WO2010137711A1 - 半導体用シール組成物、半導体装置および半導体装置の製造方法 - Google Patents
半導体用シール組成物、半導体装置および半導体装置の製造方法 Download PDFInfo
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- WO2010137711A1 WO2010137711A1 PCT/JP2010/059151 JP2010059151W WO2010137711A1 WO 2010137711 A1 WO2010137711 A1 WO 2010137711A1 JP 2010059151 W JP2010059151 W JP 2010059151W WO 2010137711 A1 WO2010137711 A1 WO 2010137711A1
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- resin
- interlayer insulating
- insulating layer
- sealing composition
- semiconductor
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- 229910052737 gold Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- XPMZASMGMPTBMA-UHFFFAOYSA-N methoxy-[2-[methoxy(dimethyl)silyl]ethyl]-dimethylsilane Chemical compound CO[Si](C)(C)CC[Si](C)(C)OC XPMZASMGMPTBMA-UHFFFAOYSA-N 0.000 description 1
- DDBXHJPSBDINQC-UHFFFAOYSA-N methoxy-[6-[methoxy(dimethyl)silyl]hexyl]-dimethylsilane Chemical compound CO[Si](C)(C)CCCCCC[Si](C)(C)OC DDBXHJPSBDINQC-UHFFFAOYSA-N 0.000 description 1
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 description 1
- RLSUOUMJBQZFNR-UHFFFAOYSA-N n-phenyl-n-trimethylsilylaniline Chemical compound C=1C=CC=CC=1N([Si](C)(C)C)C1=CC=CC=C1 RLSUOUMJBQZFNR-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000656 polylysine Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 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
- 238000013519 translation Methods 0.000 description 1
- IABYZNQNTMUZFK-UHFFFAOYSA-N tributoxy(fluoro)silane Chemical compound CCCCO[Si](F)(OCCCC)OCCCC IABYZNQNTMUZFK-UHFFFAOYSA-N 0.000 description 1
- VBSUMMHIJNZMRM-UHFFFAOYSA-N triethoxy(2-phenylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC1=CC=CC=C1 VBSUMMHIJNZMRM-UHFFFAOYSA-N 0.000 description 1
- IZRJPHXTEXTLHY-UHFFFAOYSA-N triethoxy(2-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CC[Si](OCC)(OCC)OCC IZRJPHXTEXTLHY-UHFFFAOYSA-N 0.000 description 1
- NRYWFNLVRORSCA-UHFFFAOYSA-N triethoxy(6-triethoxysilylhexyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCC[Si](OCC)(OCC)OCC NRYWFNLVRORSCA-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- XVYIJOWQJOQFBG-UHFFFAOYSA-N triethoxy(fluoro)silane Chemical compound CCO[Si](F)(OCC)OCC XVYIJOWQJOQFBG-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- MRBRVZDGOJHHFZ-UHFFFAOYSA-N triethoxy-(3-triethoxysilylphenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC([Si](OCC)(OCC)OCC)=C1 MRBRVZDGOJHHFZ-UHFFFAOYSA-N 0.000 description 1
- YYJNCOSWWOMZHX-UHFFFAOYSA-N triethoxy-(4-triethoxysilylphenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=C([Si](OCC)(OCC)OCC)C=C1 YYJNCOSWWOMZHX-UHFFFAOYSA-N 0.000 description 1
- NKLYMYLJOXIVFB-UHFFFAOYSA-N triethoxymethylsilane Chemical compound CCOC([SiH3])(OCC)OCC NKLYMYLJOXIVFB-UHFFFAOYSA-N 0.000 description 1
- WILBTFWIBAOWLN-UHFFFAOYSA-N triethyl(triethylsilyloxy)silane Chemical compound CC[Si](CC)(CC)O[Si](CC)(CC)CC WILBTFWIBAOWLN-UHFFFAOYSA-N 0.000 description 1
- UBMUZYGBAGFCDF-UHFFFAOYSA-N trimethoxy(2-phenylethyl)silane Chemical compound CO[Si](OC)(OC)CCC1=CC=CC=C1 UBMUZYGBAGFCDF-UHFFFAOYSA-N 0.000 description 1
- JCGDCINCKDQXDX-UHFFFAOYSA-N trimethoxy(2-trimethoxysilylethyl)silane Chemical compound CO[Si](OC)(OC)CC[Si](OC)(OC)OC JCGDCINCKDQXDX-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- KNYWDHFOQZZIDQ-UHFFFAOYSA-N trimethoxy-(2-trimethoxysilylphenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1[Si](OC)(OC)OC KNYWDHFOQZZIDQ-UHFFFAOYSA-N 0.000 description 1
- KBFAHPBJNNSTGX-UHFFFAOYSA-N trimethoxy-(3-trimethoxysilylphenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC([Si](OC)(OC)OC)=C1 KBFAHPBJNNSTGX-UHFFFAOYSA-N 0.000 description 1
- TUQLLQQWSNWKCF-UHFFFAOYSA-N trimethoxymethylsilane Chemical compound COC([SiH3])(OC)OC TUQLLQQWSNWKCF-UHFFFAOYSA-N 0.000 description 1
- IVZTVZJLMIHPEY-UHFFFAOYSA-N triphenyl(triphenylsilyloxy)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)O[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 IVZTVZJLMIHPEY-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01L21/76829—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
-
- 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
- H01L21/02296—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
- H01L21/02343—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a liquid
-
- 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
- H01L21/02296—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
- H01L21/02362—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment formation of intermediate layers, e.g. capping layers or diffusion barriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—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
-
- 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
- H01L21/76829—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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/05—Bonding or intermediate layer characterised by chemical composition, e.g. sealant or spacer
- C09K2323/055—Epoxy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to a semiconductor sealing composition, a semiconductor device, and a method for manufacturing a semiconductor device.
- low-k materials materials having a low dielectric constant having a porous structure
- the semiconductor interlayer insulating layer having such a porous structure when the porosity is increased in order to further lower the dielectric constant, a metal component such as copper embedded as a wiring material enters the pores in the semiconductor interlayer insulating layer. In some cases, the dielectric constant is increased and a leakage current is generated.
- a semiconductor device manufacturing method using a porous low dielectric constant material is formed by etching by using a micellar surfactant for wet cleaning after etching.
- a technique for sealing pores on the side wall surface of the groove is disclosed.
- International Publication No. 09/012184 when a low-k material has a hydrophobic surface, the hydrophilic / hydrophobic property of the material can be obtained by adding a polyvinyl alcohol-based amphiphilic polymer to the surface. Techniques for controlling are disclosed.
- JP 2006-352042 A discloses a semiconductor polishing composition containing a cationic polymer and a surfactant.
- a surfactant that does not have a micellar structure may enter the pores on the side wall surface of the groove to increase the relative dielectric constant.
- the adhesion between the interlayer insulating layer and the wiring material may be reduced by the micelle.
- a bulky layer is likely to be formed due to hydrogen bonding between polyvinyl alcohol-based amphiphilic polymers. In some cases, the adhesion of the wiring material is reduced.
- the present invention is capable of forming a thin resin layer, can suppress diffusion of a metal component into a porous interlayer insulating layer, and has excellent adhesion to a wiring material. It is an object to provide a semiconductor device and a manufacturing method thereof.
- the first aspect of the present invention contains a resin having two or more cationic functional groups and a weight average molecular weight of 2,000 to 100,000, and the contents of sodium and potassium are each 10 wt ppb or less on an element basis.
- a semiconductor-use sealing composition having a volume average particle diameter of 10 nm or less measured by a dynamic light scattering method.
- the resin preferably has a cationic functional group equivalent of 43 to 430.
- the cationic functional group is preferably at least one selected from a primary amino group and a secondary amino group, and the resin is more preferably a polyethyleneimine or a polyethyleneimine derivative.
- the 2nd aspect of this invention is a manufacturing method of a semiconductor device including the sealing composition provision process which makes the said sealing composition for semiconductors contact the interlayer insulation layer formed on the board
- the interlayer insulating layer preferably contains porous silica, and has a silanol residue derived from the porous silica on the surface thereof.
- the method further includes a step of forming a concave groove having a width of 10 nm to 32 nm in the interlayer insulating layer, and the sealing composition applying step applies the semiconductor sealing composition to the interlayer insulating layer on the side surface of the concave groove. More preferably, it is a process.
- the third aspect of the present invention includes a porous interlayer insulating layer, a resin layer having a cationic functional group and a resin having a weight average molecular weight of 2000 to 100,000 and a thickness of 0.3 nm to 5 nm, A semiconductor device having a structure in which layers made of copper are arranged in this order. It is preferable that a copper barrier layer is further disposed between the resin layer and the copper layer.
- a thin resin layer can be formed, the diffusion of a metal component into a porous interlayer insulating layer can be suppressed, and a semiconductor sealing composition having excellent adhesion to a wiring material, and this
- the semiconductor device used and the manufacturing method thereof can be provided.
- the semiconductor sealing composition of the present invention is used, for example, to form a resin layer covering pores formed on a porous interlayer insulating layer, and has a weight average molecular weight having two or more cationic functional groups. Contains at least one resin of 2000 to 100,000, the content of sodium and potassium is 10 wt ppb or less on an element basis, respectively, and the volume average particle diameter measured by the dynamic light scattering method is 10 nm or less It is.
- the semiconductor sealing composition having such a structure When the semiconductor sealing composition having such a structure is applied to an interlayer insulating layer having a porous structure, for example, two or more cationic functional groups of the resin are adsorbed on the interlayer insulating layer in a multipoint manner, and the interlayer The pores (pores) present on the surface of the insulating layer are covered with the resin layer. Thereby, diffusion of the metal component into the porous interlayer insulating layer can be suppressed. Furthermore, since the resin layer formed by the resin is a thin layer (for example, 5 nm or less), it has excellent adhesion between the interlayer insulating layer and the wiring material formed on the interlayer insulating layer via the resin layer. A change in dielectric constant can be suppressed.
- the semiconductor sealing composition of the present invention contains at least one resin having a weight average molecular weight of 2,000 to 100,000 and having two or more cationic functional groups.
- the resin has two or more cationic functional groups, but may further have an anionic functional group or a nonionic functional group as necessary.
- the resin may have a repeating unit structure having a cationic functional group, or may have a random structure formed by branching polymerization of monomers constituting the resin without having a specific repeating unit structure. It may have a structure.
- the resin does not have a specific repeating unit structure, and has a random structure formed by branching polymerization of monomers constituting the resin. Is preferred.
- the cationic functional group is not particularly limited as long as it is a functional group that can be positively charged.
- an amino group, a quaternary ammonium group, etc. can be mentioned. Of these, at least one selected from a primary amino group and a secondary amino group is preferable from the viewpoint of suppressing diffusion of the metal component.
- the nonionic functional group may be a hydrogen bond accepting group or a hydrogen bond donating group.
- a hydroxyl group, a carbonyl group, an ether bond, etc. can be mentioned.
- the anionic functional group is not particularly limited as long as it is a functional group that can be negatively charged. Examples thereof include a carboxylic acid group, a sulfonic acid group, and a sulfuric acid group.
- the resin may be one having two or more cationic functional groups in one molecule, but is preferably a polymer having a high cation density from the viewpoint of suppressing diffusion of the metal component.
- the cationic functional group equivalent is preferably 43 to 430, more preferably 200 to 400.
- the surface of the porous interlayer insulating layer is hydrophobized by a known method, for example, the method described in International Publication No. 04/026765, International Publication No. 06/025501, etc.
- the polarity of the surface It is also preferred to be 200-400 since the density of the group is reduced.
- the cationic functional group equivalent means the weight average molecular weight per cationic functional group, and the weight average molecular weight (Mw) of the resin is divided by the number of cationic functional groups (n) contained in the resin corresponding to one molecule. (Mw / n). The larger the cationic functional group equivalent, the lower the density of the cationic functional group, while the smaller the cationic functional group equivalent, the higher the density of the cationic functional group.
- the cationic functional group has a main chain in the specific unit structure. It may be included as at least a part, may be included as at least a part of the side chain, and may further be included as at least a part of the main chain and at least a part of the side chain. Furthermore, when the specific unit structure contains two or more cationic functional groups, the two or more cationic functional groups may be the same or different.
- the cationic functional group is a ratio of the main chain length of the specific unit structure to the average distance between the adsorption points (for example, silanol residues) of the cationic functional group present on the porous interlayer insulating layer (hereinafter referred to as “ The relative distance between the cationic functional groups ”is sometimes included to be 0.08 to 1.2, and is preferably included to be 0.08 to 0.6. It is more preferable. With such an embodiment, the resin can be more efficiently adsorbed on the porous interlayer insulating layer more efficiently.
- the specific unit structure preferably has a molecular weight of 30 to 500, more preferably 40 to 200, from the viewpoint of adsorptivity to the interlayer insulating layer.
- the molecular weight of a specific unit structure means the molecular weight of the monomer which comprises a specific unit structure.
- the specific unit structure in the present invention preferably has a relative distance between the cationic functional groups of 0.08 to 1.2 and a molecular weight of 30 to 500 from the viewpoint of adsorptivity to the interlayer insulating layer. More preferably, the relative distance between the cationic functional groups is 0.08 to 0.6, and the molecular weight is 40 to 200.
- the specific unit structure containing a cationic functional group is specifically derived from a unit structure derived from ethyleneimine, a unit structure derived from allylamine, a unit structure derived from diallyldimethylammonium salt, or vinylpyridine.
- Examples include a unit structure, a unit structure derived from lysine, a unit structure derived from methylvinylpyridine, and a unit structure derived from p-vinylpyridine.
- the resin may further include at least one of a unit structure containing a nonionic functional group and a unit structure containing an anionic functional group.
- a unit structure containing the nonionic functional group include a unit structure derived from vinyl alcohol, a unit structure derived from alkylene oxide, and a unit structure derived from vinyl pyrrolidone.
- unit structure containing an anionic functional group specifically, a unit structure derived from styrene sulfonic acid, a unit structure derived from vinyl sulfate, a unit structure derived from acrylic acid, a unit structure derived from methacrylic acid, maleic Examples include a unit structure derived from an acid and a unit structure derived from fumaric acid.
- the specific unit structures when the resin contains two or more types of specific unit structures, the specific unit structures may be different from each other in the type or number of polar groups, molecular weight, and the like.
- the two or more specific unit structures may be included as a block copolymer or a random copolymer.
- the resin may further include at least one repeating unit structure other than the specific unit structure (hereinafter sometimes referred to as “second unit structure”).
- the specific unit structure and the second unit structure may be included as a block copolymer or a random copolymer.
- the second unit structure is not particularly limited as long as it is a unit structure derived from a monomer polymerizable with the monomer constituting the specific unit structure. Examples include unit structures derived from olefins.
- the resin in the present invention has a specific structure that does not have a specific repeating unit structure and has a random structure formed by branching polymerization of monomers constituting the resin
- the cationic functional group has a main chain. Or at least a part of the side chain, and may be further included as at least a part of the main chain and at least a part of the side chain.
- the monomer that can constitute such a resin include ethyleneimine and derivatives thereof.
- the resin containing a cationic functional group in the present invention include polyethyleneimine (PEI), polyallylamine (PAA), polydiallyldimethylammonium (PDDA), polyvinylpyridine (PVP), polylysine, and polymethylpyridylvinyl (PMPyV). ), Protonated poly (p-pyridylvinylene) (R-PHPyV), and derivatives thereof.
- PEI polyethyleneimine
- PAA polyallylamine
- PAA polydiallyldimethylammonium
- PVP polyvinylpyridine
- PMPyV polymethylpyridylvinyl
- R-PHPyV Protonated poly (p-pyridylvinylene)
- polyethyleneimine (PEI) or a derivative thereof, polyallylamine (PAA), or the like is preferable
- polyethyleneimine (PEI) or a derivative thereof is more preferable.
- Polyethyleneimine can be generally produced by polymerizing ethyleneimine by a commonly used method.
- a polymerization catalyst, polymerization conditions, and the like can also be appropriately selected from those generally used for polymerization of ethyleneimine.
- the reaction can be carried out at 0 to 200 ° C. in the presence of an effective amount of an acid catalyst such as hydrochloric acid.
- ethyleneimine may be addition-polymerized based on polyethyleneimine.
- the polyethyleneimine in the present invention may be a homopolymer of ethyleneimine or a compound copolymerizable with ethyleneimine, for example, a copolymer of amines and ethyleneimine.
- JP-B 43-8828, JP-B 49-33120 and the like can be referred to.
- the polyethyleneimine in the present invention may be obtained using crude ethyleneimine obtained from monoethanolamine.
- JP-A-2001-2213958 can be referred to.
- Polyethyleneimine produced as described above is not only a partial structure in which ethyleneimine is ring-opened and bonded in a straight chain, but also a branched partial structure and a linear partial structure are cross-linked. It has a complicated skeleton having a partial structure and the like.
- a resin having a cationic functional group having such a structure the resin is more efficiently adsorbed at multiple points. Furthermore, the coating layer is more effectively formed by the interaction between the resins.
- the resin in the present invention is also preferably a polyethyleneimine derivative.
- the polyethyleneimine derivative is not particularly limited as long as it is a compound that can be produced using the polyethyleneimine. Specific examples include a polyethyleneimine derivative in which an alkyl group (preferably having 1 to 10 carbon atoms) or an aryl group is introduced into polyethyleneimine, a polyethyleneimine derivative obtained by introducing a crosslinkable group such as a hydroxyl group into polyethyleneimine, and the like. be able to.
- These polyethyleneimine derivatives can be produced by a method usually performed using the polyethyleneimine. Specifically, for example, it can be produced according to the method described in JP-A-6-016809.
- polyethyleneimine and derivatives thereof in the present invention may be commercially available.
- it can be appropriately selected from polyethyleneimine and derivatives thereof commercially available from Nippon Shokubai Co., Ltd., BASF, etc.
- the resin has a weight average molecular weight of 2,000 to 100,000, preferably 10,000 to 80,000, and more preferably 20,000 to 60,000.
- the weight average molecular weight of the resin is more than 100,000. If it is larger, the size of the resin becomes larger than the wiring interval, the resin may not enter the concave groove in which the wiring material is embedded, and the pores on the side surfaces of the groove may not be sufficiently covered.
- the weight average molecular weight is less than 2000
- the resin molecule size is smaller than the pore diameter on the interlayer insulating layer, and the resin molecules enter the pores on the interlayer insulating layer to cause the dielectric constant of the interlayer insulating layer. May rise. Also, there are cases where adsorption does not occur at multiple points.
- a weight average molecular weight is measured using the GPC apparatus normally used for the molecular weight measurement of resin.
- the resin is a resin having a critical micelle concentration in an aqueous solvent of 1% by weight or more or that does not substantially form a micelle structure.
- substantially not forming a micelle structure means that micelles are not formed under normal conditions such as in an aqueous solvent at room temperature, that is, the critical micelle concentration cannot be measured.
- the resin in the present invention is preferably polyethyleneimine having a weight average molecular weight of 2000 to 100,000 and a cationic functional group equivalent of 43 to 430, and having a weight average molecular weight of 10,000 to 80,000, More preferred is a polyethyleneimine having a group equivalent of 200 to 400. With this mode, the diffusion of the metal component into the interlayer insulating layer is more effectively suppressed, and the adhesion between the interlayer insulating layer and the wiring material is further improved.
- the content of the resin in the semiconductor sealing composition of the present invention is not particularly limited, and may be 0.01 to 1.0% by weight, for example, 0.02 to 0.3% by weight. Is preferred. Moreover, based on the area and pore density of the surface which forms a resin layer using the semiconductor sealing composition of this invention, content of the said resin in the said composition can also be adjusted.
- the contents of sodium and potassium are each 10 wt ppb or less on an element basis. If the content of sodium or potassium exceeds 10 wt ppb on an element basis, leakage current may occur.
- the semiconductor sealing composition of the present invention may contain a solvent as required in addition to the resin.
- the solvent in the present invention is not particularly limited as long as the resin is uniformly dissolved and does not easily form micelles.
- water preferably ultrapure water
- a water-soluble organic solvent for example, alcohol etc.
- the boiling point of the solvent is not particularly limited, but is preferably 210 ° C. or lower, and more preferably 160 ° C. or lower.
- the boiling point of the solvent is within the above range, for example, when a cleaning step or a drying step is provided after the step of bringing the semiconductor sealing composition of the present invention described later into contact with the interlayer insulating layer, the insulating property of the interlayer insulating layer is provided.
- the solvent can be removed at a low temperature that does not cause the seal composition to peel off from the interlayer insulating layer.
- the semiconductor sealing composition of the present invention may further contain a cation such as cesium ion, if necessary, as long as the effects of the present invention are not impaired.
- a cation such as cesium ion
- the resin in the semiconductor sealing composition can be more uniformly spread on the interlayer insulating layer.
- the semiconductor sealing composition of the present invention does not contain a compound that corrodes or dissolves the interlayer insulating layer.
- the main material of the interlayer insulating layer is an inorganic compound such as silica
- the fluorine compound or the like is contained in the composition of the present invention, the interlayer insulating layer is dissolved and the insulating property is impaired. As a result, the relative dielectric constant may increase.
- the semiconductor sealing composition of the present invention preferably contains only a compound having a boiling point of 210 ° C. or lower, preferably 160 ° C. or lower, or a compound that does not decompose even when heated to 250 ° C.
- the “compound that is not decomposable even when heated to 250 ° C.” is a compound whose weight change after holding at 250 ° C. under nitrogen for 1 hour with respect to the weight measured at 25 ° C. is less than 50%. I mean.
- the semiconductor sealing composition of the present invention has a volume average particle diameter measured by a dynamic light scattering method of 10 nm or less.
- the volume average particle diameter exceeds 10 nm, the adhesion with the wiring material may be deteriorated, or the diffusion of the metal component to the interlayer insulating layer may not be sufficiently suppressed.
- the volume average particle size is determined by using the ELSZ-2 manufactured by Otsuka Electronics Co., Ltd. at 23-26 ° C., the dynamic light scattering method (the temporal fluctuation of the scattered light observed by the dynamic light scattering method is measured by (E.g., conditions such as 70 times of integration and 1 time of repetition).
- the volume average particle diameter exceeds 10 nm, specifically, when micelles (average particle diameter is 10 nm or more) are formed in the composition, or wiring is formed in the composition. This is the case where abrasive grains such as metal oxides used for polishing copper (chemical mechanical polishing) are contained.
- abrasive grains such as metal oxides used for polishing copper (chemical mechanical polishing) are contained.
- micelles having a large particle size are formed in the semiconductor seal composition, for example, when the semiconductor seal composition of the present invention is applied to the manufacture of a semiconductor device having a wiring interval of 32 nm or less, the semiconductor seal The resin constituting the composition may not sufficiently enter the concave groove in which the wiring material is embedded, and may not sufficiently cover the pores on the side surface of the groove.
- the pH of the semiconductor sealing composition of the present invention is not particularly limited, but the pH is preferably higher than the isoelectric point of the interlayer insulating layer from the viewpoint of the adsorptivity of the resin to the interlayer insulating layer.
- the pH of the said sealing composition for semiconductors is the range of pH in which the said cationic functional group is a cation state.
- the isoelectric point of the interlayer insulating layer is the isoelectric point indicated by the compound constituting the interlayer insulating layer.
- the isoelectric point is around pH 2 (25 ° C).
- the range of pH the cationic functional group is in a state of a cation refers to the pH of the semiconductor sealing composition is less than or equal to pK b of a resin containing a cationic functional group.
- pK b is 8-9, when polyethyleneimine, pK b is 7-11.
- the pH of the semiconductor sealing composition can be appropriately selected according to the type of compound constituting the interlayer insulating layer and the type of resin, and is preferably pH 2 to 11, for example, pH 7 More preferably, it is ⁇ 11.
- pH (25 degreeC) is measured using the pH measuring apparatus used normally.
- a manufacturing method of a semiconductor device of the present invention is a manufacturing method of a semiconductor device having an interlayer insulating layer on a substrate, and includes a sealing composition applying step of contacting the semiconductor sealing composition with the interlayer insulating layer, If necessary, it further includes other steps.
- the interlayer insulating layer in the present invention is composed of a low dielectric constant material and is not particularly limited as long as it is porous, but preferably contains porous silica and has a silanol residue derived from porous silica on the surface. . When the silanol residue interacts with a cationic functional group contained in the resin, a thin layer made of the resin is formed so that the resin covers pores on the interlayer insulating layer.
- porous silica As the porous silica in the present invention, porous silica usually used for an interlayer insulating layer of a semiconductor device can be used without particular limitation. For example, uniform mesopores utilizing the self-organization of an organic compound and an inorganic compound that are hydrothermally synthesized in a sealed heat-resistant container using silica gel and a surfactant described in the WO 91/11390 pamphlet. And oxides having the above-mentioned properties, and the condensates of alkoxysilanes and surfactants described in Nature, 1996, 379 (page 703) or Supramolecular Science, 1998, 5 (page 247).
- the porous silica etc. which are made can be mentioned. Especially, it is preferable to use the porous silica formed using the composition for porous silica formation containing the specific siloxane compound shown below.
- composition for forming porous silica includes (A) a hydrolyzate of an alkoxysilane compound, (B) a hydrolyzate of a siloxane compound represented by the following general formula (1),
- R A and R B are each independently a hydrogen atom, a phenyl group, a —C a H 2a + 1 group, a — (CH 2 ) b (CF 2 ) c CF 3 group, or a —C d H represents a 2d-1 group, provided that R A and R B are not simultaneously hydrogen atoms.
- R C and R D each represent a single bond that connects a silicon atom and an oxygen atom to form a cyclic siloxane structure, or each independently represents a hydrogen atom, a phenyl group, a —C a H 2a + 1 group, It represents a — (CH 2 ) b (CF 2 ) c CF 3 group or a —C d H 2d-1 group.
- a represents an integer of 1 to 6
- b represents an integer of 0 to 4
- c represents an integer of 0 to 10
- d represents an integer of 2 to 4
- n represents an integer of 3 or more.
- porous silica-forming composition of this embodiment porous silica having both a low dielectric constant and high mechanical strength can be formed.
- the composition for forming porous silica in the present invention may further comprise a solvent such as water or an organic solvent, a catalyst, or the like, if necessary.
- the composition in the present invention contains a hydrolyzate of an alkoxysilane compound (excluding an alkoxysilane compound which is a siloxane compound represented by the general formula (1)) as the component (A).
- the alkoxysilane compound is hydrolyzed (and polycondensed as necessary) to become a hydrolyzate (component (A)).
- the hydrolyzate is a component that forms the main skeleton of the resulting porous material, and is preferably a dense inorganic polymer.
- the alkoxysilane compound undergoes polycondensation at the site of silanol groups generated by hydrolysis of alkoxy groups (alkoxy groups bonded to silicon atoms) to form an inorganic polymer.
- the component (A) as a dense inorganic polymer, it is preferable that at least two alkoxy groups are contained in one molecule of the alkoxysilane compound to be used.
- two or more alkoxy groups may be bonded to one silicon atom.
- the alkoxysilane compound may be a compound in which two or more bond units in which one alkoxy group is bonded to one silicon are contained in the same molecule.
- the alkoxysilane compound is selected from the group consisting of a compound represented by the following general formula (i), a compound represented by the following general formula (ii), and a compound represented by the following general formula (iii). It is preferable that it is at least one kind.
- R 1 s may be the same or different and each represents a —C a H 2a + 1 group or a phenyl group, and a is an integer of 1 to 6. ]
- R 2 represents a —C a H 2a + 1 group, a phenyl group, — (CH 2 ) c (CF 2 ) b CF 3 group, a hydrogen atom, or a fluorine atom, and when x is 2 or less, 2 R 3 may be the same or different from each other, and each represents a —C a H 2a + 1 group or a phenyl group, x is an integer of 0 to 3, a is an integer of 1 to 6, and b is an integer of 0 to 10 , C is an integer of 0-4. ]
- R 5 and R 6 may be the same or different from each other, and each represents a —C a H 2a + 1 group or a phenyl group, a is an integer of 1 to 6, b is an integer of 0 to 10, and c is an integer of 0 to 4. Indicates an integer.
- A represents an oxygen atom, a — (CH 2 ) d — group, or a phenylene group, and d is an integer of 1 to 6.
- alkoxysilane compound in the present invention include quaternary alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetrabutoxysilane; trimethoxyfluorosilane, triethoxyfluorosilane, and triisopropoxy.
- quaternary alkoxyfluorosilanes such as fluorosilane and tributoxyfluorosilane;
- Tertiary alkylalkylsilanes such as trimethoxymethylsilane, triethoxymethylsilane, trimethoxyethylsilane, triethoxyethylsilane, trimethoxypropylsilane, triethoxypropylsilane;
- Tertiary alkoxyarylsilanes such as trimethoxyphenylsilane, triethoxyphenylsilane, trimethoxychlorophenylsilane, triethoxychlorophenylsilane;
- Tertiary alkoxy phenethyl silane such as trimethoxy phenethyl silane, triethoxy phenethyl silane;
- Secondary alkoxyalkylsilanes such as dimethoxydimethylsilane and diethoxydimethylsilane;
- one or more selected from the above alkoxysilane compounds can be used.
- the composition for forming porous silica in the present invention contains (B) at least one hydrolyzate of a siloxane compound represented by the general formula (1).
- the siloxane compound represented by the general formula (1) is preferably a cyclic siloxane compound, and more preferably a cyclic siloxane compound represented by the following general formula (2).
- R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are each independently a hydrogen atom, a phenyl group, a —C a H 2a + 1 group, — (CH 2 ) b (CF 2 ) c represents a CF 3 group or a —C d H 2d-1 group.
- R 8 and R 9 are not simultaneously hydrogen atoms
- R 10 and R 11 are not simultaneously hydrogen atoms
- R 12 and R 13 are not simultaneously hydrogen atoms.
- a represents an integer of 1 to 6
- b represents an integer of 0 to 4
- c represents an integer of 0 to 10
- d represents an integer of 2 to 4, respectively.
- L represents an integer of 0 to 8
- m represents an integer of 0 to 8
- n represents an integer of 0 to 8, and 3 ⁇ L + m + n ⁇ 8.
- cyclic siloxane compound examples include tris (3,3,3-trifluoropropyl) trimethylcyclotrisiloxane, triphenyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane, 1,3,5,7-tetra.
- the cyclic siloxane compound that can be used in the present invention may be one or more of these. Of the above cyclic siloxanes, 1,3,5,7-tetramethylcyclotetrasiloxane is particularly preferred.
- the composition for forming porous silica in the present invention contains (C) at least one surfactant.
- the surfactant is not particularly limited, and for example, a surfactant having a molecular weight of 200 to 5000 is preferable. When the molecular weight is small, sufficient pores may not be formed, and thus the dielectric constant of the porous silica may not be lowered. When the molecular weight is large, the formed pores become too large and obtained. The mechanical strength of the porous silica may decrease.
- Preferable examples include the following surfactants.
- a compound having a long-chain alkyl group and a hydrophilic group preferably has 8 to 24 carbon atoms, and more preferably has 12 to 18 carbon atoms.
- the hydrophilic group include a quaternary ammonium salt, an amino group, a nitroso group, a hydroxy group, and a carboxyl group, and among them, a quaternary ammonium salt or a hydroxy group is preferable.
- an alkylammonium salt represented by the following general formula (x) is preferable as the surfactant.
- the vacancies formed will have a more appropriate size, and the target compound will be sufficient in the gas phase reaction after vacancy formation. It penetrates into the pores and the intended polymerization reaction is likely to occur.
- polyalkylene oxide structure examples include a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, and a polybutylene oxide structure.
- the compound having a polyalkylene oxide structure include polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxybutylene block copolymer; polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether, Ether type compounds such as oxyethylene alkylphenyl ether; ether ester type compounds such as polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene sorbitol fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester; Etc.
- one or more selected from the above surfactants can be used.
- composition in the present invention contains at least one element (D) having an electronegativity of 2.5 or less (element (D)).
- element (D) used in the present invention has, for example, the effect of increasing the reactivity between the component (A) and the component (B), and increasing the hydrophobicity and mechanical strength of the finally obtained porous material. is there.
- the organic functional group of the component (B) is extracted by the element (D) to become a reactive site, and as a result, the component (B) is efficiently converted into the component ( It is presumed that a dense inorganic polymer is formed by combining with the component A).
- the (D) element is an element having a reversible bonding state with respect to the elements in the composition such as Si, O, and C.
- an element having a Pauling's electronegativity different from Si, O, and C is preferable.
- an element having an electronegativity lower than an electronegativity of 3.5 is preferable, an element having an electronegativity lower than an electronegativity of 2.5 is more preferable, and an electronegativity of Si is 1 More preferred are elements having an electronegativity of less than .8.
- the metal element contained in the porous material is required to have a property of being stably present in the porous material regardless of any stress, particularly an electrical stress. Further, the metal element is required to have a property of not adversely affecting elements other than the porous material (porous film) in the object to which the porous material is applied, for example, in a semiconductor device. When the element contained at this time is a normal metal element, it adversely affects the performance of the semiconductor itself, which is not preferable.
- the element (D) a large element having an ionic radius of 1.6 mm or more which is difficult to move even when some electrical stress is applied to the porous film is preferable. Further, as the element (D), a heavy element (element having an atomic number of 55 or more) classified into the sixth period in the periodic table is preferable in terms of atomic weight of 130 or more.
- Typical (D) elements that satisfy the above-described conditions and can be used in the present invention include, for example, B, Al, P, Zn, Ga, Ge, As, Se, In, Sn, Sb, Te, Rb, and Cs. Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, At, and a lanthanoid. Further, at least one element selected from the group consisting of Cs, Ba, lanthanoid, Hf, P, Pb, Bi, Po, Se, Te, As, Rb, Al, and Sn is preferable. More preferably, it is at least one element selected from the group consisting of Cs, Ba, La, Hf, Ta, W and lanthanoid. Moreover, these elements should just exist in at least 1 sort (s) in the composition in this invention.
- the method for introducing the (D) element may be a method for introducing the (D) element itself or a method for introducing a compound containing the (D) element, and the addition method is particularly limited. Is not to be done.
- the compound containing the element (D) is not particularly limited, and examples thereof include nitrate compounds, oxide compounds, organometallic compounds, and basic compounds.
- it may be a known compound containing the element (D) in the present invention. Using these compounds, the element (D) can be introduced. Under the present circumstances, it is preferable to introduce
- composition for forming porous silica in the present invention preferably contains (E) a hydrolyzate of a disilyl compound represented by the following general formula (3).
- E a hydrolyzate of a disilyl compound represented by the following general formula (3).
- R 14 to R 19 each independently represent a hydrogen atom, a phenyl group, a —C a H 2a + 1 group, or a — (CH 2 ) b (CF 2 ) c CF 3 group.
- a represents an integer of 1 to 6
- b represents an integer of 0 to 4
- c represents an integer of 0 to 10, respectively.
- X represents an oxygen atom or a> NR 20 group
- R 20 represents a hydrogen atom or a —C e H 2e + 1 group
- e represents an integer of 1 to 3.
- disilyl compound represented by the general formula (3) examples include hexamethyldisilazane, hexaethyldisilazane, hexaphenyldisilazane, hexamethyldisiloxane, hexaethyldisiloxane, hexaphenyldisiloxane. Examples thereof include siloxane.
- the disilyl compound that can be used in the present invention can be used alone or in combination of two or more thereof. Of the disilyl compounds, hexamethyldisiloxane is preferred.
- examples of other silyl compounds include trimethylsilyl chloride, triethylsilyl chloride, trimethylsilyldimethylamine, trimethylsilyldiethylamine, trimethylsilyldiphenylamine, and the like.
- the interlayer insulating layer in the present invention is formed by, for example, applying the porous silica-forming composition on a substrate to form a composition layer, heat-treating the formed composition layer, and heat-treating the composition layer. It can be formed by irradiating with UV rays.
- the substrate is not particularly limited, and examples thereof include glass, quartz, silicon wafer, stainless steel, and plastic.
- the shape is not particularly limited, and may be any of a plate shape, a dish shape, and the like.
- the method for applying the composition to the substrate is not particularly limited, and examples thereof include general methods such as spin coating, casting, and dipping.
- a substrate is placed on a spinner, a coating solution is dropped onto the substrate, and the rotation is performed at 100 to 10,000 rpm.
- a precursor material which is a silica sol containing the component (A), the component (B), the surfactant (C) and the element (D) is obtained on the substrate.
- the obtained composition layer is heat-treated in the next step.
- the heating temperature in the heat-sensitive heat treatment is preferably 80 to 400 ° C.
- the heat treatment here refers to heat treatment at a temperature of less than 200 ° C. (low temperature heat treatment) for the purpose of removing volatile components such as an organic solvent and water, and heat treatment of a surfactant added for pore formation. Any heat treatment (high temperature heat treatment) at 200 ° C. or higher for the purpose of decomposing and removing is included. Since the precursor material immediately after coating is in a state where an organic solvent or water is adsorbed in the precursor material, it is preferable to remove volatile components by low-temperature heat treatment.
- the temperature of the low-temperature heat treatment is 80 to 200 ° C., preferably 100 to 150 ° C.
- the time required for the low-temperature heat treatment may be 1 minute or more, but if it exceeds a certain time, the curing rate becomes extremely slow. Therefore, considering the efficiency, 1 to 60 minutes is preferable.
- the method for heating the silica sol is not particularly limited, and any known method for heating the sol can be employed.
- high-temperature heat treatment is performed.
- the heating temperature in the high-temperature heat treatment the higher the temperature, the easier the decomposition of the surfactant.
- the temperature is 400 ° C. or lower, more preferably 350 ° C. or lower.
- a temperature of at least 200 ° C. or more, preferably 300 ° C. or more is preferable considering the process time.
- high-temperature heating can be performed by a known method without any particular limitation in the heating atmosphere, such as nitrogen, oxygen, hydrogen, air, etc., but when performed in a semiconductor process, wiring resistance increases due to oxidation of Cu wiring. It is preferable to carry out in a non-oxygen atmosphere.
- the non-oxidizing atmosphere indicates that the oxygen concentration during firing (high-temperature heat treatment) is 50 ppm or less.
- a form in which the above-described composition layer is first heat-treated at 80 ° C. to 200 ° C. and then heat-treated at 300 ° C. to 400 ° C. is particularly preferable.
- the wavelength of ultraviolet light is preferably 10 nm to 400 nm, more preferably 150 nm to 250 nm. If it is this range, it has sufficient energy to cut
- the ultraviolet intensity affects the functional group cleavage time, and the higher the ultraviolet intensity, the shorter the time. Therefore, the intensity is preferably 1 mW / cm 2 to 50 mW / cm 2 , more preferably 5 mW / cm 2 to 20 mW / cm 2 .
- the ultraviolet irradiation temperature is preferably 10 to 400 ° C., more preferably 150 to 350 ° C., and particularly preferably 200 to 350 ° C.
- a high temperature is preferable because the reaction rate is improved in the cleavage between the functional group and the silicon atom by ultraviolet irradiation and the reaction between the functional group-cut site and silanol.
- the pressure during the ultraviolet irradiation can be preferably carried out in the range of 0.01 kPa to 101.3 kPa.
- the oxygen concentration is preferably controlled to 10 ppm or less.
- the method for bringing the semiconductor sealing composition of the present invention into contact with the interlayer insulating layer is not particularly limited, and a commonly used method can be used.
- a dipping method for example, see US Pat. No. 5,208,111
- a spray method for example, Schlenoff et al., Langmuir, 16 (26), 9968, 2000, Izquierdo et al., Langmuir, 21 (16), 7558, 2005
- Spin coat method see, for example, Lee et al., Langmuir, 19 (18), 7592, 2003, J. Polymer Science, part B, polymer physics, 42, 3654, 2004
- the like for example, a dipping method (for example, see US Pat. No. 5,208,111), a spray method (for example, Schlenoff et al., Langmuir, 16 (26), 9968, 2000, Izquierdo et al., Langmuir, 21 (16), 7558, 2005
- the resin layer made of the resin can be formed in a thin layer on the interlayer insulating layer by using the semiconductor sealing composition containing the resin.
- the thickness of the resin layer is not particularly limited, but is, for example, 0.3 nm to 5 nm, preferably 0.5 nm to 2 nm.
- the semiconductor sealing composition contains a resin having a cationic functional group equivalent of 43 to 430, and the semiconductor sealing composition has a pH of the interlayer insulating layer or the like. It is preferably within a pH range that is not less than the electric point and the cationic functional group is in a cationic state, more preferably 2 to 11, and still more preferably 7 to 11. .
- the resin is more efficiently adsorbed on the interlayer insulating layer.
- the isoelectric point of the interlayer insulating layer and the pH range in which the cationic functional group is in the cation state are as described above.
- the concentration of the resin contained in the semiconductor sealing composition used in the sealing composition application step of the present invention is preferably less than the critical micelle concentration of the resin.
- the resin can be applied to the interlayer insulating layer in a thin layer shape (for example, 5 nm or less, preferably 2 nm or less), and an increase in dielectric constant can be suppressed.
- the method for manufacturing a semiconductor device of the present invention further includes a step of forming a concave groove having a width of 10 nm to 32 nm in the interlayer insulating layer, and the step of applying the sealing composition includes an interlayer insulation on at least the side surface of the concave groove.
- the step is preferably a step of bringing the semiconductor sealing composition into contact with the layer.
- the step of forming a concave groove having a width of 10 nm to 32 nm in the interlayer insulating layer can be performed according to the manufacturing process conditions of a semiconductor device that is normally used.
- a groove having a desired pattern can be formed by forming a hard mask and a photoresist on the interlayer insulating layer and etching according to the pattern of the photoresist.
- the dipping method, spray method, and spin coating method described above can be used as a method of bringing the semiconductor sealing composition into contact with the interlayer insulating layer on the side surface of the concave groove.
- the dipping method, spray method, and spin coating method described above can be used as a method of bringing the semiconductor sealing composition into contact with the interlayer insulating layer on the side surface of the concave groove.
- the process performed normally such as a wiring formation process
- the wiring formation step can be performed according to known process conditions. For example, copper wiring is formed by metal CVD, sputtering, or electrolytic plating, and the film is smoothed by CMP. Next, a cap film is formed on the surface of the film. Further, if necessary, a hard mask can be formed and multilayered by repeating the above steps, and the semiconductor device of the present invention can be manufactured.
- a barrier film (copper barrier layer) forming step can be further provided after the sealing composition applying step and before the wiring forming step.
- the barrier film forming step can be performed in accordance with commonly used process conditions.
- a barrier film made of a titanium compound such as titanium nitride or a tantalum compound such as tantalum nitride can be formed by vapor deposition (CVD).
- CVD vapor deposition
- the semiconductor device of the present invention includes a porous interlayer insulating layer, a resin layer having a weight average molecular weight of 2000 to 100,000 having two or more cationic functional groups, and a thickness of 0.3 nm to 5 nm.
- a layer made of copper has a structure arranged in this order, and includes other layers as necessary. Since a resin layer containing a specific resin is disposed between the interlayer insulating layer and the wiring material, generation of leakage current and the like is suppressed even in a fine circuit configuration of 32 nm or less, and excellent characteristics are exhibited. be able to.
- a copper barrier layer (preferably a layer made of a tantalum compound) is further disposed between the resin layer and the wiring material containing copper.
- the semiconductor device of the present invention can be manufactured by the method for manufacturing a semiconductor device.
- composition for forming porous silica An aqueous cesium nitrate solution was added to 300 g of the precursor solution until the Cs concentration became 15 ppm. Next, 1.7 g of 1,3,5,7-tetramethylcyclotetrasiloxane was added and stirred at 25 ° C. for 1 hour to obtain a composition for forming porous silica. At this time, the amount of 1,3,5,7-tetramethylcyclotetrasiloxane added was 10 mol% with respect to tetraethoxysilane.
- a porous silica forming composition (1.0 mL) was dropped onto the silicon wafer surface, rotated at 2000 rpm for 60 seconds, applied to the silicon wafer surface, then applied at 150 ° C. for 1 minute in a nitrogen atmosphere, and then at 350 ° C. for 10 minutes. Heat-treated for minutes. Then, it heated to 350 degreeC within the chamber equipped with the 172 nm excimer lamp, and the interlayer insulation layer (porous silica film
- the obtained interlayer insulating layer had a relative dielectric constant k of 2.0 and an elastic modulus E of 6.60 GPa.
- the density was measured in the usual manner using an XRD apparatus (Rigaku Corporation, TPR-In-Plane), with an X-ray power supply of 50 kV, 300 mA, and a wavelength of 1.5418 mm, in a scanning range of 0 to 1.5 °. It was measured.
- the relative dielectric constant was measured by a conventional method at a frequency of 1 MHz in an atmosphere of 25 ° C. and a relative humidity of 30% using a mercury probe apparatus (SSM5130).
- the elastic modulus was measured by a conventional method using a nanoindenter (Hysitron, Triboscope) at an indentation depth of 1/10 or less of the film thickness.
- Example 1 Polyethyleneimine aqueous solution 1 (PEI, manufactured by BASF, weight average molecular weight 25,000, 250 mg / 100 mL, pH 10.52, cationic property was obtained by using the interlayer insulating layer (hereinafter sometimes referred to as “low-k”) obtained above.
- the functional group equivalent 309) was contacted by a spray method (solution contact time 20 seconds, spray distance 10 cm) using a commercially available spray bottle “AIR-BOY” (Carl Roth GmbH). Next, water was contacted by a spray method (contact time of ultrapure water 10 seconds, spray distance 10 centimeters) using a spray bottle similar to the above.
- the resin layer was formed on the interlayer insulating layer by drying with air blow.
- evaluation was "A”.
- A The difference in contact angle exceeded 30 °.
- B The difference in contact angle was 20 ° or more and 30 or less.
- C The difference in contact angle was less than 20 °.
- a cross-sectional sample of sample 1 (low-k / PEI / Cu) obtained above was prepared using SMI2050 (manufactured by Seiko Instruments Inc.) as the FIB processing apparatus. Using a JEM-2200FS (manufactured by JEOL Ltd., acceleration voltage 220 kV) as a transmission electron microscope, the cross section of the sample in which the metal copper film was formed on the resin layer was observed, and the diffusion depth of the metal component was measured. The diffusion depth of the metal component was 0 nm.
- Adhesion evaluation 1 In the same manner as described above, a sample (Si / PEI) in which a resin layer was formed on a silicon wafer was produced. A metal copper film was formed on the resin layer in the same manner as above except that this was used, and a sample (Si / PEI / Cu) was produced. When the adhesion of the metal copper film was evaluated for the obtained sample (Si / PEI / Cu) as follows, the evaluation was “A” level.
- Adhesion evaluation 2 In the same manner as described above, a sample (low-k / PEI) in which a resin layer was formed on an interlayer insulating layer (low-k) was produced. A metal copper film was formed on the resin layer in the same manner as described above except that this was used to prepare a sample (low-k / PEI / Cu). The obtained sample (low-k / PEI / Cu) was evaluated for the adhesion of the metal copper film as follows. The evaluation was “B”.
- Example 1 a sample C1 was produced in the same manner as in Example 1 except that ultrapure water was used instead of the polyethyleneimine aqueous solution.
- the sample C1 obtained above was evaluated for the diffusion of the metal component in the same manner as in Example 1.
- the diffusion depth of the metal component was 20 nm, which was a practically problematic level.
- the evaluation was “A” level.
- the evaluation was performed in the same manner as the adhesion evaluation 2 of Example 1, Since the resin layer was not formed on the insulating layer, the evaluation was “A” level, and the evaluation result of the difference in water contact angle was “C”.
- the volume average particle diameter by the dynamic light scattering method was below the detection limit.
- Example 2 a resin layer was formed in the same manner as in Example 1 except that a polyethylene glycol aqueous solution (PEG, manufactured by Wako Pure Chemical Industries, Ltd., 100 mg / 100 mL, weight average molecular weight 10,000) was used instead of the polyethyleneimine aqueous solution.
- Sample C2 was prepared.
- the thickness of the resin layer formed in the same manner as in Example 1 was estimated, it was 5 nm or less.
- the adhesiveness was evaluated in the same manner as in the above-mentioned adhesiveness evaluation 2, the evaluation was “D” and the adhesiveness was poor.
- the evaluation result of the difference in water contact angle was “B”.
- the volume average particle diameter determined by the dynamic light scattering method was below the detection limit ( ⁇ 10 nm).
- the RMS When the morphology of the surface of the resin layer was observed with an atomic force microscope, the RMS was about 50 nm, and a thin uniform layer could not be formed.
- the volume average particle diameter determined by the dynamic light scattering method was 99.5 nm as a result of histogram analysis.
- a thin resin layer can be formed by bringing the semiconductor sealing composition of the present invention into contact with the porous interlayer insulating layer to form a resin layer, and the metal to the porous interlayer insulating layer can be formed. It can be seen that the diffusion of components can be suppressed and the adhesion of the wiring material is excellent.
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Abstract
Description
このような多孔質構造を有する半導体層間絶縁層においては、誘電率をさらに低下させるために空隙率を大きくすると、配線材料として埋め込まれる銅などの金属成分が半導体層間絶縁層中の細孔に入り込みやすくなり、誘電率が上昇したり、リーク電流が発生したりする場合があった。
また例えば、国際公開第09/012184号パンフレットには、low-k材料が疎水性の表面を有する場合に、ポリビニルアルコール系両親媒性ポリマーをその表面に付与することで材料の親水性・疎水性を制御する技術が開示されている。
さらに例えば、特開2006-352042号公報には、カチオン性ポリマーと界面活性剤を含む半導体研磨用組成物が開示されている。
また、国際公開第09/012184号パンフレットに記載の技術では、ポリビニルアルコール系両親媒性ポリマー間の水素結合により、嵩高い層が形成されやすく、これによる比誘電率の上昇や、層間絶縁層と配線材料の密着性の低下が発生する場合があった。
すなわち本発明の第1の態様は、2以上のカチオン性官能基を有する重量平均分子量が2000~100000の樹脂を含有し、ナトリウムおよびカリウムの含有量がそれぞれ元素基準で10重量ppb以下であって、動的光散乱法で測定された体積平均粒子径が10nm以下である半導体用シール組成物である。
前記樹脂は、カチオン性官能基当量が43~430であることが好ましい。
また前記カチオン性官能基が1級アミノ基および2級アミノ基から選択された少なくとも1種であることが好ましく、前記樹脂がポリエチレンイミンまたはポリエチレンイミン誘導体であることがより好ましい。
前記層間絶縁層は、多孔質シリカを含み、その表面に前記多孔質シリカに由来するシラノール残基を有することが好ましい。
前記層間絶縁層に10nm~32nm幅の凹状の溝が形成される工程をさらに含み、前記シール組成物付与工程は、前記凹状の溝の側面の層間絶縁層に前記半導体用シール組成物を付与する工程であることがより好ましい。
本発明の半導体用シール組成物は、例えば、多孔質の層間絶縁層上に形成された細孔を被覆する樹脂層を形成するために用いられ、2以上のカチオン性官能基を有する重量平均分子量が2000~100000の樹脂の少なくとも1種を含有し、ナトリウムおよびカリウムの含有量が、それぞれ元素基準で10重量ppb以下であって、動的光散乱法で測定された体積平均粒子径が10nm以下である。
かかる構成の半導体用シール組成物を、多孔質構造を有する層間絶縁層に付与すると、例えば、前記樹脂が有する2以上のカチオン性官能基が前記層間絶縁層上に多点吸着して、前記層間絶縁層の表面に存在する細孔(ポア)が樹脂層によって被覆される。これにより多孔質の層間絶縁層への金属成分の拡散を抑制することができる。さらに、前記樹脂が形成する樹脂層は薄層(例えば、5nm以下)であるため、層間絶縁層と、樹脂層を介して層間絶縁層上に形成された配線材料との密着性に優れ、比誘電率の変化を抑制することができる。
本発明の半導体用シール組成物は、2以上のカチオン性官能基を有する重量平均分子量が2000~100000の樹脂の少なくとも1種を含む。
前記樹脂は、カチオン性官能基の少なくとも1種を2以上有するものであるが、必要に応じて、アニオン性官能基やノニオン性官能基をさらに有していてもよい。また前記樹脂は、カチオン性官能基を有する繰り返し単位構造を有するものであってもよく、また特定の繰り返し単位構造を持たず、樹脂を構成するモノマーが分岐的に重合して形成されるランダムな構造を有するものであってもよい。本発明においては、金属成分の拡散抑制の観点から、前記樹脂は特定の繰り返し単位構造を持たず、樹脂を構成するモノマーが分岐的に重合して形成されるランダムな構造を有するものであることが好ましい。
また前記ノニオン性官能基は、水素結合受容基であっても、水素結合供与基であってもよい。例えば、ヒドロキシ基、カルボニル基、エーテル結合等を挙げることができる。
さらに前記アニオン性官能基は、負電荷を帯びることができる官能基であれば特に制限はない。例えば、カルボン酸基、スルホン酸基、硫酸基等を挙げることができる。
さらに多孔質の層間絶縁層の表面を公知の方法、例えば、国際公開第04/026765号パンフレット、国際公開第06/025501号パンフレットなどに記載の方法で疎水化処理した場合は、前記表面の極性基の密度が減少するので、200~400であることもまた好ましい。
ここでカチオン性官能基当量とは、カチオン性官能基当たりの重量平均分子量を意味し、樹脂の重量平均分子量(Mw)を、1分子に相当する樹脂が含むカチオン性官能基数(n)で除して得られる値(Mw/n)である。このカチオン性官能基当量が大きいほどカチオン性官能基の密度が低く、一方、カチオン性官能基当量が小さいほどカチオン性官能基の密度が高い。
さらに前記特定単位構造がカチオン性官能基を2以上含む場合、2以上のカチオン性官能基は同一であっても異なっていてもよい。
また前記カチオン性官能基は、多孔質層間絶縁層上に存在するカチオン性官能基の吸着点(例えば、シラノール残基)間の平均距離に対する、特定単位構造の主鎖長の比(以下、「カチオン性官能基間の相対距離」ということがある)が、0.08~1.2となるように含まれていることが好ましく、0.08~0.6となるように含まれていることがより好ましい。かかる態様であることで樹脂が多孔質の層間絶縁層上に、より効率的に多点吸着しやすくなる。
本発明における特定単位構造は、層間絶縁層への吸着性の観点から、カチオン性官能基間の相対距離が0.08~1.2であって、分子量が30~500であることが好ましく、カチオン性官能基間の相対距離が0.08~0.6であって、分子量が40~200であることがより好ましい。
前記ノニオン性官能基を含む単位構造として、具体的には、ビニルアルコールに由来する単位構造、アルキレンオキシドに由来する単位構造、ビニルピロリドンに由来する単位構造等を挙げることができる。
前記第2の単位構造としては、前記特定単位構造を構成するモノマーと重合可能なモノマーに由来する単位構造であれば特に制限はない。例えば、オレフィンに由来する単位構造等を挙げることができる。
かかる樹脂を構成し得るモノマーとしては、例えば、エチレンイミンおよびその誘導体を挙げることができる。
また本発明におけるポリエチレンイミンは、モノエタノールアミンから得られる粗エチレンイミンを用いて得られたものであってもよい。具体的には例えば特開2001-2123958号公報等を参照することができる。
これらのポリエチレンイミン誘導体は、上記ポリエチレンイミンを用いて通常行われる方法により製造することができる。具体的には例えば、特開平6―016809号公報等に記載の方法に準拠して製造することができる。
例えば、本発明の半導体用シール組成物を、配線間隔が32nm以下で層間絶縁層上の細孔直径が2nm程度である半導体装置の製造に適用する場合、前記樹脂の重量平均分子量が100000よりも大きいと、樹脂の大きさが配線間隔よりも大きくなり、樹脂が、配線材料が埋め込まれる凹状の溝に入り込めず、溝の側面の細孔が十分に被覆されない場合がある。また、重量平均分子量が2000未満であると、層間絶縁層上の細孔直径よりも樹脂分子の大きさが小さくなり、樹脂分子が層間絶縁層上の細孔に入り込んで層間絶縁層の誘電率が上昇する場合がある。また多点で吸着しない場合がある。
尚、重量平均分子量は、樹脂の分子量測定に通常用いられるGPC装置を用いて測定される。
本発明の半導体用シール組成物は、ナトリウムおよびカリウムの含有量がそれぞれ元素基準で10重量ppb以下である。ナトリウムまたはカリウムの含有量がそれぞれ元素基準で10重量ppbを越えると、リーク電流が発生する場合がある。
なお前記「250℃まで加熱しても分解性を有さない化合物」とは、25℃で測定した重量に対する、250℃、窒素下で1時間保持した後の重量の変化が50%未満の化合物のことをいう。
本発明において体積平均粒子径は、大塚電子社製ELSZ-2を用い、23-26℃において、動的光散乱法(動的光散乱法で観測された散乱光の時間的揺らぎを、光子相関法を用いて解析する方法、例えば、積算回数70回、繰り返し回数1回などの条件)で測定される。
半導体用シール組成物中に粒子径の大きいミセルが形成されていると、例えば、本発明の半導体用シール組成物を配線間隔が32nm以下である半導体装置の製造に適用する場合に、半導体用シール組成物を構成する樹脂が、配線材料が埋め込まれる凹状の溝に充分に入り込むことができず、溝の側面の細孔を充分に被覆できない場合がある。
また、前記カチオン性官能基がカチオンの状態であるpHの範囲とは、半導体用シール組成物のpHが、カチオン性官能基を含む樹脂のpKb以下であることをいう。例えば、カチオン性官能基を含む樹脂がポリアリルアミンである場合、pKbは8~9であり、ポリエチレンイミンである場合、pKbは7~11である。
すなわち、本発明において半導体用シール組成物のpHは、層間絶縁層を構成する化合物種類と、樹脂の種類とに応じて適宜選択することができ、例えば、pH2~11であることが好ましく、pH7~11であることがより好ましい。
尚、pH(25℃)は通常用いられるpH測定装置を用いて測定される。
本発明の半導体装置の製造方法は、基板上に層間絶縁層を有する半導体装置の製造方法であって、前記半導体用シール組成物を、前記層間絶縁層に接触させるシール組成物付与工程を含み、必要に応じて、その他の工程をさらに含んで構成される。
本発明における層間絶縁層は、低誘電率材料から構成され、多孔質性であれば特に制限はないが、多孔質シリカを含み、表面に多孔質シリカに由来するシラノール残基を有することが好ましい。前記シラノール残基が、前記樹脂に含まれるカチオン性官能基と相互作用することにより、前記樹脂が層間絶縁層上の細孔を被覆するように前記樹脂からなる薄層が形成される。
本発明における多孔質シリカとしては、半導体装置の層間絶縁層に通常用いられる多孔質シリカを特に制限なく用いることができる。例えば、WO91/11390パンフレットに記載されたシリカゲルと界面活性剤等とを用いて、密封した耐熱性容器内で水熱合成する有機化合物と無機化合物との自己組織化を利用した均一なメソ細孔を持つ酸化物や、Nature誌、1996年、379巻(703頁)またはSupramolecular Science誌、1998年、5巻(247頁等)に記載されたアルコキシシラン類の縮合物と界面活性剤とから製造される多孔質シリカ等を挙げることができる。
中でも、以下に示す特定のシロキサン化合物を含む多孔質シリカ形成用組成物を用いて形成される多孔質シリカを用いることが好ましい。
本発明における多孔質シリカ形成用組成物は、(A)アルコキシシラン化合物の加水分解物と、(B)下記一般式(1)で表されるシロキサン化合物の加水分解物と、
RC及びRDは、ケイ素原子と酸素原子とを相互に連結して環状シロキサン構造を形成する単結合を表すか、または、それぞれ独立に、水素原子、フェニル基、-CaH2a+1基、-(CH2)b(CF2)cCF3基、もしくは-CdH2d-1基を表す。
aは1~6の整数を、bは0~4の整数を、cは0~10の整数を、dは2~4の整数を、nは3以上の整数をそれぞれ表わす。)
また本発明における多孔質シリカ形成用組成物は、必要に応じて、水や有機溶剤等の溶媒、触媒等をさらに含んで構成することができる。
前記加水分解物は、得られる多孔質材料の主骨格を形成する成分であり、緻密な無機ポリマーであることが好ましい。
前記アルコキシシラン化合物は、アルコキシ基(ケイ素原子に結合したアルコキシ基)の加水分解により生じたシラノール基の部位で重縮合し、無機ポリマーを形成する。このため、緻密な無機ポリマーとして(A)成分を得るためには、使用するアルコキシシラン化合物1分子中に少なくともアルコキシ基が2つ以上含まれることが好ましい。ここで、アルコキシ基は、1つのケイ素原子に2つ以上結合してもよい。また、前記アルコキシシラン化合物は、1つのケイ素に1つのアルコキシ基が結合した結合単位が、同一分子内に2つ以上含まれる化合物であってもよい。
〔式中、R1は互いに同一でも異なってもよく、それぞれ-CaH2a+1基、またはフェニル基を示し、aは1~6の整数である。〕
〔式中、R2は、-CaH2a+1基、フェニル基、-(CH2)c(CF2)bCF3基、水素原子、またはフッ素原子を示し、xが2以下の場合、2以上のR3は互いに同一でも異なってもよく、それぞれ-CaH2a+1基、またはフェニル基を示し、xは0~3の整数、aは1~6の整数、bは0~10の整数、cは0~4の整数である。〕
〔式中、y、zは互いに同一でも異なってもよく、0~2の整数、R4及びR7は互いに同一でも異なってもよく、それぞれ、-CaH2a+1基、フェニル基、-(CH2)c(CF2)bCF3基、水素原子、又はフッ素原子を示す。R5及びR6は互いに同一でも異なってもよく、それぞれ-CaH2a+1基、又はフェニル基を示し、aは1~6の整数、bは0~10の整数、cは0~4の整数を示す。Aは、酸素原子、-(CH2)d-基、又はフェニレン基を示し、dは1~6の整数である。〕
トリメトキシフェネチルシラン、トリエトキシフェネチルシラン等の3級アルコキシフェネチルシラン;
aは1~6の整数を、bは0~4の整数を、cは0~10の整数を、dは2~4の整数をそれぞれ表わす。
Lは0~8の整数を、mは0~8の整数を、nは0~8の整数をそれぞれ表わし、かつ3≦L+m+n≦8である。
本発明において用いられ得る環状シロキサン化合物は、これらの中から1種又は2種以上を用いることができる。上記環状シロキサンのうち、1,3,5,7-テトラメチルシクロテトラシロキサンが特に好ましい。
前記界面活性剤としては特に制限はないが、例えば、分子量200~5000の界面活性剤が好ましい。分子量が小さい場合には、十分な空孔が形成されないため多孔質シリカの低誘電率化ができない場合があり、また、分子量が大きい場合には、形成される空孔が大きくなりすぎ、得られる多孔質シリカの機械強度が低下する場合がある。
好ましくは、例えば、以下の界面活性剤を挙げることができる。
ここで、長鎖アルキル基としては、好ましくは炭素原子数8~24のもの、さらに好ましくは炭素原子数12~18のものである。また、親水基としては、例えば、4級アンモニウム塩、アミノ基、ニトロソ基、ヒドロキシ基、カルボキシル基等が挙げられ、なかでも4級アンモニウム塩、又はヒドロキシ基であることが好ましい。
前記界面活性剤として具体的には、次の一般式(x)で示されるアルキルアンモニウム塩が好ましい。
〔上記一般式(x)中、aは0~2の整数であり、bは0~4の整数であり、nは8~24の整数であり、mは0~12の整数であり、Lは1~24の整数であり、Xは水酸化物イオン、ハロゲン化物イオン、HSO4 -又は1価の有機アニオンを表す。〕
ここで、ポリアルキレンオキシド構造としてはポリエチレンオキシド構造、ポリプロピレンオキシド構造、ポリテトラメチレンオキシド構造、ポリブチレンオキシド構造等を挙げることができる。
前記ポリアルキレンオキサイド構造を有する化合物としては、具体的には、ポリオキシエチレンポリオキシプロピレンブロックコポリマー、ポリオキシエチレンポリオキシブチレンブロックコポリマー;ポリオキシエチレンポリオキシプロピレンアルキルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル等のエーテル型化合物;ポリオキシエチレングリセリン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリエチレンソルビトール脂肪酸エステル、ソルビタン脂肪酸エステル、プロピレングリコール脂肪酸エステル、ショ糖脂肪酸エステル等のエーテルエステル型化合物;等を挙げることができる。
本発明における組成物は、(D)電気陰性度が2.5以下の元素((D)元素)の少なくとも1種を含有する。
本発明で用いる(D)元素は、例えば、前記(A)成分と前記(B)成分との反応性を高め、最終的に得られる多孔質材料の疎水性、及び、機械強度を高める効果がある。
また、(D)元素としては、原子量では130以上、具体的には周期律表における第6周期に分類される重い元素(原子番号55以上の元素)が好ましい。
これらの化合物を用いて、(D)元素を導入することができる。この際、これらの化合物と、水やアルコール等の有機溶媒と、の混合物として導入することが好ましい。
Xは、酸素原子、または>NR20基を表し、R20は水素原子または-CeH2e+1基を表し、eは1~3の整数を表わす。
また、一般式(3)で表されるジシリル化合物は、その他のシリル化合物と併用してもよい。その他のシリル化合物としては、塩化トリメチルシリル、塩化トリエチルシリル、トリメチルシリルジメチルアミン、トリメチルシリルジエチルアミン、トリメチルシリルジフェニルアミン等が挙げられる。
前記基板としては、特に制限されず、例えば、ガラス、石英、シリコンウエハ、ステンレス、プラスチック等を挙げることができる。またその形状も、特に制限されず、板状、皿状等のいずれであってもよい。
該感熱処理における加熱温度は、80~400℃が好ましい。
ここでいう加熱処理とは、有機溶媒、水などの揮発成分を除去することを目的とした200℃未満での加熱処理(低温加熱処理)と、空孔形成のため添加した界面活性剤を熱分解除去することを目的とした200℃以上での加熱処理(高温加熱処理)のいずれの加熱処理についても含まれる。
塗布直後の前駆体材料は、有機溶媒や水が前駆体材料中に吸着した状態であるので、低温加熱処理により、揮発成分を除去することが好ましい。
前記低温加熱処理の温度は、80~200℃、好ましくは100~150℃である。この温度であれば、有機溶媒、水のような揮発成分が除去され、しかも、急激な加熱による組成物層の膨れ、剥がれ等の不都合は生じない。低温加熱処理に要する時間は、1分以上あればよいが、ある時間を超えると硬化速度は極端に遅くなるので、効率を考えれば1~60分が好ましい。
シリカゾルを加熱させる方法としては特に制限されず、ゾルを加熱させるための公知の方法をいずれも採用できる。
前記高温加熱処理における加熱温度は、高温ほど界面活性剤の分解が容易となるが、半導体プロセス上の問題を考慮すれば、400℃以下好ましくは、350℃以下の温度であることがより好ましい。少なくとも200℃以上、好ましくは300℃以上の温度がプロセス時間も考慮すると好ましい。また、高温加熱は、窒素、酸素、水素、空気など、加熱雰囲気に特に制限はなく公知の方法によって実施できるが、半導体プロセスで実施する場合では、Cu配線の酸化により配線抵抗が上昇するため、非酸素雰囲気下で実施することが好ましい。ここでいう非酸化性雰囲気とは、焼成(高温加熱処理)時の酸素濃度が50ppm以下であることを示す。
例えば、紫外線の波長は、好ましくは10nm~400nm、さらに好ましくは150nm~250nmである。この範囲であれば、上述の(B)成分中の官能基をケイ素原子から切断するだけの十分なエネルギーを持つ。紫外線強度は、官能基の切断時間などに影響を及ぼし、紫外線強度が高いほど、時間が短縮されるので、好ましくは1mW/cm2~50mW/cm2、さらに好ましくは5mW/cm2~20mW/cm2である。
前記層間絶縁層の等電点、および前記カチオン性官能基がカチオンの状態であるpHの範囲については、既述の通りである。
かかる態様であることで、層間絶縁層に形成された凹状の溝の側面を構成する層間絶縁層上に存在する細孔を効果的に被覆することができ、前記凹状の溝に配線材料を埋め込む場合に、配線材料を構成する金属成分が層間絶縁層中に拡散することを抑制することができる。
尚、凹状の溝の側面とは、基板と平行な面に対してほぼ直交するように形成された面を意味する。
本発明においては、前記半導体用シール組成物を層間絶縁層に接触させた後、必要に応じて洗浄工程や乾燥工程をさらに設けてもよい。
配線形成工程は、公知のプロセス条件に従って行うことができる。例えば、メタルCVD法、スパッタリング法または電解メッキ法により銅配線を形成し、CMPにより膜を平滑化する。次いでその膜の表面にキャップ膜を形成する。さらに必要であれば、ハードマスクを形成し、上記の工程を繰り返すことで多層化することができ、本発明の半導体装置を製造することができる。
前記バリア膜形成工程は、通常用いられるプロセス条件に従って行うことができる。前記シール組成物付工程後に、例えば、気相成長法(CVD)により、窒化チタン等のチタン化合物や窒化タンタル等のタンタル化合物からなるバリア膜を形成することができる。本発明においては、タンタル化合物からなるバリア膜を形成することが好ましい。
本発明の半導体装置は、多孔質の層間絶縁層と、2以上のカチオン性官能基を有する重量平均分子量が2000~100000の樹脂を含み、厚さが0.3nm~5nmである樹脂層と、銅からなる層と、がこの順で配置された構造を備え、必要に応じてその他の層を含んで構成される。層間絶縁層と配線材料との間に、特定の樹脂を含む樹脂層が配置されていることで32nm以下の微細な回路構成であってもリーク電流等の発生が抑制され、良好な特性を示すことができる。
本発明においては、前記樹脂層と前記銅を含む配線材料との間に、銅バリア層(好ましくは、タンタル化合物からなる層)がさらに配置されていることが好ましい。
尚、本発明の半導体装置は、前記半導体装置の製造方法によって製造することができる。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書に参照により取り込まれる。
テトラエトキシシラン(山中セミコンダクター製、電子工業グレード、Si(OC2H5)4)。
1,3,5,7-テトラメチルシクロテトラシロキサン(トリケミカル社製の環状シロキサン化合物、電子工業グレード、(CH3Si(H)O)4)。
ポリオキシエチレン(20)ステアリルエーテル(シグマケミカル社製、商品名:Brij78、C18H37(CH2CH2O)2OH)を、電子工業用エタノールに溶解した後、イオン交換樹脂を用いて10ppb以下まで脱金属処理を施したものである。
硝酸セシウム水溶液(和光純薬、特級、CsNO3)中のセシウム(Cs)。
ヘキサメチルジシロキサン(アルドリッチ製、((CH3)3Si)2O)を蒸留精製したものである。
脱金属処理された抵抗値18MΩ以上の純水。
エタノール(和光純薬製、電子工業グレード、C2H5OH)
1-プロピルアルコール(関東化学製、電子工業グレード、CH3CH2CH2OH)
2-ブチルアルコール(関東化学製、電子工業グレード、CH3(C2H5)CHOH)。
1,3,5,7-テトラメチルシクロテトラシロキサン(トリケミカル社製、電子工業グレード、(CH3Si(H)O)4)。
90.9gのテトラエトキシシランと70.9gのエタノールを室温下で混合攪拌した後、1mol/Lの硝酸80mLを添加し、50℃で1時間撹拌した。次に、20.9gのポリオキシエチレン(20)ステアリルエーテルを280gのエタノールで溶解した溶液を滴下混合した。混合後、30℃で4時間撹拌した。得られた溶液を25℃、30hPaの減圧下、90gになるまで濃縮した。濃縮後、1-プロピルアルコールと2-ブチルアルコールを体積で1:1に混合した溶液を添加し、前駆体溶液1885gを得た。
前駆体溶液300gに硝酸セシウム水溶液をCs濃度が15ppmとなるまで添加した。次いで、1,3,5,7-テトラメチルシクロテトラシロキサン1.7gを添加し、25℃で1時間撹拌し、多孔質シリカ形成用組成物を得た。この時の1,3,5,7-テトラメチルシクロテトラシロキサンの添加量は、テトラエトキシシランに対して10モル%であった。
多孔質シリカ形成用組成物1.0mLをシリコンウエハ表面上に滴下し、2000rpmで60秒間回転させて、シリコンウエハ表面に塗布した後、窒素雰囲気下150℃で1分間、次いで、350℃で10分間加熱処理した。その後、172nmエキシマランプを装備したチャンバー内で350℃まで加熱し、圧力1Paで出力14mW/cm2により、紫外線を10分間照射することにより、層間絶縁層(多孔質シリカ膜)を得た。
得られた層間絶縁層の密度は、0.887g/cm3であった。
また、得られた層間絶縁層の、比誘電率kは2.0、弾性率Eは6.60GPaであった。
また比誘電率は、水銀プローブ装置(SSM5130)を用い、25℃、相対湿度30%の雰囲気下、周波数1MHzにて常法により比誘電率を測定した。
また弾性率は、ナノインデンテーター(Hysitron社、Triboscope)により、膜厚の1/10以下の押し込み深さで常法により弾性率を測定した。
上記で得られた層間絶縁層(以下「low-k」ということがある)に、ポリエチレンイミン水溶液1(PEI、BASF社製、重量平均分子量25,000、250mg/100mL、pH10.52、カチオン性官能基当量309)を、市販のスプレーボトル”AIR-BOY”(Carl Roth GmbH社製)を用いて、スプレー法(溶液の接触時間20秒、スプレー距離10センチメートル)で接触させた。次いで水を、上記と同様のスプレーボトルを用いて、スプレー法(超純水の接触時間10秒、スプレー距離10センチメートル)により接触させた。エアブローにより乾燥させて、層間絶縁層上に樹脂層を形成した。その後、23℃55%の恒温恒湿環境に15時間以上保管した試料(low-k/PEI)について以下の評価を行なった。
尚、「水」、には、超純水(Millipore社製Milli-Q水、抵抗18MΩ・cm(25℃)以下)を使用した。
得られた試料(以下、「low-k/PEI」ということがある)について、FACE固体表面エナジー解析装置(CA-XE型)を用いて、水の接触角を23℃55%RHの環境下で常法により測定したところ、13.2°であった。
~評価基準~
A:接触角の差が30°を超えていた。
B:接触角の差が20°以上30以下であった。
C:接触角の差が20°未満であった。
得られた試料(low-k/PEI)について、XPS装置としてESCALAB220iXL(VG社製)を用い、X線源AlKα、分析領域φ1mmの条件で、形成された樹脂層の元素組成を測定したところ、上記で得られた層間絶縁層(low-k)と比較して増加した組成は、C/N=2.34であった。これにより、ポリエチレンイミンの層が形成されたことが確認できた。
また原子間力顕微鏡により樹脂層表面の形態観察を行ったところ、RMSが0.369nm(層間絶縁層のみで0.403nm)であり、均一な厚みの層が形成されていた。
得られた試料(low-k/PEI)の樹脂層上にスパッタリングにより金属銅膜を形成して試料1(以下、「low-k/PEI/Cu」ということがある)を作製した。
得られた試料1(low-k/PEI/Cu)を目視により観察したところ、樹脂層上に金属銅色の金属膜が形成されていることが確認できた。
尚、スパッタリングは、装置としてHSM-521(島津製作所製)を用い、設定電流0.4A、設定電圧440V、Ar雰囲気下、スパッタ時間2分10秒の条件で行なった。
上記で得られた試料1(low-k/PEI/Cu)について、表面形状測定装置として、DEKTAK3(Veeco Metrology Group社製、version 3.22b FP/J)を用いて形成された金属膜の膜厚を測定したところ、50nm~100nmであった。
上記で得られた試料1(low-k/PEI/Cu)について、FIB加工装置としてSMI2050(セイコーインスツルメンツ社製)を用いて、断面試料を作製した。透過型電子顕微鏡としてJEM-2200FS(日本電子社製、加速電圧220kV)を用いて樹脂層上に金属銅膜が形成された試料の断面を観察して、金属成分の拡散深度を測定したところ、金属成分の拡散深度は0nmであった。
上記で得られた試料1(low-k/PEI/Cu)の断面を上記と同様にして観察し、元素マッピングを行った。ポリエチレンイミンに由来する窒素原子の分布状態から、形成された樹脂層の厚さを見積もったところ、5nm以下であった。
上記と同様にして、シリコンウエハ上に樹脂層を形成した試料(Si/PEI)を作製した。これを用いた以外は上記と同様にして樹脂層上に金属銅膜を形成し、試料(Si/PEI/Cu)を作製した。得られた試料(Si/PEI/Cu)について金属銅膜の密着性を以下のようにして評価したところ、評価は「A」レベルであった。
測定試料を窒素・水素雰囲気下、350℃で30分加熱処理した後、23℃55%の恒温恒湿環境に15時間以上保管した。その後、JIS K5600に準じた碁盤目試験(ただしテープとして、ニチバン社製のセロハンテープ(CT405AP-18 幅18mm)を使用した)を行い、下記評価基準に従って密着性を評価した。
A:カットの縁が完全に滑らかで、どの格子の目にもはがれがなかった。
B:カットの交差点における小さなはがれがあった。クロスカット部分で影響を受けたのは5%以下だった。
C:カットの縁に沿ってまたは交差点においてはがれがあった。クロスカット部分で影響を受けたのは5%を越えて15%以下だった。
D:カットの縁に沿って部分的または大はがれが生じ、格子の目において部分的または全面的なはがれがあった。クロスカット部分で影響を受けたのは15%を越えて35%以下だった。
E:カットの縁に沿って部分的または大はがれが生じ、数箇所の格子の目において部分的または全面的なはがれがあった。クロスカット部分で影響を受けたのは15%を越えて35%以下だった。
F:カットの縁に沿って部分的または大はがれが生じ、多数箇所の格子の目において部分的または全面的なはがれがあった。クロスカット部分で影響を受けたのは35%を越えていた。
上記と同様にして、層間絶縁層(low-k)上に樹脂層を形成した試料(low-k/PEI)を作製した。これを用いた以外は上記と同様にして樹脂層上に金属銅膜を形成し、試料(low-k/PEI/Cu)を作製した。得られた試料(low-k/PEI/Cu)について金属銅膜の密着性を以下のようにして評価したところ、評価は「B」であった。
測定試料を、23℃、55%の恒温恒湿環境に15時間以上保管した。その後、JIS K5600に準じた碁盤目試験(ただしテープとして、ニチバン社製のセロハンテープ(CT405AP-18 幅18mm)を使用した)を行った。露出した面を光学顕微鏡(株式会社ハイロックス製デジタルマイクロスコープKH-7700)、電界放出型走査電子顕微鏡(JEOL製JSM-6701F)、表面形状測定装置(DEKTAK3(Veeco Metrology Group社製、version 3.22b FP/J))により形態を観察した。さらに各露出面はJEOL製エネルギー分散形X線分析装置(EX-37001)を用いて元素分析を実施して同定した。下記評価基準に従って密着性を評価した。
A:low-k材料の残存面積が、10%未満(Si露出面積が90%以上)
B:low-k材料の残存面積が、10%以上30%未満(Si露出面積が70%以上90%未満)
C:low-k材料の残存面積が、30%以上90%未満(Si露出面積が10%以上70%未満)
D:low-k材料の残存面積が、90%以上(Si露出面積が10%未満)
実施例1におけるポリエチレンイミン水溶液1について、大塚電子製ELSZ-2を用いて動的光散乱法により体積平均粒子径を測定したところ、検出限界以下(<10nm)であった。
尚、測定条件は、積算回数70回、繰り返し回数1回、解析条件は、ヒストグラム解析、キュムラント解析を用いた。
実施例1において、ポリエチレンイミン水溶液の代わりに、超純水を用いた以外は実施例1と同様にして、試料C1を作製した。
上記で得られた試料C1について、実施例1と同様にして金属成分の拡散評価を行なったところ、金属成分の拡散深度は20nmであり、実用上問題のあるレベルだった。
また、金属膜の密着性を実施例1の密着性評価1と同様にして評価したところ、評価は「A」レベルであり、実施例1の密着性評価2と同様にして評価したところ、層間絶縁層の上に樹脂層が形成されていないため、評価は「A」レベルであり、水の接触角の差の評価結果は「C」であった。
尚、動的光散乱法による体積平均粒子径は、検出限界以下であった。
実施例1において、ポリエチレンイミン水溶液の代わりに、ポリエチレングリコール水溶液(PEG、和光純薬社製、100mg/100mL、重量平均分子量10000)を用いた以外は実施例1と同様にして、樹脂層を形成した試料C2を作製した。
実施例1と同様にして形成された樹脂層の厚さを見積もったところ、5nm以下であった。
さらに上記密着性評価2と同様にして、密着性を評価したところ評価は「D」であり、密着性に劣っていた。水の接触角の差の評価結果は「B」であった。
尚、動的光散乱法による体積平均粒子径は、検出限界以下(<10nm)であった。
国際公開2009/087961号パンフレットの段落番号[0283]合成例A6に準拠して、エチレン重合体の末端にポリエチレングリコール鎖が結合したポリマー(数平均分子量6115、以下「AB3」と称する)を調製し、これを超純水に溶解して、AB3水溶液(100mg/mL、pH7.64)を得た。
上記で得られたAB3水溶液を用いたこと以外は、実施例1と同様にして、層間絶縁層(low-k)上に樹脂層を形成した試料C3を作製した。水の接触角の差の評価結果は「B」であった。
原子間力顕微鏡により樹脂層表面の形態観察を行ったところ、RMSが約50nmであり、薄い均一な層を形成することができなかった。
尚、動的光散乱法による体積平均粒子径は、ヒストグラム解析の結果、99.5nmであった。
Claims (9)
- 2以上のカチオン性官能基を有する重量平均分子量が2000~100000の樹脂を含有し、ナトリウムおよびカリウムの含有量がそれぞれ元素基準で10重量ppb以下であって、動的光散乱法で測定された体積平均粒子径が10nm以下である、半導体用シール組成物。
- 前記樹脂は、カチオン性官能基当量が43~430である、請求項1に記載の半導体用シール組成物。
- 前記カチオン性官能基は、1級アミノ基および2級アミノ基から選択された少なくとも1種である、請求項1または請求項2に記載の半導体用シール組成物。
- 前記樹脂は、ポリエチレンイミンまたはポリエチレンイミン誘導体である、請求項1~請求項3のいずれか1項に記載の半導体用シール組成物。
- 請求項1~請求項4のいずれか1項に記載の半導体用シール組成物を、基板上に形成された層間絶縁層に付与するシール組成物付与工程を含む、半導体装置の製造方法。
- 前記層間絶縁層は、多孔質シリカを含み、その表面に前記多孔質シリカに由来するシラノール残基を有する、請求項5に記載の半導体装置の製造方法。
- 前記層間絶縁層に10nm~32nm幅の凹状の溝が形成される工程をさらに含み、
前記シール組成物付与工程は、少なくとも前記凹状の溝の側面の層間絶縁層に、前記半導体用シール組成物を接触させる、請求項5または請求項6に記載の半導体装置の製造方法。 - 多孔質の層間絶縁層と;
2以上のカチオン性官能基を有する重量平均分子量が2000~100000の樹脂を含み、厚さが0.3nm~5nmである樹脂層と;
銅からなる層と;
がこの順で配置された構造を備える、半導体装置。 - 前記樹脂層と前記銅からなる層との間に、銅バリア層がさらに配置された、請求項8に記載の半導体装置。
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EP2357664A1 (en) | 2011-08-17 |
JP2011103490A (ja) | 2011-05-26 |
CN102224577A (zh) | 2011-10-19 |
EP2357664A4 (en) | 2014-07-30 |
TWI423402B (zh) | 2014-01-11 |
US20110241210A1 (en) | 2011-10-06 |
JPWO2010137711A1 (ja) | 2012-11-15 |
KR20110086573A (ko) | 2011-07-28 |
SG173429A1 (en) | 2011-09-29 |
KR101186719B1 (ko) | 2012-09-27 |
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US8304924B2 (en) | 2012-11-06 |
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