TW201714995A - CMP slurry composition for organic film and polishing method using the same - Google Patents
CMP slurry composition for organic film and polishing method using the same Download PDFInfo
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- TW201714995A TW201714995A TW105131511A TW105131511A TW201714995A TW 201714995 A TW201714995 A TW 201714995A TW 105131511 A TW105131511 A TW 105131511A TW 105131511 A TW105131511 A TW 105131511A TW 201714995 A TW201714995 A TW 201714995A
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- Prior art keywords
- substituted
- organic film
- unsubstituted
- slurry composition
- group
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- 239000000203 mixture Substances 0.000 title claims abstract description 97
- 238000005498 polishing Methods 0.000 title claims abstract description 79
- 239000002002 slurry Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 20
- 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 22
- 238000000227 grinding Methods 0.000 claims description 25
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 23
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 48
- 125000003118 aryl group Chemical group 0.000 description 31
- 125000000524 functional group Chemical group 0.000 description 22
- 125000000753 cycloalkyl group Chemical group 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 125000003342 alkenyl group Chemical group 0.000 description 8
- 125000000392 cycloalkenyl group Chemical group 0.000 description 8
- 125000004404 heteroalkyl group Chemical group 0.000 description 8
- 125000001072 heteroaryl group Chemical group 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 125000003282 alkyl amino group Chemical group 0.000 description 7
- 125000000304 alkynyl group Chemical group 0.000 description 7
- 125000004104 aryloxy group Chemical group 0.000 description 7
- 125000001188 haloalkyl group Chemical group 0.000 description 7
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
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- 150000003624 transition metals Chemical class 0.000 description 7
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- 125000004446 heteroarylalkyl group Chemical group 0.000 description 6
- -1 iron halogen salt Chemical class 0.000 description 6
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- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 5
- 125000004366 heterocycloalkenyl group Chemical group 0.000 description 5
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- 150000003839 salts Chemical class 0.000 description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003172 aldehyde group Chemical group 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 239000004640 Melamine resin Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 125000005275 alkylenearyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000004405 heteroalkoxy group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000007517 polishing process Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
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- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 238000000560 X-ray reflectometry Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- BCZWPKDRLPGFFZ-UHFFFAOYSA-N azanylidynecerium Chemical compound [Ce]#N BCZWPKDRLPGFFZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002738 chelating agent Chemical class 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- DLDWUFCUUXXYTB-UHFFFAOYSA-N (2-oxo-1,2-diphenylethyl) 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 DLDWUFCUUXXYTB-UHFFFAOYSA-N 0.000 description 1
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 description 1
- DAJPMKAQEUGECW-UHFFFAOYSA-N 1,4-bis(methoxymethyl)benzene Chemical compound COCC1=CC=C(COC)C=C1 DAJPMKAQEUGECW-UHFFFAOYSA-N 0.000 description 1
- GTVWPXDPNQJYNV-UHFFFAOYSA-N 1-methoxyindole Chemical compound C1=CC=C2N(OC)C=CC2=C1 GTVWPXDPNQJYNV-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- NJQJGRGGIUNVAB-UHFFFAOYSA-N 2,4,4,6-tetrabromocyclohexa-2,5-dien-1-one Chemical compound BrC1=CC(Br)(Br)C=C(Br)C1=O NJQJGRGGIUNVAB-UHFFFAOYSA-N 0.000 description 1
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 1
- MXVMRHIWTSFDPU-UHFFFAOYSA-N 2-chlorobenzenecarboximidamide Chemical compound NC(=N)C1=CC=CC=C1Cl MXVMRHIWTSFDPU-UHFFFAOYSA-N 0.000 description 1
- NXKOSHBFVWYVIH-UHFFFAOYSA-N 2-n-(butoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound CCCCOCNC1=NC(N)=NC(N)=N1 NXKOSHBFVWYVIH-UHFFFAOYSA-N 0.000 description 1
- KFVIYKFKUYBKTP-UHFFFAOYSA-N 2-n-(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCNC1=NC(N)=NC(N)=N1 KFVIYKFKUYBKTP-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- 241000751119 Mila <angiosperm> Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
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- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005227 alkyl sulfonate group Chemical group 0.000 description 1
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- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
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- FZIZEIAMIREUTN-UHFFFAOYSA-N azane;cerium(3+) Chemical compound N.[Ce+3] FZIZEIAMIREUTN-UHFFFAOYSA-N 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- HUYREUUJFLHEDE-UHFFFAOYSA-N cyclohexanecarbohydrazide Chemical compound NNC(=O)C1CCCCC1 HUYREUUJFLHEDE-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- JOAJYEIQYSPWHF-UHFFFAOYSA-N naphthalene-1,4-dione;hydrochloride Chemical compound Cl.C1=CC=C2C(=O)C=CC(=O)C2=C1 JOAJYEIQYSPWHF-UHFFFAOYSA-N 0.000 description 1
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- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
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- 230000003746 surface roughness Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 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
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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- 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
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Abstract
Description
本發明是有關於一種用於有機膜的化學機械研磨（chemical mechanical polishing，CMP）漿料組成物及使用其的研磨方法。The present invention relates to a chemical mechanical polishing (CMP) slurry composition for an organic film and a polishing method using the same.
近來，隨著半導體裝置的積體化程度及效能的提高，互連圖案的線寬變得更窄且互連圖案變成多層的。為提高在半導體裝置的製造中所執行的光微影的準確度，每一製程中各層之間的平整度是關鍵因素。當前，化學機械研磨（CMP）製程已作為一種平整技術而突顯。CMP製程可依據欲研磨的材料而被分類成氧化物膜CMP、金屬CMP、多晶矽CMP、有機膜CMP等。Recently, as the degree of integration and performance of semiconductor devices have increased, the line width of interconnect patterns has become narrower and interconnect patterns have become multilayered. In order to improve the accuracy of photolithography performed in the manufacture of semiconductor devices, the flatness between layers in each process is a key factor. Currently, chemical mechanical polishing (CMP) processes have been highlighted as a leveling technique. The CMP process can be classified into an oxide film CMP, a metal CMP, a polysilicon CMP, an organic film CMP, or the like depending on the material to be polished.
採用CMP以研磨有機膜（C-SOH）的半導體製程的一個實例包括層間介電層（interlayer dielectric，ILD）製程。所述ILD製程為藉由移除過量的有機膜（C-SOH）來形成精細圖案的製程。One example of a semiconductor process using CMP to polish an organic film (C-SOH) includes an interlayer dielectric (ILD) process. The ILD process is a process of forming a fine pattern by removing excess organic film (C-SOH).
典型的用於有機膜的CMP漿料組成物包含例如三氯化鈦等還原劑。然而，此種典型的CMP漿料組成物不會在ILD製程中提供有機膜相對於無機膜的所需選擇性比。A typical CMP slurry composition for an organic film contains a reducing agent such as titanium trichloride. However, such a typical CMP slurry composition does not provide the desired selectivity ratio of the organic film to the inorganic film in the ILD process.
在韓國專利公開案第2014-00125316 A號中揭露了本發明的背景技術。The background art of the present invention is disclosed in Korean Patent Publication No. 2014-00125316 A.
本發明的態樣提供一種具有有機膜相對於無機膜的高選擇性比的用於有機膜的CMP漿料組成物。Aspects of the present invention provide a CMP slurry composition for an organic film having a high selectivity ratio of an organic film to an inorganic film.
本發明的另一態樣提供一種具有高研磨速率、及包含高碳含量的有機膜相對於無機膜的高選擇性比的用於有機膜的CMP漿料組成物。Another aspect of the present invention provides a CMP slurry composition for an organic film having a high polishing rate and a high selectivity ratio of an organic film containing a high carbon content to an inorganic film.
本發明的再一態樣提供一種使用所述用於有機膜的CMP漿料組成物的研磨方法。Still another aspect of the present invention provides a grinding method using the CMP slurry composition for an organic film.
根據本發明的一個態樣，一種用於有機膜的CMP漿料組成物包含氧化鈰及硝酸鈰（III）且具有約100或高於100的選擇性比，如由方程式1所計算： 選擇性比=α/β --- （1）， 其中α是對有機膜的研磨速率（埃/分鐘）且β是對無機膜的研磨速率（埃/分鐘）。According to one aspect of the invention, a CMP slurry composition for an organic film comprises cerium oxide and cerium (III) nitrate and has a selectivity ratio of about 100 or higher, as calculated by Equation 1: Selectivity Ratio = α / β -- - (1), where α is the polishing rate (angstrom/minute) to the organic film and β is the polishing rate (angstrom/minute) to the inorganic film.
所述有機膜可具有約90原子%或大於約90原子%的碳含量。The organic film may have a carbon content of about 90 atom% or greater than about 90 atom%.
所述氧化鈰可具有約10奈米至約150奈米的平均粒徑。The cerium oxide may have an average particle diameter of from about 10 nanometers to about 150 nanometers.
所述氧化鈰可以約0.01重量%（wt%）至約10.0重量%的量存在於所述漿料組成物中。The cerium oxide may be present in the slurry composition in an amount from about 0.01% by weight (wt%) to about 10.0% by weight.
所述硝酸鈰可以約0.01重量%至約5.0重量%的量存在於所述漿料組成物中。The cerium nitrate may be present in the slurry composition in an amount from about 0.01% to about 5.0% by weight.
所述CMP漿料組成物可具有約3至約5的pH。The CMP slurry composition can have a pH of from about 3 to about 5.
所述有機膜可具有約0.5克/立方公分至約2.5克/立方公分的膜密度及約0.4十億帕或大於約0.4十億帕的硬度。The organic film can have a film density of from about 0.5 grams per cubic centimeter to about 2.5 grams per cubic centimeter and a hardness of about 0.4 billion Pascals or greater than about 0.4 billion Pascals.
根據本發明的另一態樣，一種研磨有機膜的方法包括使用以上所述的用於有機膜的CMP漿料組成物來研磨有機膜。According to another aspect of the present invention, a method of polishing an organic film includes grinding an organic film using the CMP slurry composition for an organic film described above.
本發明提供一種具有有機膜相對於無機膜的高選擇性比、高研磨速率、及對具有高碳含量的有機膜的高選擇性比的CMP漿料組成物及使用其的研磨方法。The present invention provides a CMP slurry composition having a high selectivity ratio of an organic film to an inorganic film, a high polishing rate, and a high selectivity ratio to an organic film having a high carbon content, and a polishing method using the same.
以下，將詳細闡述本發明的實施例。用於有機膜的 CMP 漿料組成 物 Hereinafter, embodiments of the invention will be described in detail. The CMP slurry composition for an organic film
根據本發明的一個實施例的一種用於有機膜的CMP漿料組成物可包含氧化鈰及硝酸鈰（III）。因此，根據所述實施例的所述CMP漿料組成物可藉由提高對被提供作為研磨目標的有機膜的研磨速率同時降低對無機膜的研磨速率來保證有機膜相對於無機膜的高選擇性比。A CMP slurry composition for an organic film according to an embodiment of the present invention may include cerium oxide and cerium (III) nitrate. Therefore, the CMP slurry composition according to the embodiment can ensure a high selection of the organic film relative to the inorganic film by increasing the polishing rate of the organic film provided as the polishing target while reducing the polishing rate of the inorganic film. Sex ratio.
所述有機膜是包含碳-氫鍵的碳系膜，例如C旋塗硬遮罩（C-spin-on hard mask，C-SOH）膜、非晶碳層（amorphous carbon layer，ACL）、或NCP膜。具體而言，C-SOH膜較佳作為研磨目標，乃因所述CMP漿料組成物具有對C-SOH膜的優異研磨選擇性。The organic film is a carbon-based film containing a carbon-hydrogen bond, such as a C-spin-on hard mask (C-SOH) film, an amorphous carbon layer (ACL), or NCP film. Specifically, the C-SOH film is preferred as the polishing target because the CMP slurry composition has excellent polishing selectivity to the C-SOH film.
所述無機膜可由氧化矽及氮化矽中的至少一者形成，但並非僅限於此。The inorganic film may be formed of at least one of cerium oxide and cerium nitride, but is not limited thereto.
氧化鈰（CeO2 ）是金屬氧化物磨料，並可以高研磨速率來研磨具有高碳含量的有機膜。具體而言，氧化鈰可藉由防止在研磨被提供作為研磨目標的有機膜時產生劃痕來提高經研磨表面的平整度。Cerium oxide (CeO 2 ) is a metal oxide abrasive and can grind an organic film having a high carbon content at a high polishing rate. Specifically, cerium oxide can improve the flatness of the ground surface by preventing scratches from occurring when the organic film provided as the polishing target is provided by the grinding.
氧化鈰以球形顆粒的形式提供，且可具有約10奈米至約150奈米（例如，約30奈米至約70奈米）的平均粒徑。在此尺寸範圍內，氧化鈰可獲得對被提供作為研磨目標的有機膜的足夠的研磨速率，且可提高經研磨表面的平整度而不產生劃痕。Cerium oxide is provided in the form of spherical particles and may have an average particle size of from about 10 nanometers to about 150 nanometers (e.g., from about 30 nanometers to about 70 nanometers). Within this size range, cerium oxide can obtain a sufficient polishing rate for the organic film provided as a grinding target, and can improve the flatness of the ground surface without causing scratches.
氧化鈰可以約0.01重量%至約10.0重量%（例如，約0.05重量%至約5.0重量%）的量存在於CMP漿料組成物中。在此範圍內，氧化鈰可獲得對被提供作為研磨目標的有機膜的足夠的研磨速率，且可提高分散穩定性而不產生劃痕。較佳地，氧化鈰具有高的平均粒徑且以少量存在於CMP漿料組成物中，以達成對有機膜的高研磨速率及對無機膜的低研磨速率。The cerium oxide may be present in the CMP slurry composition in an amount from about 0.01% to about 10.0% by weight (eg, from about 0.05% to about 5.0% by weight). Within this range, cerium oxide can obtain a sufficient polishing rate for the organic film provided as a grinding target, and can improve dispersion stability without causing scratches. Preferably, cerium oxide has a high average particle size and is present in a small amount in the CMP slurry composition to achieve a high polishing rate for the organic film and a low polishing rate for the inorganic film.
硝酸鈰（III）可以水合物（例如由式Ce(NO3 )3 表示的鹽）的形式提供。與典型還原劑（例如，三氯化鈦）相比，硝酸鈰可提高對有機膜的研磨速率同時降低對無機膜的研磨速率，藉此保證對有機膜的高選擇性。The cerium (III) nitrate may be provided in the form of a hydrate (for example, a salt represented by the formula Ce(NO 3 ) 3 ). Compared to a typical reducing agent (for example, titanium trichloride), cerium nitrate can increase the polishing rate of the organic film while reducing the polishing rate of the inorganic film, thereby ensuring high selectivity to the organic film.
硝酸鈰（III）可以離子化合物或螯合化合物的形式存在於CMP漿料組成物中。當以離子化合物或螯合化合物的形式使用時，硝酸鈰（III）可提供對有機膜的高研磨速率同時降低對無機膜的研磨速率，藉此保證對有機膜的高選擇性。The cerium (III) nitrate may be present in the CMP slurry composition in the form of an ionic compound or a chelating compound. When used in the form of an ionic compound or a chelating compound, cerium (III) nitrate can provide a high polishing rate to the organic film while reducing the polishing rate of the inorganic film, thereby ensuring high selectivity to the organic film.
硝酸鈰（III）可以約0.01重量%至約5.0重量%、較佳約0.01重量%至約2.0重量%、更佳約0.04重量%至約0.4重量%的量存在於CMP漿料組成物中。在此範圍內，硝酸鈰（III）可提供對有機膜的高研磨速率同時降低對無機膜的研磨速率，藉此保證對有機膜的高選擇性。The cerium (III) nitrate may be present in the CMP slurry composition in an amount from about 0.01% to about 5.0% by weight, preferably from about 0.01% to about 2.0% by weight, more preferably from about 0.0% to about 0.4% by weight. Within this range, cerium (III) nitrate can provide a high polishing rate to the organic film while reducing the polishing rate of the inorganic film, thereby ensuring high selectivity to the organic film.
根據本發明的所述實施例的所述CMP漿料組成物可具有約100或大於約100、具體而言約300至約500的選擇性比，如由方程式1所計算： 選擇性比=α/β --- （1）， 其中α是對有機膜的研磨速率（埃/分鐘）且β是對無機膜的研磨速率（埃/分鐘）。The CMP slurry composition according to the embodiment of the invention may have a selectivity ratio of about 100 or greater than about 100, specifically about 300 to about 500, as calculated by Equation 1: selectivity ratio = a /β --- (1), where α is the polishing rate (angstrom/minute) to the organic film and β is the polishing rate (angstrom/minute) to the inorganic film.
在某些實施例中，所述CMP漿料組成物可為酸性的。在該些實施例中，所述CMP漿料組成物可提高對有機膜的研磨選擇性，且可提高對有機膜的研磨速率及經研磨表面的平整度。具體而言，所述CMP漿料組成物可具有約3至約5的pH。舉例而言，所述CMP漿料組成物可使用pH調節劑而被調節成具有處於此範圍內的pH。所述pH調節劑可包括：無機酸，例如硝酸及硫酸中的至少一者；以及有機酸，例如具有5或小於5的pKa的有機酸，例如醋酸及檸檬酸中的至少一者，但並不僅限於此。In certain embodiments, the CMP slurry composition can be acidic. In these embodiments, the CMP slurry composition can increase the polishing selectivity to the organic film and can increase the polishing rate of the organic film and the flatness of the ground surface. In particular, the CMP slurry composition can have a pH of from about 3 to about 5. For example, the CMP slurry composition can be adjusted to have a pH within this range using a pH adjusting agent. The pH adjusting agent may include: at least one of a mineral acid such as nitric acid and sulfuric acid; and an organic acid such as an organic acid having a pKa of 5 or less, such as at least one of acetic acid and citric acid, but Not limited to this.
所述pH調節劑可以約0.01重量%至約5.0重量%、較佳約0.01重量%至約2.0重量%、更佳約0.04重量%至約0.4重量%的量存在於CMP漿料組成物中。在此範圍內，所述pH調節劑可提供對被提供作為研磨目標的有機膜的高研磨速率同時降低對無機膜的研磨速率，藉此保證對有機膜的高選擇性。The pH adjusting agent may be present in the CMP slurry composition in an amount from about 0.01% to about 5.0% by weight, preferably from about 0.01% to about 2.0% by weight, more preferably from about 0.0% to about 0.4% by weight. Within this range, the pH adjuster can provide a high polishing rate to the organic film provided as an abrasive target while reducing the polishing rate to the inorganic film, thereby ensuring high selectivity to the organic film.
所述CMP漿料組成物可更包含氧化劑。所述氧化劑藉由使具有高碳含量的有機膜的表面層氧化而有利於對所述有機膜進行研磨，且使所述有機膜能夠具有均勻的表面以在藉由研磨而暴露出無機膜時達成經研磨表面的良好表面粗糙度。此外，所述氧化劑有利於移除無機膜上的殘餘有機膜，藉此使得所述有機膜能夠均勻地受到研磨。The CMP slurry composition may further comprise an oxidizing agent. The oxidizing agent facilitates grinding the organic film by oxidizing a surface layer of an organic film having a high carbon content, and enables the organic film to have a uniform surface to expose the inorganic film by grinding. A good surface roughness of the ground surface is achieved. Further, the oxidizing agent facilitates removal of the residual organic film on the inorganic film, thereby enabling the organic film to be uniformly ground.
具體而言，所述氧化劑可包含呈多價氧化態的金屬鹽及過渡金屬螯合物中的至少一者。在本文中，用語「多價」是指二價或高於二價，例如三價或高於三價、或者四價或高於四價。In particular, the oxidizing agent may comprise at least one of a metal salt and a transition metal chelate in a multivalent oxidation state. As used herein, the term "multivalent" means divalent or higher than divalent, such as trivalent or higher, or tetravalent or higher.
呈多價氧化態的金屬鹽提高對有機膜的研磨速率同時降低對無機膜的研磨速率。所述金屬鹽可包含例如過渡金屬、鑭系元素等金屬，且可另外包含鹵素、銨、硝酸鹽等。具體而言，所述金屬鹽可包含鈰銨鹽、鐵鹵素鹽、硝酸鐵等，例如硝酸鈰銨、硝酸鐵、氯化鐵等。The metal salt in the multivalent oxidation state increases the polishing rate of the organic film while reducing the polishing rate of the inorganic film. The metal salt may contain a metal such as a transition metal, a lanthanoid element, and may additionally contain a halogen, an ammonium, a nitrate, or the like. Specifically, the metal salt may include a cerium ammonium salt, an iron halogen salt, iron nitrate, or the like, such as ammonium cerium nitrate, iron nitrate, iron chloride, or the like.
所述過渡金屬螯合物提高對有機膜的研磨速率同時降低對無機膜的研磨速率。The transition metal chelate compound increases the polishing rate of the organic film while reducing the polishing rate of the inorganic film.
在所述過渡金屬螯合物中，過渡金屬可包括通常已知的III族至XII族過渡金屬，例如鐵、銅、錳及鉻。所述螯合物可包括草酸、經胺基取代的羧酸（例如，胺基多羧酸（例如亞胺基二乙酸、乙烯二胺二琥珀酸、亞胺基二琥珀酸、乙二胺四乙酸及氮基三乙酸）、α-胺基酸（例如甘胺酸及β-胺基酸））、經羥基取代的羧酸（例如，乙醇酸、乳酸、及含羥基的多羧酸（例如蘋果酸、檸檬酸及酒石酸））、膦醯基羧酸、胺基膦酸及其組合。舉例而言，所述過渡金屬螯合物可包括含Fe的化合物（包含丙二胺四乙酸-Fe）及含Mn的化合物（包含丙二胺四乙酸-Mn）中的至少一者，但並非僅限於此。In the transition metal chelate, the transition metal may include a generally known Group III to XII transition metal such as iron, copper, manganese, and chromium. The chelate may include oxalic acid, an amine-substituted carboxylic acid (eg, an amine polycarboxylic acid (eg, iminodiacetic acid, ethylene diamine disuccinic acid, imidodisuccinic acid, ethylenediamine four) Acetic acid and nitrogen triacetic acid), α-amino acids (such as glycine and β-amino acids), hydroxy-substituted carboxylic acids (for example, glycolic acid, lactic acid, and hydroxyl-containing polycarboxylic acids (for example) Malic acid, citric acid and tartaric acid), phosphinyl carboxylic acid, aminophosphonic acid and combinations thereof. For example, the transition metal chelate may include at least one of a Fe-containing compound (including propylenediaminetetraacetic acid-Fe) and a Mn-containing compound (including propylenediaminetetraacetic acid-Mn), but not Limited to this.
所述氧化劑可以約0.001重量%至約15重量%（例如，約0.01重量%至約5重量%或約0.05重量%至約3重量%）的量存在於CMP漿料組成物中。在此範圍內，所述CMP漿料組成物可維持對有機膜的合適的蝕刻特性。當所述CMP漿料組成物為酸性時，所述氧化劑展現出良好穩定性，藉此所述CMP漿料組成物可提高對有機膜的研磨速率，提高對經研磨表面的平整程度，且提高對無機膜的研磨選擇性。The oxidizing agent may be present in the CMP slurry composition in an amount from about 0.001% to about 15% by weight (eg, from about 0.01% to about 5% by weight or from about 0.05% to about 3% by weight). Within this range, the CMP slurry composition can maintain suitable etching characteristics for the organic film. When the CMP slurry composition is acidic, the oxidizing agent exhibits good stability, whereby the CMP slurry composition can increase the polishing rate of the organic film, improve the flatness of the ground surface, and improve Grinding selectivity to inorganic membranes.
所述CMP漿料組成物可更包含添加劑。舉例而言，所述CMP漿料組成物可更包含研磨促進劑作為添加劑。所述研磨促進劑可藉由抑制對無機膜的研磨速率而提高對無機膜的研磨選擇性。所述研磨促進劑可包含有機酸，例如蘋果酸、甲酸、戊二酸、草酸、鄰苯二甲酸、琥珀酸、酒石酸、馬來酸及丙二酸中的至少一者。所述研磨促進劑可以0.02重量%至0.5重量%的量存在於CMP漿料組成物中。在此範圍內，所述研磨促進劑不會對研磨速率、漿料的分散穩定性及有機膜的表面特性產生不利影響。CMP 漿料組成 物的研磨目標 The CMP slurry composition may further comprise an additive. For example, the CMP slurry composition may further comprise a polishing accelerator as an additive. The polishing accelerator can improve the polishing selectivity to the inorganic film by suppressing the polishing rate of the inorganic film. The polishing accelerator may comprise at least one of an organic acid such as malic acid, formic acid, glutaric acid, oxalic acid, phthalic acid, succinic acid, tartaric acid, maleic acid, and malonic acid. The grinding accelerator may be present in the CMP slurry composition in an amount of from 0.02% by weight to 0.5% by weight. Within this range, the polishing accelerator does not adversely affect the polishing rate, the dispersion stability of the slurry, and the surface characteristics of the organic film. Grinding target of CMP slurry composition
以下，將詳細闡述作為根據本發明的所述CMP漿料組成物的研磨目標的有機膜。Hereinafter, an organic film which is a polishing target of the CMP slurry composition according to the present invention will be explained in detail.
本文所用的用語「經取代」意指對應官能基的至少一個氫原子經羥基、鹵素原子、亞硫醯基、硫醇基、氰基、胺基、C1 至C30 烷基、C2 至C30 烯基、C2 至C30 炔基、C3 至C30 環烷基、C3 至C30 環烯基、C6 至C30 芳基、C7 至C30 芳基烷基、C1 至C20 雜烷基、C2 至C30 雜環烷基、C2 至C30 雜環烯基、C2 至C30 雜芳基、C2 至C30 雜芳基烷基、C1 至C20 烷基胺基、C1 至C30 烷氧基、C6 至C30 芳氧基、C1 至C20 醛基、C1 至C40 烷基醚基、C7 至C20 芳基伸烷基醚基、C1 至C30 鹵代烷基、含P的官能基、含B的官能基或其組合取代。The term "substituted" as used herein means at least one hydrogen atom corresponding to a functional group via a hydroxyl group, a halogen atom, a sulfinyl group, a thiol group, a cyano group, an amine group, a C 1 to C 30 alkyl group, a C 2 to C 30 alkenyl, C 2 to C 30 alkynyl, C 3 to C 30 cycloalkyl, C 3 to C 30 cycloalkenyl, C 6 to C 30 aryl, C 7 to C 30 arylalkyl, C 1 to C 20 heteroalkyl, C 2 to C 30 heterocycloalkyl, C 2 to C 30 heterocycloalkenyl, C 2 to C 30 heteroaryl, C 2 to C 30 heteroarylalkyl, C 1 To C 20 alkylamino, C 1 to C 30 alkoxy, C 6 to C 30 aryloxy, C 1 to C 20 aldehyde, C 1 to C 40 alkyl ether, C 7 to C 20 Substituted alkyl ether group, C 1 to C 30 haloalkyl group, P containing functional group, B containing functional group or a combination thereof.
在本文中，「含P的官能基」可由式A表示，且「含B的官能基」可由式B表示： ＜式A＞ *-(O)n -(CH2 )m -P(=O)(Ra )(Rb ) ＜式B＞ *-B(Rc )(Rd )， 其中n為0或1；m為0至10的整數；且 Ra 、Rb 、Rc 、及Rd 分別獨立地為氫、羥基、經取代或未經取代的C1 至C20 烷基、經取代或未經取代的C2 至C20 烯基、經取代或未經取代的C3 至C20 環烷基、經取代或未經取代的C1 至C20 鹵代烷基、經取代或未經取代的C1 至C20 烷基磺酸酯基、經取代或未經取代的C1 至C20 烷基磺醯基、經取代或未經取代的C2 至C20 烷基醯胺基、經取代或未經取代的C3 至C20 烷基酯基、經取代或未經取代的C2 至C20 氰基烷基、經取代或未經取代的C1 至C20 烷氧基、經取代或未經取代的C6 至C30 芳基、經取代或未經取代的C6 至C30 芳基烷基或經取代或未經取代的C6 至C30 芳氧基，或 Ra 及Rb 或Rc 及Rd 連接至彼此以形成經取代或未經取代的C3 至C20 環烷基或經取代或未經取代的C3 至C20 雜環烷基。Herein, the "P-containing functional group" may be represented by Formula A, and the "B-containing functional group" may be represented by Formula B: <Formula A> *-(O) n -(CH 2 ) m -P(=O (R a )(R b ) <Formula B> *-B(R c )(R d ), wherein n is 0 or 1; m is an integer of 0 to 10; and R a , R b , R c , And R d are each independently hydrogen, hydroxy, substituted or unsubstituted C 1 to C 20 alkyl, substituted or unsubstituted C 2 to C 20 alkenyl, substituted or unsubstituted C 3 To a C 20 cycloalkyl group, a substituted or unsubstituted C 1 to C 20 haloalkyl group, a substituted or unsubstituted C 1 to C 20 alkyl sulfonate group, a substituted or unsubstituted C 1 To a C 20 alkylsulfonyl group, a substituted or unsubstituted C 2 to C 20 alkylguanidino group, a substituted or unsubstituted C 3 to C 20 alkyl ester group, substituted or unsubstituted C 2 to C 20 cyanoalkyl, substituted or unsubstituted C 1 to C 20 alkoxy, substituted or unsubstituted C 6 to C 30 aryl, substituted or unsubstituted C 6 to C 30 arylalkyl or substituted or unsubstituted C 6 to C 30 aryloxy group, or R a and R b or R c and R d are connected to each other to form by taking Or unsubstituted C 3 to C 20 cycloalkyl, or a substituted or unsubstituted C 3 to C 20 heterocycloalkyl.
較佳地，含P的官能基為含P及O的官能基，例如，-P(=O)(OH)2 、-O-P(=O)(OH)2 、-P(=O)(OCH2 CH3 )2 及-P(=O)(C2 H4 C6 H5 )(OCH2 CH3 )，且含B的官能基為含B及O的官能基，例如，-B(OH)2 、-B(H)(CH3 )及-B(CH2 CH3 )2 。Preferably, the functional group containing P is a functional group containing P and O, for example, -P(=O)(OH) 2 , -OP(=O)(OH) 2 , -P(=O)(OCH 2 CH 3 ) 2 and -P(=O)(C 2 H 4 C 6 H 5 )(OCH 2 CH 3 ), and the functional group containing B is a functional group containing B and O, for example, -B(OH 2 , -B(H)(CH 3 ) and -B(CH 2 CH 3 ) 2 .
當無機膜沈積於圖案化晶圓（例如，圖案化矽晶圓）上時，有機膜填充在其中形成的貫穿孔（via-hole）。CMP漿料組成物需要以足夠的研磨速率來研磨有機膜以使所沈積膜平坦化，需要提高經研磨表面的平整程度，且需要使得能夠在研磨之後輕易地移除無機膜上的殘餘物。無機膜可由氧化矽及氮化矽中的至少一者形成，但並非僅限於此。無機膜可具有少於約1原子%（例如，0原子%至約1原子%，例如0原子%）的碳含量。When an inorganic film is deposited on a patterned wafer (eg, a patterned germanium wafer), the organic film fills a via-hole formed therein. The CMP slurry composition needs to grind the organic film at a sufficient polishing rate to planarize the deposited film, it is necessary to increase the flatness of the ground surface, and it is necessary to make it easy to remove the residue on the inorganic film after grinding. The inorganic film may be formed of at least one of cerium oxide and cerium nitride, but is not limited thereto. The inorganic film may have a carbon content of less than about 1 atomic % (eg, 0 atomic % to about 1 atomic %, such as 0 atomic %).
有機膜可依據有機膜的材料而具有顯著不同的研磨速率及研磨後的平整度。根據本發明的所述CMP漿料組成物是用於研磨具有高碳含量的有機膜的組成物。當使用CMP漿料組成物來研磨有機膜時，CMP漿料組成物可提高研磨速率且具有對無機膜的高選擇性。The organic film may have significantly different polishing rates and flatness after polishing depending on the material of the organic film. The CMP slurry composition according to the present invention is a composition for grinding an organic film having a high carbon content. When the CMP slurry composition is used to grind the organic film, the CMP slurry composition can increase the polishing rate and have high selectivity to the inorganic film.
在某些實施例中，有機膜可具有90原子%或大於90原子%（例如，約90原子%至約99原子%或約95原子%至約99原子%）的碳含量。在此範圍內，當以氧化鈰進行研磨時，有機膜可以高研磨速率受到研磨而不會遭受劃傷，且可展現出經研磨表面的高平整程度。此外，有機膜可具有約0.5克/立方公分至約2.5克/立方公分（例如，約1.0克/立方公分至約2.0克/立方公分或約1.2克/立方公分至約1.6克/立方公分）的膜密度。在此範圍內，當以氧化鈰進行研磨時，有機膜可以高研磨速率受到行研磨而不會遭受劃傷，且可展現出經研磨表面的高平整程度。此外，有機膜可具有0.4十億帕或大於0.4十億帕（例如，約1.0十億帕或大於約1.0十億帕、約1.3十億帕或大於約1.3十億帕、或約1.3十億帕至約1.5十億帕）的硬度。在此範圍內，當以氧化鈰進行研磨時，有機膜可以高研磨速率受到研磨而不會遭受劃傷，且可展現出經研磨表面的高平整程度。In certain embodiments, the organic film can have a carbon content of 90 atomic percent or greater than 90 atomic percent (eg, from about 90 atomic percent to about 99 atomic percent or from about 95 atomic percent to about 99 atomic percent). Within this range, when grinding with cerium oxide, the organic film can be ground at a high polishing rate without being scratched, and can exhibit a high degree of flatness of the ground surface. Additionally, the organic film can have from about 0.5 grams per cubic centimeter to about 2.5 grams per cubic centimeter (eg, from about 1.0 grams per cubic centimeter to about 2.0 grams per cubic centimeter or from about 1.2 grams per cubic centimeter to about 1.6 grams per cubic centimeter). Film density. Within this range, when grinding with cerium oxide, the organic film can be subjected to line grinding at a high polishing rate without being scratched, and can exhibit a high degree of flatness of the ground surface. Additionally, the organic film can have 0.4 billion Pascals or greater than 0.4 billion Pascals (eg, about 1.0 billion Pascals or greater than about 1.0 billion Pascals, about 1.3 billion Pascals, or greater than about 1.3 billion Pascals, or about 1.3 billion Pa to a hardness of about 1.5 billion Pa). Within this range, when grinding with cerium oxide, the organic film can be ground at a high polishing rate without being scratched, and can exhibit a high degree of flatness of the ground surface.
此外，根據本發明的所述有機膜可具有實質上為0毫克KOH/克的酸值。在使用包含聚合物磨料的典型CMP漿料組成物來研磨有機膜的情形中，存在研磨速率降低的問題。相反，根據本發明的所述CMP漿料組成物可保證對應用於CMP製程而言足夠的有機膜研磨速率。用語「實質上」意指酸值不僅為0毫克KOH/克，且為具有可接受誤差裕度的0毫克KOH/克。Further, the organic film according to the present invention may have an acid value of substantially 0 mgKOH/g. In the case of using an exemplary CMP slurry composition comprising a polymer abrasive to grind an organic film, there is a problem that the polishing rate is lowered. In contrast, the CMP slurry composition according to the present invention can ensure a sufficient organic film polishing rate corresponding to the CMP process. The term "substantially" means that the acid value is not only 0 mg KOH/g, but also 0 mg KOH/g with an acceptable margin of error.
具體而言，根據本發明的所述有機膜可藉由將有機膜組成物塗佈至無機膜上然後在例如200℃至400℃的高溫下進行烘烤而生產。Specifically, the organic film according to the present invention can be produced by coating an organic film composition onto an inorganic film and then baking it at a high temperature of, for example, 200 ° C to 400 ° C.
所述有機膜組成物可包括含經取代或未經取代的芳族基的化合物。The organic film composition may include a compound containing a substituted or unsubstituted aromatic group.
本文所用的用語「含經取代或未經取代的芳族基的化合物」是指在烘烤之後不會分解的化合物且使得由包含所述化合物的組成物形成的有機膜能夠具有高碳含量。未經取代的芳族基可為具有單環結構或其中稠和有二個或更多個環的多環結構的C6 至C100 （例如，C6 至C50 ）未經取代的芳族基。舉例而言，未經取代的芳族基可包含由式3-1至式3-26表示的化合物。 ＜式3-1＞＜式3-2＞＜式3-3＞＜式3-4＞＜式3-5＞＜式3-6＞＜式3-7＞＜式3-8＞＜式3-9＞＜式3-10＞＜式3-11＞＜式3-12＞＜式3-13＞＜式3-14＞＜式3-15＞＜式3-16＞＜式3-17＞＜式3-18＞＜式3-19＞＜式3-20＞＜式3-21＞＜式3-22＞＜式3-23＞＜式3-24＞＜式3-25＞＜式3-26＞其中Z1 至Z18 分別獨立地為單鍵、經取代或未經取代的C1 至C20 伸烷基、經取代或未經取代的C2 至C20 伸烯基、經取代或未經取代的C2 至C20 伸炔基、經取代或未經取代的C3 至C20 伸環烷基、經取代或未經取代的C3 至C20 伸環烯基、經取代或未經取代的C6 至C20 伸芳基、經取代或未經取代的C2 至C20 伸雜芳基、-(C=O)-、-NRe -、-CRf Rg -、氧（O）、硫（S）或其組合（Re 、Rf 、及Rg 分別獨立地為氫、經取代或未經取代的C1 至C10 烷基、鹵素原子、經取代或未經取代的C6 至C20 伸芳基、經取代或未經取代的C2 至C20 伸雜芳基或其組合）。The phrase "compound containing a substituted or unsubstituted aromatic group" as used herein means a compound which does not decompose after baking and enables an organic film formed of a composition containing the compound to have a high carbon content. The unsubstituted aromatic group may be a C 6 to C 100 (for example, C 6 to C 50 ) unsubstituted aromatic group having a single ring structure or a polycyclic structure in which two or more rings are fused. base. For example, the unsubstituted aromatic group may include a compound represented by Formula 3-1 to Formula 3-26. <Form 3-1> <Form 3-2> <Formula 3-3> <Formula 3-4> <Formula 3-5> <Formula 3-6> <Formula 3-7> <Formula 3-8> <Formula 3-9> <Formula 3-10> <Formula 3-11> <Formula 3-12> <Formula 3-13> <Formula 3-14> <Formula 3-15> <Formula 3-16> <Formula 3-17> <Formula 3-18> <Formula 3-19> <Formula 3-20> <Formula 3-21> <Formula 3-22> <Formula 3-23> <Formula 3-24> <Formula 3-25> <Formula 3-26> Wherein Z 1 to Z 18 are each independently a single bond, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 2 to C 20 alkyl group, substituted or unsubstituted Substituted C 2 to C 20 alkynyl, substituted or unsubstituted C 3 to C 20 cycloalkyl, substituted or unsubstituted C 3 to C 20 cycloalkenyl, substituted or unsubstituted Substituted C 6 to C 20 extended aryl, substituted or unsubstituted C 2 to C 20 heteroaryl, -(C=O)-, -NR e -, -CR f R g -, oxygen ( O), sulfur (S) or a combination thereof (R e , R f , and R g are each independently hydrogen, substituted or unsubstituted C 1 to C 10 alkyl, halogen atom, substituted or unsubstituted C 6 to C 20 extended aryl, substituted or unsubstituted C 2 to C 20 heteroaryl or a combination thereof).
以下，將更詳細地闡述包括含經取代或未經取代的芳族基的化合物的有機膜組成物。Hereinafter, an organic film composition including a compound containing a substituted or unsubstituted aromatic group will be explained in more detail.
在第一實施例中，所述有機膜組成物可包括含有由式4表示的單元的化合物作為含經取代或未經取代的芳族基的化合物： ＜式4＞其中a滿足1≤n＜190； R1 為氫、羥基、鹵素原子、烯丙基、亞硫醯基、硫醇基、氰基、經取代或未經取代的胺基、經取代或未經取代的C1 至C30 烷基、經取代或未經取代的C1 至C30 雜烷基、經取代或未經取代的C2 至C30 烯基、經取代或未經取代的C2 至C30 炔基、經取代或未經取代的C3 至C30 環烷基、經取代或未經取代的C2 至C30 雜環烷基、經取代或未經取代的C3 至C30 環烯基、經取代或未經取代的C6 至C30 芳基、經取代或未經取代的C7 至C30 芳基烷基、經取代或未經取代的C2 至C30 雜環烯基、經取代或未經取代的C2 至C30 雜芳基、經取代或未經取代的C2 至C30 雜芳基烷基、經取代或未經取代的C1 至C20 烷基胺基、經取代或未經取代的C1 至C30 烷氧基、經取代或未經取代的C1 至C30 雜烷氧基、經取代或未經取代的C6 至C30 芳氧基、經取代或未經取代的C1 至C20 醛基、經取代或未經取代的C1 至C40 烷基醚基、經取代或未經取代的C7 至C20 芳基伸烷基醚基、經取代或未經取代的C1 至C30 鹵代烷基、含P的官能基、含B的官能基或其組合； R2 為氫、胺基、經取代或未經取代的C1 至C30 烷氧基、經取代或未經取代的C6 至C20 芳氧基、二烷基胺基（-NRR'、R及R'分別獨立地為經取代或未經取代的C1 至C10 烷基或經取代或未經取代的C6 至C10 芳基）、羥基、鹵素原子、烯丙基、亞硫醯基、硫醇基、氰基、經取代或未經取代的胺基、經取代或未經取代的C1 至C30 烷基、經取代或未經取代的C1 至C30 雜烷基、經取代或未經取代的C2 至C30 烯基、經取代或未經取代的C2 至C30 炔基、經取代或未經取代的C3 至C30 環烷基、經取代或未經取代的C2 至C30 雜環烷基、經取代或未經取代的C3 至C30 環烯基、經取代或未經取代的C6 至C30 芳基、經取代或未經取代的C7 至C30 芳基烷基、經取代或未經取代的C2 至C30 雜環烯基、經取代或未經取代的C2 至C30 雜芳基、經取代或未經取代的C2 至C30 雜芳基烷基、經取代或未經取代的C1 至C20 烷基胺基、經取代或未經取代的C1 至C30 雜烷氧基、經取代或未經取代的C6 至C30 芳氧基、經取代或未經取代的C1 至C20 醛基、經取代或未經取代的C1 至C40 烷基醚基、經取代或未經取代的C7 至C20 芳基伸烷基醚基、經取代或未經取代的C1 至C30 鹵代烷基、含P的官能基、含B的官能基或其組合；且 R3 為選自由下式表示的經取代或未經取代的化合物中的任一者：。In the first embodiment, the organic film composition may include a compound containing a unit represented by Formula 4 as a compound having a substituted or unsubstituted aromatic group: <Formula 4> Wherein a satisfies 1 ≤ n <190; R 1 is hydrogen, hydroxy, halogen atom, allyl, sulfinylene, thiol, cyano, substituted or unsubstituted amine, substituted or unsubstituted Substituted C 1 to C 30 alkyl, substituted or unsubstituted C 1 to C 30 heteroalkyl, substituted or unsubstituted C 2 to C 30 alkenyl, substituted or unsubstituted C 2 To C 30 alkynyl, substituted or unsubstituted C 3 to C 30 cycloalkyl, substituted or unsubstituted C 2 to C 30 heterocycloalkyl, substituted or unsubstituted C 3 to C 30 cycloalkenyl, substituted or unsubstituted C 6 to C 30 aryl, substituted or unsubstituted C 7 to C 30 arylalkyl, substituted or unsubstituted C 2 to C 30 hetero Cycloalkenyl, substituted or unsubstituted C 2 to C 30 heteroaryl, substituted or unsubstituted C 2 to C 30 heteroarylalkyl, substituted or unsubstituted C 1 to C 20 Alkylamino, substituted or unsubstituted C 1 to C 30 alkoxy, substituted or unsubstituted C 1 to C 30 heteroalkoxy, substituted or unsubstituted C 6 to C 30 aryloxy, substituted or non-substituted C 1 to C 20 aldehyde groups, substituted or Substituted by a C 1 to C 40 alkyl ether group, a substituted or unsubstituted C 7 to C 20 alkylene aryl ether group, substituted or non-substituted C 1 to C 30 haloalkyl, containing the P a functional group, a B-containing functional group or a combination thereof; R 2 is hydrogen, an amine group, a substituted or unsubstituted C 1 to C 30 alkoxy group, a substituted or unsubstituted C 6 to C 20 aryloxy group a base, a dialkylamino group (-NRR', R and R' are each independently a substituted or unsubstituted C 1 to C 10 alkyl group or a substituted or unsubstituted C 6 to C 10 aryl group) , hydroxy, halogen atom, allyl, sulfinyl, thiol, cyano, substituted or unsubstituted amino, substituted or unsubstituted C 1 to C 30 alkyl, substituted or Unsubstituted C 1 to C 30 heteroalkyl, substituted or unsubstituted C 2 to C 30 alkenyl, substituted or unsubstituted C 2 to C 30 alkynyl, substituted or unsubstituted C 3 to C 30 cycloalkyl, substituted or unsubstituted C 2 to C 30 heterocycloalkyl, substituted or unsubstituted C 3 to C 30 cycloalkenyl, substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 7 to C 30 aralkyl Alkyl, substituted or unsubstituted heterocyclyl C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 30 heteroaryl group, a substituted or unsubstituted C 2 to C 30 heteroaryl Alkyl, substituted or unsubstituted C 1 to C 20 alkylamino, substituted or unsubstituted C 1 to C 30 heteroalkoxy, substituted or unsubstituted C 6 to C 30 An aryloxy group, a substituted or unsubstituted C 1 to C 20 aldehyde group, a substituted or unsubstituted C 1 to C 40 alkyl ether group, a substituted or unsubstituted C 7 to C 20 aryl group An alkyl ether group, a substituted or unsubstituted C 1 to C 30 haloalkyl group, a P-containing functional group, a B-containing functional group or a combination thereof; and R 3 is selected from the group consisting of substituted or unsubstituted Any of the substituted compounds: .
舉例而言，R2 可為經取代或未經取代的C1 至C10 烷氧基。For example, R 2 can be a substituted or unsubstituted C 1 to C 10 alkoxy group.
包含由式4表示的單元的化合物可在對有機膜組成物進行烘烤之後提高有機膜的碳含量、膜密度、及硬度。在韓國專利第10-0866015號中揭露了製備所述材料的更詳細製程。The compound containing the unit represented by Formula 4 can increase the carbon content, film density, and hardness of the organic film after baking the organic film composition. A more detailed process for preparing the material is disclosed in Korean Patent No. 10-0866015.
除包含由式4表示的單元的化合物之外，根據第一實施例的所述有機膜組成物可更包含交聯組分、酸觸媒及有機溶劑中的至少一者。具體而言，根據第一實施例的所述組成物可包括1重量%至20重量%的包含由式4表示的單元的化合物、0.1重量%至5重量%的交聯組分、0.001重量%至0.05重量%的酸觸媒、及75重量%至98.8重量%的有機溶劑。The organic film composition according to the first embodiment may further contain at least one of a crosslinking component, an acid catalyst, and an organic solvent, in addition to the compound containing the unit represented by Formula 4. Specifically, the composition according to the first embodiment may include 1% by weight to 20% by weight of a compound containing a unit represented by Formula 4, 0.1% by weight to 5% by weight of a crosslinking component, 0.001% by weight Up to 0.05% by weight of acid catalyst, and 75% by weight to 98.8% by weight of organic solvent.
所述交聯組分可包含三聚氰胺樹脂（例如，N-甲氧基甲基-三聚氰胺樹脂或N-丁氧基甲基-三聚氰胺樹脂）、甲基化脲樹脂或丁基化脲樹脂、胺基樹脂、由式5表示的甘脲衍生物、由式6表示的雙環氧化合物及由式7表示的三聚氰胺衍生物中的至少一者。 ＜式5＞＜式6＞＜式7＞ The crosslinking component may comprise a melamine resin (for example, N-methoxymethyl-melamine resin or N-butoxymethyl-melamine resin), a methylated urea resin or a butylated urea resin, an amine group. At least one of a resin, a glycoluril derivative represented by Formula 5, a diepoxide compound represented by Formula 6, and a melamine derivative represented by Formula 7. <式5> <Formula 6> <Formula 7>
所述酸觸媒可包含對甲苯磺酸一水合物、吡啶對甲苯磺酸酯、2,4,4,6-四溴環己二烯酮、安息香甲苯磺酸酯、2-硝基苯甲基甲苯磺酸酯及有機磺酸的烷基酯中的至少一者。所述有機溶劑可為但不限於能夠充分溶解含經取代或未經取代的芳族基的化合物的任一有機溶劑。舉例而言，所述有機溶劑可包含丙二醇單甲醚乙酸酯、環己酮、乳酸乙酯等。The acid catalyst may comprise p-toluenesulfonic acid monohydrate, pyridine p-toluenesulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobyl At least one of a tosylate and an alkyl ester of an organic sulfonic acid. The organic solvent may be, but not limited to, any organic solvent capable of sufficiently dissolving a compound containing a substituted or unsubstituted aromatic group. For example, the organic solvent may include propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, and the like.
所述有機膜可藉由將根據第一實施例的所述有機膜組成物塗佈至500埃至4000埃的厚度然後在200℃至400℃下烘烤1秒至10分鐘來生產，但並非僅限於此。The organic film can be produced by coating the organic film composition according to the first embodiment to a thickness of 500 angstroms to 4000 angstroms and then baking at 200 ° C to 400 ° C for 1 second to 10 minutes, but not Limited to this.
在第二實施例中，所述有機膜組成物可包含由式8表示的化合物作為含經取代或未經取代的芳族基的化合物： ＜式8＞其中R4 至R9 及X1 至X6 分別獨立地為氫、羥基、鹵素原子、烯丙基、亞硫醯基、硫醇基、氰基、經取代或未經取代的胺基、經取代或未經取代的C1 至C30 烷基、經取代或未經取代的C1 至C30 雜烷基、經取代或未經取代的C2 至C30 烯基、經取代或未經取代的C2 至C30 炔基、經取代或未經取代的C3 至C30 環烷基、經取代或未經取代的C2 至C30 雜環烷基、經取代或未經取代的C3 至C30 環烯基、經取代或未經取代的C6 至C30 芳基、經取代或未經取代的C7 至C30 芳基烷基、經取代或未經取代的C2 至C30 雜環烯基、經取代或未經取代的C2 至C30 雜芳基、經取代或未經取代的C2 至C30 雜芳基烷基、經取代或未經取代的C1 至C20 烷基胺基、經取代或未經取代的C1 至C30 烷氧基、經取代或未經取代的C1 至C30 雜烷氧基、經取代或未經取代的C6 至C30 芳氧基、經取代或未經取代的C1 至C20 醛基、經取代或未經取代的C1 至C40 烷基醚基、經取代或未經取代的C7 至C20 芳基伸烷基醚基、經取代或未經取代的C1 至C30 鹵代烷基、含P的官能基、含B的官能基或其組合；且 n1 至n6 分別獨立地介於0至2的範圍且滿足2≤n1 +n2 +n3 +n4 +n5 +n6 ≤6。In the second embodiment, the organic film composition may include a compound represented by Formula 8 as a compound having a substituted or unsubstituted aromatic group: <Formula 8> Wherein R 4 to R 9 and X 1 to X 6 are each independently hydrogen, hydroxy, halogen atom, allyl, sulfinylene, thiol, cyano, substituted or unsubstituted amino group, Substituted or unsubstituted C 1 to C 30 alkyl, substituted or unsubstituted C 1 to C 30 heteroalkyl, substituted or unsubstituted C 2 to C 30 alkenyl, substituted or unsubstituted Substituted C 2 to C 30 alkynyl, substituted or unsubstituted C 3 to C 30 cycloalkyl, substituted or unsubstituted C 2 to C 30 heterocycloalkyl, substituted or unsubstituted C 3 to C 30 cycloalkenyl, substituted or unsubstituted C 6 to C 30 aryl, substituted or unsubstituted C 7 to C 30 arylalkyl, substituted or unsubstituted C 2 To a C 30 heterocycloalkenyl group, a substituted or unsubstituted C 2 to C 30 heteroaryl group, a substituted or unsubstituted C 2 to C 30 heteroarylalkyl group, a substituted or unsubstituted C 1 to C 20 alkylamino, substituted or unsubstituted C 1 to C 30 alkoxy, substituted or unsubstituted C 1 to C 30 heteroalkoxy, substituted or unsubstituted C 6 to C 30 aryloxy group, a substituted or non-substituted C 1 to C 20 aldehyde group, A substituted or non-substituted C 1 to C 40 alkyl ether group, a substituted or unsubstituted C 7 to C 20 alkylene aryl ether group, substituted or non-substituted C 1 to C 30 haloalkyl, a functional group containing P, a functional group containing B, or a combination thereof; and n 1 to n 6 are each independently in the range of 0 to 2 and satisfy 2 ≤ n 1 + n 2 + n 3 + n 4 + n 5 + n 6 ≤ 6.
舉例而言，R4 至R9 分別獨立地為經取代或未經取代的C1 至C10 烷基、經取代或未經取代的C6 至C20 芳基、經取代或未經取代的C3 至C20 環烷基、經取代或未經取代的C3 至C20 環烯基、含P的官能基或含B的官能基。For example, R 4 to R 9 are each independently a substituted or unsubstituted C 1 to C 10 alkyl group, a substituted or unsubstituted C 6 to C 20 aryl group, substituted or unsubstituted. C 3 to C 20 cycloalkyl, substituted or unsubstituted C 3 to C 20 cycloalkenyl, P-containing functional group or B-containing functional group.
舉例而言，X1 至X6 分別獨立地為氫、羥基、經取代或未經取代的C1 至C20 烷基胺基、胺基、含P的官能基或含B的官能基。For example, X 1 to X 6 are each independently hydrogen, hydroxy, substituted or unsubstituted C 1 to C 20 alkylamino, amine, P-containing or B-containing functional group.
除根據第二實施例的所述有機膜組成物包含由式8表示的化合物來替代包含由式4表示的單元的化合物作為含經取代或未經取代的芳族基的化合物之外，根據第二實施例的所述有機膜組成物實質上相同於根據第一實施例的所述有機膜組成物。因此，以下將僅詳細地闡述由式8表示的化合物。The organic film composition according to the second embodiment contains a compound represented by Formula 8 in place of a compound containing a unit represented by Formula 4 as a compound having a substituted or unsubstituted aromatic group, The organic film composition of the second embodiment is substantially the same as the organic film composition according to the first embodiment. Therefore, only the compound represented by Formula 8 will be explained in detail below.
由式8表示的化合物可為在不同位置包含取代基的二或更多種化合物的混合物。此外，由式8表示的化合物包含展現出對短波長（例如，193奈米或248奈米）的強吸收的芳香環，且因此即使在無特定觸媒的情況下仍可在高溫下進行交聯，包含由式8表示的化合物的有機膜組成物可防止因觸媒、尤其是因酸而造成的污染。由式8表示的芳族化合物可具有500克/莫耳至4,000克/莫耳的平均分子量。在此範圍內，所述有機膜組成物可形成具有合適厚度或良好特性的有機膜。The compound represented by Formula 8 may be a mixture of two or more compounds containing a substituent at different positions. Further, the compound represented by Formula 8 contains an aromatic ring exhibiting strong absorption to a short wavelength (for example, 193 nm or 248 nm), and thus can be subjected to high temperature even in the absence of a specific catalyst. The organic film composition containing the compound represented by Formula 8 can prevent contamination by a catalyst, especially due to an acid. The aromatic compound represented by Formula 8 may have an average molecular weight of from 500 g/mol to 4,000 g/mol. Within this range, the organic film composition can form an organic film having a suitable thickness or good characteristics.
由式8表示的化合物可在對有機膜組成物進行烘烤之後提高有機膜的碳含量、膜密度、及硬度。由式8表示的化合物可藉由典型方法（例如，藉由使乙醯氯、苯甲醯氯、萘甲醯氯、或環己烷羰醯氯與蔻反應、然後對所產生材料進行還原）來製備，但並非僅限於此。在韓國專利第10-1311942號中揭露了製備由式8表示的化合物的更詳細製程。The compound represented by Formula 8 can increase the carbon content, film density, and hardness of the organic film after baking the organic film composition. The compound represented by Formula 8 can be obtained by a typical method (for example, by reacting acetamidine chloride, benzamidine chloride, naphthoquinone chloride, or cyclohexanecarbonyl hydrazine with hydrazine, and then reducing the resulting material) To prepare, but not limited to this. A more detailed process for preparing the compound represented by Formula 8 is disclosed in Korean Patent No. 10-1311942.
在第三實施例中，所述有機膜組成物可包含選自以下化合物（i）、（ii）及（iii）中的含芳族基的聚合物作為含經取代或未經取代的芳族基的化合物： （i）包含由式9表示的單元的化合物； （ii）包含由式9表示的單元的化合物與包含由式10表示的單元的化合物的混合物；以及 （iii）包含由式11表示的單元的化合物。 ＜式9＞＜式10＞＜式11＞其中b、c、d及e分別獨立地為1至750；2≤c+d＜1500； R10 為選自由下式表示的經取代或未經取代的化合物中的任一者：； R11 為氫、羥基、鹵素原子、亞硫醯基、硫醇基、氰基、經取代或未經取代的胺基、經取代或未經取代的C1 至C30 烷基、經取代或未經取代的C1 至C30 雜烷基、經取代或未經取代的C2 至C30 烯基、經取代或未經取代的C2 至C30 炔基、經取代或未經取代的C3 至C30 環烷基、經取代或未經取代的C1 至C30 雜環烷基、經取代或未經取代的C3 至C30 環烯基、經取代或未經取代的C6 至C30 芳基、經取代或未經取代的C7 至C30 芳基烷基、經取代或未經取代的C1 至C20 雜烷基、經取代或未經取代的C2 至C30 雜環烯基、經取代或未經取代的C2 至C30 雜芳基、經取代或未經取代的C2 至C30 雜芳基烷基、經取代或未經取代的C1 至C20 烷基胺基、經取代或未經取代的C1 至C30 烷氧基、經取代或未經取代的C6 至C30 芳氧基、經取代或未經取代的C1 至C20 醛基、經取代或未經取代的C1 至C40 烷基醚基、經取代或未經取代的C7 至C20 芳基伸烷基醚基、經取代或未經取代的C1 至C30 鹵代烷基、含P的官能基、含B的官能基或其組合； R12 為選自由下式表示的經取代或未經取代的化合物中的一者：； R13 為選自由下式表示的經取代或未經取代的化合物中的任一者：； R14 為選自由下式表示的經取代或未經取代的化合物中一者：； R15 為選自由下式表示的經取代或未經取代的化合物中的任一者：；且 R10 、R13 、及R15 中的R分別獨立地為氫、經取代或未經取代的C1 至C30 烷基、經取代或未經取代的C1 至C30 雜烷基、經取代或未經取代的C2 至C30 烯基、經取代或未經取代的C2 至C30 炔基、經取代或未經取代的C3 至C30 環烷基、經取代或未經取代的C1 至C30 雜環烷基、經取代或未經取代的C3 至C30 環烯基、經取代或未經取代的C6 至C30 芳基、經取代或未經取代的C7 至C30 芳基烷基、經取代或未經取代的C1 至C20 雜烷基、經取代或未經取代的C2 至C30 雜環烯基、經取代或未經取代的C2 至C30 雜芳基、經取代或未經取代的C2 至C30 雜芳基烷基、經取代或未經取代的C1 至C20 烷基胺基、經取代或未經取代的C1 至C30 鹵代烷基、含P的官能基、含B的官能基或其組合。In a third embodiment, the organic film composition may comprise an aromatic group-containing polymer selected from the following compounds (i), (ii) and (iii) as a substituted or unsubstituted aromatic group a compound of the formula: (i) a compound comprising a unit represented by Formula 9; (ii) a mixture of a compound comprising a unit represented by Formula 9 and a compound comprising a unit represented by Formula 10; and (iii) comprising Formula 11 The compound of the unit indicated. <式9> <Formula 10> <Form 11> Wherein b, c, d and e are each independently from 1 to 750; 2 ≤ c + d <1500; R 10 is any one selected from the group consisting of substituted or unsubstituted compounds represented by the formula: R 11 is hydrogen, a hydroxyl group, a halogen atom, a sulfinyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C 1 to C 30 alkyl group, substituted Or unsubstituted C 1 to C 30 heteroalkyl, substituted or unsubstituted C 2 to C 30 alkenyl, substituted or unsubstituted C 2 to C 30 alkynyl, substituted or unsubstituted C 3 to C 30 cycloalkyl, substituted or unsubstituted C 1 to C 30 heterocycloalkyl, substituted or unsubstituted C 3 to C 30 cycloalkenyl, substituted or unsubstituted C 6 to C 30 aryl, substituted or unsubstituted C 7 to C 30 arylalkyl, substituted or unsubstituted C 1 to C 20 heteroalkyl, substituted or unsubstituted C 2 To a C 30 heterocycloalkenyl group, a substituted or unsubstituted C 2 to C 30 heteroaryl group, a substituted or unsubstituted C 2 to C 30 heteroarylalkyl group, a substituted or unsubstituted C 1 to C 20 alkylamino, substituted or unsubstituted C 1 to C 30 alkoxy, substituted or unsubstituted C 6 to C 30 aryloxy, substituted or unsubstituted C 1 to C 20 aldehyde group, substituted or non-substituted C 1 to C 40 alkyl ether group A substituted or unsubstituted C 7 to C 20 alkylene aryl ether group, substituted or non-substituted C 1 to C 30 haloalkyl, P-containing functional group, the functional group or combinations thereof containing the B; R & lt 12 is one selected from the group consisting of substituted or unsubstituted compounds represented by the following formula: ; R 13 is any one selected from the group consisting of substituted or unsubstituted compounds represented by the formula: ; R 14 is one selected from the group consisting of substituted or unsubstituted compounds represented by the formula: ; R 15 is any one selected from the group consisting of substituted or unsubstituted compounds represented by the formula: And R in R 10 , R 13 , and R 15 are each independently hydrogen, substituted or unsubstituted C 1 to C 30 alkyl, substituted or unsubstituted C 1 to C 30 heteroalkyl , substituted or unsubstituted C 2 to C 30 alkenyl, substituted or unsubstituted C 2 to C 30 alkynyl, substituted or unsubstituted C 3 to C 30 cycloalkyl, substituted or Unsubstituted C 1 to C 30 heterocycloalkyl, substituted or unsubstituted C 3 to C 30 cycloalkenyl, substituted or unsubstituted C 6 to C 30 aryl, substituted or unsubstituted Substituted C 7 to C 30 arylalkyl, substituted or unsubstituted C 1 to C 20 heteroalkyl, substituted or unsubstituted C 2 to C 30 heterocycloalkenyl, substituted or unsubstituted Substituted C 2 to C 30 heteroaryl, substituted or unsubstituted C 2 to C 30 heteroarylalkyl, substituted or unsubstituted C 1 to C 20 alkylamino, substituted or not Substituted C 1 to C 30 haloalkyl, P containing functional group, B containing functional group or a combination thereof.
除根據第三實施例的所述有機膜組成物包含含芳族基的聚合物來替代包含由式4表示的單元的化合物作為含經取代或未經取代的芳族基的化合物之外，根據第三實施例的所述有機膜組成物實質上相同於根據第一實施例的所述有機膜組成物。因此，以下將僅詳細地闡述含芳族基的聚合物。The organic film composition according to the third embodiment contains an aromatic group-containing polymer instead of the compound containing the unit represented by Formula 4 as a compound having a substituted or unsubstituted aromatic group, according to The organic film composition of the third embodiment is substantially the same as the organic film composition according to the first embodiment. Therefore, only the aromatic group-containing polymer will be explained in detail below.
所述含芳族基的聚合物可在對有機膜組成物進行烘烤之後提高有機膜的碳含量、膜密度及硬度，且可藉由典型方法來製備。在韓國專利第10-0908601號中揭露了更詳細內容。The aromatic group-containing polymer can increase the carbon content, film density and hardness of the organic film after baking the organic film composition, and can be prepared by a typical method. More details are disclosed in Korean Patent No. 10-0908601.
在第四實施例中，所述有機膜組成物可包含選自以下中的至少兩者作為含經取代或未經取代的芳族基的化合物：包含由式4表示的單元的化合物；由式8表示的化合物；以及選自化合物（i）、（ii）及（iii）中的含芳族基的聚合物。除根據第四實施例的所述有機膜組成物包含以上所述的化合物中的至少兩者之外，根據第四實施例的所述有機膜組成物實質上相同於根據第一實施例的所述有機膜組成物。研磨有機膜的方法 In the fourth embodiment, the organic film composition may include at least two selected from the group consisting of a compound having a substituted or unsubstituted aromatic group: a compound containing a unit represented by Formula 4; a compound represented by 8; and an aromatic group-containing polymer selected from the group consisting of compounds (i), (ii) and (iii). The organic film composition according to the fourth embodiment is substantially the same as the first embodiment except that the organic film composition according to the fourth embodiment contains at least two of the above-described compounds An organic film composition. Method of grinding organic film
接下來，將闡述根據本發明的一種研磨有機膜的方法。Next, a method of grinding an organic film according to the present invention will be explained.
根據本發明的所述研磨有機膜的方法可包括：研磨具有高碳含量的有機膜，其中所述用於有機膜的CMP漿料組成物可包括根據本發明的實施例的所述用於有機膜的CMP漿料組成物。The method of polishing an organic film according to the present invention may include: grinding an organic film having a high carbon content, wherein the CMP slurry composition for an organic film may include the organic layer according to an embodiment of the present invention The CMP slurry composition of the film.
圖1（a）是具有矽晶圓、無機層及有機碳層的堆疊結構的有機膜的剖視圖，其中將矽晶圓100圖案化成具有雕刻圖案。所述有機膜是藉由以下方式來製作：在矽晶圓100上沈積無機膜110、在所述無機膜上形成有機膜120、然後在200℃至400℃下進行烘烤。圖1（a）中的虛線T指示假想研磨終止線。在將用於有機膜的CMP漿料組成物塗佈至圖1（a）中所示的有機膜上後，在所述CMP漿料組成物上放置研磨墊，然後藉由使矽晶圓100旋轉來研磨所述有機膜直至研磨終止線T，藉此獲得其中所述有機膜經研磨的矽晶圓，如在圖（1）b中所示。1(a) is a cross-sectional view of an organic film having a stacked structure of a germanium wafer, an inorganic layer, and an organic carbon layer, in which the germanium wafer 100 is patterned to have an engraved pattern. The organic film is formed by depositing an inorganic film 110 on the germanium wafer 100, forming an organic film 120 on the inorganic film, and then baking at 200 ° C to 400 ° C. A broken line T in Fig. 1(a) indicates a virtual polishing end line. After the CMP slurry composition for the organic film is applied onto the organic film shown in FIG. 1(a), a polishing pad is placed on the CMP slurry composition, and then the wafer 100 is patterned. The organic film was rotated to grind the termination line T, thereby obtaining a germanium wafer in which the organic film was ground, as shown in Fig. (1)b.
接著，將參照某些實例更詳細地闡述本發明。應理解，提供該些實例僅是為了說明，且不應被視為以任何方式限制本發明。製備實例 有機膜 組成物的製備 Next, the present invention will be explained in more detail with reference to certain examples. The examples are provided for illustrative purposes only and are not to be considered as limiting the invention in any way. Preparation of an example organic film composition
將包括溫度計、冷凝器、機械攪拌器及滴液漏斗的2,000毫升3頸燒瓶浸入140℃下的油浴中。藉由磁體在加熱板上執行加熱及攪拌，且將冷凝器中冷卻水的溫度設定為40℃。向反應器中添加220克1.0莫耳1-甲氧基芘及138克1.0莫耳1,4-雙甲氧基甲基苯，且然後溶解於656克丙二醇單甲醚乙酸酯中。其後，向反應器中添加4.6克0.03莫耳硫酸二乙酯。使反應器的溫度維持於130℃。藉由在聚合期間以定期時間間隔量測反應產物的分子量來確定反應完成點。此處，藉由以下方式來製備用於量測分子量的樣本：將1克反應產物驟冷至室溫，然後以四氫呋喃作為溶劑來稀釋0.02克反應產物，以使得所述溶液具有4重量%的固體含量。為在反應完成點處完成反應，向反應器中添加4.48克0.03莫耳三乙醇胺作為中和劑，然後對所述組分進行攪拌。接下來，將反應產物緩慢冷卻至室溫。以500克丙二醇單甲醚乙酸酯來稀釋所述反應產物。接著，向2,000毫升分液漏斗中添加溶劑。製備了比率為90:10克/克的甲醇與乙二醇的混合物4千克。在劇烈攪拌下向醇混合物中逐滴地添加所合成聚合物溶液。自燒瓶的底面得到生成的聚合物，且將上清液分開儲存。在移除上清液之後，藉由在減壓下在60℃下進行旋轉蒸發10分鐘而自最終反應產物移除甲醇。A 2,000 ml 3-neck flask including a thermometer, a condenser, a mechanical stirrer, and a dropping funnel was immersed in an oil bath at 140 °C. Heating and stirring were performed on the hot plate by a magnet, and the temperature of the cooling water in the condenser was set to 40 °C. To the reactor were added 220 g of 1.0 mol of 1-methoxyindole and 138 g of 1.0 mol of 1,4-bismethoxymethylbenzene, and then dissolved in 656 g of propylene glycol monomethyl ether acetate. Thereafter, 4.6 g of 0.03 mol of diethyl sulfate was added to the reactor. The temperature of the reactor was maintained at 130 °C. The reaction completion point was determined by measuring the molecular weight of the reaction product at regular intervals during the polymerization. Here, a sample for measuring molecular weight was prepared by quenching 1 g of the reaction product to room temperature, and then diluting 0.02 g of the reaction product with tetrahydrofuran as a solvent so that the solution had 4 wt% Solid content. To complete the reaction at the reaction completion point, 4.48 g of 0.03 mol triethanolamine was added to the reactor as a neutralizing agent, and then the components were stirred. Next, the reaction product was slowly cooled to room temperature. The reaction product was diluted with 500 g of propylene glycol monomethyl ether acetate. Next, a solvent was added to a 2,000 ml separatory funnel. A mixture of methanol and ethylene glycol at a ratio of 90:10 g/g was prepared at 4 kg. The synthesized polymer solution was added dropwise to the alcohol mixture with vigorous stirring. The resulting polymer was obtained from the bottom surface of the flask, and the supernatant was separately stored. After the supernatant was removed, methanol was removed from the final reaction product by rotary evaporation at 60 ° C for 10 minutes under reduced pressure.
藉由使用四氫呋喃的凝膠滲透層析法（GPC）來量測所得共聚物的分子量及分散度。結果，獲得了包含由式12表示的單元且具有4,000克/莫耳的重量平均分子量及2.3的分散度的聚合物。 ＜式12＞其中a平均為11，且Me為甲基。The molecular weight and dispersion of the obtained copolymer were measured by gel permeation chromatography (GPC) using tetrahydrofuran. As a result, a polymer comprising the unit represented by Formula 12 and having a weight average molecular weight of 4,000 g/mol and a degree of dispersion of 2.3 was obtained. <Formula 12> Where a is an average of 11, and Me is a methyl group.
將0.8克所製備聚合物、0.2克由式4表示的交聯劑（保徳林克（Powderlink）1174，氰特工業公司（Cytec Industries Inc.））、及2毫克吡啶對甲苯磺酸酯溶解於9克丙二醇單甲醚乙酸酯中，然後過濾所述溶液，藉此製備有機膜組成物。有機膜 的製備 0.8 g of the prepared polymer, 0.2 g of a crosslinking agent represented by Formula 4 (Powderlink 1174, Cytec Industries Inc.), and 2 mg of pyridine p-toluenesulfonate were dissolved. In an amount of 9 g of propylene glycol monomethyl ether acetate, the solution was then filtered, whereby an organic film composition was prepared. Preparation of organic film
在具有雕刻圖案的圖案化晶圓的表面上沈積5,000埃厚的氧化矽層作為研磨終止層，然後形成2,650埃厚的有機膜以填充所述氧化矽層的表面上的雕刻圖案。所述有機膜是藉由將製備實例1的有機膜組成物塗佈至氧化矽層上然後在400℃下進行烘烤來生產。A 5,000 angstrom thick yttria layer was deposited as a polishing stop layer on the surface of the patterned wafer having the engraved pattern, and then an organic film of 2,650 angstroms thick was formed to fill the engraved pattern on the surface of the yttrium oxide layer. The organic film was produced by coating the organic film composition of Preparation Example 1 onto a ruthenium oxide layer and then baking at 400 °C.
施加在製備實例1中所製備的有機膜組成物並在400℃下烘烤120秒以獲得具有4,700埃至4,800埃的厚度的樣品。使用奈米硬度計（海思創（Hysitron）TI750 Ubi）來量測所述樣品的硬度。具體而言，藉由將奈米硬度計的尖端裝載於樣品上達5秒、保持所述尖端2秒、並在5秒內卸載所述尖端來量測硬度。所述樣品具有0.9十億帕的硬度。使用元素分析儀（EA1112，賽默有限公司（Thermo Co., Ltd.））對同一樣品量測碳含量。具體而言，藉由在O2 的存在下燃燒精確量的樣品來量測所述碳含量。所述樣品具有72原子%的碳含量。使用X射線反射率（X-ray reflectivity，XRR）測試儀（X'Pert PRO，帕納科有限公司（PANalytical Co., Ltd.））對同一樣品量測膜密度。具體而言，藉由將所述樣品的經由X射線照射而獲得的繞射圖案與已知繞射圖案進行比較來量測膜密度。所述樣品具有1.4克/立方公分的膜密度。對同一樣品量測酸值。所述樣品具有0毫克KOH/克的酸值。實例 1 至實例 2 及比較例 1 至比較例 4 The organic film composition prepared in Preparation Example 1 was applied and baked at 400 ° C for 120 seconds to obtain a sample having a thickness of 4,700 Å to 4,800 Å. The hardness of the sample was measured using a nano hardness tester (Hysitron TI750 Ubi). Specifically, the hardness was measured by loading the tip of the nanometer durometer on the sample for 5 seconds, holding the tip for 2 seconds, and unloading the tip within 5 seconds. The sample has a hardness of 0.9 billion Pascals. The carbon content was measured on the same sample using an elemental analyzer (EA1112, Thermo Co., Ltd.). Specifically, the carbon content is measured by burning a precise amount of the sample in the presence of O 2 . The sample had a carbon content of 72 atom%. The film density was measured for the same sample using an X-ray reflectivity (XRR) tester (X'Pert PRO, PANalytical Co., Ltd.). Specifically, the film density is measured by comparing a diffraction pattern obtained by X-ray irradiation of the sample with a known diffraction pattern. The sample had a film density of 1.4 g/cm 3 . Measure the acid value for the same sample. The sample had an acid number of 0 mg KOH/g. Example 1 to Example 2 and Comparative Example 1 to Comparative Example 4
製備包含表1中列出的組分的CMP漿料組成物（單位：以所述組成物的總量計的重量%），且在以下條件下對包括氧化矽層及有機膜的圖案化晶圓進行研磨。（ 1 ） CMP 漿料組成 物的組分的詳細內容 A CMP slurry composition (unit: wt% based on the total amount of the composition) containing the components listed in Table 1 was prepared, and patterned crystals including a ruthenium oxide layer and an organic film under the following conditions The circle is ground. ( 1 ) Details of the components of the CMP slurry composition
（A）磨料 （a1）使用具有60奈米的平均粒徑的膠體氧化鈰（蘇威有限公司（SOLVAY Co., Ltd.））。 （a2）使用具有30奈米的平均粒徑的膠體氧化鈰（扶桑有限公司（FUSO Co., Ltd.））。(A) Abrasive (a1) Colloidal cerium oxide (SOLVAY Co., Ltd.) having an average particle diameter of 60 nm was used. (a2) A colloidal cerium oxide (FUSO Co., Ltd.) having an average particle diameter of 30 nm was used.
（B）還原劑 （b1）使用硝酸鈰（奧德裏奇有限公司（Aldrich Co., Ltd.））。 （b2）使用三氯化鈦（關東有限公司（KANTO Co., Ltd.））。(B) Reducing agent (b1) A cerium nitrate (Aldrich Co., Ltd.) was used. (b2) Use of titanium trichloride (KANTO Co., Ltd.).
（C）pH調節劑：使用硝酸（三電化學有限公司（Samchun Chemical Co., Ltd.））。（ 2 ）研磨條件以及研磨速率及選擇性比的量測 (C) pH adjuster: Nitric acid (Samchun Chemical Co., Ltd.) was used. ( 2 ) Grinding conditions and measurement of polishing rate and selectivity ratio
使用H0800 CMP墊（富士紡有限公司（FUJIBO Co., Ltd.））作為研磨墊。在0.8磅/平方英吋（psi）的壓縮壓力、200毫升/分鐘的漿料流率、60轉/分鐘的工作台速度、及55轉/分鐘的磁頭速度的條件下，使用200毫米米拉（MIRRA）研磨機（應用材料（AMAT）有限公司）來執行研磨1分鐘，然後量測研磨速率。結果示於表1中。在研磨所述有機膜之後，使用薄膜厚度量測儀器（ST4000，科美儀器有限公司（K-MAC Co., Ltd.））在經研磨膜的經研磨表面上量測經研磨膜的厚度（單位：埃），然後根據所量測厚度來計算研磨速率（單位：埃/分鐘）。基於所量測研磨速率藉由方程式1來計算選擇性比： 選擇性比= α/β ---（1） 其中α是對有機膜的研磨速率（埃/分鐘）且β是對無機膜的研磨速率（埃/分鐘）。 表1
如表1所示，可以看出，包含氧化鈰及硝酸鈰的實例1及實例2的漿料組成物具有對有機膜的高研磨速率及有機膜相對於無機膜的高選擇性比。As shown in Table 1, it can be seen that the slurry compositions of Examples 1 and 2 containing cerium oxide and cerium nitrate have a high polishing rate to the organic film and a high selectivity ratio of the organic film to the inorganic film.
相反，可以看出，不包含氧化鈰或硝酸鈰的比較例1至比較例4的漿料組成物具有對有機膜的低研磨速率及有機膜相對於無機膜的低選擇性比。On the contrary, it can be seen that the slurry compositions of Comparative Examples 1 to 4 which do not contain cerium oxide or cerium nitrate have a low polishing rate to the organic film and a low selectivity ratio of the organic film to the inorganic film.
應理解，在不背離本發明的精神及範圍的條件下，熟習此項技術者可做出各種潤飾、改變、變更及等效實施例。It will be appreciated that various modifications, changes, alterations and equivalents may be made by those skilled in the art without departing from the spirit and scope of the invention.
100‧‧‧矽晶圓
110‧‧‧無機膜
120‧‧‧有機膜
T‧‧‧研磨終止線100‧‧‧矽 wafer
110‧‧‧Inorganic film
120‧‧‧ Organic film
T‧‧‧Making termination line
圖1（a）及圖1（b）是根據本發明的一個實施例的一種研磨有機膜的方法的圖。1(a) and 1(b) are views of a method of polishing an organic film according to an embodiment of the present invention.
100‧‧‧矽晶圓 100‧‧‧矽 wafer
110‧‧‧無機膜 110‧‧‧Inorganic film
120‧‧‧有機膜 120‧‧‧ Organic film
T‧‧‧研磨終止線 T‧‧‧Making termination line
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| US3240580A (en) * | 1961-04-03 | 1966-03-15 | Libbey Owens Ford Glass Co | Glass polishing compositions of rare earth nitrates |
| GB1145224A (en) * | 1967-04-04 | 1969-03-12 | Libbey Owens Ford Glass Co | Glass polishing |
| FR2604443A1 (en) * | 1986-09-26 | 1988-04-01 | Rhone Poulenc Chimie | CERIUM POLISHING COMPOSITION FOR POLISHING ORGANIC GLASSES |
| US7887714B2 (en) * | 2000-12-25 | 2011-02-15 | Nissan Chemical Industries, Ltd. | Cerium oxide sol and abrasive |
| US6589100B2 (en) * | 2001-09-24 | 2003-07-08 | Cabot Microelectronics Corporation | Rare earth salt/oxidizer-based CMP method |
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