JP4812838B2 - 多孔質絶縁膜の形成方法 - Google Patents
多孔質絶縁膜の形成方法 Download PDFInfo
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- JP4812838B2 JP4812838B2 JP2008525919A JP2008525919A JP4812838B2 JP 4812838 B2 JP4812838 B2 JP 4812838B2 JP 2008525919 A JP2008525919 A JP 2008525919A JP 2008525919 A JP2008525919 A JP 2008525919A JP 4812838 B2 JP4812838 B2 JP 4812838B2
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- raw material
- insulating film
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- film
- organic silica
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- 238000000034 method Methods 0.000 title claims description 50
- 239000002994 raw material Substances 0.000 claims description 200
- 239000007789 gas Substances 0.000 claims description 62
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 61
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 230000015572 biosynthetic process Effects 0.000 claims description 26
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 26
- -1 silica compound Chemical class 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 23
- 239000004065 semiconductor Substances 0.000 claims description 21
- 125000004122 cyclic group Chemical group 0.000 claims description 20
- 150000001722 carbon compounds Chemical class 0.000 claims description 18
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 10
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 10
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 10
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 10
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 24
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- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- 229910052681 coesite Inorganic materials 0.000 description 2
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- 238000004132 cross linking Methods 0.000 description 2
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- WMIYKQLTONQJES-UHFFFAOYSA-N hexafluoroethane Chemical compound FC(F)(F)C(F)(F)F WMIYKQLTONQJES-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 2
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- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 0 CCC*(C)N(C)*C(OC)=CC Chemical compound CCC*(C)N(C)*C(OC)=CC 0.000 description 1
- HILVORLFDSOFOE-UHFFFAOYSA-N CN[O](C=C)O[O](C=C)(N)OC Chemical compound CN[O](C=C)O[O](C=C)(N)OC HILVORLFDSOFOE-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005441 aurora Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 238000007740 vapor deposition Methods 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
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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
- H01L21/02109—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
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- H01L21/02126—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 containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- 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
- H01L21/02205—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 the layer being characterised by the precursor material for deposition
- H01L21/02208—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02214—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
- H01L21/02216—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
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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
- H01L21/02—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
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
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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
- H01L21/312—Organic layers, e.g. photoresist
- H01L21/3121—Layers comprising organo-silicon compounds
- H01L21/3122—Layers comprising organo-silicon compounds layers comprising polysiloxane compounds
- H01L21/3124—Layers comprising organo-silicon compounds layers comprising polysiloxane compounds layers comprising hydrogen silsesquioxane
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- 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
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31604—Deposition from a gas or vapour
- H01L21/31633—Deposition of carbon doped silicon oxide, e.g. SiOC
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- H—ELECTRICITY
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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
- H01L21/02—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
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31695—Deposition of porous oxides or porous glassy oxides or oxide based porous glass
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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
- 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
- H01L21/7682—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 the dielectric comprising air gaps
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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
- H01L21/70—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
- H01L21/76835—Combinations of two or more different dielectric layers having a low dielectric constant
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- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/10—Applying interconnections to be used for carrying current between separate components within a device
- H01L2221/1005—Formation and after-treatment of dielectrics
- H01L2221/1042—Formation and after-treatment of dielectrics the dielectric comprising air gaps
- H01L2221/1047—Formation and after-treatment of dielectrics the dielectric comprising air gaps the air gaps being formed by pores in the dielectric
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Plasma & Fusion (AREA)
- Formation Of Insulating Films (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
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Description
前記直鎖状有機シリカ構造を持つ原料の直鎖状有機シリカ化合物が、下記式11に示す構造であり、R5は不飽和炭素化合物、R6、R7、R8は飽和炭素化合物であり、R5はビニル基又はアリル基、R6、R7、R8はメチル基、エチル基、プロピル基、イソプロピル基、ブチル基のいずれかであることを特徴とする絶縁膜の形成方法を提供する。
の原料の気体と、直鎖状有機シリカ構造を持つ1種以上の原料の気体とを、プラズマ反応
によって成膜させた有機シリカ膜の形成方法であり、環状有機シリカ構造を持つ原料は主
骨格に3員環SiO環状構造を持ち、かつ直鎖状有機シリカ構造を持つ原料の元素組成比
がH/C≧1.6、C/Si≧5、H/Si≧8であり、かつこれら原料の側鎖に少なく
とも1つの不飽和炭化水素基を持ち、
前記直鎖状有機シリカ構造を持つ原料の直鎖状有機シリカ化合物が、下記式11に示す構造であり、R5は不飽和炭素化合物、R6、R7、R8は飽和炭素化合物であり、R5はビニル基又はアリル基、R6、R7、R8はメチル基、エチル基、プロピル基、イソプロピル基、ブチル基のいずれかであることを特徴とする方法に向けられる。
本発明を用いて、層間絶縁膜として好適な絶縁膜を、少なくとも1種以上の有機シロキサン原料を反応室に供給し、プラズマ気相成長法によって絶縁膜を形成することができる。
成膜には第一有機シロキサン原料101にR1にビニル基、R2にイソプロピル基からなる式1(式3)で示される原料を、第二有機シロキサン原料103にはR3にビニル基、R4にメチル基からなる式6(式7)で示される原料を使用した。第一有機シロキサン原料と第二有機シロキサン原料比(モル比)は1:9〜9:1である。
環状構造を持つ原料が3員環SiO環状構造を持つ原料と比較し開環しやすいと考えられる。
成膜には第一有機シロキサン原料101にR1にビニル基、R2にエチル基からなる式1で示される原料を、第二有機シロキサン原料103にはR3にビニル基、R4にメチル基からなる式6(式7)で示される原料を使用した。第一有機シロキサン原料と第二有機シロキサン原料比(モル比)は8:2である。
成膜には第一有機シロキサン原料101にR1にエチル基、R2にイソプロピル基からなる式1(式4)で示される原料を、第二有機シロキサン原料103にはR3にビニル基、R4にメチル基からなる式6(式7)で示される原料を使用した。第一有機シロキサン原料と第二有機シロキサン原料比(モル比)は7:3である。
成膜には第一有機シロキサン原料101にR1にビニル基、R2にn−ブチル基からなる式1(式5)で示される原料を、第二有機シロキサン原料103にはR3にビニル基、R4にメチル基からなる式6(式7)で示される原料を使用した。第一有機シロキサン原料と第二有機シロキサン原料比(モル比)は6:4である。
成膜には第一有機シロキサン原料101にR1にビニル基、R2にイソプロピル基からなる式1(式3)で示される原料を、第二有機シロキサン原料103にはR3にビニル基、R4に水素からなる式6(式8)で示される原料を使用した。第一有機シロキサン原料と第二有機シロキサン原料比(モル比)は5:5である。
成膜には第一有機シロキサン原料101にR1にビニル基、R2にイソプロピル基からなる式1(式3)で示される原料を、第二有機シロキサン原料103にはR3にメチルビニル基、R4に水素からなる式6(式10)で示される原料を使用した。第一有機シロキサン原料と第二有機シロキサン原料比(モル比)は3:7である。
成膜には第一有機シロキサン原料101にR1にビニル基、R2にイソプロピル基からなる式1(式3)で示される原料を、第二有機シロキサン原料103にはR3にメチルビニル基、R4にメチル基からなる式6(式9)で示される原料を使用した。第一有機シロキサン原料と第二有機シロキサン原料比(モル比)は1:9である。
成膜には第一有機シロキサン原料101にR1にビニル基、R2にイソプロピル基からなる式1(式3)で示される原料のみを使用した。
成膜には第一有機シロキサン原料101にR1にビニル基、R2にメチル基からなる式6(式7)で示される原料のみを使用した。
本実施の形態では気化制御ユニットVU1の原料タンク102内に3員環SiO環状構造を持つ原料、気化制御ユニットVU2の原料タンク102内に直鎖状SiO構造を持つ原料を使い、成膜を行った。それ以外の条件は第1の実施の形態と同じとした。
成膜には第一有機シロキサン原料101にR1にビニル基、R2にイソプロピル基からなる式1(式3)で示される原料を、第二有機シロキサン原料103にはR5にビニル基、R6にイソプロピル基、R7、R8にメチル基からなる式11(式12)で示される原料を使用した。第一有機シロキサン原料と第二有機シロキサン原料比(モル比)は1:9〜9:1である。
成膜には第一有機シロキサン原料101にR1にビニル基、R2にメチル基からなる式1(式2)で示される原料を、第二有機シロキサン原料103にはR5にビニル基、R6にイソプロピル基、R7、R8にメチル基からなる式11(式12)で示される原料を使用した。第一有機シロキサン原料と第二有機シロキサン原料比(モル比)は2:8である。
成膜には第一有機シロキサン原料101にR1にエチル基、R2にイソプロピル基からなる式1(式4)で示される原料を、第二有機シロキサン原料103にはR5にビニル基、R6にイソプロピル基、R7、R8にメチル基からなる式11(式12)で示される原料を使用した。第一有機シロキサン原料と第二有機シロキサン原料比(モル比)は3:7である。
成膜には第一有機シロキサン原料101にR1にビニル基、R2にn−ブチル基からなる式1(式5)で示される原料を、第二有機シロキサン原料103にはR5にビニル基、R6にイソプロピル基、R7、R8にメチル基からなる式11(式12)で示される原料を使用した。第一有機シロキサン原料と第二有機シロキサン原料比(モル比)は4:6である。
比較例としてSiOCH膜であるAuroraTM膜を作製し、その膜強度と密着強度を測定した。
比較例としてSiOCH膜であるBlack DiamondTM膜を作製し、その膜強度と密着強度を測定した。
次に本発明における第3の実施の形態について説明する。図1Aに示す従来のデュアルダマシン配線構造は、下層配線201上に、キャップ膜(SiCN)202、ビア層間低誘電率膜203、エッチングストッパー膜204、配線層間低誘電率膜205、ハードマスク206、キャップ膜(SiCN)207が積層されており、ビア層間低誘電率膜203中のビア及び配線層間低誘電率膜205中の配線溝には、周囲にバリア膜209が形成されて、銅208が埋め込まれている。図1Bのデュアルダマシン構造は、図1の構造から実効被誘電率を下げた構造である。
成膜には第一有機シロキサン原料101にR1にビニル基、R2にイソプロピル基からなる式1(式3)で示される原料を、第二有機シロキサン原料103にはR5にビニル基、R6にイソプロピル基、R7、R8にメチル基からなる式11(式12)で示される原料を使用した。
成膜には第一有機シロキサン原料101にR1にビニル基、R2にイソプロピル基からなる式1(式3)で示される原料を、第二有機シロキサン原料103にはR3にビニル基、R4にメチル基からなる式6(式7)でされる原料を使用した。ビア層間低誘電率膜203成膜のために第一有機シロキサン原料と第二有機シロキサン原料をモル比で3:7に混合しチャンバー内で成膜を行った後、第二有機シロキサン原料の供給を止めるためVU2の110aと118aのバルブをクローズし、第一有機シロキサン原料のみを使い配線層間低誘電率膜205を形成する。次に第一有機シロキサン原料の供給を止めるためVU1の110aと118aのバルブをクローズし、第二有機シロキサン原料のみを使いハードマスク206’を形成した。
比較例5としてビア層間低誘電率膜203にAurora、エッチングストッパー膜204にはSiO2、配線層間低誘電率膜205に第一有機シロキサン原料、ハードマスク206にSiO2を使った(図1A参照)。
Claims (13)
- 環状有機シリカ構造を持つ2種以上の原料の気体をプラズマ反応によって成膜させた有機シリカ膜の形成方法であり、主骨格に3員環SiO環状構造を持つ原料と4員環SiO環状構造をもつ原料からなり、かつこれら原料の少なくとも1種は側鎖に少なくとも1つの不飽和炭化水素基を持つことを特徴とする絶縁膜の形成方法。
- 環状有機シリカ構造を持つ1種以上の原料の気体と、直鎖状有機シリカ構造を持つ1種以上の原料の気体とを、プラズマ反応によって成膜させた有機シリカ膜の形成方法であり、前記環状有機シリカ構造を持つ原料は主骨格に3員環SiO環状構造を持ち、かつ前記直鎖状有機シリカ構造を持つ原料の元素組成比がH/C≧1.6、C/Si≧5、H/Si≧8であり、かつこれら原料の少なくとも1種は、側鎖に少なくとも1つの不飽和炭化水素基を持ち、
前記直鎖状有機シリカ構造を持つ原料の直鎖状有機シリカ化合物が、下記式11に示す構造であり、R5は不飽和炭素化合物、R6、R7、R8は飽和炭素化合物であり、R5はビニル基又はアリル基、R6、R7、R8はメチル基、エチル基、プロピル基、イソプロピル基、ブチル基のいずれかであることを特徴とする絶縁膜の形成方法。
- 前記シリカ構造を持つ原料が、それぞれ異なる気化器により気体化し反応容器に導入されることを特徴とする請求項1又は2に記載の絶縁膜の形成方法。
- 前記シリカ構造を持つ原料が同一の気化器により気体化し反応容器に導入されることを特徴とする請求項1又は2に記載の絶縁膜の形成方法。
- 請求項1乃至9のいずれか一項に記載の絶縁膜の形成方法により形成される絶縁膜であって、
前記絶縁膜において少なくともアモルファスカーボンが含まれることを特徴とする絶縁膜。 - 請求項1乃至9のいずれか一項に記載の絶縁膜の形成方法により形成される絶縁膜を含む半導体デバイスであって、
前記絶縁膜にアモルファスカーボンが含まれ、かつ、前記アモルファスカーボンがSp2構造とSp3構造を兼ね備えることを特徴とする半導体デバイス。 - 請求項10に記載の絶縁膜を含む半導体デバイスであって、
前記絶縁膜に含まれるアモルファスカーボンがSp2構造とSp3構造を兼ね備えることを特徴とする半導体デバイス。 - 請求項11又は12に記載の半導体デバイスであって、
前記絶縁膜において有機シリカ構造を持つ原料の比を変化させて形成された絶縁膜を2層以上持つことを特徴とする半導体デバイス。
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JP5262144B2 (ja) * | 2008-01-31 | 2013-08-14 | 日本電気株式会社 | 半導体デバイス及びその製造方法 |
JP5554951B2 (ja) * | 2008-09-11 | 2014-07-23 | ルネサスエレクトロニクス株式会社 | 半導体装置の製造方法 |
JP2010153824A (ja) * | 2008-11-18 | 2010-07-08 | Renesas Electronics Corp | 多孔質絶縁膜の製造方法、半導体装置の製造方法、及び半導体装置 |
JP2010278330A (ja) * | 2009-05-29 | 2010-12-09 | Renesas Electronics Corp | 半導体装置及び半導体装置の製造方法 |
JP2011166106A (ja) * | 2010-01-13 | 2011-08-25 | Renesas Electronics Corp | 半導体装置の製造方法及び半導体装置 |
JP2011155077A (ja) * | 2010-01-26 | 2011-08-11 | Renesas Electronics Corp | 半導体装置の製造方法 |
JP5864095B2 (ja) * | 2010-02-18 | 2016-02-17 | ルネサスエレクトロニクス株式会社 | 半導体装置の製造方法 |
JP2011199059A (ja) * | 2010-03-19 | 2011-10-06 | Renesas Electronics Corp | 半導体装置およびその製造方法 |
JP2012074651A (ja) * | 2010-09-30 | 2012-04-12 | Renesas Electronics Corp | 半導体装置、及び、その製造方法 |
JP6131575B2 (ja) * | 2011-12-22 | 2017-05-24 | 東ソー株式会社 | 環状シロキサン化合物の製造方法およびジシロキサン化合物 |
TW201348496A (zh) * | 2012-02-15 | 2013-12-01 | Renesas Electronics Corp | 多孔性絕緣膜的製造方法以及包含該膜的半導體裝置 |
FR2987626B1 (fr) * | 2012-03-05 | 2015-04-03 | Commissariat Energie Atomique | Procede de collage direct utilisant une couche poreuse compressible |
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US10170308B1 (en) * | 2017-10-11 | 2019-01-01 | International Business Machines Corporation | Fabricating semiconductor devices by cross-linking and removing portions of deposited HSQ |
JP7126381B2 (ja) * | 2018-05-21 | 2022-08-26 | 東京エレクトロン株式会社 | 成膜装置および成膜方法 |
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