JP2018064119A - 多孔質低誘電率膜上に細孔封止層を設けるための方法及び組成物 - Google Patents
多孔質低誘電率膜上に細孔封止層を設けるための方法及び組成物 Download PDFInfo
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ACXIAEKDVUJRSK-UHFFFAOYSA-N methyl(silyloxy)silane Chemical compound C[SiH2]O[SiH3] ACXIAEKDVUJRSK-UHFFFAOYSA-N 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- XKSPIBLHTAKAHP-UHFFFAOYSA-N n-[[dimethyl(methylamino)silyl]oxy-dimethylsilyl]methanamine Chemical compound CN[Si](C)(C)O[Si](C)(C)NC XKSPIBLHTAKAHP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005244 neohexyl group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
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- 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
- H01L21/02126—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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- 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
- C23C16/44—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 method of coating
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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
- H01L21/04—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
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
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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
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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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- 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
- C23C16/44—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 method of coating
- C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- C23C16/45536—Use of plasma, radiation or electromagnetic fields
- C23C16/45542—Plasma being used non-continuously during the ALD reactions
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- 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
- C23C16/44—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 method of coating
- C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
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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
- H01L21/02205—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
- H01L21/02211—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 being a silane, e.g. disilane, methylsilane or chlorosilane
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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
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- 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
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- 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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- 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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- 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
- H01L21/02263—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
- H01L21/0228—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 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
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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
- H01L21/04—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
- H01L21/3105—After-treatment
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- 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
- H01L21/3105—After-treatment
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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
- H01L21/76822—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc.
- H01L21/76826—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc. by contacting the layer with gases, liquids or plasmas
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- 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
- H01L21/76829—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 characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
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- 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
- H01L21/76829—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 characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
- H01L21/76831—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 characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers in via holes or trenches, e.g. non-conductive sidewall liners
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
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Abstract
【解決手段】多孔質低誘電率(「低k」)層の少なくとも表面に、本明細書で細孔封止層と称される追加の薄い誘電体膜を設けることにより、多孔質低k層の細孔を封止して、下にある層の誘電率のさらなる減損を防ぐための組成物を含む方法及び当該組成物が本明細書で記載される。一態様において、この方法は、低誘電率膜を少なくとも1種の有機ケイ素化合物と接触させて吸収有機ケイ素化合物を提供する工程、前記吸収有機ケイ素化合物を紫外線、プラズマ又はその両方で処理する工程、及び細孔封止層の所望の厚さが形成されるまで繰り返す工程を含む。
【選択図】なし
Description
本出願は、2014年8月14日出願の米国仮特許出願第62/037,392号に関する優先権及び特典を請求し、その全体が参照により本明細書中に援用される。
a)反応器中に多孔質低誘電率層を有する基材を提供する工程、
b)前記基材を、式A〜G
c)前記反応器をパージガスでパージする工程、
d)前記反応器中にプラズマを導入して前記吸収有機ケイ素化合物と反応させる工程、並びに
e)前記反応器をパージガスでパージし、細孔封止膜の所望の厚さが前記表面上に形成され、封止された誘電率層が得られるまで工程b)〜e)を繰り返す工程
を含む方法が提供される。幾つかの実施形態では、多孔質低誘電率層は第1の誘電率を有し、封止された低誘電率層は第2の誘電率を有し、第1の誘電率と第2の誘電率の差は0.5以下である。この又は他の実施形態では、多孔質低誘電率層は金属をさらに含み、多孔質低誘電体膜上の細孔封止層の第1の堆積速度は、金属上の細孔封止層の第2の堆積速度と比較して2倍〜10倍大きい。
a)反応器中に多孔質低誘電率層を有する基材を提供する工程、
b)前記基材を、式A〜G
c)前記反応器をパージガスでパージする工程、
d)前記反応器中にプラズマを導入して前記吸収有機ケイ素化合物と反応させる工程、
e)前記反応器をパージガスでパージし、細孔封止膜の所望の厚さが前記表面上に形成されるまで工程b)〜e)を繰り返す工程
を含む。
a)反応器中に多孔質低誘電率層を有する基材を提供する工程、
b)前記基材を、式A〜G
c)前記反応器をパージガスでパージする工程、
d)前記反応器中にプラズマを導入して前記吸収有機ケイ素化合物と反応させる工程、
e)前記反応器をパージガスでパージする工程、
f)式A〜Gを有するが工程b)における少なくとも1種の有機ケイ素化合物とは異なる少なくとも1種の有機ケイ素化合物を前記反応器中に導入する工程、
g)前記反応器をパージガスでパージする工程、
h)前記反応器中にプラズマを導入して吸収有機ケイ素化合物と反応させる工程、並びに
i)前記反応器をパージガスでパージし、前記膜の所望の厚さが得られるまで工程b)〜i)を繰り返す工程
を含む方法が提供される。幾つかの実施形態では、工程f)の前に工程b)〜e)を複数のサイクル繰り返す。一つの特定の実施形態では、ジエトキシメチルシランなどのSi−H結合を有する有機ケイ素化合物を工程b)で使用して銅酸化物の銅金属への還元を可能にし、こうして多孔質低k誘電体層の表面での細孔封止層の選択的堆積を容易にする。
様々な型の細孔封止層及び様々な伝導体(conductions)を堆積させるための様々な実験を200ミリメートル(mm)ウェハー上で実施し、その上に2.2の誘電率を有する多孔質ジエトキシメチルシラン膜の層を構造形成体ジエトキシメチルシラン(DEMS)前駆体及びポロゲン前駆体シクロオクタンから堆積させ、米国特許出願公開第2007/0299239号明細書に記載のように紫外線(UV)硬化した。
この例では本出願者等は、このプロセスで非窒素含有前駆体又はガスを使用することによって細孔封止層の誘電率を比較的低く保った。本出願者等はまた、銅表面の酸化を防ぐために酸素又は他のオキシダントの使用を排除した。損傷した多孔質低k膜を有機ケイ素化合物トリメトキシメチルシラン(C4H12O3Si)と接触させ、かつヘリウムプラズマで処理した。各サイクルにおいて、有機ケイ素前駆体化合物を反応器中に流し、その損傷した多孔質低k誘電体膜の表面に浴びせた後に200ワットHeプラズマを15秒間ぶつけ、次いでパージした。この過程を約10〜30回繰返して細孔封止層を得た。この細孔封止層は、観察される変色がないことによって、又は30サイクルの処理後にトルエン蒸気の拡散による楕円偏光スペクトルのシフトがないことによって立証されるようにトルエンが損傷した多孔質低k膜中に拡散していないので有効とみなされた。次に、Ta2O5層を続いて10サイクルの処理でウェハー(その上に細孔封止層を堆積されている)上に堆積させた。Ta含有層を堆積させた後、蛍光X線分析(XRE)によって試験されるように細孔中へのTaの拡散の兆候は存在しなかった。したがって損傷した細孔は、トリメトキシメチルシランとの10サイクルの接触及びHeプラズマによる処理の後、細孔封止層の形成によって封止される。
上記有機ケイ素化合物ジイソプロピルジメトキシシラン(C8H20OSi)を使用して細孔封止層を堆積した。これは、損傷していない低k膜と比較して誘電率を劇的に上昇させることなく細孔を封止するのに適していることが分かった。30サイクルまでの処理の場合、低k膜の誘電率は2.2の出発値から2.29の処理後の値まで増加(すなわち+0.09の変化)したに過ぎない。この有機ケイ素化合物はまた、Cu基材に対する比較的良好な選択性をもたらすことが分かった。すなわち20サイクルの処理の場合、低k膜上の細孔封止層の厚さが約20Åであるのに対し、Cu基材上の細孔封止層の厚さは3.4Å未満であり、約6:1の選択性を示した。
上記ジメチルジアセトキシシラン(C6H12O4Si)を使用して細孔封止層を堆積した。損傷した多孔質低k膜は、この有機ケイ素化合物との10サイクルの接触、次いでHeプラズマ処理で完全に封止された。この膜の堆積速度は〜1.2Å/サイクルであり、これは細孔が約1.2ナノメートル(nm)の厚さを有する細孔封止層で封止できることを示す。一方、キャップ層の誘電率は4未満であり、これもまたkの変化を低減する可能性がある。Ta2O5の堆積及びXRF分析は、細孔が封止され、細孔中へのTaの拡散がないことを示した。
式C7H16OSiを有する有機ケイ素前駆体1−メトキシ−1−エトキシ−1−シラシクロペンタンを上記と同様に試験した。NH3で損傷した膜は、10サイクルのHe又はArプラズマ処理で完全に封止することができる。Ta2O5の堆積及びXRF分析は、細孔が封止され、細孔中へのTaの拡散がないことを示す。動的SIMSのデータはまた、界面における劇的なTa濃度の降下を示し、これは本明細書中で述べた方法の10サイクルよる良好な細孔封止効果を示している。
上記と同様に損傷した多孔質低k誘電体膜を、式C8H22O6Si2を有する有機ケイ素化合物1,2−ビス(トリメトキシシリル)エタン((CH3O)3Si−(CH2)2−Si(OCH3)3)に接触させた。これを上記と同様にEP試験を使用して試験し、トルエンの拡散はなくEP試験に合格した。変色は観察されず、またエリプソメーターによるシフトは生じなかった。XRF分析はまた、1,2−ビス(トリメトキシシリル)エタンによる10サイクルの処理後の細孔中へのTaの拡散がないことを示した。
[1]
細孔封止層を形成するための方法であって、
a)反応器中に多孔質低誘電率層を有する基材を提供する工程、
b)前記基材を、式A〜G
c)前記反応器をパージガスでパージする工程、
d)前記反応器中にプラズマを導入して前記吸収有機ケイ素化合物と反応させる工程、並びに
e)前記反応器をパージガスでパージし、前記細孔封止層の所望の厚さが前記表面上に形成され、封止された誘電率層が得られるまで工程b)〜e)を繰り返す工程
を含む、方法。
[2]
前記少なくとも1種の有機ケイ素化合物が式Aを有する化合物を含み、トリメトキシメチルシラン、ジメトキシジメチルシラン、トリエトキシメチルシラン、ジエトキシジメチルシラン、トリメトキシシラン、ジメトキシメチルシラン、ジエトキシメチルシラン、ジメトキシビニルメチルシラン、ジメトキシジビニルシラン、ジエトキシビニルメチルシラン、及びジエトキシジビニルシランからなる群より選択される、項目1に記載の方法。
[3]
前記少なくとも1種の有機ケイ素化合物が式Bを有する化合物を含み、1,1,3,3−テトラメトキシ−1、3−ジメチルジシロキサン、1,1,3,3−テトラエトキシ−1,3−ジメチルジシロキサン、1,3−ジメトキシ−1,1,3,3−テトラメチルジシロキサン、及び1,3−ジエトキシ−1,1,3,3−テトラメチルジシロキサンからなる群より選択される、項目1に記載の方法。
[4]
前記少なくとも1種の有機ケイ素化合物が式Cを有する化合物を含み、ジメチルジアセトキシシラン及びメチルトリアセトキシシランからなる群より選択される、項目1に記載の方法。
[5]
前記少なくとも1種の有機ケイ素化合物が式Dを有する化合物を含み、1,1,3,3−テトラアセトキシ−1,3−ジメチルジシロキサン及び1,3−テトラアセトキシ−1,1,3,3−テトラメチルジシロキサンからなる群より選択される、項目1に記載の方法。
[6]
前記少なくとも1種の有機ケイ素化合物が式Eを有する化合物を含み、1−メチル−1−メトキシ−1−シラシクロペンタン、1−メチル−1−エトキシ−1−シラシクロペンタン、1−メチル−1−イソ−プロポキシ−1−シラシクロペンタン、1−メチル−1−n−プロポキシ−1−シラシクロペンタン、1−メチル−1−n−ブトキシ−1−シラシクロペンタン、1−メチル−1−sec−ブトキシ−1−シラシクロペンタン、1−メチル−1−イソ−ブトキシ−1−シラシクロペンタン、1−メチル−1−tert−ブトキシ−1−シラシクロペンタン、1−メトキシ−1−シラシクロペンタン、1−エトキシ−1−シラシクロペンタン、1−メチル−1−メトキシ−1−シラシクロブタン、1−メチル−1−エトキシ−1−シラシクロブタン、1−メトキシ−1−シラシクロブタン、及び1−エトキシ−1−シラシクロブタンからなる群より選択される、項目1に記載の方法。
[7]
前記少なくとも1種の有機ケイ素化合物が式Fを有する化合物を含み、1,2−ビス(ジメトキシメチルシリル)メタン、1,2−ビス(ジエトキシメチルシリル)メタン、1,2−ビス(ジメトキシメチルシリル)エタン、及び1,2−ビス(ジエトキシメチルシリル)エタンからなる群より選択される、項目1に記載の方法。
[8]
前記細孔封止層の厚さが約5nm以下である、項目1に記載の方法。
[9]
前記細孔封止層の厚さが約3nm以下である、項目1に記載の方法。
[10]
前記細孔封止層の厚さが約1nm以下である、項目1に記載の方法。
[11]
前記多孔質低誘電率層が第1の誘電率を有し、封止された低誘電率層が第2の誘電率を有し、前記第1の誘電率と前記第2の誘電率の差が0.5以下である、項目1に記載の方法。
[12]
前記差が0.4以下である、項目11に記載の方法。
[13]
前記差が0.2以下である、項目11に記載の方法。
[14]
前記多孔質低誘電率層が金属をさらに含み、多孔質低誘電体膜上の前記細孔封止層の第1の堆積速度と前記金属上の前記細孔封止層の第2の堆積速度が2倍〜10倍大きい、項目1に記載の方法。
[15]
プラズマ強化原子層堆積プロセス(PEALD)、プラズマ強化サイクリック化学気相成長プロセス(PECCVD)又はプラズマ強化ALD様プロセスによって細孔封止層を形成する方法であって、
a)反応器中に多孔質低誘電率層を有する基材を提供する工程、
b)前記基材を、式A〜G
c)前記反応器をパージガスでパージする工程、
d)前記反応器中にプラズマを導入して前記吸収有機ケイ素化合物と反応させる工程、
e)前記反応器をパージガスでパージする工程、
f)式A〜Gを有するが工程b)における少なくとも1種の有機ケイ素化合物とは異なる少なくとも1種の有機ケイ素化合物を前記反応器中に導入する工程、
g)前記反応器をパージガスでパージする工程、
h)前記反応器中にプラズマを導入して吸収有機ケイ素化合物と反応させる工程、並びに
i)前記反応器をパージガスでパージし、前記膜の所望の厚さが得られるまで工程b)〜i)を繰り返す工程
を含む、方法。
[16]
工程f)の前に工程b)〜e)を複数のサイクル繰り返す、項目15に記載の方法。
Claims (16)
- 細孔封止層を形成するための方法であって、
a)反応器中に多孔質低誘電率層を有する基材を提供する工程、
b)前記基材を、式A〜G
c)前記反応器をパージガスでパージする工程、
d)前記反応器中にプラズマを導入して前記吸収有機ケイ素化合物と反応させる工程、並びに
e)前記反応器をパージガスでパージし、前記細孔封止層の所望の厚さが前記表面上に形成され、封止された誘電率層が得られるまで工程b)〜e)を繰り返す工程
を含む、方法。 - 前記少なくとも1種の有機ケイ素化合物が式Aを有する化合物を含み、トリメトキシメチルシラン、ジメトキシジメチルシラン、トリエトキシメチルシラン、ジエトキシジメチルシラン、トリメトキシシラン、ジメトキシメチルシラン、ジエトキシメチルシラン、ジメトキシビニルメチルシラン、ジメトキシジビニルシラン、ジエトキシビニルメチルシラン、及びジエトキシジビニルシランからなる群より選択される、請求項1に記載の方法。
- 前記少なくとも1種の有機ケイ素化合物が式Bを有する化合物を含み、1,1,3,3−テトラメトキシ−1、3−ジメチルジシロキサン、1,1,3,3−テトラエトキシ−1,3−ジメチルジシロキサン、1,3−ジメトキシ−1,1,3,3−テトラメチルジシロキサン、及び1,3−ジエトキシ−1,1,3,3−テトラメチルジシロキサンからなる群より選択される、請求項1に記載の方法。
- 前記少なくとも1種の有機ケイ素化合物が式Cを有する化合物を含み、ジメチルジアセトキシシラン及びメチルトリアセトキシシランからなる群より選択される、請求項1に記載の方法。
- 前記少なくとも1種の有機ケイ素化合物が式Dを有する化合物を含み、1,1,3,3−テトラアセトキシ−1,3−ジメチルジシロキサン及び1,3−テトラアセトキシ−1,1,3,3−テトラメチルジシロキサンからなる群より選択される、請求項1に記載の方法。
- 前記少なくとも1種の有機ケイ素化合物が式Eを有する化合物を含み、1−メチル−1−メトキシ−1−シラシクロペンタン、1−メチル−1−エトキシ−1−シラシクロペンタン、1−メチル−1−イソ−プロポキシ−1−シラシクロペンタン、1−メチル−1−n−プロポキシ−1−シラシクロペンタン、1−メチル−1−n−ブトキシ−1−シラシクロペンタン、1−メチル−1−sec−ブトキシ−1−シラシクロペンタン、1−メチル−1−イソ−ブトキシ−1−シラシクロペンタン、1−メチル−1−tert−ブトキシ−1−シラシクロペンタン、1−メトキシ−1−シラシクロペンタン、1−エトキシ−1−シラシクロペンタン、1−メチル−1−メトキシ−1−シラシクロブタン、1−メチル−1−エトキシ−1−シラシクロブタン、1−メトキシ−1−シラシクロブタン、及び1−エトキシ−1−シラシクロブタンからなる群より選択される、請求項1に記載の方法。
- 前記少なくとも1種の有機ケイ素化合物が式Fを有する化合物を含み、1,2−ビス(ジメトキシメチルシリル)メタン、1,2−ビス(ジエトキシメチルシリル)メタン、1,2−ビス(ジメトキシメチルシリル)エタン、及び1,2−ビス(ジエトキシメチルシリル)エタンからなる群より選択される、請求項1に記載の方法。
- 前記細孔封止層の厚さが約5nm以下である、請求項1に記載の方法。
- 前記細孔封止層の厚さが約3nm以下である、請求項1に記載の方法。
- 前記細孔封止層の厚さが約1nm以下である、請求項1に記載の方法。
- 前記多孔質低誘電率層が第1の誘電率を有し、封止された低誘電率層が第2の誘電率を有し、前記第1の誘電率と前記第2の誘電率の差が0.5以下である、請求項1に記載の方法。
- 前記差が0.4以下である、請求項11に記載の方法。
- 前記差が0.2以下である、請求項11に記載の方法。
- 前記多孔質低誘電率層が金属をさらに含み、多孔質低誘電体膜上の前記細孔封止層の第1の堆積速度と前記金属上の前記細孔封止層の第2の堆積速度が2倍〜10倍大きい、請求項1に記載の方法。
- プラズマ強化原子層堆積プロセス(PEALD)、プラズマ強化サイクリック化学気相成長プロセス(PECCVD)又はプラズマ強化ALD様プロセスによって細孔封止層を形成する方法であって、
a)反応器中に多孔質低誘電率層を有する基材を提供する工程、
b)前記基材を、式A〜G
c)前記反応器をパージガスでパージする工程、
d)前記反応器中にプラズマを導入して前記吸収有機ケイ素化合物と反応させる工程、
e)前記反応器をパージガスでパージする工程、
f)式A〜Gを有するが工程b)における少なくとも1種の有機ケイ素化合物とは異なる少なくとも1種の有機ケイ素化合物を前記反応器中に導入する工程、
g)前記反応器をパージガスでパージする工程、
h)前記反応器中にプラズマを導入して吸収有機ケイ素化合物と反応させる工程、並びに
i)前記反応器をパージガスでパージし、前記膜の所望の厚さが得られるまで工程b)〜i)を繰り返す工程
を含む、方法。 - 工程f)の前に工程b)〜e)を複数のサイクル繰り返す、請求項15に記載の方法。
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