 90 atom% or more.
상기 세리아는 평균 입경이 약 10 내지 약 150nm일 수 있다.The ceria may have an average particle diameter of about 10 to about 150 nm.
상기 세리아는 상기 조성물 중 약 0.01 내지 약 10.0중량%로 포함될 수 있다.The ceria may be included in about 0.01 to about 10.0% by weight of the composition.
상기 세륨질산염은 상기 조성물 중 약 0.01 내지 약 5.0중량%로 포함될 수 있다.The cerium nitrate may be included in about 0.01 to about 5.0% by weight of the composition.
상기 CMP 슬러리 조성물은 pH가 약 3 내지 약 5일 수 있다.The CMP slurry composition may have a pH of about 3 to about 5.
상기 유기막은 막 밀도가 약 0.5 내지 약 2.5g/cm3이고 경도가 약 0.4GPa 이상일 수 있다.The organic layer may have a film density of about 0.5 to about 2.5 g / cm 3 and a hardness of about 0.4 GPa or more.
본 발명의 유기막 연마 방법은 상기 유기막 CMP 슬러리 조성물을 사용하여 유기막을 연마하는 단계를 포함할 수 있다.The organic film polishing method of the present invention may include polishing the organic film using the organic film CMP slurry composition.
본 발명은 무기막 대비 유기막에 대한 선택비가 우수하며, 탄소 함량이 높은 유기막에 대하여 선택비 및 연마량이 우수한 CMP 슬러리 조성물 및 이를 이용한 연마방법을 제공한다.The present invention provides a CMP slurry composition excellent in selectivity and polishing amount with respect to an organic film having an excellent organic matter compared to an inorganic film and having a high carbon content and a polishing method using the same.
도 1은 본 발명 일 실시예의 유기막 연마 방법의 모식도이다.1 is a schematic diagram of an organic film polishing method of an embodiment of the present invention.
유기막Organic membrane
CMPCMP
슬러리 조성물 Slurry composition
본 발명 일 실시예의 유기막 CMP 슬러리 조성물은 세리아 및 세륨질산염을 포함할 수 있다. 그 결과, 본 발명의 연마 대상인 유기막의 연마량을 증대시키고 무기막의 연마량을 감소시켜 무기막 대비 유기막에 대한 우수한 선택비를 확보할 수 있다.The organic film CMP slurry composition of one embodiment of the present invention may include ceria and cerium nitrate. As a result, by increasing the polishing amount of the organic film to be polished of the present invention and by reducing the polishing amount of the inorganic film, it is possible to secure an excellent selectivity for the organic film compared to the inorganic film.
상기 유기막은 탄소-수소 결합을 함유하는 카본계막으로서 C-SOH(spin on hardmask)막, ACL(amorphous carbon layer) 또는 NCP막을 예시할 수 있으며, C-SOH막이 유기막에 대한 선택적인 연마 효과가 우수하다는 점에서 본 발명의 연마 대상으로 보다 바람직하다.The organic layer may include a C-SOH (spin on hardmask) film, an amorphous carbon layer (ACL), or an NCP film as a carbon-based film containing a carbon-hydrogen bond, and the C-SOH film has a selective polishing effect on the organic film. It is more preferable as the grinding | polishing object of this invention from an excellent point.
상기 무기막은 실리콘 산화물, 실리콘 질화물 중 하나 이상으로 형성된 막일 수 있지만, 이에 제한되지 않는다.The inorganic film may be a film formed of at least one of silicon oxide and silicon nitride, but is not limited thereto.
세리아(CeO2)는 금속산화물 연마제로서 탄소 함량이 높은 유기막을 높은 연마량으로 연마할 수 있다. 특히 본 발명의 연마 대상인 유기막 연마시 스크래치 등이 발생하지 않게 하여 연마면 평탄도를 높일 수 있었다. 세리아는 산화제가 없거나 극히 적어도 연마량을 높일 수 있다. Ceria (CeO 2 ) is a metal oxide abrasive and can polish an organic film having a high carbon content with a high polishing amount. In particular, the polishing surface flatness could be increased by preventing scratches and the like from occurring during polishing of the organic film, which is the polishing target of the present invention. Ceria may be free of oxidants or at least increase the amount of polishing.
세리아는 구형의 입자로 평균 입경이 약 10 내지 약 150nm, 예를 들면 약 30 내지 약 70nm가 될 수 있고, 상기 범위에서 본 발명의 연마 대상인 유기막에 대해 충분한 연마량을 얻을 수 있고, 스크래치가 발생하지 않게 할 수 있으며, 평탄도를 높일 수 있다.Ceria is a spherical particle having an average particle diameter of about 10 to about 150 nm, for example, about 30 to about 70 nm, in the above range can obtain a sufficient polishing amount for the organic film to be polished of the present invention, It can be prevented from occurring and the flatness can be increased.
세리아는 CMP 슬러리 조성물 중 약 0.01 내지 약 10.0중량%, 예를 들면 약 0.05 내지 약 5.0 중량%로 포함될 수 있고, 상기 범위에서 본 발명의 연마 대상인 유기막에 대해 충분한 연마량을 얻을 수 있고, 스크래치가 발생하지 않게 할 수 있고, 분산안정성이 좋을 수 있다. 바람직하게는, 세리아의 평균 입경은 높이되 슬러리 조성물 중 함량을 낮춤으로써 유기막에 대해 향상된 연마량 및 무기막에 대해 낮은 연마량을 구현할 수 있다.Ceria may be included in about 0.01 to about 10.0% by weight, for example about 0.05 to about 5.0% by weight in the CMP slurry composition, in the above range can be obtained a sufficient polishing amount for the organic film to be polished, the scratch Can be prevented from occurring and dispersion stability can be good. Preferably, the average particle diameter of ceria is increased but the amount of slurry in the slurry composition may be lowered to achieve improved polishing amount for the organic film and lower polishing amount for the inorganic film.
세륨질산염(Cerium(III) Nitrate)로는, 예를 들면, Ce(NO3)3의 화학식을 가지는 수화물 형태의 염이 사용될 수 있다. 상기 세륨질산염은 기존에 적용되는 환원제, 예를 들어 타이타늄 트리클로라이드(Titanium trichloride) 에 비해 유기막의 연마량을 증대시키고 무기막의 연마량을 감소시켜 유기막에 대한 우수한 선택비를 확보할 수 있다.As cerium (III) Nitrate, a salt in the form of a hydrate having a chemical formula of Ce (NO 3 ) 3 can be used, for example. The cerium nitrate may increase the polishing amount of the organic film and reduce the polishing amount of the inorganic film, compared to conventional reducing agents, for example, titanium trichloride, to secure an excellent selection ratio for the organic film.
상기 세륨질산염은 이온 화합물 또는 킬레이트 화합물 형태로 슬러리 조성물 내 존재할 수 있으며, 상기 형태로 사용하는 경우 유기막에 대한 우수한 연마량을 제공할 수 있으며, 무기막의 연마량을 감소시켜 유기막에 대한 우수한 선택비를 확보할 수 있다.The cerium nitrate may be present in the slurry composition in the form of an ionic compound or a chelate compound, and when used in this form, may provide an excellent polishing amount for the organic film, and reduce the polishing amount of the inorganic film, thereby making an excellent choice for the organic film. Rain can be secured.
상기 세륨질산염은 전체 CMP 슬러리 조성물 중 약 0.01 내지 약 5.0 중량%, 바람직하게 약 0.01 내지 약 2.0 중량%, 더 바람직하게 약 0.04 내지 약 0.4 중량%로 포함될 수 있고, 상기 범위에서 본 발명의 연마 대상인 유기막에 대해 유기막에 대한 우수한 연마량을 제공할 수 있으며, 무기막의 연마량을 감소시켜 무기막 대비 유기막에 대한 우수한 선택비를 확보할 수 있다.The cerium nitrate may be included in about 0.01 to about 5.0% by weight, preferably about 0.01 to about 2.0% by weight, more preferably about 0.04 to about 0.4% by weight of the total CMP slurry composition, in the range of It is possible to provide an excellent polishing amount for the organic film with respect to the organic film, and to reduce the polishing amount of the inorganic film to ensure an excellent selectivity to the organic film compared to the inorganic film.
본 발명의 일 구체예에 따른 CMP 슬러리 조성물은 하기 식 1로 계산되는 선택비가 약 100 이상, 구체적으로 약 300 내지 약 500일 수 있다.The CMP slurry composition according to one embodiment of the present invention may have a selectivity calculated by Equation 1 below about 100, specifically about 300 to about 500.
[식 1][Equation 1]
선택비 = α/βSelectivity = α / β
상기 식 1에서, α는 유기막에 대한 연마량(Å/min)이며, β는 무기막에 대한 연마량(Å/min)이다.In Equation 1, α is the polishing amount (Å / min) for the organic film, and β is the polishing amount (Å / min) for the inorganic film.
구체예에 따른 CMP 슬러리 조성물은 산성일 수 있다. 이 경우, 무기막에 대한 유기막의 높은 연마선택비를 구현하는 효과가 있고, 유기막에 대한 시간당 연마량을 높이고, 평탄도를 높일 수 있다. 구체적으로 CMP 슬러리 조성물은 pH가 약 3 내지 약 5일 수 있다. 예를 들면 pH 조절제를 사용함으로써 본 발명 일 실시예의 CMP 슬러리 조성물을 상술한 범위의 pH로 조절할 수 있다. pH 조절제는 무기산 예를 들면 질산, 황산 중 하나 이상을 포함할 수 있고, 유기산 예를 들면 pKa 5이하인 유기산, 구체적으로 초산, 시트르산 중 하나 이상을 포함할 수 있지만 반드시 이제 제한되는 것은 아니다.CMP slurry compositions according to embodiments may be acidic. In this case, there is an effect of implementing a high polishing selectivity of the organic film to the inorganic film, it is possible to increase the amount of polishing per hour to the organic film, and to increase the flatness. In particular, the CMP slurry composition may have a pH of about 3 to about 5. For example, by using a pH adjuster, the CMP slurry composition of one embodiment of the present invention can be adjusted to the pH in the above-described range. The pH adjusting agent may comprise one or more of inorganic acids such as nitric acid and sulfuric acid, and may include but are not limited to organic acids such as organic acids such as pKa 5 or less, specifically one or more of acetic acid and citric acid.
상기 pH조절제는 전체 CMP 슬러리 조성물 중 약 0.01 내지 약 5.0 중량%, 바람직하게 약 0.01 내지 약 2.0 중량%, 더 바람직하게 약 0.04 내지 약 0.4 중량%로 포함될 수 있고, 상기 범위에서 본 발명의 연마 대상인 유기막에 대해 유기막에 대한 우수한 연마량을 제공할 수 있으며, 무기막의 연마량을 감소시켜 무기막 대비 유기막에 대한 우수한 선택비를 확보할 수 있다.The pH adjusting agent may be included in about 0.01 to about 5.0% by weight, preferably about 0.01 to about 2.0% by weight, more preferably about 0.04 to about 0.4% by weight of the total CMP slurry composition, in the above range It is possible to provide an excellent polishing amount for the organic film with respect to the organic film, and to reduce the polishing amount of the inorganic film to ensure an excellent selectivity to the organic film compared to the inorganic film.
CMP 슬러리 조성물은 산화제를 더 포함할 수 있다. 산화제는 탄소 함량이 높은 유기계 탄소막이 연마가 잘 되도록 하기 위해 유기막의 표면층을 산화시켜 유기막의 연마가 용이하도록 하고, 연마에 의해 무기막이 노출될 때 유기막의 표면을 고르게 하여 연마 이후에도 표면 거칠기(roughness)가 좋도록 할 수 있다. 또한, 무기막에 존재하는 유기막의 잔류물이 쉽게 제거되도록 하여 보다 균일한 연마가 되도록 할 수 있다.The CMP slurry composition may further comprise an oxidizing agent. The oxidizing agent oxidizes the surface layer of the organic film to facilitate the polishing of the organic carbon film having a high carbon content to facilitate polishing of the organic film, and evens the surface of the organic film even when the inorganic film is exposed by polishing, thereby providing surface roughness even after polishing. You can make it good. In addition, the residue of the organic film present in the inorganic film can be easily removed to allow a more uniform polishing.
구체적으로, 산화제는 다가의 산화상태를 갖는 금속염, 전이금속의 킬레이트 화합물 중 하나 이상을 포함할 수 있다. 상기 "다가"는 2가 이상, 예를 들면 3가 이상, 예를 들면 4가 이상을 의미한다.Specifically, the oxidizing agent may include at least one of a metal salt having a multivalent oxidation state and a chelate compound of a transition metal. "Multivalent" means divalent or more, for example trivalent or more, for example tetravalent or more.
다가의 산화상태를 갖는 금속염은 유기막에 대한 연마 속도를 높이고, 무기막에 대한 연마 속도를 낮출 수 있다. 금속염은 전이금속, 란탄족 원소 등의 금속을 포함할 수 있고, 추가로 할로겐, 암모늄, 니트레이트 등을 포함할 수 있다. 구체적으로, 금속염은 세릭 암모늄염, 페릭 할로겐염, 페릭 니트레이트염 등을 포함할 수 있고, 예를 들면 세릭암모늄니트레이트, 페릭 니트레이트, 페릭 클로라이드 등을 포함할 수 있다.Metal salts having a polyvalent oxidation state can increase the polishing rate for the organic film and lower the polishing rate for the inorganic film. The metal salt may include a metal such as a transition metal, a lanthanide element, and may further include halogen, ammonium, nitrate, or the like. Specifically, the metal salt may include ceric ammonium salt, ferric halogen salt, ferric nitrate salt, and the like, and may include, for example, ceric ammonium nitrate, ferric nitrate, ferric chloride, and the like.
전이금속의 킬레이트 화합물은 유기막에 대한 연마 속도를 높이고, 무기막에 대한 연마 속도를 낮출 수 있다.The chelating compound of the transition metal can increase the polishing rate for the organic film and lower the polishing rate for the inorganic film.
전이금속의 킬레이트 화합물에서, 전이금속은 주기율표 3족 내지 12족의 통상의 알려진 전이금속을 포함하는데, 예를 들면 철, 구리, 망간 또는 크롬이 될 수 있다. 킬레이트는 옥살산, 아미노-치환된 카르복시산(예: 이미노디아세트산, 에틸렌디아민디숙신산, 이미노디숙신산, 에틸렌디아민테트라아세트산, 니트릴로트리아세트산과 같은 아미노폴리카르복실레이트, 글리신과 같은 알파-아미노산, 베타-아미노산), 수산기 치환된 카르복시산(예:글리콜산, 락트산, 또한, 말산, 시트르산, 타르타르산과 같은 수신가 포함 폴리카르복시산), 포스포노카르복시산, 아미노포스폰산; 이들의 조합을 포함할 수 있다. 예를 들면, 전이금속의 킬레이트 화합물은 프로필렌디아민테트라아세트산-Fe 등을 포함하는 Fe 포함 화합물, 프로필렌디아민테트라아세트산-Mn 등을 포함하는 Mn 포함 화합물 중 하나 이상을 포함할 수 있지만 이에 제한되지 않는다.In chelating compounds of transition metals, the transition metals include conventionally known transition metals of groups 3 to 12 of the periodic table, which may be iron, copper, manganese or chromium, for example. Chelates are oxalic acid, amino-substituted carboxylic acids (e.g., iminodiacetic acid, ethylenediaminedisuccinic acid, iminodisuccinic acid, aminopolycarboxylates such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, alpha-amino acids such as glycine, beta- Amino acids), hydroxyl-substituted carboxylic acids (eg, polycarboxylic acids including recipients such as glycolic acid, lactic acid, malic acid, citric acid, tartaric acid), phosphonocarboxylic acids, aminophosphonic acids; Combinations thereof. For example, the chelating compound of the transition metal may include, but is not limited to, one or more of Fe-containing compounds including propylenediaminetetraacetic acid-Fe and the like, Mn-containing compounds including propylenediaminetetraacetic acid-Mn and the like.
산화제는 CMP 슬러리 조성물 중 약 0.001 내지 약 15중량%, 예를 들면 약 0.01 내지 약 5중량%, 예를 들면 약 0.05 내지 약 3중량%로 포함될 수 있고, 상기 범위에서 유기막에 대한 적절한 에칭성을 유지할 수 있다. CMP 슬러리 조성물은 산성이 됨으로써 산화제의 안정성을 높여 유기막에 대한 단위시간당 연마량을 높이고, 연마면의 평탄도를 좋게 하고, 무기막에 대한 연마 선택비를 높일 수 있다.The oxidant may comprise from about 0.001% to about 15% by weight, such as from about 0.01% to about 5% by weight, such as from about 0.05% to about 3% by weight, in the CMP slurry composition, with suitable etching properties for the organic film in this range. Can be maintained. As the CMP slurry composition becomes acidic, the stability of the oxidant may be increased to increase the polishing amount per unit time for the organic film, to improve the flatness of the polishing surface, and to increase the polishing selectivity for the inorganic film.
CMP 슬러리 조성물은 첨가제를 더 포함할 수도 있다. 예를 들면, CMP 슬러리 조성물은 첨가제로 연마 촉진제를 더 포함할 수 있다. 연마촉진제를 더 포함함으로써, 무기막에 대한 연마 속도를 억제하여 무기막에 대한 연마선택비를 높일 수 있다. 연마촉진제는 유기산 예를 들면 말산, 포름산, 글루타르산, 옥살산, 프탈산, 숙신산, 타르타르산, 말레산, 말론산 중 하나 이상을 포함할 수 있다. 연마촉진제는 CMP 슬러리 조성물 중 약 0.02 내지 약 0.5중량%로 포함될 수 있고, 상기 범위에서 연마량, 슬러리의 분산안정성, 유기막의 표면특성에 악영향이 없을 수 있다.The CMP slurry composition may further comprise an additive. For example, the CMP slurry composition may further include a polishing accelerator as an additive. By further including the polishing promoter, the polishing rate for the inorganic film can be suppressed to increase the polishing selectivity for the inorganic film. The polishing promoter may include one or more of an organic acid such as malic acid, formic acid, glutaric acid, oxalic acid, phthalic acid, succinic acid, tartaric acid, maleic acid, malonic acid. The polishing accelerator may be included in an amount of about 0.02 to about 0.5% by weight in the CMP slurry composition, and may have no adverse effect on the amount of polishing, dispersion stability of the slurry, and surface characteristics of the organic film in the above range.
CMPCMP
슬러리 조성물의 연마대상 Polishing Target of Slurry Composition
이하, 본 발명의 CMP 슬러리 조성물의 연마대상인 유기막에 대하여 구체적으로 설명하기로 한다.Hereinafter, the organic film to be polished of the CMP slurry composition of the present invention will be described in detail.
본 명세서에서 "치환"은 작용기 중 적어도 하나 이상의 수소 원자가 히드록시기, 할로겐 원자, 티오닐기, 티올기, 시아노기, 아미노기, C1 내지 C30 알킬기, C2 내지 C30 알케닐기, C2 내지 C30 알키닐기, C3 내지 C30 사이클로알킬기, C3 내지 C30 사이클로알케닐기, C6 내지 C30 아릴기, C7 내지 C30 아릴알킬기, C1 내지 C20 헤테로알킬기, C2 내지 C30 헤테로사이클로알킬기, C2 내지 C30 헤테로사이클로알케닐기, C2 내지 C30 헤테로아릴기, C2 내지 C30 헤테로아릴알킬기, C1 내지 C20 알킬아민기, C1 내지 C30 알콕시기, C6 내지 C30 아릴옥시기, C1 내지 C20 알데히드기, C1 내지 C40 알킬에테르기, C7 내지 C20 아릴알킬렌에테르기, C1 내지 C30 할로알킬기, P를 포함하는 작용기, B를 포함하는 작용기 또는 이들의 조합으로 치환된 것을 의미한다.In this specification, "substituted" means that at least one hydrogen atom of the functional group is a hydroxy group, a halogen atom, a thionyl group, a thiol group, a cyano group, an amino group, a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, C3 to C30 cycloalkyl group, C3 to C30 cycloalkenyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C20 heteroalkyl group, C2 to C30 heterocycloalkyl group, C2 to C30 heterocycloalkenyl group, C2 to C30 heteroaryl group , C2 to C30 heteroarylalkyl group, C1 to C20 alkylamine group, C1 to C30 alkoxy group, C6 to C30 aryloxy group, C1 to C20 aldehyde group, C1 to C40 alkylether group, C7 to C20 arylalkylene ether group, C1 To C30 haloalkyl group, a functional group including P, a functional group including B, or a combination thereof.
본 명세서에서 "P를 포함하는 작용기"는 하기 화학식 1로 표시될 수 있고, "B를 포함하는 작용기"는 하기 화학식 2로 표시될 수 있다:In the present specification, the "functional group including P" may be represented by the following Chemical Formula 1, and the "functional group including B" may be represented by the following Chemical Formula 2:
<화학식 1><Formula 1>
*-(O)n-(CH2)m-P(=O)(Ra)(Rb) *-(O) n- (CH 2 ) m -P (= O) (R a ) (R b )
<화학식 2><Formula 2>
*-B(Rc)(Rd)* -B (R c ) (R d )
상기 <화학식 1> 및 <화학식 2>에서, n은 0 또는 1이고, m은 0 내지 10의 정수이고,In <Formula 1> and <Formula 2>, n is 0 or 1, m is an integer of 0 to 10,
Ra, Rb, Rc 및 Rd은 각각 독립적으로, 수소, 수산기, 치환 또는 비치환된 C1 내지 C20의 알킬기, 치환 또는 비치환된 C2 내지 C20의 알케닐기, 치환 또는 비치환된 C3 내지 C20의 시클로알킬기, 치환 또는 비치환된 C1 내지 C20의 할로알킬기, 치환 또는 비치환된 C1 내지 C20의 알킬술포네이트기, 치환 또는 비치환된 C1 내지 C20의 알킬술포닐기, 치환 또는 비치환된 C2 내지 C20의 알킬아미드기, 치환 또는 비치환된 C3 내지 C20의 알킬에스테르기, 치환 또는 비치환된 C2 내지 C20의 시아노알킬기, 치환 또는 비치환된 C1 내지 C20의 알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C6 내지 C30 아릴알킬기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기이거나, 또는R a , R b , R c and R d are each independently hydrogen, a hydroxyl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C1 to C20 haloalkyl group, substituted or unsubstituted C1 to C20 alkylsulfonate group, substituted or unsubstituted C1 to C20 alkylsulfonyl group, substituted or unsubstituted C2 To C20 alkylamide group, substituted or unsubstituted C3 to C20 alkyl ester group, substituted or unsubstituted C2 to C20 cyanoalkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted A C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 aryloxy group, or
Ra과 Rb 또는 Rc과 Rd는 서로 연결되어 치환 또는 비치환된 C3 내지 C20의 시클로알킬기 또는 치환 또는 비치환된 C3 내지 C20의 헤테로시클로알킬기를 형성한다.R a and R b or R c and R d are connected to each other to form a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C3 to C20 heterocycloalkyl group.
바람직하게는, 상기 "P를 포함하는 작용기"는 P와 O를 포함하는 작용기로, 예를 들면, -P(=O)(OH)2, -O-P(=O)(OH)2, -P(=O)(OCH2CH3)2, -P(=O)(C2H4C6H5)(OCH2CH3) 등일 수 있고, 상기 "B를 포함하는 작용기"는 B와 O를 포함하는 작용기로 예를 들면 -B(OH)2, -B(H)(CH3), -B(CH2CH3)2 등일 수 있다.Preferably, the "functional group comprising P" is a functional group containing P and O, for example, -P (= 0) (OH) 2 , -OP (= 0) (OH) 2 , -P (═O) (OCH 2 CH 3 ) 2 , —P (═O) (C 2 H 4 C 6 H 5 ) (OCH 2 CH 3 ), and the like, wherein “the functional group comprising B” is represented by B and O For example, the functional group may include -B (OH) 2 , -B (H) (CH 3 ), -B (CH 2 CH 3 ) 2, or the like.
패턴화된 웨이퍼, 예를 들면 실리콘 웨이퍼 위에 무기막을 증착하였을 때, 유기막은 생성된 비어-홀(via-hole)을 채워주게 된다. CMP 슬러리 조성물은 증착막의 평탄화를 위하여 유기막을 충분한 연마율로 연마할 수 있어야 하고 연마면의 평탄도도 높여주어야 하여 연마 후 무기막에 잔류하는 잔류물의 제거도 쉬워야 한다. 무기막은 실리콘 산화물, 실리콘 질화물 중 하나 이상으로 형성된 막일 수 있지만, 이에 제한되지 않는다. 무기막은 탄소 함량이 약 1 atom% 미만 예를 들면 0 내지 약 1 atom% 또는 예를 들면 0 atom%가 될 수 있다.When an inorganic film is deposited on a patterned wafer, for example a silicon wafer, the organic film fills the resulting via-holes. In order to planarize the deposited film, the CMP slurry composition should be able to polish the organic film to a sufficient polishing rate and increase the flatness of the polished surface, so that the residues remaining in the inorganic film after polishing should be easily removed. The inorganic film may be a film formed of at least one of silicon oxide and silicon nitride, but is not limited thereto. The inorganic membrane may have a carbon content of less than about 1 atom%, for example 0 to about 1 atom% or for example 0 atom%.
유기막은 유기막의 재질에 따라 단위 시간당 연마량, 연마 후 평탄도가 크게 다를 수 있다. 본 발명의 유기막 CMP 슬러리 조성물은 탄소 함량이 높은 유기막을 연마하는 조성물로서, 유기막 연마시 유기막의 단위 시간당 연마량을 높이고 무기막에 대한 선택비가 높을 수 있다. The organic film may have a large difference in polishing amount per unit time and flatness after polishing depending on the material of the organic film. The organic film CMP slurry composition of the present invention is a composition for polishing an organic film having a high carbon content, and may increase the polishing amount per unit time of the organic film during the polishing of the organic film and have a high selectivity to the inorganic film.
구체예에서, 유기막은 탄소 함량이 약 90atom% 이상, 예를 들면 약 90 내지 약 99atom% 또는 예를 들면 약 95 내지 약 99atom%가 될 수 있고, 상기 범위에서 세리아로 연마시 연마량이 높고 스크래치도 발생하지 않으며 연마면의 평탄도도 높을 수 있다. 유기막은 막 밀도가 약 0.5 내지 약 2.5g/cm3, 예를 들면 약 1.0 내지 약 2.0g/cm3, 예를 들면 약 1.2 내지 약 1.6g/cm3이 될 수 있고, 상기 범위에서 세리아로 연마시 연마량이 높고 스크래치도 발생하지 않으며 연마면의 평탄도도 높을 수 있다. 유기막은 경도(hardness)가 약 0.4GPa 이상, 예를 들면 약 1.0GPa 이상, 예를 들면 약 1.3GPa 이상, 예를 들면 약 1.3 내지 약 1.5GPa이 될 수 있고, 상기 범위에서 세리아로 연마시 연마량이 높고 스크래치도 발생하지 않으며 연마면의 평탄도도 높을 수 있다.In an embodiment, the organic film may have a carbon content of about 90 atom% or more, such as about 90 to about 99 atom% or about 95 to about 99 atom%, and in the above range, the amount of polishing and the degree of scratching when polishing with ceria are high. It does not occur, and the flatness of the polishing surface may be high. The organic film has a film density of about 0.5 to about 2.5 g / cm 3 , For example, it may be about 1.0 to about 2.0g / cm 3 , for example about 1.2 to about 1.6g / cm 3 , in the above range when polishing with ceria has a high amount of polishing, no scratches and flatness of the polishing surface Can also be high. The organic film may have a hardness of about 0.4 GPa or more, for example about 1.0 GPa or more, for example about 1.3 GPa or more, for example about 1.3 to about 1.5 GPa, and in the above-mentioned range, polishing when polishing with ceria The amount is high, there is no scratch, and the flatness of the polished surface may be high.
또한, 본 발명의 연마 대상인 유기막은 산가가 실질적으로 0mgKOH/g이 될 수 있다. 종래의 고분자 연마제를 포함하는 유기막 CMP 슬러리 조성물로 본 발명의 연마 대상인 유기막을 연마할 경우 연마 속도가 낮아진다는 문제점이 있었다. 반면, 본 발명의 CMP 슬러리 조성물은 CMP 공정에 적용할 만한 유기막의 단위 시간당 연마량을 확보할 수 있다. 상기 "실질적으로"는 산가가 0mgKOH/g인 경우뿐만 아니라 0mgKOH/g에서 약간의 오차가 가감되는 것도 포함한다. In addition, the organic film to be polished of the present invention may have an acid value of substantially 0 mgKOH / g. When polishing an organic film, which is a polishing target of the present invention, with an organic film CMP slurry composition including a conventional polymer abrasive, there is a problem that the polishing rate is lowered. On the other hand, the CMP slurry composition of the present invention can secure the amount of polishing per unit time of the organic film applicable to the CMP process. The term "substantially" includes not only the case where the acid value is 0 mgKOH / g but also a slight error at 0 mgKOH / g.
구체적으로, 본 발명의 연마 대상인 유기막은 유기막 형성용 조성물을 무기막 위에 도포한 후 고온, 예를 들면 200 내지 400℃에서 열경화(baking)하여 제조될 수 있다. Specifically, the organic film to be polished of the present invention may be prepared by applying a composition for forming an organic film on an inorganic film and then thermosetting (baking) at a high temperature, for example, 200 to 400 ° C.
상기 유기막 형성용 조성물은 치환 또는 비치환된 방향족기를 갖는 화합물을 포함할 수 있다. The organic film forming composition may include a compound having a substituted or unsubstituted aromatic group.
상기 "치환 또는 비치환된 방향족기를 갖는 화합물"은 열경화 후에도 분해되지 않아서 조성물로 형성된 유기막이 높은 탄소 함량을 나타낼 수 있도록 하는 화합물을 의미한다. 상기 비치환된 방향족기는 탄소수 약 6 내지 약 100, 예를 들면, 탄소수 약 6 내지 약 50의 단일 또는 융합된(fused) 다환(polycyclic) 방향족기를 의미하는데, 구체적으로 하기 화학식 3-1 내지 3-26의 단위를 포함할 수 있다:The "compound having a substituted or unsubstituted aromatic group" refers to a compound that does not decompose even after thermal curing so that the organic film formed of the composition can exhibit a high carbon content. The unsubstituted aromatic group refers to a single or fused polycyclic aromatic group having about 6 to about 100 carbon atoms, for example, about 6 to about 50 carbon atoms, specifically, the following Chemical Formulas 3-1 to 3- Can contain 26 units:
<화학식 3-1><Formula 3-1>
<화학식 3-2><Formula 3-2>
<화학식 3-3><Formula 3-3>
<화학식 3-4><Formula 3-4>
<화학식 3-5><Formula 3-5>
<화학식 3-6><Formula 3-6>
<화학식 3-7><Formula 3-7>
<화학식 3-8><Formula 3-8>
<화학식 3-9><Formula 3-9>
<화학식 3-10><Formula 3-10>
<화학식 3-11><Formula 3-11>
<화학식 3-12><Formula 3-12>
<화학식 3-13><Formula 3-13>
<화학식 3-14><Formula 3-14>
<화학식 3-15><Formula 3-15>
<화학식 3-16><Formula 3-16>
<화학식 3-17><Formula 3-17>
<화학식 3-18><Formula 3-18>
<화학식 3-19><Formula 3-19>
<화학식 3-20><Formula 3-20>
<화학식 3-21><Formula 3-21>
<화학식 3-22><Formula 3-22>
<화학식 3-23><Formula 3-23>
<화학식 3-24><Formula 3-24>
<화학식 3-25><Formula 3-25>
<화학식 3-26><Formula 3-26>
상기 화학식 3-1 내지 3-26에서, Z1 내지 Z18은 각각 독립적으로 단일 결합, 치환 또는 비치환된 C1 내지 C20 알킬렌기, 치환 또는 비치환된 C2 내지 C20 알케닐렌기, 치환 또는 비치환된 C2 내지 C20 알키닐렌기, 치환 또는 비치환된 C3 내지 C20 사이클로알킬렌기, 치환 또는 비치환된 C3 내지 C20 사이클로알케닐렌기, 치환 또는 비치환된 C6 내지 C20 아릴렌기, 치환 또는 비치환된 C2 내지 C20 헤테로아릴렌기, -(C=O)-, -NRe-, -CRfRg-, 산소(O), 황(S) 또는 이들의 조합이고, 여기서 Re, Rf 및 Rg는 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 할로겐 원자, 치환 또는 비치환된 C6 내지 C20 아릴렌기, 치환 또는 비치환된 C2 내지 C20 헤테로아릴렌기 또는 이들의 조합이다In Formulas 3-1 to 3-26, Z 1 to Z 18 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, substituted or unsubstituted C3 to C20 cycloalkylene group, substituted or unsubstituted C3 to C20 cycloalkenylene group, substituted or unsubstituted C6 to C20 arylene group, substituted or unsubstituted C2 To C20 heteroarylene group,-(C = O)-, -NR e- , -CR f R g- , oxygen (O), sulfur (S) or a combination thereof, wherein R e , R f and R g Are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, or a combination thereof
이하, 치환 또는 비치환된 방향족기를 갖는 화합물을 포함하는 유기막 형성용 조성물의 구체예를 보다 상세히 설명한다.Hereinafter, the specific example of the composition for organic film formation containing the compound which has a substituted or unsubstituted aromatic group is demonstrated in detail.
제 1 구체예에서, 유기막 형성용 조성물은 치환 또는 비치환된 방향족기를 갖는 화합물로 하기 화학식 4을 포함하는 물질을 포함할 수 있다:In a first embodiment, the composition for forming an organic film may be a compound having a substituted or unsubstituted aromatic group may include a material including the following formula (4):
<화학식 4><Formula 4>
상기 화학식 4에서, a은 1≤a<190이고, In Formula 4, a is 1≤a <190,
R1은 수소, 히드록시기, 할로겐 원자, 알릴기, 티오닐기, 티올기, 시아노기, 치환 또는 비치환된 아미노기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C7 내지 C30 아릴알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알케닐기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴알킬기, 치환 또는 비치환된 C1 내지 C20 알킬아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C1 내지 C30 헤테로알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C1 내지 C20 알데히드기, 치환 또는 비치환된 C1 내지 C40 알킬에테르기, 치환 또는 비치환된 C7 내지 C20 아릴알킬렌에테르기, 치환 또는 비치환된 C1 내지 C30 할로알킬기, P를 포함하는 작용기, B를 포함하는 작용기 또는 이들의 조합이고,R 1 is hydrogen, a hydroxy group, a halogen atom, an allyl group, thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group , Substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkenyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C1 to C30 alkoxy group, Or an unsubstituted C1 to C30 heteroalkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a substituted or unsubstituted C1 to C20 aldehyde group, a substituted or unsubstituted C1 to C40 alkylether group, a substituted or unsubstituted A C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a functional group including P, a functional group including B, or a combination thereof,
R2는 수소, 아미노기, 치환 또는 비치환된 C1 내지 C30의 알콕시기, 치환 또는 비치환된 C6 내지 C20의 아릴옥시기, 디알킬아미노기(-NRR', 여기서 R, R'은 서로 독립적으로 치환 또는 비치환된 C1 내지 C10의 알킬기 또는 치환 또는 비치환된 C6 내지 C10의 아릴기), 히드록시기, 할로겐 원자, 알릴기, 티오닐기, 티올기, 시아노기, 치환 또는 비치환된 아미노기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C7 내지 C30 아릴알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알케닐기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴알킬기, 치환 또는 비치환된 C1 내지 C20 알킬아민기, 치환 또는 비치환된 C1 내지 C30 헤테로알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C1 내지 C20 알데히드기, 치환 또는 비치환된 C1 내지 C40 알킬에테르기, 치환 또는 비치환된 C7 내지 C20 아릴알킬렌에테르기, 치환 또는 비치환된 C1 내지 C30 할로알킬기, P를 포함하는 작용기, B를 포함하는 작용기 또는 이들의 조합이고,R 2 is hydrogen, an amino group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C20 aryloxy group, a dialkylamino group (-NRR ', where R and R' are independently substituted with each other) Or unsubstituted C1 to C10 alkyl group or substituted or unsubstituted C6 to C10 aryl group), hydroxy group, halogen atom, allyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted or Unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycle An alkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, Substituted or unsubstituted C2 to C30 heterocycloalkenyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted Or an unsubstituted C1 to C30 heteroalkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a substituted or unsubstituted C1 to C20 aldehyde group, a substituted or unsubstituted C1 to C40 alkylether group, a substituted or unsubstituted A C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a functional group including P, a functional group including B, or a combination thereof,
R3은R 3 is
중 어느 하나이다.Which is either.
예를 들면, R2는 치환 또는 비치환된 C1 내지 C10의 알콕시기가 될 수 있다.For example, R 2 may be a substituted or unsubstituted C 1 to C 10 alkoxy group.
상기 화학식 4을 포함하는 유기막 형성용 조성물은 열경화 후 탄소 함량, 막 밀도 및 경도를 높일 수 있고, 이의 보다 상세한 제조 방법은 한국등록특허 제10-0866015호를 참조한다. The composition for forming an organic film including Chemical Formula 4 may increase carbon content, film density, and hardness after thermosetting, and refer to Korean Patent No. 10-0866015 for a more detailed manufacturing method thereof.
상기 제1 구체예에 따른 유기막 형성용 조성물은 상기 화학식 4를 포함하는 물질 이외에, 가교 성분, 산 촉매 및 유기용매 중 하나 이상을 더 포함할 수 있다. 구체적으로 상기 화학식 4로 표시되는 물질 1 내지 20중량%, 가교 성분 0.1 내지 5중량%, 산 촉매 0.001 내지 0.05중량%, 및 유기 용매 75 내지 98.8중량%를 포함할 수 있다.The composition for forming an organic film according to the first embodiment may further include at least one of a crosslinking component, an acid catalyst, and an organic solvent, in addition to the material containing Formula 4 above. Specifically, it may include 1 to 20% by weight of the material represented by Formula 4, 0.1 to 5% by weight of the crosslinking component, 0.001 to 0.05% by weight of the acid catalyst, and 75 to 98.8% by weight of the organic solvent.
가교 성분은 멜라민 수지(구체예로 N-메톡시메틸-멜라민수지, N-부톡시메틸멜라민수지), 메틸화되거나 부틸화된 우레아 수지, 아미노 수지, 하기 화학식 5의 글리콜루릴 유도체, 하기 화학식 6의 비스에폭시 화합물, 하기 화학식 7의 멜라민 유도체 중 하나 이상을 포함할 수 있다:The crosslinking component may be a melamine resin (eg, N-methoxymethyl-melamine resin, N-butoxymethylmelamine resin), methylated or butylated urea resin, amino resin, glycoluril derivative of Formula 5, A bisepoxy compound, one or more of the melamine derivatives of Formula 7:
<화학식 5><Formula 5>
<화학식 6><Formula 6>
<화학식 7><Formula 7>
산 촉매는 p-톨루엔술폰산 모노 하이드레이트, 피리디늄 p-톨루엔 술포네이트, 2,4,4,6-테트라브로모시클로헥사디엔온, 벤조인 토실레이트, 2-니트로벤질 토실레이트, 유기술폰산의 알킬에스테르 중 하나 이상을 포함할 수 있다. 유기용매는 치환 또는 비치환된 방향족기를 갖는 화합물에 대한 충분한 용해성을 갖는 유기용매라면 특별히 한정되지 않는데, 예를 들면 프로필렌글리콜모노메틸에테르아세테이트, 사이클로헥사논, 에틸락테이트 등을 들 수 있다.Acid catalysts include p-toluenesulfonic acid monohydrate, pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, alkyl of euphonic acid It may include one or more of the esters. The organic solvent is not particularly limited as long as it is an organic solvent having sufficient solubility in a compound having a substituted or unsubstituted aromatic group, and examples thereof include propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate and the like.
제1 구체예의 유기막 형성용 조성물을 약 500 내지 약 4000Å의 두께로 코팅하고, 약 200 내지 약 400℃에서 약 10초 내지 약 10분 동안 열경화시켜 유기막을 형성할 수 있지만, 이에 제한되지 않는다.The organic film-forming composition of the first embodiment may be coated with a thickness of about 500 to about 4000 kPa, and thermally cured at about 200 to about 400 ° C. for about 10 seconds to about 10 minutes to form an organic film, but is not limited thereto. .
제 2 구체예에서, 유기막 형성용 조성물은 치환 또는 비치환된 방향족기를 갖는 화합물로 하기 화학식 8로 표시되는 물질을 포함할 수 있다: In a second embodiment, the composition for forming an organic film may be a compound having a substituted or unsubstituted aromatic group and may include a material represented by Formula 8 below:
<화학식 8><Formula 8>
상기 화학식 8에서, R4 내지 R9, X1 내지 X6은 각각 독립적으로, 수소, 히드록시기, 할로겐 원자, 알릴기, 티오닐기, 티올기, 시아노기, 치환 또는 비치환된 아미노기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C7 내지 C30 아릴알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알케닐기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴알킬기, 치환 또는 비치환된 C1 내지 C20 알킬아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C1 내지 C30 헤테로알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C1 내지 C20 알데히드기, 치환 또는 비치환된 C1 내지 C40 알킬에테르기, 치환 또는 비치환된 C7 내지 C20 아릴알킬렌에테르기, 치환 또는 비치환된 C1 내지 C30 할로알킬기, P를 포함하는 작용기, B를 포함하는 작용기 또는 이들의 조합이고In Formula 8, R 4 to R 9 , X 1 to X 6 are each independently hydrogen, hydroxy group, halogen atom, allyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted or Unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycle Alkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or Unsubstituted C2 to C30 heterocycloalkenyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C2 0 alkylamine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 heteroalkoxy group, substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C1 to C20 aldehyde group, A substituted or unsubstituted C1 to C40 alkylether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a functional group comprising P, a functional group including B or these Is a combination of
n1 내지 n6은 각각 독립적으로 0 내지 2의 범위에 있고, 2≤ n1+n2+n3+n4+n5+n6≤6이다).n 1 to n 6 are each independently in a range of 0 to 2, and 2 ≦ n 1 + n 2 + n 3 + n 4 + n 5 + n 6 ≦ 6 ).
예를 들면, R4 내지 R9은 각각 독립적으로 치환 또는 비치환된 C1 내지 C10의 알킬기, 치환 또는 비치환된 C6 내지 C20의 아릴기, 치환 또는 비치환된 C3 내지 C20의 사이클로알킬기, 치환 또는 비치환된 C3 내지 C20의 사이클로알케닐기, P를 포함하는 작용기 또는 B를 포함하는 작용기가 될 수 있다. For example, R 4 to R 9 are each independently a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or It may be an unsubstituted C3 to C20 cycloalkenyl group, a functional group including P, or a functional group including B.
예를 들면, X1 내지 X6은 각각 독립적으로 수소, 히드록시기, 치환 또는 비치환된 C1 내지 C20의 알킬아민기, 아미노기, P를 포함하는 작용기, B를 포함하는 작용기가 될 수 있다.For example, X 1 to X 6 may be each independently hydrogen, a hydroxy group, a substituted or unsubstituted C 1 to C 20 alkylamine group, an amino group, a functional group including P, a functional group including B.
치환 또는 비치환된 방향족기를 갖는 화합물로 상기 화학식 4로 표시되는 물질 대신에 상기 화학식 8로 표시되는 물질을 포함하는 것을 제외하고는 제1 구체예의 유기막 조성물과 실질적으로 동일하다. 이에, 이하에서는 상기 화학식 8로 표시되는 물질에 대해서만 설명한다.The compound having a substituted or unsubstituted aromatic group is substantially the same as the organic film composition of the first embodiment except for including the material represented by the formula (8) instead of the material represented by the formula (4). Therefore, hereinafter, only the substance represented by Chemical Formula 8 will be described.
상기 화학식 8로 표시되는 물질은 치환기의 위치가 서로 상이한 2 이상의 화합물의 혼합물일 수 있고, 짧은 파장 영역(예:193nm, 248nm)에서 강한 흡수를 갖는 방향족 고리를 포함하여, 특별한 촉매를 사용하지 않더라도 높은 온도에서 가교 반응이 진행되므로 촉매 특히 산에 의한 오염을 방지할 수 있고, 화학식 8의 방향족기 화합물은 평균분자량이 약 500 내지 약 4000이 될 수 있고, 상기 범위에서 유기막의 두께 구현 또는 양호한 박막을 형성할 수 있다.The material represented by Chemical Formula 8 may be a mixture of two or more compounds having different positions of substituents, and may include an aromatic ring having strong absorption in a short wavelength region (eg, 193 nm and 248 nm), even if no special catalyst is used. Since the cross-linking reaction proceeds at a high temperature, it is possible to prevent contamination by a catalyst, especially an acid, and the aromatic group compound of Formula 8 may have an average molecular weight of about 500 to about 4000. Can be formed.
상기 화학식 8로 표시되는 물질은 유기막 조성물의 열경화 후 탄소 함량, 막 밀도 및 경도를 높일 수 있다. 상기 화학식 8로 표시되는 물질은 통상의 방법으로 제조될 수 있으며, 예를 들면 코로넨에 아세틸클로라이드, 벤조일클로라이드, 나프토일클로라이드, 사이클로헥산카르보닐클로라이드를 반응시키고, 환원시켜 제조될 수 있지만, 이에 제한되지 않는다. 보다 상세한 제조 방법은 한국등록특허 제10-1311942호를 참고한다.The material represented by Chemical Formula 8 may increase carbon content, film density, and hardness after thermal curing of the organic film composition. The material represented by Chemical Formula 8 may be prepared by a conventional method, for example, it may be prepared by reacting and reducing acetyl chloride, benzoyl chloride, naphthoyl chloride, cyclohexanecarbonyl chloride to coronene, but It is not limited. For more detailed manufacturing method refer to Korea Patent Registration No. 10-1311942.
제3 구체예에서, 유기막 조성물은 치환 또는 비치환된 방향족기를 갖는 화합물로 하기 (i), (ii), (iii) 중에서 선택되는 방향족기 함유 중합체를 포함할 수 있다:In a third embodiment, the organic film composition may include an aromatic group-containing polymer selected from (i), (ii) and (iii) as a compound having a substituted or unsubstituted aromatic group:
(i) 하기 화학식 9로 표시되는 단위를 포함하는 화합물,(i) a compound comprising a unit represented by the following formula (9),
(ii) 하기 화학식 9로 표시되는 단위를 포함하는 화합물과 하기 화학식 10로 표시되는 단위를 포함하는 화합물과의 혼합물,(ii) a mixture of a compound comprising a unit represented by the following formula (9) with a compound comprising a unit represented by the following formula (10),
(iii) 하기 화학식 11으로 표시되는 단위를 포함하는 화합물.(iii) A compound comprising a unit represented by the following formula (11).
<화학식 9><Formula 9>
<화학식 10><Formula 10>
<화학식 11><Formula 11>
(상기 화학식 9 내지 11에서, b, c, d 및 e는 각각 독립적으로 1 내지 750이며, 2≤≤c+d<1500이고,(In the formulas 9 to 11, b, c, d and e are each independently 1 to 750, 2≤≤ c + d <1500,
R10은R 10 is
중 어느 하나이고,Any one of
R11은 수소, 히드록시기, 할로겐 원자, 티오닐기, 티올기, 시아노기, 치환 또는 비치환된 아미노기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C7 내지 C30 아릴알킬기, 치환 또는 비치환된 C1 내지 C20 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알케닐기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴알킬기, 치환 또는 비치환된 C1 내지 C20 알킬아민기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C6 내지 C30 아릴옥시기, 치환 또는 비치환된 C1 내지 C20 알데히드기, 치환 또는 비치환된 C1 내지 C40 알킬에테르기, 치환 또는 비치환된 C7 내지 C20 아릴알킬렌에테르기, 치환 또는 비치환된 C1 내지 C30 할로알킬기, P를 포함하는 작용기, B를 포함하는 작용기 또는 이들의 조합이고,R 11 is hydrogen, a hydroxy group, a halogen atom, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or Unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkenyl group , Substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted Is an unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a substituted or unsubstituted C1 to C20 aldehyde group, a substituted or unsubstituted C1 to C40 alkylether group, a substituted or unsubstituted C7 To C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a functional group including P, a functional group including B, or a combination thereof,
R12는R 12 is
중 어느 하나이고,Any one of
R13은R 13 is
중 어느 하나이고,Any one of
R14은R 14 is
중 어느 하나이고,Any one of
R15는R 15 is
중 어느 하나이고,Any one of
R10, R13, R15에서, R은 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C3 내지 C30 사이클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로사이클로알킬기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C7 내지 C30 아릴알킬기, 치환 또는 비치환된 C1 내지 C20 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로사이클로알케닐기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴알킬기, 치환 또는 비치환된 C1 내지 C20 알킬아민기, 치환 또는 비치환된 C1 내지 C30 할로알킬기, P를 포함하는 작용기, B를 포함하는 작용기 또는 이들의 조합이다.In R 10 , R 13 , R 15 , each R is independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, substituted Or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkenyl group, substituted or unsubstituted C2 to C30 hetero An aryl group, a substituted or unsubstituted C2 to C30 heteroarylalkyl group, a substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C1 to C30 haloalkyl group, including P Vessel, a functional group or combinations thereof containing the B.
치환 또는 비치환된 방향족기를 갖는 화합물로 상기 화학식 4로 표시되는 물질 대신에 상기 방향족기 함유 중합체를 포함하는 것을 제외하고는 제1 구체예의 유기막 조성물과 실질적으로 동일하다. 이에, 이하에서는 방향족기 함유 중합체에 대해서만 설명한다.The compound having a substituted or unsubstituted aromatic group is substantially the same as the organic film composition of the first embodiment except that the aromatic group-containing polymer is included instead of the material represented by the formula (4). Therefore, hereinafter, only the aromatic group-containing polymer will be described.
방향족기 함유 중합체는 유기막 조성물의 열경화 후 탄소 함량, 막 밀도 및 경도를 높일 수 있고, 통상의 방법으로 제조할 수 있고, 보다 상세한 내용은 한국등록특허 제10-0908601을 참조한다.The aromatic group-containing polymer may increase carbon content, film density and hardness after thermal curing of the organic film composition, and may be prepared by a conventional method, and refer to Korean Patent No. 10-0908601 for more details.
제4 구체예에서, 유기막 조성물은 치환 또는 비치환된 방향족기를 갖는 화합물로 상기 화학식 4를 포함하는 물질; 상기 화학식 8로 표시되는 물질; 상기 (i), (ii), (iii) 중에서 선택되는 방향족기 함유 중합체 중 2종 이상을 포함할 수 있다. 2 종 이상을 포함하는 것을 제외하고는 제1 구체예의 조성물과 실질적으로 동일하다.In a fourth embodiment, the organic film composition is a compound having a substituted or unsubstituted aromatic group material comprising the formula (4); A substance represented by Formula 8; It may contain two or more of the aromatic group-containing polymers selected from the above (i), (ii) and (iii). It is substantially the same as the composition of the first embodiment except that it contains two or more kinds.
유기막Organic membrane
연마 방법 Polishing method
본 발명의 유기막 연마 방법은 유기막 CMP 슬러리 조성물을 사용하여 탄소함량이 높은 유기막을 연마하는 단계를 포함하고, 유기막 CMP 슬러리 조성물은 본 발명 실시예의 유기막 CMP 슬러리 조성물을 포함할 수 있다. The organic film polishing method of the present invention may include polishing an organic film having a high carbon content using the organic film CMP slurry composition, and the organic film CMP slurry composition may include the organic film CMP slurry composition of the embodiment of the present invention.
이하, 도 1의 (a)를 참조하면, 도 1의 (a)는 유기막 연마 전 실리콘 웨이퍼, 무기막, 유기막의 적층 상태를 나타낸 것으로, 실리콘 웨이퍼(100)가 음각으로 패턴화되어 국부적으로 오목부가 형성되고, 실리콘 웨이퍼(100) 위에 무기막(110)을 증착하고, 무기막 위에 유기막(120)을 도포하고 200℃ 내지 400℃에서 열경화시켜 제조한다. 도 1의 (a)에서 T는 가상의 연마 정지선을 나타낸다. 도 1의 (a)의 유기막 위에 유기막 CMP 슬러리 조성물을 도포하고 연마패드를 설치한 후 실리콘 웨이퍼(100)을 회전시킴으로써 연마하게 되고, 연마 정지선(T)에 도달할 때까지 연마하여 도 1의 (b)의 연마 정지선(T)까지 연마한다.Hereinafter, referring to FIG. 1A, FIG. 1A illustrates a lamination state of a silicon wafer, an inorganic film, and an organic film before polishing an organic film, and the silicon wafer 100 is intaglio patterned locally. A recess is formed, and an inorganic film 110 is deposited on the silicon wafer 100, an organic film 120 is coated on the inorganic film, and manufactured by thermal curing at 200 ° C. to 400 ° C. FIG. In FIG. 1A, T represents an imaginary polishing stop line. After coating the organic film CMP slurry composition on the organic film of FIG. 1A and installing the polishing pad, the silicon wafer 100 is rotated and polished, and polished until the polishing stop line T is reached. Polish to the polishing stop line T of (b).
이하 실시예를 들어 본 발명을 보다 구체적으로 설명하나 하기 실시예들은 단지 설명을 위한 것으로서 본 발명의 보호 범위를 제한하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are merely illustrative and are not intended to limit the protection scope of the present invention.
제조예Production Example
유기막Organic membrane
형성용 조성물 제조 Formation composition preparation
온도계, 콘덴서, 기계교반기, 및 적가 깔때기를 구비한 2000ml 3구 플라스크를 준비한 후 140의 오일욕조 속에 담궜다. 가열과 자석에 의한 교반을 핫플레이트 위에서 행하였으며 콘덴서의 냉각수 온도는 40로 고정하였다. 1mol의 1-메톡시피렌 220g을 반응기에 가하고, 1.0mol의 1,4-비스메톡시메틸벤젠 138g을 가한 후 656g의 프로필렌글리콜모노메틸에테르아세테이트에 녹였다. 그후 0.03mol의 디에틸설페이트 4.6g을 첨가하였다. 반응기의 온도를 130로 유지하였다. 중합이 진행되는 동안 일정 시간 간격으로 분자량을 측정하여 반응완료시점을 결정하였다. 이때 분자량을 측정하기 위한 샘플은 1g의 반응물을 채취하여 상온으로 급랭시킨 후 그 중 0.02g을 취하여 용매인 테트라히드로푸란을 사용하여 고형분이 4중량%가 되도록 희석시켜 준비하였다. 결정된 반응완료시점에서 반응 종결을 위해 중화제로 0.03mol의 트리에탄올아민 4.48g을 반응기에 첨가하고 교반하였다. 그 후 반응물을 상온으로 서서히 냉각하였다. 상기 반응물을 500g의 프로필렌글리콜모노메틸에테르아세테이트를 이용하여 희석하였다. 그 후 용매를 2000ml의 분리깔때기에 가하였다. 90:10 g/g 비의 메탄올:에틸렌글리콜 혼합물을 4kg 준비하였다. 상기 합성된 고분자 용액을 격렬한 교반 하에서 상기 알콜 혼합물에 적하하였다. 결과물인 고분자는 플라스크 바닥면에 수집되었고, 상등액은 별도로 보관하였다. 상등액을 제거한 후 60℃에서 10분 동안 감압하 회전 증발에 의해 최종 반응물의 메탄올을 제거하였다.A 2000 ml three-necked flask equipped with a thermometer, a condenser, a mechanical stirrer, and a dropping funnel was prepared and soaked in a 140 oil bath. Heating and stirring with magnets were performed on a hotplate and the cooling water temperature of the condenser was fixed at 40. 220 g of 1 mol of 1-methoxypyrene was added to the reactor, and 138 g of 1.0 mol of 1,4-bismethoxymethylbenzene was added and then dissolved in 656 g of propylene glycol monomethyl ether acetate. Then 4.6 g of 0.03 mol of diethylsulfate were added. The temperature of the reactor was maintained at 130. During the polymerization, the molecular weight was measured at regular time intervals to determine the completion time of the reaction. At this time, the sample for measuring the molecular weight was prepared by diluting 1 g of the reactant, quenching to room temperature, 0.02 g of the sample was diluted to 4% by weight using tetrahydrofuran as a solvent. At the completion of the reaction, 0.03 mol of triethanolamine 4.48 g was added to the reactor as a neutralizing agent and terminated. The reaction was then slowly cooled to room temperature. The reaction was diluted with 500 g of propylene glycol monomethyl ether acetate. The solvent was then added to a 2000 ml separatory funnel. 4 kg of a methanol: ethylene glycol mixture in a 90:10 g / g ratio were prepared. The synthesized polymer solution was added dropwise to the alcohol mixture under vigorous stirring. The resulting polymer was collected at the bottom of the flask and the supernatant was stored separately. After removing the supernatant, methanol of the final reaction product was removed by rotary evaporation under reduced pressure for 10 minutes at 60 ℃.
얻어진 공중합체의 분자량 및 분산도를 테트라하이드로푸란 하에서 GPC에 의해 측정한 결과 중량평균분자량 4000, 분산도 2.3의 하기 화학식 12의 단위를 포함하는 고분자를 얻었다.The molecular weight and dispersion degree of the obtained copolymer were measured by GPC under tetrahydrofuran, and the polymer containing the unit of the following formula (12) of the weight average molecular weight 4000 and dispersion degree 2.3 was obtained.
<화학식 12><Formula 12>
(평균 a=11, Me는 메틸기)(Average a = 11, Me is methyl group)
상기에서 제조한 고분자 0.8g, 상기 화학식 5의 가교제 0.2g(Powderlink 1174, Cytec Industries Inc)과 피리디늄 p-톨루엔술포네이트 2mg을 프로필렌글리콜모노메틸에테르아세테이트 9g에 넣어서 녹인 후 여과하여 유기막 형성용 조성물을 제조하였다.0.8 g of the polymer prepared above, 0.2 g of a crosslinking agent of Formula 5 (Powderlink 1174, Cytec Industries Inc), and 2 mg of pyridinium p-toluenesulfonate were dissolved in 9 g of propylene glycol monomethyl ether acetate, and then filtered to form an organic film. The composition was prepared.
유기막Organic membrane
제조 Produce
표면에 음각 패턴이 형성된 패턴 웨이퍼 상에 연마 정지막으로 5000Å 두께의 실리카막을 증착하고, 실리카막 표면에 형성된 음각 패턴을 충진하기 위하여 2650Å 두께의 유기막을 형성하였다. 유기막은 상기 유기막 형성용 조성물을 실리카막 위에 도포하고, 400℃에서 열경화시켜 제조하였다.A 5000 mm thick silica film was deposited on the pattern wafer having the negative pattern formed on the surface thereof, and an organic film of 2650 mm thick was formed to fill the negative pattern formed on the surface of the silica film. The organic film was prepared by applying the composition for forming an organic film on a silica film and thermosetting at 400 ° C.
상기 유기막 형성용 조성물을 도포하고 400℃에서 120초동안 열경화시켜 제조된 두께 4700 내지 4800Å의 시편에 대해 Nanoindentor(Hysitron TI750 Ubi)를 사용하여 경도를 측정하였다. Nanoindentor의 팁이 시편에 5초 동안 들어가고(loading), 2초 동안 머무른 후(holding) 5초 동안 빠져나오는(unloading) 방법으로 측정하였고, 경도는 0.9GPa이 되었다. 동일 시편에 대해 원소분석기 (EA1112, Thermo)를 사용하여 탄소 함량을 측정하였다. 구체적으로 정확한 양의 시료를 O2 공존 하에서 연소시켜 탄소 함량을 측정하였고, 탄소 함량은 72atom%이었다. 동일 시편에 대해 XRR(X-RAY REFLECTIVITY) 장치(X'Pert PRO, PANalytical)를 사용하여 막 밀도를 측정하였다. 구체적으로 X선을 조사시켜 나온 회절 패턴을 기존에 알고 있는 회절 패턴과 비교하여 측정하였고, 막밀도는 1.4g/cm3이었다. 동일 시편에 대해 산가를 측정하였고, 산가는 0mgKOH/g이었다. The hardness was measured using a Nanoindentor (Hysitron TI750 Ubi) for the specimen of the thickness of 4700 ~ 4800 Å prepared by applying the organic film-forming composition and thermal curing at 400 ℃ for 120 seconds. The tip of the nanoindentor was measured by loading the specimen for 5 seconds, holding for 2 seconds and then unloading for 5 seconds, and the hardness was 0.9 GPa. The carbon content was measured using an elemental analyzer (EA1112, Thermo) on the same specimen. Specifically, the exact amount of the sample was burned under O 2 coexistence to measure the carbon content, the carbon content was 72 atom%. Membrane density was measured on the same specimen using an X-RAY REFLECTIVITY (XRR) instrument (X'Pert PRO, PANalytical). Specifically, the diffraction pattern irradiated with X-rays was measured by comparing with a known diffraction pattern, and the film density was 1.4 g / cm 3 . The acid value was measured for the same specimen, and the acid value was 0 mg KOH / g.
실시예Example
1-2 및 1-2 and
비교예Comparative example
1-4 1-4
하기 표 1의 성분(전체 조성물 대비 중량%)을 포함하는 CMP 슬러리 조성물을 제조하고, 상기 실리카막 및 유기막이 형성된 패턴 웨이퍼를 하기의 연마 조건으로 연마하였다.To prepare a CMP slurry composition comprising the components of Table 1 (% by weight relative to the total composition), and the patterned wafer formed with the silica film and the organic film was polished under the following polishing conditions.
(1) (One)
CMPCMP
슬러리 조성물 각 성분의 사양 Specification of each composition of slurry composition
(A) 연마제(A) abrasive
(a1) 평균입경이 60㎚의 콜로이달 세리아(SOLVAY社)를 사용하였다.(a1) Colloidal ceria (SOLVAY Corporation) having an average particle diameter of 60 nm was used.
(a2) 평균입경이 30nm의 콜로이달 실리카(FUSO社)를 사용하였다.(a2) Colloidal silica (FUSO Co., Ltd.) having an average particle diameter of 30 nm was used.
(B) 환원제(B) reducing agent
(b1) 세륨질산염(Cerium nitrate)(Aldrich社)을 사용하였다. (b1) Cerium nitrate (Aldrich) was used.
(b2) 티타늄 트리클로라이드(Titanium trichloride)(KANTO社)를 사용하였다.(b2) Titanium trichloride (KANTO) was used.
(C) pH 조절제: 삼전순약사의 질산을 사용하였다.(C) pH adjuster: Nitric acid of Samjeon Pure Pharmaceutical Co., Ltd. was used.
((
2)연마2) polishing
조건, 연마속도 및 선택비 측정 Condition, grinding speed and selectivity measurement
연마 패드로는 FUJIBO社의 H0800 CMP 패드를 사용하였다. 어플라이드머티리얼(Applied Materials; AMAT)社의 200mm MIRRA 장비를 사용하여 하강압력 0.8psi, 슬러리 유속 200mL/분, 평삭반(platen) 속도 60rpm과 헤드(head) 속도 55rpm으로 하여 1분간 연마를 수행한 후 연마량을 측정하여 하기 표 1에 나타내었다. 상기와 같이 연마를 수행한 후 연마면에 대해 박막 두께 측정기(ST4000, K-MAC)을 사용하여 연마막의 두께(단위:Å)를 측정하고, 측정된 두께로부터 연마량(단위:Å/min)을 계산한다. 선택비는 측정된 연마량 기초로 하기 식 1에 의하여 계산하였다.FUJIBO's H0800 CMP pad was used as the polishing pad. After 1 minute polishing using Applied Materials (AMAT) 200mm MIRRA equipment with a down pressure of 0.8psi, slurry flow rate of 200mL / min, platen speed of 60rpm and head speed of 55rpm The amount of polishing was measured and shown in Table 1 below. After polishing as described above, the thickness (unit: mm) of the polishing film was measured on the polished surface using a thin film thickness meter (ST4000, K-MAC), and the amount of polishing (unit: mm / min) was measured from the measured thickness. Calculate The selectivity was calculated by the following formula 1 on the basis of the measured polishing amount.
[식 1][Equation 1]
선택비 = α/βSelectivity = α / β
상기 식 1에서, α는 유기막에 대한 연마량(Å/min)이며, β는 무기막에 대한 연마량(Å/min)이다.In Equation 1, α is the polishing amount (Å / min) for the organic film, and β is the polishing amount (Å / min) for the inorganic film.
| 구분division | 실시예 Example | 비교예Comparative example | |||||
| 1One | 22 | 1One | 22 | 33 | 44 | ||
| (A)(A) | (a1)(a1) | 0.050.05 | 0.050.05 | -- | -- | 0.050.05 | 0.300.30 |
| (a2)(a2) | -- | -- | 0.050.05 | 0.300.30 | -- | -- | |
| (B)(B) | (b1)(b1) | 0.040.04 | 0.400.40 | 0.400.40 | 0.400.40 | -- | -- |
| (b2)(b2) | -- | -- | -- | -- | 0.400.40 | 0.400.40 | |
| (C)(C) | 0.010.01 | 0.020.02 | 0.010.01 | 0.020.02 | 0.050.05 | 0.050.05 | |
| 슬러리 조성물의 pHPH of slurry composition | 4.54.5 | 3.73.7 | 4.64.6 | 3.93.9 | 4.44.4 | 4.54.5 | |
| 연마량(Å/min)Polishing amount (Å / min) | 유기막(α)Organic film (α) | 33003300 | 26802680 | 55 | 66 | 3030 | 4545 |
| 무기막(β)Inorganic membrane (β) | 88 | 77 | 2121 | 1414 | 1212 | 1616 | |
| 선택비(α/β)Selection ratio (α / β) | 413413 | 383383 | 0.20.2 | 0.40.4 | 2.52.5 | 2.82.8 | |
상기 표 1에서 나타난 바와 같이, 본원발명의 세리아 및 세륨질산염을 포함한 실시예 1 및 2의 경우, 유기막에 대한 연마량이 높고, 무기막 대비 유기막에 대한 선택비가 높은 것을 확인할 수 있다.As shown in Table 1, in Examples 1 and 2 including ceria and cerium nitrate of the present invention, it can be confirmed that the polishing amount for the organic film is high, the selectivity for the organic film is high compared to the inorganic film.
반면에 본원발명의 세리아 또는 세륨질산염을 동시에 포함하지 않은 비교예 1 내지 4의 경우, 유기막에 대한 연마량이 낮고, 무기막 대비 유기막에 대한 선택비가 낮은 것을 확인할 수 있다.On the other hand, in Comparative Examples 1 to 4, which do not include the ceria or cerium nitrate of the present invention, it can be confirmed that the polishing amount for the organic film is low, and the selectivity for the organic film is low compared to the inorganic film.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.
Claims (8)
- 세리아; 및 세륨질산염을 포함하고,Ceria; And cerium nitrate,하기 식 1에 의한 선택비가 약 100 이상인 유기막 CMP 슬러리 조성물:An organic film CMP slurry composition having a selectivity of about 100 or more according to Formula 1 below:[식 1][Equation 1]선택비 = α/βSelectivity = α / β(상기 식 1에서, α는 유기막에 대한 연마량(Å/min)이며, β는 무기막에 대한 연마량(Å/min)이다).(In Formula 1, α is the polishing amount (Å / min) for the organic film, and β is the polishing amount (Å / min) for the inorganic film).
- 제1항에 있어서, 유기막은 탄소 함량이 약 90atom% 이상인 것을 특징으로 하는 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 1, wherein the organic film has a carbon content of about 90 atom% or more.
- 제1항에 있어서, 상기 세리아는 평균 입경이 약 10 내지 약 150nm인 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 1 wherein the ceria has an average particle diameter of about 10 to about 150 nm.
- 제1항에 있어서, 상기 세리아는 상기 조성물 중 약 0.01 내지 약 10.0중량%로 포함되는 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 1, wherein the ceria comprises from about 0.01 to about 10.0 weight percent of the composition.
- 제1항에 있어서, 상기 세륨질산염은 상기 조성물 중 약 0.01 내지 약 5.0중량%로 포함되는 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 1, wherein the cerium nitrate comprises about 0.01 to about 5.0 weight percent of the composition.
- 제1항에 있어서, 상기 조성물은 pH가 약 3 내지 약 5인 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 1 wherein the composition has a pH of about 3 to about 5. 3.
- 제1항에 있어서, 상기 유기막은 막 밀도가 약 0.5 내지 약 2.5g/cm3이고 경도가 약 0.4GPa 이상인 유기막 CMP 슬러리 조성물.The organic film CMP slurry composition of claim 1, wherein the organic film has a film density of about 0.5 to about 2.5 g / cm 3 and a hardness of about 0.4 GPa or more.
- 제1항 내지 제7항 중 어느 한 항의 유기막 CMP 슬러리 조성물을 사용하여 유기막을 연마하는 단계를 포함하는 유기막 연마방법.An organic film polishing method comprising polishing an organic film using the organic film CMP slurry composition according to any one of claims 1 to 7.
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| WO2017057936A1 true WO2017057936A1 (en) | 2017-04-06 |
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| PCT/KR2016/010940 WO2017057936A1 (en) | 2015-10-02 | 2016-09-30 | Organic film cmp slurry composition and polishing method using same |
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| Country | Link |
|---|---|
| KR (1) | KR101900543B1 (en) |
| CN (1) | CN108138029B (en) |
| TW (1) | TWI613269B (en) |
| WO (1) | WO2017057936A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111315836A (en) * | 2017-11-10 | 2020-06-19 | 三星Sdi株式会社 | Organic film CMP slurry composition and polishing method using the same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102343437B1 (en) * | 2018-11-16 | 2021-12-24 | 삼성에스디아이 주식회사 | Cmp slurry composition for amorphous carbon layer and method for polishing using the same |
| KR102570805B1 (en) * | 2019-11-01 | 2023-08-24 | 삼성에스디아이 주식회사 | Cmp slurry composition for polishing tungsten pattern wafer and method for polishing tungsten pattern wafer using the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3240580A (en) * | 1961-04-03 | 1966-03-15 | Libbey Owens Ford Glass Co | Glass polishing compositions of rare earth nitrates |
| US4769073A (en) * | 1986-09-26 | 1988-09-06 | Rhone-Poulenc Chimie | Ceric oxide/cerous salt organic glass polishing compositions |
| US20030060135A1 (en) * | 2001-09-24 | 2003-03-27 | Cabot Microelectronics Corporation | Rare earth salt/oxidizer-based cmp method |
| KR20140125316A (en) * | 2013-04-17 | 2014-10-28 | 제일모직주식회사 | Cmp slurry composition for organic film and polishing method using the same |
| KR20150010570A (en) * | 2013-07-17 | 2015-01-28 | 삼성전자주식회사 | CMP composition for polishing an organic layer and method of forming a semiconductor device using the composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1145224A (en) * | 1967-04-04 | 1969-03-12 | Libbey Owens Ford Glass Co | Glass polishing |
| US7887714B2 (en) * | 2000-12-25 | 2011-02-15 | Nissan Chemical Industries, Ltd. | Cerium oxide sol and abrasive |
| WO2005110679A1 (en) * | 2004-05-19 | 2005-11-24 | Nissan Chemical Industries, Ltd. | Composition for polishing |
| KR101667788B1 (en) * | 2013-12-31 | 2016-10-19 | 제일모직 주식회사 | Hardmask composition, and method of forming patterns using the hardmask composition |
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2015
- 2015-10-02 KR KR1020150139395A patent/KR101900543B1/en active IP Right Grant
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2016
- 2016-09-30 TW TW105131511A patent/TWI613269B/en active
- 2016-09-30 WO PCT/KR2016/010940 patent/WO2017057936A1/en active Application Filing
- 2016-09-30 CN CN201680056927.4A patent/CN108138029B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3240580A (en) * | 1961-04-03 | 1966-03-15 | Libbey Owens Ford Glass Co | Glass polishing compositions of rare earth nitrates |
| US4769073A (en) * | 1986-09-26 | 1988-09-06 | Rhone-Poulenc Chimie | Ceric oxide/cerous salt organic glass polishing compositions |
| US20030060135A1 (en) * | 2001-09-24 | 2003-03-27 | Cabot Microelectronics Corporation | Rare earth salt/oxidizer-based cmp method |
| KR20140125316A (en) * | 2013-04-17 | 2014-10-28 | 제일모직주식회사 | Cmp slurry composition for organic film and polishing method using the same |
| KR20150010570A (en) * | 2013-07-17 | 2015-01-28 | 삼성전자주식회사 | CMP composition for polishing an organic layer and method of forming a semiconductor device using the composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111315836A (en) * | 2017-11-10 | 2020-06-19 | 三星Sdi株式会社 | Organic film CMP slurry composition and polishing method using the same |
| CN111315836B (en) * | 2017-11-10 | 2022-03-15 | 三星Sdi株式会社 | Organic film CMP slurry composition and polishing method using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101900543B1 (en) | 2018-09-20 |
| TWI613269B (en) | 2018-02-01 |
| KR20170040452A (en) | 2017-04-13 |
| CN108138029B (en) | 2021-05-18 |
| CN108138029A (en) | 2018-06-08 |
| TW201714995A (en) | 2017-05-01 |
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