TW202003730A - 塗佈膜形成組成物及半導體裝置之製造方法 - Google Patents
塗佈膜形成組成物及半導體裝置之製造方法 Download PDFInfo
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- TW202003730A TW202003730A TW108111847A TW108111847A TW202003730A TW 202003730 A TW202003730 A TW 202003730A TW 108111847 A TW108111847 A TW 108111847A TW 108111847 A TW108111847 A TW 108111847A TW 202003730 A TW202003730 A TW 202003730A
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- Prior art keywords
- coating film
- mass
- forming composition
- propylene glycol
- insulating layer
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- 238000000576 coating method Methods 0.000 title claims abstract description 74
- 239000011248 coating agent Substances 0.000 title claims abstract description 67
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- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims abstract description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims abstract description 6
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- XYVQFUJDGOBPQI-UHFFFAOYSA-N Methyl-2-hydoxyisobutyric acid Chemical compound COC(=O)C(C)(C)O XYVQFUJDGOBPQI-UHFFFAOYSA-N 0.000 claims abstract description 4
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 claims abstract description 4
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- 229910052802 copper Inorganic materials 0.000 claims description 15
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Chemical group CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- 229910021426 porous silicon Inorganic materials 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- -1 halide ion Chemical class 0.000 claims description 5
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 claims description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 4
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- 239000012433 hydrogen halide Chemical group 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical group O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 3
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 3
- 125000005372 silanol group Chemical group 0.000 claims description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical group NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 abstract description 15
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- 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 6
- 229920001577 copolymer Polymers 0.000 description 6
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- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- QNVNLUSHGRBCLO-UHFFFAOYSA-N 5-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 0.000 description 2
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- 239000002202 Polyethylene glycol Substances 0.000 description 2
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- 238000007611 bar coating method Methods 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
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- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
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- H—ELECTRICITY
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- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/32—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers using masks
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- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
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Abstract
本發明提供塗佈膜形成組成物及使用其之半導體裝置之製造方法,該塗佈膜形成組成物包含:(a)含有以下述式(1a)或(1b)表示之構造單位之聚合物,以及(b)溶劑,其含有1~49質量%之選自由丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚、2-羥基異丁酸甲酯、3-乙氧基丙酸乙酯及乳酸乙酯所成之群中之至少1種有機溶劑及51~99質量%之水。
Description
本發明有關塗佈膜形成組成物及半導體裝置之製造方法。
於進展微細化之半導體裝置的領域中,為了防止作為配線材料而嵌埋入半導體之層間絕緣層之銅等的金屬成分擴散,提案有形成樹脂層(專利文獻1)。然而,要求不於配線上形成樹脂層之方式,維持配線表面之電性連接。非專利文獻1中記載,使用包含聚伸乙基亞胺且以甲酸調整pH之組成物,可於SiO2
上選擇性形成有機膜。
[先前技術文獻]
[專利文獻]
[專利文獻1] 國際公開第2010/137711號
[非專利文獻]
[非專利文獻1] J. Phys. Chem. C 2015, 119, 22882-22888
[發明欲解決之課題]
非專利文獻1中記載之技術,必須於組成物中添加作為pH調整劑之甲酸。甲酸由於在日本係被指定為有毒及有害物質取締法中之有害物質,故包含甲酸之材料的使用不適於工業化。
本發明係鑒於前述情況而完成者,目的在於提供不使用甲酸等之使用受限制之化學物質,而可於具有包含銅之配線層與以氧化矽等為代表之絕緣層之基板上的該絕緣層上選擇性形成塗佈膜之塗佈膜形成組成物、以及使用其之半導體裝置之製造方法。
[用以解決課題之手段]
本發明人等為達成前述目的而重複積極檢討之結果,發現藉由包含特定二烯丙胺系聚合物及特定有機溶劑與水之混合溶劑之組成物,可解決上述課題,因而完成本發明。
亦即,本發明提供下述塗佈膜形成組成物及半導體裝置之製造方法。
1. 一種塗佈膜形成組成物,其包含
(a)含有以下述式(1a)或(1b)表示之構造單位之聚合物,以及
(b)溶劑,其含有1~49質量%之選自由丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚、2-羥基異丁酸甲酯、3-乙氧基丙酸乙酯及乳酸乙酯所成之群中之至少1種有機溶劑及51~99質量%之水,
(式中,X為乙酸、丙酸、胺基磺酸或鹵化氫,Y-
為硫酸氫離子、硫酸甲酯離子、硫酸乙酯離子或鹵化物離子,R1
為氫原子或甲基,R2
及R3
分別獨立為甲基或乙基)。
2. 如1之塗佈膜形成組成物,其中前述聚合物進而含有以下述式(2)表示之構造單位,。
3. 如1或2之塗佈膜形成組成物,其中(b)溶劑含有1~30質量%之前述有機溶劑及70~99質量%之水。
4. 一種半導體裝置之製造方法,其包含將如1至3中任一項之塗佈膜形成組成物塗佈於形成有絕緣層及包含銅之配線層的基板上之該絕緣層及該配線層之表面,進行烘烤而形成塗佈膜之步驟,及使用水選擇性去除前述配線層上之該塗佈膜之步驟。
5. 如4之半導體裝置之製造方法,其中前述絕緣層係以SiO2
為主成分。
6. 如4或5之半導體裝置之製造方法,其中前述絕緣層係以多孔質氧化矽為主成分,於其表面具有源自前述多孔質氧化矽之矽烷醇殘基。
[發明效果]
本發明之塗佈膜形成組成物由於不含甲酸等之使用受限制之化學物質,故工業上可使用。又,藉由使用本發明之塗佈膜形成組成物,可以簡便方法於絕緣層上選擇性形成塗佈膜。
式(1a)中,X為乙酸、丙酸、胺基磺酸或鹵化氫。作為前述鹵化氫較好為氯化氫、溴化氫、碘化氫等。作為X較好為乙酸或胺基磺酸。
式(1b)中,Y-
為硫酸氫離子、硫酸甲酯離子、硫酸乙酯離子或鹵化物離子。作為前述鹵化物離子舉例為氯化物離子、溴化物離子、碘化物離子等。作為Y-
較好為硫酸乙酯離子。
式(1a)中,R1
為氫原子或甲基。式(1b)中,R2
及R3
分別獨立為甲基或乙基)。
前述聚合物為含有以式(1a)或(1b)表示之構造單位與以式(2)表示之構造單位的共聚物時,該共聚物可為以式(1a)或(1b)表示之構造單位與以式(2)表示之構造單位交替鍵結的交替共聚物,亦可為該等構造單位無規鍵結之無規共聚物,但特佳為交替共聚物。
前述聚合物亦可含有前述構造單位以外之構造單位(以下稱為其他構造單位)。作為其他構造單位,舉例為例如源自(甲基)丙烯醯胺者、源自烯丙胺、N-甲基烯丙胺、N,N-二甲基烯丙胺等之單烯丙胺者、源自單烯丙胺之乙酸鹽、鹽酸鹽、氫溴酸鹽、丙酸、胺基磺酸等之酸加成鹽者。
(a)成分之聚合物為前述共聚物時,以式(1a)或(1b)表示之構造單位與以式(2)表示之構造單位之含有比,以莫耳計,較好為99/1~50/50之範圍附近,更好為90/10~50/50之範圍附近,再更好為50/50或其附近。又,含有其他構成單位時,其含有比例,於全構成單位中,通常為10莫耳%以下,但較好為5莫耳%以下。
(a)成分之聚合物的重量平均分子量(Mw)較好為300~1,000,000,更好為500~500,000,又更好為800~100,000,再更好為1,000~ 50,000。又,本發明中(a)成分之聚合物的Mw係藉由凝膠滲透層析(GPC)所得之聚乙二醇換算測定值。
作為(a)成分之聚合物可藉以往習知方法合成,或可使用市售品。作為前述市售品舉例為NITTOBO MEDICAL(股)製之PAA-D11-HCL、PAA-D41-HCL、PAA-D19-HCL、PAA-D19A、PAS-21CL、PAS-M-1L、PAS-M-1、PAS-22SA-40、PAS-M-1A、PAS-H-1L、PAS-H-5L、PAS-H-10L、PAS-24、PAS-92、PAS-92A、PAS-2401、PAS-2201CL、PAS-A-1、PAS-A-5、PAS-2141CL、PAS-J-81L、PAS-J-81、PAS-J-41、PAS-880等。
本發明之組成物中,(a)成分之含量,基於成膜性之觀點,較好為0.1~20質量%,更好為1~5質量%。
[(b)溶劑]
(b)成分之溶劑係含有1~49質量%之選自由丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚、2-羥基異丁酸甲酯、3-乙氧基丙酸乙酯及乳酸乙酯所成之群中之至少1種有機溶劑及51~99質量%之水者。前述有機溶劑之含量若未達1質量%,則有塗佈性降低之情況,若超過49質量%,則有(a)成分之聚合物溶解度降低之情況。
作為前述有機溶劑,較好為丙二醇單甲醚或丙二醇單甲醚乙酸酯,更好為丙二醇單甲醚。
(b)溶劑中,前述有機溶劑之含量較好為1~30質量%,更好為5~25質量%,又更好為10~20質量%。水之含量,較好為70~99質量%,更好為75~95質量%,又更好為80~90質量%。
[其他成分]
本發明之組成物,於不損及本發明效果之範圍內,亦可含有前述成分以外之成分(以下稱為其他成分)。作為其他成分,舉例為界面活性劑等之各種添加劑。界面活性劑係用以提高本發明之組成物對基板之塗佈性的添加物。作為界面活性劑,可使用如非離子系界面活性劑、氟系界面活性劑之習知界面活性劑。
[半導體裝置之製造方法]
本發明之半導體裝置之製造方法係包含將前述塗佈膜形成組成物塗佈於形成有絕緣層及包含銅之配線層(以下稱為銅配線層)的基板上之該絕緣層及該銅配線層之表面,進行烘烤而形成塗佈膜之步驟,及使用水選擇性去除前述銅配線層上之該塗佈膜之步驟者。
作為前述絕緣層舉例為例如含有SiO2
者、或含有多孔質氧化矽、SiOF、SiCO、氫化倍半矽氧烷、甲基化倍半矽氧烷等之low-k材料者。前述絕緣層於該等中較好為以SiO2
為主成分者,或以多孔質氧化矽為主成分,且其表面具有源自前述多孔質氧化矽之矽烷醇基者。又,本發明中之主成分意指含有比率最大之成分。
作為形成有前述絕緣層與銅配線層之基板舉例為例如於矽等之半導體基板上之絕緣層上所形成之圖型上,以電解鍍敷等方法形成銅配線,藉由化學機械研磨(CMP)平坦化而獲得者。且作為形成有前述絕緣層與銅配線層之基板,亦舉例有CMP後,進而設置絕緣層等而多層化,形成溝槽或通孔者。
作為塗佈前述塗佈膜形成組成物之方法,使用以往習知方法即可,舉例為旋轉塗佈法、澆鑄塗佈法、刮板塗佈法、浸漬塗佈法、輥塗佈法、棒塗佈法、模嘴塗佈法、噴墨法、印刷法等。
將前述塗佈膜形成組成物塗佈於基板上之該絕緣層及該銅配線層之表面後,進行烘烤而形成塗佈膜。此時,烘烤溫度較好為50~300℃,更好為70~250℃。又,烘烤時間較好為10秒~10分鐘,更好為30秒~2分鐘。
所得塗佈膜之厚度較好為0.1~200nm,更好為1~100nm。
形成塗佈膜後,使用水選擇性去除前述銅配線層上之該塗佈膜。塗佈膜之去除方法舉例為將水塗佈於前述塗佈膜上,將前述銅配線層上之該塗佈膜溶解、去除之方法。此時,作為水的塗佈方法,舉例為旋轉塗佈法、澆鑄塗佈法、刮板塗佈法、浸漬塗佈法、輥塗佈法、棒塗佈法、模嘴塗佈法、噴墨法、印刷法等。
藉由上述說明之方法,可於絕緣層表面選擇性形成有機膜。前述有機膜具有防止配線之金屬成分朝絕緣層擴散,且作為絕緣層之保護膜等功能。
[實施例]
以下,舉例合成例及實施例更詳細說明本發明,但本發明不限定於下述實施例。
[合成例1]
於丙二醇單甲醚35.60g中添加對苯二甲酸二縮水甘油酯(NAGASE CHEMTEX(股)製,DENACOL(註冊商標) EX711) 5.00g、5-羥基間苯二甲酸(東京化成工業(股)製) 3.15g及氯化苄基三乙銨(東京化成工業(股)製) 0.20g,予以溶解。反應容器經氮氣置換後,於135℃反應4小時,獲得聚合物溶液。該聚合物對於丙二醇單甲醚之溶解性良好,該溶液即使冷卻至室溫亦不產生白濁。進行GPC分析(溶離液:四氫呋喃,校正線:標準聚苯乙烯)後,所得溶液中之聚合物的Mw為15,673,分散度為3.39。本合成例所得之聚合物係具有以下述式(3)表示之構造單位及以下述式(4)表示之構造單位者。
[1]塗佈膜形成組成物之調製
[實施例1-1]
於包含二烯丙胺乙酸鹽・二氧化硫共聚物0.15g之水溶液(NITTOBO MEDICAL(股)製,PAS-92A) 0.80g中,添加超純水11.2g及丙二醇單甲醚3g,製作塗佈膜形成組成物A。
[比較例1-1]
於合成例1所得之含聚合物固形分0.24g之聚合物溶液1.3g中,添加聚乙二醇單甲醚12.8g及丙二醇單甲醚乙酸酯5.9g,製作塗佈膜形成組成物B。本比較例之塗佈膜形成組成物B中包含之聚合物並不相當於含有以前述式(1a)或(1b)表示之構造單位的聚合物。
[比較例1-2]
於包含二烯丙胺乙酸鹽・二氧化硫共聚物0.15g之水溶液(NITTOBO MEDICAL(股)製,PAS-92A) 0.80g中,添加超純水14.2g,製作塗佈膜形成組成物C。本比較例之塗佈膜形成組成物C中包含之溶劑係有機溶劑含量未達1質量%(0質量%)。
[比較例1-3]
於包含二烯丙胺乙酸鹽・二氧化硫共聚物0.15g之水溶液(NITTOBO MEDICAL(股)製,PAS-92A) 0.80g中,添加超純水6.8g及丙二醇單甲醚7.4g,製作塗佈膜形成組成物。但,本比較例所製作之塗佈膜形成組成物發生聚合物沉澱。本比較例之塗佈膜形成組成物中包含之溶劑係有機溶劑含量超過49質量%。
[2]塗佈膜形成評價
對於以300nm厚蒸鍍氧化矽之基板(以下稱為SiO2
基板),使用SAMCO(股)製之蝕刻機進行10分鐘、O2
灰化。隨後,所得SiO2
基板切成3cm見方,使用於對絕緣層之塗佈性評價。且,使用接觸角計DM-701(協和界面科學(股)製),測定前述SiO2
基板之水接觸角,作為膜形成前之水接觸角。
將以100nm厚蒸鍍銅之基板(以下稱為Cu基板)於0.5mol/L硫酸溶液中浸漬5分鐘,隨後以超純水洗淨,乾燥。隨後,所得Cu基板切成3cm見方,使用於對絕緣層之塗佈性評價。且,使用接觸角計DM-701(協和界面科學(股)製),測定前述Cu基板之水接觸角,作為膜形成前之水接觸角。
[實施例2-1]
使用旋轉塗佈器(BREWER SCIENCE公司製)將塗佈膜形成組成物A塗佈於切成3cm見方之前述SiO2
基板及Cu基板上,於100℃烘烤60秒,形成塗佈膜。隨後,於前述塗佈膜上使用旋轉塗佈器(BREWER SCIENCE公司製)塗佈超純水,保持60秒,去除前述SiO2
基板及Cu基板上之塗佈膜後,使用接觸角計DM-701(協和界面科學(股)製),測定水接觸角。結果示於表1。
[比較例2-1]
使用旋轉塗佈器(BREWER SCIENCE公司製)將塗佈膜形成組成物B塗佈於切成3cm見方之前述SiO2
基板及Cu基板上,於100℃烘烤60秒,形成塗佈膜。隨後,於前述塗佈膜上使用旋轉塗佈器(BREWER SCIENCE公司製)塗佈丙二醇單甲醚/丙二醇單甲醚乙酸酯=7/3(質量比),保持60秒,去除前述SiO2
基板及Cu基板上之塗佈膜後,使用接觸角計DM-701(協和界面科學(股)製),測定水接觸角。結果示於表1。
[實施例2-2]
除了將烘烤溫度設為200℃以外,以與實施例2-1同樣的方法測定水接觸角。結果示於表2。
[比較例2-2]
除了將烘烤溫度設為200℃以外,以與比較例2-1同樣的方法測定水接觸角。結果示於表2。
[比較例2-3]
欲將塗佈膜形成組成物C藉由前述方法塗佈於前述SiO2
基板及Cu基板上,但於任一基板均無法均勻塗佈。
由實施例2-1及2-2顯示使用本發明之塗佈膜形成組成物A於SiO2
基板上形成塗佈膜時,於該塗佈膜形成前後,接觸角產生變化,故藉由水並未去除該塗佈膜,而殘留於SiO2
基板上。另一方面,於Cu基板上形成塗佈膜時,於該塗佈膜形成前後,接觸角幾乎未變化,故顯示藉由水去除該塗佈膜。
由比較例2-1及2-2顯示塗佈膜形成組成物B於Cu基板上形成塗佈膜時,於其形成前後,接觸角產生變化,故藉由丙二醇單甲醚/丙二醇單甲醚乙酸酯=7/3(質量比)並未去除該塗佈膜,而殘留於Cu基板上。亦即,顯示由塗佈膜形成組成物B所得之塗佈膜無法藉由丙二醇單甲醚/丙二醇單甲醚乙酸酯=7/3(質量比)自Cu基板上去除。
由以上結果顯示,藉由使用本發明之組成物,可於絕緣層上選擇性形成塗佈膜。
Claims (6)
- 如請求項1或2之塗佈膜形成組成物,其中(b)溶劑含有1~30質量%之前述有機溶劑及70~99質量%之水。
- 一種半導體裝置之製造方法,其包含將如請求項1至3中任一項之塗佈膜形成組成物塗佈於形成有絕緣層及包含銅之配線層的基板上之該絕緣層及該配線層之表面,進行烘烤而形成塗佈膜之步驟,及使用水選擇性去除前述配線層上之該塗佈膜之步驟。
- 如請求項4之半導體裝置之製造方法,其中前述絕緣層係以SiO2 為主成分。
- 如請求項4或5之半導體裝置之製造方法,其中前述絕緣層係以多孔質氧化矽為主成分,於其表面具有源自前述多孔質氧化矽之矽烷醇殘基。
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